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Studies in Natural
Products Chemistry
Volume 52
Edited by
Atta-ur-Rahman, FRS
International Center for Chemical and Biological Sciences
H.E.J. Research Institute of Chemistry
University of Karachi
Karachi, Pakistan
Elsevier
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Contributors
Eugene V. Babaev (69), Moscow State University, Moscow, Russia; Moscow Institute
of Physics and Technology, Moscow, Russia
Luiz C.A. Barbosa (115), Universidade Federal de Minas Gerais, Belo Horizonte, MG,
Brazil; Universidade Federal de Viçosa, Viçosa, MG, Brazil
Hailey M. Cambra (193), Worcester Polytechnic Institute, Worcester, MA,
United States
Monika Celuch (1), Institute of Nuclear Chemistry and Technology, Warsaw, Poland
Madhubrata Chaudhury (373), Presidency University, Kolkata, India
Li Chen (269), Université Paris Sud, Université Paris Saclay, Châtenay-Malabry,
France
Matthew R. Desrosiers (193), Worcester Polytechnic Institute, Worcester, MA,
United States
Abhijit Dey (373), Presidency University, Kolkata, India
Françoise Dumas (269), Université Paris Sud, Université Paris Saclay, Châtenay-
Malabry, France
Martha Estrella Garcı́a-Pérez (231), Universidad Michoacana de San Nicolás de
Hidalgo, Morelia, Mich, Mexico
Subhalakshmi Ghosh (303), Jadavpur University, Kolkata, India
Banasri Hazra (303), Jadavpur University, Kolkata, India
Sudipta Hazra (303), Jadavpur University, Kolkata, India
Kinga Hęclik (1), University of Rzeszów, Rzeszow, Poland
Pierre Betu Kasangana (231), Université Laval, Québec, QC, Canada
Joanna Kisa1a (1), University of Rzeszów, Rzeszow, Poland
Mohammad Kousara (269), Université Paris Sud, Université Paris Saclay, Châtenay-
Malabry, France
Franck Le Bideau (269), Université Paris Sud, Université Paris Saclay, Châtenay-
Malabry, France
Agnieszka Mas1owska (1), University of Rzeszów, Rzeszow, Poland
Anuradha Mukherjee (373), MMHS, Dakshin Brasat, West Bengal, India
Antonio Pérez-Gálvez (159), Instituto de la Grasa, CSIC, Seville, Spain
xiii
xiv Contributors
Diana C.G.A. Pinto (337), Department of Chemistry & Organic Chemistry, Natural
Products and Food Stuffs (QOPNA), University of Aveiro, Campus de Santiago,
Aveiro, Portugal
Dariusz Pogocki (1), University of Rzeszów, Rzeszow, Poland; Institute of Nuclear
Chemistry and Technology, Warsaw, Poland
Dina Rassias (193), Worcester Polytechnic Institute, Worcester, MA, United States
Marı́a Roca (159), Instituto de la Grasa, CSIC, Seville, Spain
Ana M.L. Seca (337), cE3c-Centre for Ecology, Evolution and Environmental
Changes/Azorean Biodiversity Group & Faculty of Sciences and Technology,
University of Azores, Rua Mãe de Deus, Ponta Delgada, Portugal; Department of
Chemistry & Organic Chemistry, Natural Products and Food Stuffs (QOPNA),
University of Aveiro, Campus de Santiago, Aveiro, Portugal
Artur M.S. Silva (337), Department of Chemistry & Organic Chemistry, Natural
Products and Food Stuffs (QOPNA), University of Aveiro, Campus de Santiago,
Aveiro, Portugal
Tatjana Stevanovic (231), Université Laval, Québec, QC, Canada
Melissa J. Towler (193), Worcester Polytechnic Institute, Worcester, MA,
United States
Eduardo V.V. Varejão (115), Universidade Federal de Viçosa, Viçosa, MG, Brazil
Jodieh O.S. Varejão (115), Universidade Federal de Minas Gerais, Belo Horizonte,
MG, Brazil; Universidade Federal de Viçosa, Viçosa, MG, Brazil
Pamela J. Weathers (193), Worcester Polytechnic Institute, Worcester, MA,
United States
Lai Wei (269), Université Paris Sud, Université Paris Saclay, Châtenay-Malabry,
France
Preface
This 52nd volume of Studies in Natural Product Chemistry presents 10

outstanding chapters contributed by leading experts of their respective fields.
The synthesis of nanoparticles has become a hot topic due to their various
applications in medical, biomedical, ocular, and other scientific fields. Pogocki
et al. present a review on the recent development in the biosynthesis of metal
nanoparticles, metal oxide nanoparticles, coreeshell, and bimetallic systems
nanoparticles in natural environments. 2-Aminoimidazoles (AI) are important
basic compounds obtained from marine sponges. In Chapter 2, Babaev dis-
cusses the synthesis of 2-aminoimidazoles from other heterocycles.
A variety of novel bioactive metabolites that have been isolated from
marine organisms with great structural diversity. Furanocembranolides
constitute a group of such natural compounds. Barbosa et al. present a review
on the biological sources, isolation, and bioactivity of furanocembranolides.
The major synthetic strategies to obtain key structural subunits and to the total
synthesis of a range of natural furanocembranolides and analogs are also
discussed.
Phyllobilins represent a family of chlorophyll catabolites that are structurally
similar to tetrapyrroles. Roca and Pérez-Gálvez review the recent findings about
structure, methods of analysis, and isolation of phyllobilins, and the relationship
between structure of phyllobilins and possible physiological actions in Chapter
4. Artemisinin isolated from the Artemisia annua has been used widely for
treating malaria. This naturally occurring compound has a diverse effect on the
immune system. Weathers et al. assessed the isolation and therapeutic efficacy
as well as the mechanisms of action of this molecule in Chapter 5.
In Chapter 6, Stevanovic et al. have analyzed the pharmacology of
bioactive polyphenols isolated from the forest biomass. These polyphenols are
important therapeutic applicants for diseases like diabetes and psoriasis. The
marine environment is a rich natural source of bioactive natural compounds
and pharmacological agents. Heterocyclic sesquiterpenes are a class of ter-
penes comprising over 500 representatives and having strong anticancer po-
tential. A detailed discussion on the antifeedant, antiinfective, and cytotoxic
activities of nonhalogenated heterocyclic sesquiterpenes (NH-HTSQTs) is
presented by Dumas et al. in Chapter 7.
It is important to identify the molecular target for developing a new drug
against any infectious disease. Phytochemicals are the substances that are
xv
xvi Preface
naturally found in plants and can act as a valuable source for designing novel
therapeutic agents. Hazra et al. present an overview of the recent findings on
some important phytochemicals, their molecular targets, and mechanism of
action against leishmania parasites in Chapter 8. Further in Chapter 9, Seca
et al. describe the biological activities of parthenolide and parthenolide-like
sesquiterpene lactones isolated from several families of plants, fungi, and
invertebrates. These are biologically active compounds with potential thera-
peutic and medical applications against cancer, inflammation, septic shock,
and others syndromes.
The family Apocynaceae contains approximately 250 genera and 2000
species. Many alkaloids that are isolated from this family are clinically
important. The origin, pharmacology, medicinal significance, structural, and
biological properties of these compounds have been discussed by Dey et al. in
Chapter 10.
I hope that this volume will be of great interest for the readers. I would like
to appreciate the efforts Ms. Taqdees Malik and Ms. Humaira Hashmi for their
help and assistance in the preparation of this volume. I am also grateful to
Mr. Mahmood Alam for the editorial support.
Prof. Atta-Ur-Rahman, FRS

International Center for Chemical and Biological Sciences
H.E.J. Research Institute of Chemistry
University of Karachi
Karachi, Pakistan
Chapter 1
Natural Environments for

Nanoparticles Synthesis of
Metal, Metal Oxides,
CoreeShell and Bimetallic
Systems
Joanna Kisała,*, 1 Kinga Hęclik,* Agnieszka Masłowska,* Monika Celuchx,
Dariusz Pogocki*,x,1
*University of Rzeszów, Rzeszow, Poland; xInstitute of Nuclear Chemistry and Technology,
Warsaw, Poland
1
Corresponding authors: E-mail: pogo@univ.rzeszow.pl; jkisala@univ.rzeszow.pl
Chapter Outline
Introduction 2 Metal Oxide Nanoparticles 20
Key Concepts of Biological Zinc Oxide (ZnO) 20
Nanosynthesis, State of the Art 4 Titanium Dioxide (TiO2) 21
Biosynthesis of NPs by Bacteria 6 Zirconium Dioxide (ZrO2) 22
Metal Nanoparticles 6 Biosynthesis of NPs in Plant
Silver 6 Extracts 23
Gold 9 Metal Nanoparticles 23
Copper 11 Silver 23
Metal Oxide Nanoparticles 12 Gold 30
Zinc Oxide (ZnO) 12 Copper 34
Titanium Dioxide (TiO2) 13 Metal Oxide NPs 35
Biosynthesis of NPs by Fungi 15 Copper Oxide (CuO) 35
Metal Nanoparticles 15 Zinc Oxide (ZnO) 36
Silver 15 Titanium Dioxide (TiO2) 38
Gold 18 Zirconium Dioxide (ZrO2) 40
Studies in Natural Products Chemistry, Vol. 52. http://dx.doi.org/10.1016/B978-0-444-63931-8.00001-1

Copyright © 2017 Elsevier B.V. All rights reserved. 1
2 Studies in Natural Products Chemistry
Core@Shell and Mixed NPs 41 Summary 60

Ti/Ni 41 Terms, Abbreviations, and
Cu@Cu2O 48 Acronyms 61
Au@Ag Core Shell NPs and Acknowledgments 62
Ag/Au Bimetallic NPs 49 References 62
Mechanistic Concepts 53
INTRODUCTION
Since the advent of nanotechnology (the last quarter century), a plethora of NPs
synthesis methods has been developed. The synthetic pathways are established
based on the two main philosophies or ideas: (1) top-downdmethods of
controlled “crumbling” of macroscopic materials by the mechanical or chemical
techniques until the size of the particles reaches the nanoscale [1], and (2)
bottom-updmethods of molecular nanotechnology assembling organic or
inorganic nanostructures (e.g., NPs) from very small blocks; atom by atom,
molecule by molecule, or nanoparticle by nanoparticledaccording on expected
properties of the nanostructure. This quite complicated and sophisticated
approach (CVD methods, solegel process, chemical reduction of metal salts)
allows gradual increase of precursory particles, i.e., nucleation, where every step
of such synthesis can utilize different blocks (atoms, molecules, etc.) [2]. Well-
known techniques, such as ball milling process, photolithography, and electron
beam lithography, anodization, and ion etching and plasma etching (PE), belong
to top-down type of approach. Both general pathways can be accomplished in
various environments, i.e., solutions, gas phase, supercritical fluids, or vacuum
[3]. So far, chemical and physicalechemical methods dominate in current
technological practice. The main disadvantages of physical methods are the
quality of the product. Moreover, these methods require costly vacuum systems
or equipments to prepare nanoparticles.
The efficiency of the chemical synthesis methods to the utmost degree
depends on the availability of particular reagents, metals, metal oxides, inor-
ganic metal salts, or its metalorganic precursors [4]. The other main disad-
vantages are demanding reaction conditions such as certain range of
temperature and pressure, application of inflammable solvents, etc. The use-
fulness of the method can be additionally limited by the lack of its scalability
and/or control of the crystalline suspension [5]. Several types of NPs chemical
synthesis methods can be distinguished: the gas phase, the solegel [3,4], the
sonochemical processes [6], the hydrodynamic cavitation technology [7], the
microemulsion method [8], and the high energy milling (machining) [9,10].
Chemical and physical nanoparticles preparation methods are not eco-
friendly, due to the requirement of hazardous chemicals, production of
Natural Environments Chapter j 1 3
dangerous by-products, low material conversions, and high energy demand

[11]. Moreover, expensive production and generation of NPs of specific,
mainly spherical shape, limits the range of their properties, and their potential
applications [11,12]. Therefore a movement “toward greener nanosynthesis”
in recent years definitely directs to the “bio-based” [13] or “bio-inspired” [14]
approaches.
Biosynthesized nanoparticles are widely used in different areas including
targeted drug delivery, cancer treatment, gene therapy and DNA analysis,
antibacterial agents, biosensors, enhancing reaction rates, separation science,
and magnetic resonance imaging (MRI) due to their biocompatible surface
potential.
Biological methods utilize naturally occurring compounds and therefore
seem to possess less of disadvantages typical to chemical synthesis. One of the
basic principles of bionanotechnology is the ability of biomolecules to self-
assemble into supramolecular structures. Such ability has directed the inter-
est of scientists and engineers to develop novel bottom-up approaches to
nanostructure fabrication. Biological self-assembly that occurs at the molec-
ular scale is often reversible, self-correcting, and self-healing. The shape and
size of self-assembled structures are complexly controlled on the nanoscale.
Size and shape are crucial attributes to the tunability of NPs. Controlling these
parameters using biological methods will be essential in developing new
nanostructures; therefore bionanotechnology takes advantage of natural bio-
mechanisms to create NPs using biological molecules or organisms as pre-
cursors or seeds for growth [15e18].
Complex interactions between microorganisms and metals are quite well
documented [19e21]. Since the advent at the beginning of 21st century,
various biological methods of metallic NPs synthesis, made of Au, Ag, Pt, Zr,
Ti, and many others metals and metal alloys, have appeared in the laboratory
practice. The range of applied microorganisms is also quite wide including
actinobacteria, bacteria, fungi, yeasts, and viruses [12,22e29].
The ability of microorganisms to reduce metals, which is widely applied in
bioremediation and bioleaching, recently made them useful and eco-friendly
nano-factories [12,30].
Numerous unicellular organisms are able to produce mineral structures
from inorganic materials in intracellular or extracellular space [12,30]. NPs
synthesized by microorganisms are relatively stable but generally not
monodispersive [30]. One of the ways to overcome the difficulties is an
optimization of some factors influencing synthesis, e.g., microorganisms
breeding [31] or the attempts to the combinatorial approach such as photo-
biological methods [28].
Deep understanding of the mechanisms of nanoparticle synthesis on the
cellular, biochemical, and molecular levels provides crucial information that
should improve speed, quality, and useful properties of NPs, being a key to
biomimetics [28]. On the molecular level biomimetic synthesis apply standard
redox reactions executed in or by selected microorganism [32e34], enzymes

[35,36], fungi [37e39], and plant or plant extracts [40,41].
KEY CONCEPTS OF BIOLOGICAL NANOSYNTHESIS, STATE

OF THE ART
It must be admitted that the precise mechanism of nanoparticle synthesis is
still far from the understanding. For metal NPs, the subject was excellently
reviewed in the book of Rai and Duran [42], and just recently by groups of
Yang and Li [14], and Choudhary [29].
It is generally assumed that some biological structures and molecules are
able to make a distinction between particular metal ions, and the others are
“specialized” in the synthesis. Furthermore, the mechanism of synthesis in the
intracellular and extracellular space is different, depending on various biological
factors. In the intracellular synthesis the interactions on cell wall seems crucial.
As negatively charged, the wall binds positively charged metal ions due to
columbic forces. The cell wall is rich in naturally immobilized molecules of
enzymes, which are able to chemically bind metal ions and cause their bio-
reduction to metals forming particles. Some particles, limited mainly by size
and shape, are able to diffuse through the wall to the extracellular fluid. This
mechanical concept has been applied to explain the intramolecular synthesis of
metal NPs by fungi Verticillium sp. by Mukherjee and coworkers [5]. They have
given the following names for three major steps of the mechanism: (1) trapping,
(2) bioreduction, and (3) synthesis. The trapping step is then the cells on surface
of fungi get the contact with metal cations, and the cations are held by the
electrostatic forces. Bioreduction by the cell wall enzymes is followed by ag-
gregation (synthesis) of metallic nanoclusters [5]. For some organisms, like
common Lactobacillus sp. strains found in buttermilk, another preliminary
extracellular step can be distinguisheddnamely nucleation of metal cation
clusters, in which small nanoclusters (nuclei or seeds) of atoms are formed.
Here, particle growth appears to occur via intracellular reduction of the metal
ions, while most of the smaller metal clusters that nucleate the growth of NPs
are diffused into the cell from the reducing extracellular fluid. It is worth
noticing that the nuclei of NPs are also formed within the cell [33]. Seems
reasonable to assume that pH-decrease would lower nucleation efficiency, due to
the competition between protons and metal cations for the negatively charged
places of the cell membranedthe initial nucleation sites [33].
In the intracellular biosynthesis, the second bioreduction step of metal NPs
(e.g., Ag and Au) production relays upon synthesis of NADH-dependent
nitrate reductase (Fig. 1.1) [43e47].
Certainly, the reactions different from reduction are performed by the other
enzymes, e.g., synthesis of the CdS quantum dots from Cd assisted by yeasts
Schizosaccharomyces pombe has been considered to be dependent on a stress
protein response [48].
aqueos solution
Ag+ AgNO3 NO3-
NADH
NAD+
+
Ag
Enzyme narGHIJ
e nitrate (NADH-dependent
reductase nitrate reductase)
Ag0
Bacillus licheniformis cell
FIGURE 1.1 Scheme of Ag-NPs formation from AgNO3 within the cells of Bacillus lichen-
oformis [47].
Control over the size and shape of NPs is the main challenge of the
synthesis. It has been shown that such control can be achieved in the bio-
logical environment simply by varying physicochemical parameters. For
example, Gurunathan et al. were able to control the size of Ag-NPs, formed
in Escherichia coli strain, by managing temperature, pH, and concentration
of AgNO3 [49,50]. Based on the experience with various microorganisms, it
has been hypothesized that the size of Ag-NPs is related to surface density of
the nuclei: increase of pH and/or decrease of temperature induces high
density of small size nuclei causing production of numerous smaller NPs
(Fig. 1.2) [51].
Lower temperature Higher temperature

acidic pH alkaline pH
nucleus silver nanocrystals
silver ions that deposits

FIGURE 1.2 Scheme of size adjustment Ag-NPs [51].
In the last decade a lot of articles have been published in the field of
biologically assisted synthesis of noble metals (i.e., Ag, Au) NPs [14,29].
Therefore, in following chapters we will try to focus on some recently issued
papers. We decide to almost literally quote these of quite well-documented,
reproducible synthetic procedures that are followed by reasonable explana-
tion of their achievements. However, at the end of the paper we made an
attempt to rationalize mechanistic considerations.
BIOSYNTHESIS OF NPs BY BACTERIA

The data on the nanoparticles synthesized by bacteria described in this section
are presented in Table 1.1.
Metal Nanoparticles
Silver
For the production of Ag-NPs, Hosseini-Abari and coworkers utilized vege-
tative cells and spores of Bacillus stratosphericus isolated from soil [52].
Vegetative cells and spore solution were separately added into aqueous solu-
tion of AgNO3 and the control (aqueous solution without AgNO3) [53]. In
order to complete Ag-NPs production, the suspensions were incubated at room
temperature, from 5 up to 20 h, whereas Ag-NPs formation was examined by
UVeVis absorption spectra measurement at different time intervals. The pH
value equal to 7 has been found to be the best for Ag-NPs synthesis (see
Fig. 1.3). One can hypothesize that neutral pH is the optimal for performance
of the enzymes involved in the process (see below).
The XRD, TEM, and EDS techniques have shown that NPs aggregates on
the spore surface are of the size in the 2e20 nm range [53].
The exact mechanism for Ag-NPs production by bacteria has not yet been
understood [53,54]. However, NADH-dependent enzymes, nitrate reductase,
and catalase had to be considered as participants of the possible mechanisms
FIGURE 1.3 Effect of pH ranges on Ag-NPs synthesis by the spores [53].

TABLE 1.1 Bacterial Nanoparticles Synthesis
Nanoparticles
No Type Bacteria Species Reducing/Capping Agent Description References
1. Ag Bacillus stratosphericus Dipicolinic acid Structure: crystalline fcc [53]
NSNP KC480583 Shape: spherical, triangular
Bacillus stratosphericus Size range: 2e20 nm
spores
2. Ag Bacillus subtilis ATCC Nitrate reductase, other Structure: no data [54]
6633 peptides/proteins Shape: spherical
Size range: 5e50 nm
3. Au Stenotrophomonas NADPH-dependent Structure: no data [57]
maltophilia reductase enzyme Shape: oval Retracted
Diameter: 40 nm
Natural Environments Chapter j 1

4. Au Pseudomonas Enzyme secreted by biomass Structure: crystalline [58]
fluorescens Shape: spherical
Size range: 20e80 nm
5. Au Zooglea ramigera Proteins Structure: crystalline fcc [59]
MTCC 3547 Shape: spherical
Size determined by XRD: 4e16 nm
Size range determined by DLS:
15e90 nm
6. Ag AEMB Protein, NADH-dependent Structure: crystalline [60]
Au Klebsiella pneumoniae reductase Shape: spherical
Lactobacillus Size range: 5e65 nm
amylotrophicious
Salmonella enterica
7
Continued
TABLE 1.1 Bacterial Nanoparticles Synthesisdcont’d

Nanoparticles
No Type Bacteria Species Reducing/Capping Agent Description References
7. Cu; CuO Serratia sp. Protein/peptides of MW 25 Structure: crystalline [63]
and 52 kDa Shape: CuOdtriangular, Cu2Odstars,
Cu4O3dtriangular, Cudspherical
A mixture of NPs metallic and oxide
8. Cu2O; CuO Escherichia coli Peptides of MW 25e52 kDa Structure: crystalline [64]
Shape: quasispherical
A mixture of NPs: Cu2O and CuO
9. ZnO Anabaena sp. L31 Mycosporinedamino Structure: crystalline fcc [66]
acids like Shape: spherical, hexagonal
Size average: 80 nm
10. ZnO Lactobacillus sp. Oxidoreductase, groups on Structure: crystalline [68]
the cell wall Shape: spherical
Size range: 8e35 nm
11. TiO2 Bacillus subtilis Electronegative surface Structure: crystalline, anatase [70]
FJ460362 functional group as carboxyl, Shape: spherical
phosphoryl, hydroxyl Size range: 10e30 nm
12. TiO2 Aeromonas hydrophila Glycyl-L-proline, glycyl-L- Structure: crystalline [71]
MTCC-1739 glutamic, uric acid, 1-leucyl- Shape: smooth, spherical, uneven
D-leucine Size average: 40.5 nm
13. TiO2 Actinobacteria colonies Alkynes, aldehydes Structure: [72]
Shape: spherical
Size average: 58 nm
[31,51,55]. Saifuddin et al. reported that nitrate reductase activity together

with electron-shuttling and other peptides/proteins may be responsible for Ag-
NPs synthesis by Bacillus subtilis [54]. In order to identify the main mecha-
nism of Ag-NPs synthesis by the spores, their enzymatic activities such as
nitrate reductase, laccase, and catalase were assayed. Surprisingly, the spores
did not show any nitrate reductase activity; moreover, laccase and catalase
activities were also negligible. On the other hand, the vegetative cells of
B. stratosphericus may not survive in the AgNO3 solution. There are many
factors, including enzymes or electron donor groups in vegetative cells, which
can be effective in the production of Ag-NPs from AgNO3; however, Ag ions
are toxic to cells, and some organisms do not have mechanisms coping with
such toxicity. Since the vegetative cells of B. stratosphericus cannot produce
Ag-NPs, the other factors, which can be detected only in the spores, have to be
responsible for the synthesis. Therefore, dipicolinic acid (DPA), which is
formed during sporulation, was suspected as a possible factor, playing an
important role in the formation of NPs by spores of Bacillus species.
Furthermore, Hosseini-Abari’s results demonstrated that the B. stratosphericus
spores contain relatively high concentration of DPA. To confirm the hypothesis
of the potential role of DPA in Ag-NPs formation, the experiment was fol-
lowed in vitro by standard DPA (CAS 499-83-2). Indeed, the standard DPA
alone can produce Ag-NPs of the 20e100 nm size. In addition, an enhance-
ment in the synthesis was observed with an increase of DPA concentrations.
Since DPA has two carboxylic groups effective for the synthesis, such
observation fits well with Kilin and coworkers, ab initio-computation studies
revealing carboxylate groups mediation in the Ag-NPs formation [56].
Gold
Nangia et al. demonstrated [57] the synthesis of Au-NPs by a novel bacterial
strain isolated from a site near the gold mines located in Eastern India. A
promising mechanism for the biosynthesis of Au-NPs by this strain, and their
stabilization via charge capping was investigated. The Au-NPs biosynthesis
from chloroauric acid (HAuCl4) involves specific NADPH-dependent reduc-
tase enzyme that converts AuIII to Au0 through electron shuttle enzymatic
reduction. A solution of HAuCl4 in a suspension of Stenotrophomonas mal-
tophilia living cells (at 25 C) changed progressively from light yellow to
cherry red showing formation of Au-NPs. The spectra revealed a strong ab-
sorption at nearly 530 nm after 8 h of incubation, gradually showing a red shift
with time. The intense plasmon resonance band and TEM images indicated the
formation of spherical Au-NPs of c. 40 nm diameter. The EDS spectroscopy
confirmed the presence of Au-NPs in the suspension, whereas cryo-TEM
imaging showed the presence of Au-NPs on the inner cytoplasmic mem-
brane. It is likely that some Au3þ cations can cross the cell barrier through ion-
transport channel and can be reduced within the cytoplasm by the enzymes
NADPH NADP+
reductase NH2
O N
-O P O CH2
O NH2
O H H
3+ 0
Au Au H H
N
N
OH OH
N N
-O PH O CH2
O
O- H H
H H
OH
NADPH O
-O P O
O
Au0
FIGURE 1.4 Proposed mechanism of Au-NPs synthesis by Stenotrophomonas maltophilia

through enzymatic reduction [57].
present on the cytoplasmic membrane. The study suggested that the biosyn-
thesis of Au-NPs and their stabilization via charge capping in S. maltophilia
involved NADPH-dependent reductase enzyme that converts Au3þ to Au0
through electron shuttle enzymatic metal-reduction process. For more evi-
dence, biomass was incubated with various concentrations of NADPH
(0.05e0.8 mM NADPH). Control experiments, without the addition of cell-
free extract either in the presence or the absence of NADPH, showed no
change in the color of suspension. However, addition of NADPH in the cell-
free extract showed the Au-NPs formation. This confirms the formation of
Au-NPs only in the presence of both biomass and NADPH. Zeta potential
measurements of Au-NPs showed a peak at 16.7 mV, explained by capping
of Au-NPs by negatively charged phosphate ions from NADP. Based on these
findings, a schematic representation of the potential mechanism of Au-NPs
synthesis by S. maltophilia through enzymatic reduction is proposed
(Fig. 1.4). The enzyme involved in the synthesis of Au-NPs that reduces metal
ions to metallic NPs may be a particular reductase of gene expression induced
by the specific ions.
Radhika and Suman in their investigation [58] used the gram-negative soil
proteobacteria Pseudomonas fluorescens to produce Ag-NPs of uniform size and
distribution that are stable in the solution. The bacteria were incubated for 48 h
with broth containing auric chloride (AuCl3) solution at 37 C and pH in the range
6e7. The color of the reaction solution turned from pale yellow to deep red
indicating the formation of Au-NPs, i.e., the auric chloride ions ðAuCl4 Þ were
reduced during the exposure to bacterial biomass. The synthesized Au-NPs of the
size 20e80 nm were characterized by UVeVis, TEM, SEM, and FTIR.
Srivastava and Mukhopadhyay reported synthesis of Au-NPs with bacte-

rium Zooglea ramigera [59]. (Such bacteria could be found in sludge, where
they are responsible for its flocculation.) Thoroughly washed wet biomass was
added in HAuCl4 and kept in the incubator shaker at 30 C for 24 h. The au-
thors studied and optimized various reaction parameters: pH, reagent con-
centration, and time. The high SPR intensity was observed over the pH range
of 2e6. Increase in pH caused the rise of NPs size. A similar trend was
observed for the concentration of HAuCl4 effect. The optimum parameters for
Au-NPs synthesis were determined as pH 3, 1.5 mM HAuCl4, and 96 h. The
TEM image showed that the synthesized NPs were well dispersed and uniform
of spherical shape within the size-range of 4e16 nm. The SAED pattern
confirmed the crystalline nature of the particles with the crystalline size of
19 nm estimated from the XRD measurement using Scherer’s formula,
whereas DLS analysis revealed the hydrodynamic diameter of NPs were in the
range of 15e90 nm (25 nm average). The PDI index was 0.356, indicating
high NPs suspension stability.
Kumar et al. has reported a simple and efficient extracellular biosynthesis
of Au-NPs from HAuCl4 using AEMB [60] in the procedure quite similar to
that presented above. Biosynthesized Au-NPs were characterized by UVeVis,
TEM, X-ray XRD, and FTIR. The results demonstrated that obtained NPs
were spherical of the size in 5e65 nm. Three dominant bacterial species
Klebsiella pneumoniae, Lactobacillus amylotrophicious, and Salmonella
enterica have been identified in the mixed culture as responsible for effective
gold bioreduction. From FTIR measurement that has been carried out, one can
conclude that Au-NPs could bind to free amino or carboxylate groups in
the protein; these groups appear responsible for the reduction and stabilization
of NPs.
Kumar et al. summarized their observation in the preliminary mechanism
of Ag and Au bioreduction to NPs (shown on Fig. 1.5) that is in general
agreement with those considered for other bacterial strains [43,46]. The first
step involves the uptake of Agþ or Au3þ and formation of the complex with
AEMB. In the second step, the NADH-dependent reductase, which may have
been secreted from the AEMB culture, have bioreduced Agþ/Au3þ into Ag-
NPs/Au-NPs, respectively.
Copper
Copper NPs have also gained significant attention from the scientific com-
munity as a more economically viable alternative to noble metals NPs [61,62].
The synthesis of Cu-NPs in metallic form is challenging due to its propensity
for surface oxidation; therefore general fabrication protocols typically involve
a laborious process under controlled environment. Conversely, bacteria like
Serratia sp. isolated from insect gut and E. coli, when challenged with aqueous
copper precursors, were able to synthesize a mixture of copper and copper
Ag+ or Au3+
uptake of ions and complex formation
AEMB Culture
NADH
e
NAD+
Ag or Au NPs
silver and gold

reduction protein
FIGURE 1.5 The possible mechanism involved in the bioreduction of Agþ or Au3þ to Ag-NPs or
Au-NPs [60].
oxides, quasispherical NPs, and nonstoichiometric NPs of size in the range

10e40 nm [63,64]. It was postulated that two proteins/peptides of molecular
weight 25 and 52 kDa might be involved in the reduction and stabilization of
these NPs, which is yet to be fully investigated [64].
Metal Oxide Nanoparticles

Zinc Oxide (ZnO)
Selvarajan et al. [65] have described a low-cost, simple method for the
biosynthesis of ZnO-NPs using reproducible bacteria, Lactobacillus plantarum
as an eco-friendly reducing and capping agent. L. plantarum is a nonpatho-
genic (the most abundant bacteria distributed worldwide in the majority of the
food products), gram-positive, facultative anaerobe of the largest genome
among all lactic acid bacteria. Like most of the bacteria, L. plantarum has a
negative electrokinetic potential, which easily attracts the cations triggering
off the biosynthesis. The culture solution was added with ZnSO4 aqueous
solution and heated in a water bath up to 80 C for 10 min. The white pre-
cipitate at the bottom of the flask indicated that ZnO-NPs were deposited. The
NPs were characterized by XRD, FTIR, UV, SEM, FE-TEM, and Zeta po-
tential. The ZnO-NPs were pure and crystalline in nature (hexagonal), poly-
dispersed, and roughly spherical in shape with maximum particles in the size
range within 7e19 nm with a mean diameter of c. 13 nm.
Singh et al. [66] have shown the procedure for ZnO-NPs synthesis from
Zn(NO3)2 in the cell extract of the cyanobacterium Anabaena sp. L31, at
neutral pH. After 3 days incubation at 25 C in a shaker (150 rpm/min), a
spherical with hexagonal crystalline structure ZnO-NPs of 80 nm diameter
were obtained.
Titanium Dioxide (TiO2)

Utilization of microbes has emerged as a novel technology for synthesis of
various metal oxides NPs. The control of particle shape, size, and mono-
dispersity, which is decisive for their semiconductive and photocatalytic
properties, would depend on the process parameters. Especially B. subtilis
easily undergoes adaptation with heavy metals and it can produce unusual size
and shape of inorganic NPs through either intracellular or extracellular
mechanisms [67]. Microbial-mediated synthesis of TiO2-NPs was also carried
out using Lactobacillus sp. and Bacillus sp. [68,69].
Jha et al. [68] reported usage of Lactobacillus sp. as a medium for the
synthesis of TiO2-NPs. To the prepared culture solution, TiO(OH)2 was added
and the mixture was heated on a steam bath up to 60 C for 10e20 min until the
appearance of a white solid. Then the mixture was cooled and incubated at room
temperature for additional 12e48 h. The obtained NPs were of spherical shape
with an average size of 8e35 nm. The authors believed that the difference in
size can be justified by different time scales of NPs formation. The chemical
reactions, which proceed in the culture medium, can be as given in Scheme 1.1.
Jha et al. have attempted to explain processes occurring in the mixture in
the following manner: Lactobacillus has a negative electrokinetic potential,
which readily attracts the cationsdthis step probably acts as a crux of the
biosynthesis. The capacity of Lactobacillus to grow even in the presence of
oxygen makes it “metabolically more capable.” Addition of reducing agents
like glucose tends to lower the value of oxidationereduction potential. The
oxidationereduction potential expresses the quantitative character of degree of
aerobiosis having a designated unit expressed as rH2 (the negative logarithm of
OH
O OH
H O H
H OH OH
OH H H3C H3C
HO OH
O O
H OH pyruvate lactate
+ −
NAHCO3 ⇔ Na + HCO 3
− −
HCO 3 ⇔ CO 2 + OH
TiO − ( OH ) 2 → TiO 2 + H 2 O
SCHEME 1.1 Reaction proceeded in Lactobacillus sp. medium [68].

the gaseous hydrogen partial pressure). Thus, by controlling the oxida-

tionereduction potential of the culture medium, conditions can be engineered
for the growth of anaerobes; through lowering the rH2 in the presence of
oxygen or by cultivating the aerobes in anaerobic conditions through
increasing the rH2 of the medium. Energy-yielding material glucose (which
controls the value of rH2), the ionic status of the medium pH, and overall
oxidationereduction potential (rH2, partially controlled by the bicarbonate)d
all these factors cumulatively “negotiate” the synthesis of TiO2-NPs in the
presence of Lactobacillus strain. A mildly acidic pH and lowered rH2 activates
the membrane bound oxidoreductase and makes the requisite environment for
the oxide NPs synthesis, which are formed extracellularly.
Dhandapani et al. in their study used B. subtilis (FJ460362) biomass to
react with potassium hexafluorotitanate (K2TiF6) (CAS 16919-27-0) forming
TiO2 precipitate [70]. The TiO2-NPs were formed extracellularly. The resul-
tant precipitate at different time intervals (6, 12, 24, 36, and 48 h) were
collected and transferred to an alumina crucible and heated at 500 C for 3 h, in
order to remove the bioorganic contents to get TiO2 particles. The UVeVis
spectrum exhibits a well-defined excitation absorption peak corresponding to
anatase phase of nano-TiO2. The XRD measurements confirmed the formation
of anatase crystal phase mostly. The maximum distribution of the particles size
was in the range of 15e20 nm.
Jayaseelan et al. [71] reported TiO2-NPs synthesis using the bacteria Aer-
omonas hydrophila (MTCC-1739). TiO(OH)2 was added to the culture solution
and kept at 30 C in a shaking incubator at 120 rpm for 24 h. Reaction progress
was indicated by the appearance of white precipitate in the flask. Finally the
mixture was poured on sterilized petri plates and air dried. The FTIR results
indicated that alcohols, phenols, primary amines, lactones, and aliphatic amines
have participated in the synthesis. Functional groups associated with the com-
pounds are responsible for the bioreduction of TiO(OH)2 to TiO2-NPs. The
major metabolite, which is present in the broth, is glycyl-L-proline (CAS 704-
15-4). Authors postulated that titanyl hydroxide can be dehydrated to give TiO2-
NPs by reacting with an A. hydrophila. In the first stage, one of the free electron
pairs on the oxygen picks up a hydrogen ion from glycyl-L-proline, the
TiO(OH)2 is said to be protonated. Then, protonated TiO(OH)2, loses a water
molecule to give Ti3þ, and finally another molecule of glycyl-L-proline pulls off
a hydrogen ion from the Ti3þ giving TiO2 (Scheme 1.2).
The crystalline nature of the TiO2-NPs was analyzed using XRD, indicating
only a rutile form. The crystallite sizes were found to be in the range of 40e50 nm.
Priyaragini et al. described a method of TiO2-NPs synthesis from
TiO(OH)2 using marine actinobacteria colonies isolated from marine sedi-
ments collected in South India [72]. The TiO2-NPs were characterized by
XRD, AFM, and FTIR analysis. The average particle size obtained from XRD
data was found to be about 58 nm. AFM measurements showed that TiO2-NPs
were spherical with a diameter of about 38 nm.
δ δ
H O
O O O H
Ti O Ti O
:
HO OH
N HO H
Titanyl hydroxide
-H2O
H2N
Glycyl-L-proline
NH2 O
N Ti3+
O
:
O H
O
TiO2 NPs
SCHEME 1.2 Postulated reaction of TiO2-NPs formation in Aeromonas hydrophila culture

solution [71].
BIOSYNTHESIS OF NPs BY FUNGI

Metal Nanoparticles
Silver
The biosynthesis of Ag-NPs by Penicillium purpurogenum NPMF (MTCC
7356) was studied by Nayak et al. [73]. The Ag-NPs were produced from
AgNO3 in a culture filtrate containing extracellular enzymes. The increase of
AgNO3 concentration increased the formation of AgNPdat 5 mM concen-
tration highly populated polydispersed NPs were formed. However, the yield
of Ag-NPs formation reaches a plateau at 1.5 mM AgNO3 concentration.
Change in pH of the reaction mixture leads to change in shape and size of Ag-
NPs, with higher polydispersity at lower pH. Highly monodispersed spherical
NPs of 8e10 nm diameter were formed with 1 mM AgNO3 concentration at
pH 8. But appreciable amount of Ag-NPs was obtained at 5 mM AgNO3
concentration. In order to understand the effect of the AgNO3 concentration,
the samples were examined by TEM. Highly monodispersed Ag-NPs with an
average size of 10 nm were found for 1 mM AgNO3. Few small Ag-NPs with
4e6 nm size were also observed. In case of 3 mM AgNO3 concentration
unique star-shaped aggregated Ag-NPs were found. Further, with 5 mM
AgNO3 concentration uneven shape of NPs and substantial polydispersity
were observed (Table 1.2).
Larger particles were formed at pH 4 and 5 (Fig. 1.6) with average particle
size between 40 and 55 nm and smaller particles were formed at pH 8 and 9
with average particle size between 8 and 13 nm. The NPs formed at lower pH
TABLE 1.2 Fungi Nanoparticles Synthesis
Nanoparticles
No Type Fungi Species Reducing/Capping Agent Description References
1. Ag Penicillium purpurogenum Enzymes, proteins, and other Structure: crystalline fcc [73]
NPMF (MTCC 7356) organic molecules Shape: irregular, nonuniform
Size range: 10e40 nm depending
on pH
2. Ag Penicillium atramentosum Enzymes Structure: crystalline [74]

KM Shape: spherical
Size range: 5e25 nm
3. Au Botrytis cinerea CCg149 NADH-dependent reductase Structure: crystalline [75]
Shape: spherical, triangular,
hexagonal, decahedral, pyramidal
4. Au Fusarium oxysporum NADH-dependent reductase Structure: no data [76]

Shape: spherical, triangular
Size range: 8e40 nm
5. Au Paraconiothyrium variabile Proteins Structure: crystalline [77]
Shape: spherical
Size range: 71e266 nm (estimated
by DLS)
6. Au Trichoderma harzianum Sulfur-containing proteins, Structure: fcc lattice [78]
cysteine, NADH-dependent Shape: spherical
reductase Size range: 26e34 nm
7. ZnO Candida albicans No data Structure: crystalline, würtzite [82]
Shape: quasispherical
8. TiO2 Fusarium oxysporum Nitrate-dependent reductase, Structure: crystalline, monoclinic [83]
cationic proteins of molecular Shape: irregular, quasispherical
weight 24e28 kDa Size diameter: 5e15 nm
Calcinated 300 C
9. TiO2 Aspergillus flavus MTCC Amino acids Structure: crystalline, anatase phase [86]
7369 Shape: oval, spheroidal
10. TiO2 Saccharomyces cerevisiae Quinones, membrane-bound Structure: anatase phase [68]
oxidoreductase Shape: spherical
Size average: 12.6 nm
11. ZrO2 Fusarium oxysporum cationic proteins of molecular Structure: Crystalline, monoclinic [76]
Natural Environments Chapter j 1

weight 24e28 kDa phase
Shape: Regular, quasi-spherical
Size range: 3e11 nm
Calcination: 500 C
17
FIGURE 1.6 Effect of pH on Ag-NPs size [73].
(i.e., 4 or 5) were polydispersed with various different shapes such as pyra-

midal, spherical, and ellipsoidal. Some anisotropic nanostructures were
formed with irregular contours that indicate the sample composition of a large
quantity of nonuniform NPs. However, NPs formed at pH 8 and 9 were more
uniform and mostly spherical. One may assume that the initial pH of the
culture filtrate plays an important role in determining the morphology, shape,
and size of the Ag-NPs.
The synthesis of Ag-NPs from AgNO3 has also been carried out using the
filtrate extract of novel fungal strain Penicillium atramentosum KM [74]. The
different parameters were optimized for the synthesis including concentration
of AgNO3 (1e5 mM), concentration ratio of fungal extract and AgNO3 (1:9,
2:8, 3:7, 4:6, and 5:5), time (time intervals up to 96 h of incubation), tem-
perature (5 C, 15 C, 25 C, 35 C, and 45 C) and pH (pH of 2, 5, 7, 9, and 11),
which had been identified as factors, which affect the productivity of Ag-NPs.
The Ag-NPs were analyzed by UVeVis, FTIR, XRD, and TEM. The XRD
record exhibited crystalline nature of the NPs, whereas the TEM analysis
revealed their size between 30 and 50 nm. The optimal synthesis conditions
were as follows: 3 mM AgNO3, pH 7, 25 C with concentration ratio of fungal
extract:AgNO3 1:1 (5:5) and 72 h of the incubation time.
Gold
The biosynthesis of Au-NPs from HAuCl4, by extracellular components of the
phytopathogenic fungus Botrytis cinerea was performed by Castro et al. [75].
The authors performed a series of clever experiments somewhat clarifying the
mechanism of the synthesis. The biosynthesis of Au-NPs through the use of
mycelium-free fungal culture filtrates in the presence of HAuCl4 was verified
through a gradual color change from a pale yellow to a dark purple. The color
change of the culture filtrate started immediately after mixing the components
reaching, maximum intensity after 6 h of incubation under standard conditions

(25 C, pH 7). The change was not observed in control experiments that used a
fresh culture medium in the presence of HAuCl4. This indicated that extra-
cellular molecules produced by fungi were responsible for the reduction of
Au3þ to Au0. Therefore, when the culture filtrate was exhaustively dialyzed,
the ability to synthesize the Au-NPs was lost. Nevertheless, the addition of
NADH restored the biosynthetic activity of the fungal culture filtrate, indi-
cating that a putative NADH-dependent reductase would catalyze the reaction.
Neither NADH nor the dialyzed culture filtrate alone was able to catalyze Au-
NPs formation. However, the nondialyzed denatured culture filtrate catalyzed
Au-NPs formation, in an activity that is not NADH-dependent. The EDX
analysis showed that the nanostructures were composed solely of gold,
whereas the TEM measurements showed that Au-NPs generated by the culture
filtrates were mainly spherical, triangular, hexagonal, decahedral, and pyra-
midal with approximate sizes ranging from 1 to 100 nm. The Au-NPs were
also well dispersed and without agglomeration. As the reaction temperature
increased, triangular particles gradually disappeared, and seemingly spherical
small particles with uniform morphology and size were predominantly
observed. The particles generated at 75 and 100 C were more uniform in
morphology and size and were predominated by spheroidal particles with a
diameter ranging between 5 and 10 nm.
The results obtained in the study showed that B. cinerea CCg149 secreted
molecules with the ability to catalyze the reduction of Au3þ to Au0, the initial
and essential reaction for the subsequent nucleation and formation of Au-NPs.
Furthermore, the results suggest that two alternative but exclusionary mech-
anisms for the reduction of Au3þ could operate here. The first would be an
enzymatic process catalyzed by a putative NADH-dependent reductase,
similar to that described in Fusarium oxysporum [76], whereas the second one
would be a nonenzymatic process catalyzed by molecules secreted by the
fungus, which are reactive when denatured. Such denatured molecules could
correspond to extracellular laccase, as a recent study reported that a purified
laccase from Paraconiothyrium variabile is capable of catalyzing the forma-
tion of Au-NPs from HAuCl4 [77].
Tripathi et al. applied Trichoderma harzianum biomass for synthesis of Au-
NPs [78]. The potential mechanism involved in biosynthesis has been asso-
ciated with fungi metal tolerance mechanisms [79,80]. One of the methods
exploited by fungi to tolerate the heavy metals (e.g., gold) present in their
surrounding environment is to extracellularly synthesize amino acid cysteine
that can form metal complexes. Indeed FTIR spectra from the T. harzianum
biomass Au-NPs synthesis showed peaks that correspond to the eSH group
and CH2eS bond [81], whereas GCeMS confirms that presence of cysteine
that means sulfur-containing proteins are secreted by fungal biomass. The
NADH-dependent reductase enzyme is extracellularly synthesized by fungal
biomass, which is a step of metal tolerance mechanism. NADH gives an
SOLUTION
-ν e
secretion
HAuCl4 H+ + AuCl4 NADH dependent Fungal biomass
reductase enzyme
+νe
NAD+
NADH
NADH dependent cysteine caped
reductase enzyme AuNPs
-e
Au3+
Au0 AuNPs
cysteine
FIGURE 1.7 Mechanistic representation of biomimetic Au-NPs formation in Trchoderma har-

zianum biomass [78].
electron to reductase and oxidizes into NADþ in the reaction mixture. Further,
this enzyme is oxidized by the instantaneous reduction of gold ions (Au3þ to
Au0). Then Au0 undergoes a nucleation process to get its optimum size, the
size of NPs depends on various parameters (like nature of reducing and
capping agent, temperature, pH, etc.). Cysteine has the ability to encapsulate
the Au-NPs to reduce the stress condition. This phenomenon provides stability
to the Au-NPs. The possible mechanism of fungal-mediated synthesis of Au-
NPs has been illustrated in Fig. 1.7.
Metal Oxide Nanoparticles

Zinc Oxide (ZnO)
Shamsuzzaman et al. [82] described the procedure for biosynthesis of
ZnO-NPs using Candida albicans as the capping agent, and ZnO aqueous
suspension. For the reaction, a solution of ZnO was added to the culture so-
lution and it was kept at 30 C for 24 h until a white precipitation appeared at
the bottom of the flask indicating the transformation. The reaction mixture was
cooled and incubated at room temperature for 15 h. The synthesized ZnO-NPs
were characterized by UVeVis, XRD, SEM, TEM, PL, TGA, and DTA. X-ray
diffraction measurements confirmed that the product has good crystalline
structure and the calculated crystallite size of the powder particles is about
25 nm. SEM micrograph showed the average size of NPs between 15 and
25 nm. The size and morphology of ZnO particles analyzed by TEM reveals
that most of the ZnO-NPs are quasispherical and their diameter is about
20 nm. This result is in accordance with the value calculated from the XRD
diffraction.
Titanium Dioxide (TiO2)

Bansal et al. have pioneered the synthesis of a range of oxide NPs including
silica [83], titania [83], zirconia [84], magnetite [85], and barium titanate [22]
using a plant pathogenic fungus F. oxysporum. The fungus was chosen as a
pathogen producing a vast array of extracellular hydrolases that degrade their
host plants in natural habitats; these hydrolases can hydrolyze oxide precursors
to form the respective oxide NPs in an aqueous environment at room tem-
perature. Moreover, the extracellular proteins secreted by the fungus are
believed to provide a hydrolyzing as well as confining template for the syn-
thesis of nanoscale oxide particles. F. oxysporum secretes at least two low
molecular weight cationic proteins capable of hydrolyzing aqueous anionic
complexes (SiF6 2 , TiF6 2 , and ZrF6 2 ions) to form the respective oxide NPs
(SiO2, TiO2, and ZrO2) extracellularly at room temperature. Extracellular
protein-mediated hydrolysis of the anionic complexes results in the facile
room temperature synthesis of crystalline TiO2-NPs, whereas calcination at
300 C was required for crystallization of silica. Particularly gratifying is the
fact that this fungus is capable of hydrolyzing tough metal halide precursors
under acidic conditions.
Rajakumar and coworkers synthesized TiO2-NPs using Aspergillus flavus
(MTCC 7369) as a capping agent [86]. The freshly grown and washed
mycelium was challenged with TiO2 and incubated in shaker at 200 rpm in
dark condition at 37 C. Simultaneously, a positive control of incubating the
fungus mycelium with deionized water and a negative control containing only
TiO2 solution were maintained under same conditions. TiO2-NPs were char-
acterized by FTIR, XRD, AFM, SEM, and TEM studies. The materials syn-
thesized were pure anatase TiO2 phase. The synthesized TiO2-NPs were
spherical, oval in shape, with individual NPs as well as a few aggregates
having the size of 62e74 nm. The mycelia, matted together, were more
immobile, and more capable of binding TiO2-NPs than that of the external
cellular substances that distributed in the intermycelial space.
Jha et al. [68] reported biosynthesis of TiO2-NPs in Saccharomyces cer-
evisiae biomass. For the NPs synthesis TiO(OH)2 solution was added to the
culture solution and it was heated on a steam bath up to 60 C for 10e20 min
OH
H OH
H H3C O H3C O
OH H H3C OH
HO OH
H OH OH
H3C O
H3C O
+
+ H
OH -
O
NAHCO3 ⇔ Na + HCO3−
+
HCO3− ⇔ CO2 + OH −
TiO − (OH ) 2 → TiO2 + H 2O
SCHEME 1.3 Reaction process in Saccharomyces cerevisiae culture solution [68].
until white deposition starts to appear at the bottom of the tube, indicating the
transformation. Then the culture solution was cooled and allowed to incubate
at room temperature. After 12e48 h, the culture solution was observed to have
distinctly visible coalescent white clusters deposited at the bottom of the tube.
The formation of TiO2-NPs was checked by the XRD technique. The mean
particle size is c. 12.6 nm. The chemical reactions, which proceed in the
culture medium, may be as follows (Scheme 1.3).
Zirconium Dioxide (ZrO2)

Bansal et al. describe that the exposure to biomass of the fungus F. oxysporum
[76] to an aqueous solution of K2ZrF6 results in the protein-mediated extra-
cellular hydrolysis of the zirconium hexafluoride anions and the room tem-
perature formation of crystalline ZrO2-NPs [84]. The observed particles were
fairly regular in shape, with an overall quasispherical morphology. The particle
size histogram showed the particles range in size from 3 to 11 nm with an
average size of 7.3 2.0 nm. SAED analysis of the individual particles
indicated that they were crystalline and revealed the monoclinic phase of
ZrO2. The TEM, FTIR, SAED, and XRD analysis of the products of the re-
action between K2ZrF6 with F. oxysporum indicated the formation of crys-
talline ZrO2-NPs with a fairly large amount of proteins occluded into their
structures. The biogenic ZrO2 powder was then calcined under air at 300 C for
3 h to remove the occluded proteins and promote crystallization of the oxides.
The TEM images of the ZrO2 particles showed a dramatic change in the
overall particle morphology after calcination. It is observed that the particles
show greater contrast, indicating sintering and formation of denser ZrO2
particles. SAED analysis of the sample after calcination showed sharp ring
patterns that could be indexed based on the monoclinic structure of ZrO2. This
is mirrored in the XRD pattern of the calcined ZrO2 sample that shows intense
Bragg reflections characteristic of the monoclinic phase with a small
percentage of the tetragonal phase. It is clear from the XRD results that
calcination improves the crystallinity of obtained ZrO2-NPs.
It was found that the fungus F. oxysporum secretes at least two low mo-
lecular weight cationic proteins capable of hydrolyzing aqueous ZrF6 2 to
form oxide NPs extracellularly at room temperature.
The data on the nanoparticles synthesized by fungi described in this section
are presented in Table 1.2.
BIOSYNTHESIS OF NPs IN PLANT EXTRACTS

Metal Nanoparticles
Silver
Because of the large number of articles available on the synthesis of Ag-NPs,
here, we will discuss only select ones.
The Ag-NPs were prepared by simple, capable, eco-friendly, and
biosynthesis method applying Lantana camara leaf extract [87]. To the
aqueous solution of AgNO3 was added separately L. camara leaf broth
(5e20 mL) at room temperature. The bioreduction of the silver ions was
rapid as the solution turned brownish yellow within 5 min confirming the
formation of Ag-NPs.
The phytochemical tests on L. camara have revealed the presence of lipids,
proteins, carbohydrates, and common secondary metabolites: phenolics, fla-
vonoids, terpenoids, alkaloids, and trace amounts of phytosterols, saponins,
tannins, and phycobatannin in the leaves [88e90]. FTIR study confirmed that
the L. camara leaf extract components act as bioreductants and surfactants too.
The plausible mechanism of the formation of Ag-NPs is shown in Fig. 1.8. It is
flavonoids reduction capping

bioreducing agents process process
phenolic + 0
compound Ag Ag Ag0
terpenoids
stabilization
Ag
Ag
protein layer Ag
Ag
Ag
Ag
Ag
AgNPs
FIGURE 1.8 The plausible mechanism of the formation of Ag-NPs using Lantana camara [87].
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CHAPTER IX
THE BROADENING OF CULTURE
Cramer’s business prospered. His was the only establishment in

Pittsburgh where the sale of books was the predominant feature. He
285
had long called it the “Pittsburgh Bookstore.” Oliver Ormsby,
whose store was in the brick house on Water Street, at the westerly
side of Chancery Lane, sold “Dilworth’s and Webster’s Spelling
books, testaments, and Bibles in Dutch and English, primers, toy
286 287
books, and a variety of histories, novels, etc.” William Christy
288
and John Wrenshall kept a few books, a special feature of the
latter’s business being the sale of Dr. Jonathan Edwards’s Sermons,
but compared with Cramer’s stock, the supply of books in other
hands was insignificant. Cramer was also practically the only
publisher of books in the borough. After he had been publishing for a
few years, others began the business, but their books were few in
number and generally unimportant in character. Cramer’s
advertisements were sometimes amusing. He sold his goods for
money, or in trade, and in making the announcement employed the
axiomatic language of “Poor Richard.” This was one of his naïve
notices: “I hope the ladies and all good girls and boys will not forget
to fetch me all the clean linen and cotton rags they possibly can.
Save the smallest pieces and put them in a rag bag; save them from
the fire and the ash heap. It is both honorable and profitable to save
289
rags, for our country wants them.”
He added new lines to his business. Articles which tended to
elevate and refine the standard of living were introduced. Wall
papers had been in use in the East to a limited extent since 1769,
and were no longer rare in good homes. In the West they were
scarcely known until Cramer advertised his “large stock of hanging
290
or wall papers.” He sold stationery, writing paper, Italian and hot-
pressed letter paper, wafers, quills, camel-hair pencils, inkstands,
sealing wax, red and black ink powders. Card playing was one of the
leading social diversions and he had the best English and American
playing cards. Patent medicines were largely used and Cramer
found it profitable to supply the demand. He had books of
instructions for the flute, the violin, the piano-forte, and books of
songs. His stock of English dictionaries included those of Nathan
Bailey, Dr. Samuel Johnson, Thomas Sheridan, and John Walker.
For the German population he had books in the German language,
which he often designated as “Dutch” books. He sold German
almanacs, German Bibles and testaments. Many of the German
churches, both in Pittsburgh and in the surrounding settlements, had
schools attached to their churches, where the German language was
taught in connection with English studies. For these schools Cramer
supplied the books. Ever since the cession of Louisiana to the United
States there had been a great increase in the students of the French
language among Americans, who intended either to engage in
commerce with the people of that territory, or expected to settle
291
there. The liberally advertised easy methods of learning French
induced many persons to engage in its study. For these Cramer kept
French books. He also sold Greek and Latin schoolbooks, Greek
and Latin dictionaries, and Spanish grammars.
In the early years Cramer had no press of his own. A printing
office being located at either end of the block in which he was
established, he divided his work between them. The Almanacs were
printed by John Israel, and the Navigators, by John Scull. Business
increased and he deemed it advisable to do his own printing, and on
August 14, 1805, announced that he had “received a press, and a
very handsome assortment of new type, for the purpose of printing
such literary and ecclesiastical works as may be most in
292
demand.” His publications now became more numerous and
pretentious.
He was too active to limit his energies to his business. In 1803,
he became Secretary of the Mechanical Society, and thenceforth
devoted much attention to the office, which he held for several years.
He was not an active politician, but was warmly attached to the
Republican party, and moreover had the respect of the entire
community. In 1811, when a division took place in the Republican
party in Allegheny County, and two tickets were placed in the field,
his standing was such, that he was named as a member of the
293
committee selected to bring about harmony. Like the modern
successful business man, he had a desire for the free life and clear
skies of the country, and he engaged in farming and sheep-raising.
When he died he had on the plantation of his brother-in-law, Josiah
Clark, in Washington County, a flock of one hundred and twenty-
eight sheep.
In 1808, the partnership with John Spear began, and the firm
became known as Cramer & Spear. The establishment, however,
continued to be called “Zadok Cramer’s Bookstore”; sometimes it
was advertised as “Zadok Cramer’s Classical, Literary, and Law
Bookstore.” In 1810, William Eichbaum was taken into the firm. He
had served a seven years’ apprenticeship in bookbinding with
Cramer, and with Cramer & Spear, and was the son of William
Eichbaum, the elder. It may be that young Eichbaum was the “active
youth of good morals and respectable character, wanted to learn the
bookbinding and stationery business,” for whom Cramer had
294
advertised on November 6, 1802. The firm was now Cramer,
Spear & Eichbaum, and continued as such until 1818, the year of the
death of Elizabeth Cramer, the widow of Zadok Cramer, when
Eichbaum withdrew and the firm was again changed to Cramer &
Spear.
Cramer had traveled extensively, first in pursuit of information for
his Navigators, and later in search of health. He went down the Ohio
295
in 1806. In 1810, he was in Kentucky. When the New Orleans, the
first steamboat that ran on the Western rivers was being operated
between Natchez and New Orleans, he descended the Mississippi
River in it twice, from the former to the latter place. Much of the
information in regard to the New Orleans, its structure, cost,
earnings, and length of time required between river points, is to be
296
found in the Navigators.
It would be impossible at this late day to compile a complete list
of Cramer’s publications, nor would it serve any useful purpose. He
published many schoolbooks, particularly for children in the primary
grades. His Pittsburgh and New England primers, and the United
States Spelling Book, were famous in their day. Ecclesiastical books
were in great demand, and Cramer met it. Catechisms were used as
books of primary instruction and were printed in many forms; there
were Larger Catechisms, Shorter Catechisms, the Mother’s
Catechism, and the Child’s Catechism. For the Germans he
published in German, The Shorter Catechism of Dr. Martin Luther.
The religious books that came from his press would form an endless
list. Among those having a bearing on the history of that time was,
The Marks of a Work of the Spirit, together with Remarks Respecting
the Present Astonishing Work of God, and Revival of Religion in the
297
Western Country, by J. Hughes of West Liberty. “J. Hughes,” was
the Rev. James Hughes, pastor of the Presbyterian churches at
Lower Buffalo in Washington County, and West Liberty in the
adjoining county of Ohio in Virginia, and one of the trustees of the
recently established Jefferson College, the pioneer college of the
West.
Cramer lived and flourished in an age when many of the
publications sent out in the name of religion contained the merest
drivel, or were elaborations of theories in regard to matters infinite
held by narrow-minded controversialists. The press was flooded with
them. There were publications bearing such depressing titles as The
Happy Voyage Completed, and The Sure Anchor Cast. Cramer
realized that in publishing works of this character he might be
misunderstood. This sentiment was evident in the advertisement of
at least one of his publications. On that occasion he prefaced his
notice by stating: “On the recommendation of some pious friends, we
contemplate printing, A Token for children, Being an exact account of
the Conversion, holy and exemplary Lives and Joyful Deaths of
298
several young children!”
The most pretentious of his works was religious in character, and
was published in 1807. It was A Dictionary of the Holy Bible by the
Rev. John Brown of Haddington, in Scotland, of which two editions
were printed. It was a noteworthy achievement to be accomplished
on the frontier, hundreds of miles from the center of civilization. Many
difficulties had to be overcome, not the least of which was the delay
299
occasioned by the difficulty in procuring a regular supply of paper.
The work was in two large octavo volumes, and was illustrated with
engraved pictures and maps that are still desired by collectors.
Heading the list of subscribers, was the name of President Jefferson,
of whom Cramer appears to have been an ardent admirer. In 1810,
the firm published the Select Remains of the Rev. John Brown, the
author of the Dictionary.
Cramer’s publications covered a wide range. In 1808 The
Lawyer, by George Watterson, appeared, which was imbued with the
current prejudice against lawyers, and presented a sorry spectacle of
the legal profession. The same year, a map of Pittsburgh was
published, which, if in existence to-day, would be of great interest.
One of his most valuable contributions to the literature of travel, was
Sketches of a Tour to the Western Country in 1807–1809, by F.
Cuming, published in 1810. It contained according to Reuben Gold
300
Thwaites, a “picture of American life in the West at the beginning
of the nineteenth century that for clear-cut outlines and fidelity of
presentation has the effect of a series of photographic
representations.” Another work of value was Views of Louisiana, by
Judge Henry M. Brackenridge, published in 1814. Cramer had met
Brackenridge in New Orleans, in December, 1811, while on one of
his visits to that city, and arranged with him there for the
301
publication. In 1813, The Poetical Works of Oliver Goldsmith were
brought out.
One of the most important ventures of Cramer’s entire publishing
experience, the fruition of which he did not live to see, was The
Western Gleaner or Repository for Arts, Sciences, and Literature. It
was a monthly magazine of sixty-four pages. The first number
appeared in December, 1813, four months after Cramer’s death.
Compared with magazines of the present time, it was not of the
highest order of literary merit. In its day, however, it ranked with the
best magazines published. The excellent literary taste of the editor
also appears from an incident which occurred during the early life of
the magazine. The Pittsburgh Gazette published a communication
from a disappointed aspirant for literary fame, signing himself
“Recluse,” whose poem in fourteen stanzas entitled “The Two
Roses,” had been declined by the Western Gleaner. “Recluse”
referred sarcastically to the “uncommonly profound and very
discerning editor of the Western Gleaner.”
That the editor of the Western Gleaner was more “discerning”
than the editor of the Pittsburgh Gazette, which published
“Recluse’s” effort, along with his letter, is evident from a perusal of
the poem. The first stanza, which is also the best, reads:
“The sweetest rose that ever bloomed,

Was one that, with insidious sip,
Beneath Eliza’s smiles presumed,
302
To pilfer fragrance from her lip.”
The same persistency which procured the publication of “The Two

Roses” in the Pittsburgh Gazette, enabled “Recluse” a few years
later to find a publisher for a volume of his poetry, in which “The Two
303
Roses” was one of the gems.
In one of the numbers of the magazine Judge Hugh Henry
Brackenridge contributed a poem, descriptive of his feelings on
revisiting Pittsburgh, called “On a Circuit at This Place.”
“What is there in this spot of earth

Repellant to all zest of mirth,
Heart-felt by me,
And which on being seen again,
The Hill, the River and the Plain
304
To sadden, all agree!”
Cramer realized that books having a local interest would find a

ready sale. One of these was Judge Hugh Henry Brackenridge’s
Modern Chivalry; another was his Incidents of the Insurrection in
Western Pennsylvania, which was an effort to vindicate himself for
his course in the Whisky Insurrection. Judge Addison’s impeachment
in 1803, by the Republican General Assembly, had created profound
interest in Pittsburgh. The account of the trial was immediately
published in Lancaster, then the capital of the State, and eagerly
read. Another book of local interest was Colonel James Smith’s
Captivity among the Indians Westward of Fort Pitt in the Year 1755,
published at Lexington, Kentucky, in 1799.
Although a Republican himself, Cramer’s mercantile instincts led
him to sell books written in opposition to that party. A little volume of
poems was of this class. David Bruce, a Scotchman living in the
adjacent village of Burgettstown, whom Cramer designated as “an
ingenious Scotch poet of Washington County,” had published in
1801, in Washington, Pennsylvania, a book which, while mainly
political in character, had considerable merit. Bruce was a strong
Federalist, and his volume was dedicated to Judge Addison. To the
Republicans, Brackenridge, Gallatin, McKean, and other more or
less local celebrities, Bruce’s references were disparaging. To
Brackenridge he addressed the cynical lines:
“When Whisky-Boys sedition sang,

An’ anarchy strod owre the lan’
When Folly led Rebellion’s ban’
Sae fierce an’ doure,
Fo’ks said ye sleely lent a han’
305
To mak the stoure.”
A book of the same character, but covering a wider range, and of
a higher literary tone, was The Echo. It had a local interest in that it
contained a number of clever satirical references to Judge Hugh
Henry Brackenridge. In the latter part of the eighteenth century,
Hartford was the literary center of Federalistic ideas. They were
promulgated by a group of young authors known as the “Hartford
Wits.” Included in the coterie was Richard Alsop, who was the
principal writer of The Echo. The Echo had originally appeared
serially, but in 1807, the parts were collected and published in a
volume. The allusions to Brackenridge indicated a keen sense of
humor and considerable poetic spirit. An article written by
Brackenridge had appeared in 1792 in the National Gazette of
Philadelphia, then recently established as the organ of the
Republicans, in which he urged savage reprisals against the Indians,
who were causing trouble west of Pittsburgh. To this screed, The
Echo made the mocking reply:
“I grant my pardon to that dreaming clan,

Who think that Indians have the rights of man;
Who deem the dark skinn’d chiefs those miscreants base,
Have souls like ours, and are of human race;
And say the scheme so wise, so nobly plann’d.
For rooting out these serpents from the land,
To kill their squaws, their children yet unborn,
To burn their wigwams, and pull up their corn;
By sword and fire to purge the unhallow’d train,
And kindly send them to a world of pain,
Is vile, unjust, absurd:—as if our God
One single thought on Indians e’er bestow’d,
To them his care extends, or even knew,
306
Before Columbus told him where they grew.”
On another occasion when Brackenridge was a candidate for

Congress, he published in the Aurora an appeal to the electors of his
Congressional District in which he animadverted harshly on the
educational accomplishments of General John Woods, his Federalist
opponent. This presented another opportunity for the clever writers
of The Echo to burlesque a leading Republican. The Echo gibed:
“But, to return to Woods,—to speak my mind,

His education was of narrow kind;
Nor has he since to learning much applied,
But smil’d with calm contempt on pedant pride.
His mental powers, howe’er, superior shine,
His genius glows with energy divine.
But when with mine in competition plac’d.
How low his powers, his genius sinks debas’d,
Has not my genius shone with peerless ray,
And o’er Ohio pour’d the blaze of day?
Have not my writings spread abroad my name,
And bards consign’d me to immortal fame?
Then shall John Woods with me presume to vie,
307
The brightest star that decks the western sky?”
Cramer’s books covered the entire range of literary endeavor

and among them were a majority of the contemporary publications.
The French Revolutionary movement was well represented. A work
coming under this designation was the Life and Campaigns of
General Count Alexander Suwarrow, which was of interest also
because Suwarrow’s title to fame rested at least partly on the fact
that he was the originator of the high tasseled-boot, much worn both
in military and civil circles after the year 1800. There was a flood of
Bonapartist literature. A book of this class which had a local interest
was the Life of General Jean Victor Moreau. After being exiled from
France on account of conspiring against Napoleon, this officer had
come to the United States in 1805, and made a tour of the Ohio and
Mississippi Valleys. Having passed through Pittsburgh, his name
was well known there. Works of travel were numerous. Conspicuous
in biography were the lives of Washington, Franklin, and Kotzebue,
the German playwright and novelist, then at the height of his career.
There were histories of various European countries, and William
Winterbotham’s History of the American United States. The History
of Women, if at hand to-day, would be of interest to that large body
of women who are making such herculean efforts to obtain greater
rights for their sex. Among the notable books of the day was Thomas
Jefferson’s Notes on the State of Virginia. Two editions had been
published prior to Jefferson’s becoming President. After the election
in 1800, the work was republished in a large octavo volume, for
308
which Cramer was agent in Pittsburgh. Another book which
attracted considerable attention was the History of John Adams,
Esquire, late president of the United States, by John Wood. It was a
rank Republican account of a most interesting period. It was printed
and ready for publication in December, 1801, but was suppressed at
the instigation of Aaron Burr, as being incorrect and libelous. The
book was finally published in 1802. A companion-piece to Wood’s
book, was the one by James Cheetham, which gave an account of
the suppression. It was entitled, A Narrative of the Suppression by
Col. Burr of the History of the Administration of John Adams, by a
Citizen of New York.
Philosophy was not neglected. Representative of that science
were William Enfield’s History of Philosophy, William Smellie’s
Philosophy of Natural History, Francis Hutchinson’s System of Moral
Philosophy, and Count Volney’s Law of Nature. Books relating to
trades, included the Miller and Millwright’s Guide; the Young
Carpenter’s Assistant; the New System of Gardening; the Dictionary
of Husbandry; Washington’s Letters to Arthur Young; the English
Gardener; and Elements of Architecture. Freemasonry was
described in William Preston’s Illustrations of Masonry. Among books
relating to the professions, those pertaining to divinity were most
numerous. The Methodists had increased in numbers and were in
better standing in the community. John Wrenshall was addressed as
the “Rev.” John Wrenshall, and Cramer began to sell the Memoirs of
George Whitfield, the famous exponent of Methodism. Law books
were a close second to those of divinity. There were books on state,
national, and international law. In medicine there were books for
family use, and books for physicians.
Belles-lettres and poetry formed an important department.
Predominant in belles-lettres were the writings of Addison, Steele,
and Pope in the Spectator, and its successors, the Guardian, and
the Tattler; Dr. Johnson, in his “Rambler”; and Salmagundi, when it
appeared in 1807. Junius’s Letters; the works of Lawrence Sterne;
the Posthumous Works of Jonathan Swift; and Peter Pindar’s Satires
were other books in this department. In the selection of plays, those
of Kotzebue were prominent. The English plays were represented by
George Colman, the younger’s, The Poor Gentleman, a comedy
produced in Covent Garden in 1801, and by Thomas Morton’s,
Speed the Plough, produced in 1798. Because of its authorship, The
Battle of Bunker Hill, by Judge Hugh Henry Brackenridge, had a
local interest. In the realm of poetry, were the poems of John
Pomfret, Robert Burns, Dr. Thomas Brown, Alexander Pope, John
Milton, Thomas Moore, Allan Ramsay, and Robert Southey. In this
class was Thomas Campbell’s The Pleasures of Hope; James
Beattie’s The Minstrel; Samuel Rogers’s Pleasures of Memory;
William Cowper’s Beauties of Cowper, and The Task; Joel Barlow’s
The Vision of Columbus; Robert Bloomfield’s, The Farmer’s Boy,
and A Song; James Thomson’s Seasons. Zaida, by Kotzebue;
Charlotte Temple, by Mrs. Susanna Rowson, and Don Quixote were
popular romances. In colonial days, and in the early days of the
republic, little stitched pamphlets, called chapbooks, because largely
circulated by itinerant vendors, or chapmen, were much in vogue.
Books in this form for children had a large circulation, and Cramer
carried an interesting list.
Cramer’s upright nature often led him to express opinions that
were contrary to the views obtaining in publications of his firm.
Cuming in his Tour of the Western Country, in the reference to
Pittsburgh had written: “Amusements are also a good deal attended
to, particularly the annual horse races.” On this observation Cramer
commented in a note: “We are sorry to have to acknowledge that
horse racing contrary to the express law of the State, has been more
or less practiced within the vicinity of this place for a few years back;
but we are pleased with the prospect of having it totally abolished by
the influence of its evident impropriety, danger, and wickedness,
309
operating on the minds of the more thoughtful and judicious.”
That Cramer was not alone in condemning the horse races is
apparent from a communication which had appeared in the
310
Pittsburgh Gazette six years earlier. This writer designated the
races as “a fruitful seminary of vice.” He declared that the “schools
and shops are shut up or deserted, and the youth of both sexes run
to harm, folly, and debauchery.... The money, too, which ought to be
expended in the honest maintenance of families and the payment of
debts is squandered on sharpers, gamblers and sutlers.”
If some fact or custom was referred to, which Cramer considered
morally wrong, or which might disparage Pittsburgh in the eyes of
the world at large, he spoke out vigorously in opposition. In the
311
Navigator for 1811, the statement was made that there were “two
or three whisky distilleries in the town.” This was immediately
followed in the text by a disapproval of distilleries, and a quaint
homily on the evils of intemperance. “We cannot say anything in
praise of these,” Cramer wrote. “Whisky as a medicine is good, that
is, to take it only when the system requires it and no more than is
sufficient to perform the part of a gentle stimulant; but to drink it as is
now universally practiced, is destructive of health, strength, morals,
religion, and honesty; and is a serious national calamity, in which
man sinks in the estimation of himself, and becomes an abhorrence
in the eyes of God.”
Cramer’s career was short. He had never been robust, and close
attention to business had undermined his constitution; consumption
developed. He attempted in vain to obtain relief in southern travel,
and died on August 1, 1813, just before reaching his fortieth year, at
Pensacola, Florida, while on the way to Havana, the journey having
been recommended by his physician. In Pensacola his remains were
buried and there they lie in an unmarked grave. To the last he was
planning new business projects, and preserved his cheerfulness to
the end. Not once was he known to be fretful or ill-natured. He left
his widow and one child, a daughter, Susan. The firm was continued
for many years, first by the widow, in conjunction with John Spear,
and after her death on May 5, 1818, by the daughter. The affairs of
the partnership were not wound up until July 6, 1835.
In early life the daughter married Dr. J. B. Cochran in Pittsburgh.
Becoming a widow, she removed to Beaver, Pennsylvania, with her
three children. Her children were Zadok Cramer Cochran, James
Spear Cochran, and Mary Cochran. After their mother’s death in
1854, the children removed to Coatesville, Pennsylvania. From
Coatesville they went to Freeport, Illinois. Here the two sons
engaged in teaching and conducted an academy. James later took
up the study of the law, and was admitted to the Bar. Drifting into
politics he was elected to the State Senate. The two brothers are
both dead, but the sister is still living, being the wife of Joseph
Emmert, of Freeport, Illinois.
REFERENCES
Chapter IX
285
Tree of Liberty, August 7, 1802.
286
Pittsburgh Gazette, October 10, 1800.
287
Tree of Liberty, January 16, 1802.
288
Tree of Liberty, October 8, 1803.
289
Pittsburgh Gazette, April 19, 1808.
290
Tree of Liberty, May 21, 1803.
291
Pittsburgh Gazette, January 9, 1801.
292
The Commonwealth, August 14, 1805.
293
The Commonwealth, September 29, 1811.
294
Tree of Liberty, November 6, 1802.
295
296
297
Tree of Liberty, June 4, 1803.
298
The Pittsburgh Magazine Almanac for 1810.
299
The Pittsburgh Magazine Almanac for 1807.
300
Reuben Gold Thwaites: Fortescue Cuming, Sketches of a
Tour to the Western Country in 1807–1809, Cleveland,
Ohio, 1904, p. 9.
301
H. M. Brackenridge: Views of Louisiana, Pittsburgh, 1814,
p. 4.
302
Pittsburgh Gazette, January 28, 1814.
303
The Recluse: The Art of Domestic Happiness and Other
Poems, Pittsburgh, 1817, pp. 1–317.
304
The Western Gleaner or Repository for Arts, Sciences, and
Literature, Pittsburgh, 1814, vol. ii., pp. 185–186.
305
David Bruce: Poems entirely in the Scottish Dialect,
originally written under the signature of the Scots-
Irishman, Washington, 1801, p. 46.
306
The Echo, pp. 32–39.
307
The Echo, pp. 150–151.
308
Tree of Liberty, January 24, 1801.
309
F. Cuming: Sketches of a Tour to the Western Country in
1807–1809, Pittsburgh, 1810, p. 231.
310
Pittsburgh Gazette, October 16, 1801.
311
The Navigator, Pittsburgh, 1811, p. 63.
INDEX
Adams, George, 114, 128

Adams, Henry, 81
Adams, John, 165;
History of, 200
Addison, Alexander, Judge, impeachment of, 47–48, 139, 195;
Federalist, 131, 132
Adgate & Co., 104
Allegheny County, 22, 23
Allegheny County Courts, 157
Allegheny County Militia, 74, 75
Almanacs, 4, 165, 172;
Cramer’s, 172–174;
“Common,” 174;
“Magazine,” 174
Alsop, Richard, 197
Amberson, Beelen, & Anshutz, 152
American Coast Pilot, 182
Amusements, 67–74, 186, 203
Arnold, actor, 70
Ash, Thomas, 181
Ashton, Capt. Joseph, 95, 151
Ashton & Denny, 152
Audrian, Peter, 49
Aurora, newspaper, 51
Baird, Thomas, 96, 128, 130

Baldwin, Henry, 96, 141, 148, 149;
attacked by Pentland, 145, 146
Balls, 68, 72;
for Gen. Lee, 69
Bank of Pennsylvania, branch, 93, 116
Baptists, 95
Barker, Abner, 116, 117, 132
Barker, Jeffe, 116, 117
Barker, Jeremiah, 117, 132
Barrett, William, 121
Bartholf, Francis, Baron de Belen, 152
Bates, Edward, 145
Bates, Frederick, 143, 145, 148
Bates, James, 145, 148
Bates, Tarleton, 96, 131, 141 ff.;
duel, 142–150
Bausman, Elizabeth, marriage, 125
Bausman, Jacob, 30;
varied career, 41–42
Bausman, Nicholas, 41
Bayard, Colo. Stephen, 5
Beaujolais, Count of, 111
Bedford County, 2
Beelen, Anthony, 96, 150, 152
Beelen, Francis, 152
Beltzhoover, Melchoir, 41
“Black Charley,” 39
Blunt, Edmund, American Coast Pilot, 182
Boat yards, 8, 40, 92
Books, in households, 14;
sale of, 14, 15, 27;
interest in, 27;
most popular, 169–171;
Cramer’s publications, 189 ff.;
contemporaneous history, 190;
of local interest, 195–196;
contemporary publications, 199;
in Cramer’s bookstore, 199 ff.
Bookstores, 95;
first, 27;
Cramer’s “Pittsburgh Bookstore,” 116, 163, 186, 188, 199 ff.;
Christy’s and Wrenshall’s, 184
Boyd, John, 15, 16
Brackenridge, Henry M., Judge, recollections of Grant’s Hill, 71;
account of horse racing, 73;
on the Court of Allegheny County, 118;
Views of Louisiana, 193
Brackenridge, Hugh Henry, Judge, 49, 71;
author, 26, 195, 197, 198, 202;
Modern Chivalry, 26;
political leader, 55;
Fourth of July speech, 56;
Justice of Supreme Court, 58;
opposed to Brison, 58 ff.;
and the Tree of Liberty, 62–63;
and the Whisky Insurrection, 81, 106, 124, 195;
Freemason, 95;
residence, 97, 115;
antagonizes soldiers, 115–116;
candidate for Congress, 125, 198;
attacks on, 133–134;
and impeachment of Addison, 139;
settles Gilkison’s affairs, 163;
Bruce’s lines to, 196;
satires on, in The Echo, 197–198
Braddocksfield, 119
Brantz, Lewis, notes on Pittsburgh, 9, 30
Breweries, 78, 92
Brickyards, 31, 92

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Studies in Natural Products Chemistry

Volume 52 Atta-Ur-Rahman (Eds.)

Studies in Natural Products Chemistry Volume 51 Atta-

Studies in Natural Products Chemistry Volume 53 Atta-

Studies in Natural Products Chemistry Volume 44 1st

Studies in Natural Products Chemistry Volume 41 1st

Studies in Natural Products Chemistry 50 1st Edition

Bioactive Natural Products 1st Edition Atta-Ur-Rahman

Studies in Natural Products Chemistry Volume 43 First

Studies in Natural Products Chemistry Volume 46 1st

Copyright © 2017 Elsevier B.V. All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any

Library of Congress Cataloging-in-Publication Data

British Library Cataloguing-in-Publication Data

For information on all Elsevier publications visit our

Publisher: John Fedor

This 52nd volume of Studies in Natural Product Chemistry presents 10

Prof. Atta-Ur-Rahman, FRS

Natural Environments for

Studies in Natural Products Chemistry, Vol. 52. http://dx.doi.org/10.1016/B978-0-444-63931-8.00001-1

Core@Shell and Mixed NPs 41 Summary 60

dangerous by-products, low material conversions, and high energy demand

redox reactions executed in or by selected microorganism [32e34], enzymes

KEY CONCEPTS OF BIOLOGICAL NANOSYNTHESIS, STATE

Ag+ AgNO3 NO3-

Bacillus licheniformis cell

Lower temperature Higher temperature

nucleus silver nanocrystals

silver ions that deposits

BIOSYNTHESIS OF NPs BY BACTERIA

FIGURE 1.3 Effect of pH ranges on Ag-NPs synthesis by the spores [53].

Natural Environments Chapter j 1

8 Studies in Natural Products Chemistry

[31,51,55]. Saifuddin et al. reported that nitrate reductase activity together

FIGURE 1.4 Proposed mechanism of Au-NPs synthesis by Stenotrophomonas maltophilia

Srivastava and Mukhopadhyay reported synthesis of Au-NPs with bacte-

uptake of ions and complex formation

silver and gold

oxides, quasispherical NPs, and nonstoichiometric NPs of size in the range

Metal Oxide Nanoparticles

Titanium Dioxide (TiO2)

SCHEME 1.1 Reaction proceeded in Lactobacillus sp. medium [68].

the gaseous hydrogen partial pressure). Thus, by controlling the oxida-

SCHEME 1.2 Postulated reaction of TiO2-NPs formation in Aeromonas hydrophila culture

BIOSYNTHESIS OF NPs BY FUNGI

2. Ag Penicillium atramentosum Enzymes Structure: crystalline [74]

4. Au Fusarium oxysporum NADH-dependent reductase Structure: no data [76]

Natural Environments Chapter j 1

FIGURE 1.6 Effect of pH on Ag-NPs size [73].

(i.e., 4 or 5) were polydispersed with various different shapes such as pyra-

reaching, maximum intensity after 6 h of incubation under standard conditions

FIGURE 1.7 Mechanistic representation of biomimetic Au-NPs formation in Trchoderma har-

Metal Oxide Nanoparticles

Titanium Dioxide (TiO2)

TiO − (OH ) 2 → TiO2 + H 2O

SCHEME 1.3 Reaction process in Saccharomyces cerevisiae culture solution [68].

Zirconium Dioxide (ZrO2)

BIOSYNTHESIS OF NPs IN PLANT EXTRACTS

flavonoids reduction capping

Cramer’s business prospered. His was the only establishment in

“The sweetest rose that ever bloomed,

The same persistency which procured the publication of “The Two

“What is there in this spot of earth