Functional Materials and Nanomaterials

Prof. Benjamin Dietzek

Prof. Felix H. Schacher

SS 2019
Lecture(s) (3 SWS)

Monday 12:00 – 14:00 Humboldtstraße 8, IAAC, SR 2

Thursday 10:00 – 12:00 Humboldtstraße 8, IAAC, SR 1

Seminar (1 SWS)

Thursday 10:00 – 12:00 Humboldtstraße 8, IAAC, SR 1

(… as alternative to lectures, see separate plan)

Labcourse (3 SWS)

tba
Tentative timeline / schedule L = lecture // S = seminar // X = no event

Mo 08.04. LF Thu 11.04. X

Mo 15.04. LB Thu 18.04. X
Mo 22.04. Easter Thu 25.04. LF
Mo 29.04. LF Thu 02.05. LF
Mo 06.05. LB Thu 09.05. LB
Mo 13.05. LB Thu 16.05. SF
Mo 20.05. LF Thu 23.05. SF
Mo 27.05. LF Thu 30.05. X
Mo 03.06. LF Thu 06.06. SF
Mo 10.06. Pfingsten Thu 13.06. S
Mo 17.06. L Thu 20.06. S
Mo 24.06. L Thu 27.06. L
Mo 01.07. L Thu 04.07. S
Mo 08.07. X Thu 11.07. Exams
Outline / Topics

1. Introduction and Definitions

2. Nanomaterial Synthesis
- Soft matter / polymer materials
- Self-assembly concepts
- Stoeber process
- Metal / metal oxide NPs
3. Surfaces and Interfaces
- Definitions, interfacial forces
- Surface modification of nanomaterials
- Monolayers, film preparation, film properties
4. Nanomaterial Characterization
- Spectroscopic / microscopic techniques
- Scattering, ellipsometry, QCM …
- Order and transport at interfaces
5. Applications of Nanomaterials (selected)
- Lithography, sensing, drug delivery, optics, catalysis …
What is the aim of this course?

• Understand basic concepts of nanomaterial synthesis

• Learn about surface and interface chemistry and, more important, how
control over the latter is key in several application fields

• Be familiar with a range of characterization techniques frequently used in

the context of nanomaterials  „how do I get a certain piece of
information?“

• Understand why often not one single method can be used to extract
(quantitative) information for / from nanomaterials
Introduction
What is a functional material?

www.impulse.de // JokaToons
What is a Nanomaterial?

https://oshwiki.eu/wiki/Nanomaterials
What is Nanotechnology?

… technology focusing on structures and processes in the nm range (10-9 m)

www.nih.gov // https://slideplayer.com/slide/11378587/
What is Nanotechnology?

… technology focusing on structures and processes in the nm range (10-9 m)

Highly interdisciplinary research area(s)!

1986
Kim Eric Drexler

1959 Richard Feynman

„There´s plenty of room at the bottom“
Where do I find Nanomaterials?

https://oshwiki.eu/wiki/Nanomaterials
Nanotechnology – Examples from our Daily Life

Food technology: cyclodextrines organic carrier molecules

https://www.febreze.com/en-us

SiO2 nanoparticles anti-caking agent, coatings

(anti-bacterial)

www.labo.de
„Aus dem Labor auf den Teller“ – BUND report 2008
Nanotechnology – Examples from our Daily Life

Food technology: AquaNova© / Darmstadt, Germany

Polysorbat 80
E433

w+x+y+z = 20 (ca.)

Improve solubilization / availability of hydrophobic substances!

Nanotechnology – Examples from our Daily Life

Food packaging – sensing of age / ripening

How does it work?

Sensing of aroma produced by the content (pear)

http://www.ripesense.co.nz/ripesense_gallery.html
Nanotechnology – Examples from our Daily Life

Carbon nanotubes as additives for shopping trolley handles…?

Prevention of electric shocks while being in use.

„Aus dem Labor auf den Teller“ – BUND report 2008, updated 2015/2016
Nanotechnology – Risks?

We get in contact with nanomaterials via various pathways: skin contact, food /
beverages, air, …

So far, little if known about (long-time) risks / health issues. Why is that?

- Time-consuming studies necessary to

assess risk profiles
- Development of new materials is fast(er)
- Sometimes also lack of comparability
between materials (and studies)
- …

 Many ongoing studies…

Nanochemistry – Chemistry at the Nanoscale?

With the advent of nanotechnology and the

miniaturization of materials to the nanometer scale the
surface becomes impossible to ignore:

 Nanomaterials possess large

surface areas up to 1000 m2/g
 Phenomena dependent on
surface reactivity are affected

Approximate percentage of surface atoms as a function of nanocrystal size,

assuming a spherical morphology and a PbS lattice.
Nanochemistry – Chemistry at the Nanoscale?

With the advent of nanotechnology and the

miniaturization of materials to the nanometer scale the
surface becomes impossible to ignore:

Φ
γ = ηdb
2

γ =
surface energy; η db surface density of dangling bonds
Φ =bond energy

 Different crystal faces have different surface energy

 Surface roughness and curvature are important
… resulting in different chemical and physical properties at different locations

 Dangling bonds are (highly) reactive, adsorb impurities, etc.

Ozin, Arsenault, Cademartiri – „Chemistry at the Nanoscale“

Nanochemistry – Chemistry at the Nanoscale?
Eliminates dangling bonds
Dangling bonds can
react over time:
 surface passivation

Can occur at far milder

conditions than observed
for bulk materials

Build-up of (multi-)
layers with nm In case of alloys, the formation of
precision! core-shell structures is possible
(surface enrichment of one
component)
Ozin, Arsenault, Cademartiri – „Chemistry at the Nanoscale“
Nanochemistry – Chemistry at the Nanoscale?

Different approaches possible for

the modification of a nanoparticle
surface (here polymers@iron oxide)

Polymers 2018, 10, 91 (part of a special issue on "Polymers and Block Copolymers at Interfaces and Surfaces")
Nanoparticle Surface (Modification) – So what?

- Control over solubility / dispersion stability

- Control over / prevention of secondary aggregation
- Control over shell functionality and thickness
- Introduction of targeting moieties, binding motifs, etc.
- Surface properties determine interactions with other nanomaterials or
small molecules (or interfaces)

 Self-assembly strategies
Light Scattering – a comprehensive reminder
a. Linear light matter interaction
ii. Classical description of elastic light scattering

When a sample is irradiated with light, a light weakening due to scattering

always occurs in addition to a possible absorption.
Examples: Tyndall effect (1869), blue sky, evening glow,.....

 Scattering often refers to various physical phenomena such as refraction,

diffraction and reflection that deflect a light beam from its geometric path.
 If the scattered photon has the same frequency as the incident photon, we
speak about elastic scattering.
 If additional energy is transferred, this is referred to as inelastic light
scattering (Raman effect → information of quantum states of the scatterer).
 Measuring the intensity of the elastically scattered light as a function of time is
called dynamic light scattering (→ information of structure and diffusion rate
of the scatterer).

! Note: scattering can yield wrong results e.g. when measuring the absorbance
of a sample by inducing fake peaks.
Categorization of Scattering

Considering (for practical purposes) scattering of light emitted by a HeNe laser

at 632.8 nm

Tommy Markstein

 Rayleigh scattering for particle sizes 1 𝑛𝑛𝑛𝑛 < 𝑑𝑑 < 0.1 𝜆𝜆 ≈ 60 𝑛𝑛𝑛𝑛,
 Rayleigh-Debye scattering for 60 𝑛𝑛𝑛𝑛 < 𝑑𝑑 < 200 𝑛𝑛𝑛𝑛,
 Mie scattering for 200 𝑛𝑛𝑛𝑛 < 𝑑𝑑 < 10,000 𝜆𝜆 ≈ 6 𝑚𝑚𝑚𝑚,
 Fraunhofer scattering for 6 𝑚𝑚𝑚𝑚 < 𝑑𝑑.
In analogy to the Lambert-Beer law, the total scattering power of a sample
can be described as follows:

• I0 incoming light intensity

• I(x) by scattering at sample depth x reduced intensity
• S‘ scattering coefficient

For diluted solutions, the scattering cross-section σs can be determined

directly from the turbidity of a sample using a conventional absorption
spectrometer:

1 𝐼𝐼0
�ln = 𝑆𝑆𝑆 = 𝑁𝑁 � 𝜎𝜎𝑆𝑆 N particle density.
𝑥𝑥 𝐼𝐼

The scattering cross-section is directly the effective cross-sectional area

of the scattering particles within which an incident quantum of light can
be deflected.

! Highly scattering and opaque samples require a different basis for

description → Kubelka-Munk theory.
Rayleigh scattering
 The electromagnetic field E(t) induces a time-dependent induced dipole
moment μind(t) at the oscillating dipole (core electron model), excites the dipole
to forced oscillations.

 Thus the dipole acts as a secondary radiation source, it is the starting point of
scattered light of intensity Is (radiated power per area).
 For isotropic molecules oscillating dipole oscillates vertically in the direction of
z-axis
! Note: this is the molecular analogue to the macroscopic Hertzian dipole.

𝑝𝑝⃗ 𝑡𝑡 = 𝑝𝑝⃗0 � 𝑒𝑒 −𝑖𝑖𝜔𝜔𝑡𝑡

𝜔𝜔3 𝑛𝑛 1 1
𝐸𝐸 = � 𝑛𝑛 × 𝑝𝑝⃗ × + 3𝑛𝑛 𝑛𝑛 � 𝑝𝑝⃗ − 𝑝𝑝⃗ � 3 − 2 � 𝑒𝑒 −𝑖𝑖 𝜌𝜌−𝜔𝜔𝑡𝑡
4𝜋𝜋𝜋𝜋𝑐𝑐 3 𝜌𝜌 𝜌𝜌 𝜌𝜌

2𝜋𝜋𝜋𝜋
𝜌𝜌 ≡
𝜔𝜔
Rayleigh scattering
 The electromagnetic field E(t) induces a time-dependent induced dipole
moment μind(t) at the oscillating dipole (core electron model), excites the dipole
to forced oscillations.

! Note: this is the molecular analogue to the macroscopic Hertzian dipole

𝜔𝜔3 𝑛𝑛 1 1
𝐸𝐸 = � 𝑛𝑛 × 𝑝𝑝⃗ × + 3𝑛𝑛 𝑛𝑛 � 𝑝𝑝⃗ − 𝑝𝑝⃗ � 3 − 2 � 𝑒𝑒 −𝑖𝑖 𝜌𝜌−𝜔𝜔𝑡𝑡
4𝜋𝜋𝜋𝜋𝑐𝑐 3 𝜌𝜌 𝜌𝜌 𝜌𝜌

This reduces in the far field to:

𝜔𝜔3 𝑛𝑛
𝐸𝐸 = � 𝑛𝑛 × 𝑝𝑝⃗ × � 𝑒𝑒 −𝑖𝑖 𝜌𝜌−𝜔𝜔𝑡𝑡
4𝜋𝜋𝜋𝜋𝑐𝑐 3 𝜌𝜌

The irradiated intensity is expressed by:

𝜔𝜔4 � 𝑝𝑝⃗ 2
𝐼𝐼 𝜃𝜃 = 2 3 � 1 − 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃
32𝜋𝜋 𝜀𝜀𝑐𝑐
Von Averse, CC BY-SA 3.0, https://commons.wikimedia.org/w/index.php?curid=15794244
Rayleigh scattering
 The electromagnetic field E(t) induces a time-dependent induced dipole
moment μind(t) at the oscillating dipole (core electron model), excites the dipole
to forced oscillations.

! Note: this is the molecular analogue to the macroscopic Hertzian dipole

𝜔𝜔3 𝑛𝑛 1 1
𝐸𝐸 = � 𝑛𝑛 × 𝑝𝑝⃗ × + 3𝑛𝑛 𝑛𝑛 � 𝑝𝑝⃗ − 𝑝𝑝⃗ � 3 − 2 � 𝑒𝑒 −𝑖𝑖 𝜌𝜌−𝜔𝜔𝑡𝑡
4𝜋𝜋𝜋𝜋𝑐𝑐 3 𝜌𝜌 𝜌𝜌 𝜌𝜌

This reduces in the far field to:

𝜔𝜔2 𝑛𝑛
𝐸𝐸 = � 𝑛𝑛 × 𝑝𝑝⃗ × � 𝑒𝑒 −𝑖𝑖 𝜌𝜌−𝜔𝜔𝑡𝑡
4𝜋𝜋𝜋𝜋𝑐𝑐 3 𝜌𝜌

The irradiated intensity is expressed by:

𝜔𝜔4 � 𝑝𝑝⃗ 2
𝐼𝐼 𝜃𝜃 = 2 3 � 1 − 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃
32𝜋𝜋 𝜀𝜀𝑐𝑐
 Rayleigh scattering
For scattering centres that are significantly smaller than the wavelength of the light:

(Rayleigh equation)
Distribution of Rayleigh scattered radiation when
irradiated with monochromatic, vertically polarized
light is independent of azimuth angle Θ.

 The radiation intensity is proportional to the fourth power of the frequency, ω4 or

1/λ4;
 The intensity is direction-dependent (directional characteristic); it behaves like sin2
Φ (where Φ is the angle between the scattering direction and the dipole axis).
 No intensity is scattered along the dipole axis, the maximum intensity is
perpendicular to the oscillation axis of the dipole (= z-axis)
 The scattered intensity is proportional to the square of the dipole moment and
inversely proportional to the square distance r from the emitting dipole (far field
approximation, like spherical waves from a point source)
Rayleigh scattering compared to Hertzian dipole
For scattering centres that are significantly smaller than the wavelength of the light:

(Rayleigh equation)

𝜔𝜔2 𝑛𝑛
𝐸𝐸 = � 𝑛𝑛 × 𝑝𝑝⃗ × � 𝑒𝑒 −𝑖𝑖 𝜌𝜌−𝜔𝜔𝑡𝑡
4𝜋𝜋𝜋𝜋𝑐𝑐 3 𝜌𝜌

𝜔𝜔4 � 𝑝𝑝⃗ 2
𝐼𝐼 𝜃𝜃 = 2 3
� 1 − 𝑐𝑐𝑐𝑐𝑐𝑐 2 𝜃𝜃
32𝜋𝜋 𝜀𝜀𝑐𝑐

! Note: for historic reasons (established conventions)

the two equations use to term the angle differently,
nonetheless, 𝜙𝜙 = 𝜃𝜃.
Rayleigh scattering
Often, scattering experiments do not involve polarized but unpolarized incident
radiation:
 light waves of all polarization directions are superimposed
 instead of an Φ− there is a Θ-dependence of the scattered radiation

(Rayleigh equation)

What happens if there are several particles (e.g.

molecules in a solvent)?
The scattered light waves emanating from the
individual scattering centers (e.g. atoms) of these
particles are practically always in phase and
interfere constructively (only applies to particles
that are clearly none but the light wavelength).
The physics of dusk

• at dusk sun light has to travel to a long

distance through the atomosphere
• many scattering events can take place
• blue light has a higher probability of getting
scattered (per distance travelled)
• red light reached the earth with a higher
probability.
The physics of dusk – How come though that the sky is blue?

• (again) blue light has a higher probability of

getting scattered (per distance travelled)
• however, travel distance of the light
through atmosphere is comparably short
• the scattered blue light appears as diffuse
light from all over the sky, apparently
coloring the sky blue.
Determination of molecular masses from Rayleigh scattering

𝐼𝐼𝑆𝑆 16𝜋𝜋 2 𝛼𝛼 2
= 2 4 � 𝑠𝑠𝑠𝑠𝑠𝑠2 Φ Clausius-Mosotti 𝑛𝑛2 − 1 = 4𝜋𝜋𝜋𝜋𝜋𝜋
𝐼𝐼0 𝑟𝑟 � 𝜆𝜆

Index of solvent 𝑛𝑛2 − 𝑛𝑛𝐿𝐿2 = 𝑛𝑛 − 𝑛𝑛𝐿𝐿 � 𝑛𝑛 + 𝑛𝑛𝐿𝐿

instead of index of air
= 4𝜋𝜋𝜋𝜋𝜋𝜋

𝑛𝑛 + 𝑛𝑛𝐿𝐿 𝑛𝑛 − 𝑛𝑛𝐿𝐿 𝐶𝐶
𝐶𝐶 =𝑔𝑔 � 𝑐𝑐𝑐𝑐−3 𝛼𝛼 = � �
4𝜋𝜋 𝐶𝐶 𝑁𝑁

(i) very dilute solvents, i.e. 𝑛𝑛 ≈ 𝑛𝑛𝐿𝐿

(ii) recognizing the second factor as derivative of the index of refraction
𝐶𝐶 𝑀𝑀
(iii) substituting by , i.e. molar mass and Avogadro‘s number
𝑁𝑁 𝐴𝐴

2
2𝑛𝑛𝐿𝐿 𝑑𝑑𝑑𝑑 𝑀𝑀
16𝜋𝜋 2
𝐼𝐼𝑆𝑆 4𝜋𝜋 � 𝑑𝑑𝑑𝑑 � 𝐴𝐴 2𝑛𝑛𝐿𝐿 𝑑𝑑𝑑𝑑 𝑀𝑀
= � 𝑠𝑠𝑠𝑠𝑠𝑠2 Φ 𝛼𝛼 = � �
𝐼𝐼0 𝑟𝑟 2 � 𝜆𝜆4 4𝜋𝜋 𝑑𝑑𝑑𝑑 𝐴𝐴

𝑑𝑑𝑑𝑑 2
𝐼𝐼𝑆𝑆 4𝑛𝑛𝐿𝐿2 � � 𝑀𝑀2
𝑑𝑑𝑑𝑑 2Φ
= � 𝑠𝑠𝑠𝑠𝑠𝑠
𝐼𝐼0 𝑟𝑟 2 � 𝜆𝜆4 � 𝐴𝐴2
Determination of molecular masses from Rayleigh scattering

𝑑𝑑𝑑𝑑 2
𝐼𝐼𝑆𝑆 4𝑛𝑛𝐿𝐿2� � 𝑀𝑀2
𝑑𝑑𝑑𝑑
= 2 4 2
� 𝑠𝑠𝑠𝑠𝑠𝑠2 Φ
𝐼𝐼0 𝑟𝑟 � 𝜆𝜆 � 𝐴𝐴
Scattering by larger particles
Collimated monochromatic and coherent light (laser) interacts with an extended
macomolecule

 Two scattering centers A and B (e.g. individual atoms of the molecule) are
excited out of phase and radiated out of phase accordingly-
 For an observer at the angle θ both scattering centers are differently far away
(δ), so that depending on scattering particles, refractive indices and observation
direction constructive or destructive interference occurs

Introduction of a so-called form factor that takes these interference effects into
account:
Scattering by larger particles
With increasing particle size, the scattering intensity Is increases strongly and
at the same time the distribution of the scattered light changes: a pronounced
forward scattering occurs.

! Note: the relative size of λ and the size of the scattering particle is important
→ when using X-ray light (Cu Kα-line at 1.45 Å) even molecules are big
→ scattering mainly in forward direction with only small deviations from the
axis of the incident beam
→ basis for small angle X-ray scattering (SAXS)
Scattering by larger particles
Scattering intensity and particle size

 The figure shows a model of the

normalized dependence of the scattering
intensity Is or the scattering cross section
σs as a function of the particle diameter d
in the size range between 10-3 und 200 µm

 To this end, spherical particles with a typical refractive index of nT = 1,59 were
suspended in water with nM = 1,33 and irradiated with 633 nm laser light
 The scattering was observed under an azimuth angle of θ =5 and 90°
Static light scattering
Scattering intensity depends on:
 the molecular weight of the particles
 the concentration of the particles
 the size of the particles
 the refractive index of the pure solvent
 the refractive index of the suspended
molecules
 interaction forces between particles

Static light scattering experiments allow the investigation of:

 average molecular weight of a macromolecule like a polymer or a protein in solution
 the root mean square radius by measurement of the scattering intensity at many
angles
 the size of particle suspensions in the sub-μm and supra-μm ranges, via the
Lorenz-Mie and Fraunhofer diffraction formalisms
Example: Use of in situ Rayleigh scattering to follow a chemical reaction
electrochemical
reduction
3-methyl flavin + EDTA weakly bound complex
re-oxidation
under ambient air

• aggregation is not a trivial linear effect

→ cooperation has to be taken into account,
i.e. aggregation sets in at critical micelle concentration
• Scattering at different temperatures yields Δ𝐺𝐺 = 48 𝑘𝑘𝑘𝑘�𝑚𝑚𝑚𝑚𝑚𝑚
indicating the presence of 5 – 10 H-bonds per aggregate
 Excursus
Non-Covalent Interactions (short Journey to Supramolecular Chemistry)
Supramolecular chemistry

„Chemistry of molecular assemblies and the intermolecular bond“

„The Chemistry of the non-covalent bond“

(Jean-Marie Lehn)

Oder auch:
„Chemie der Dinge, die komplexer sind als die konstituierenden Moleküle selbst“

1. „Molecules do not act if they do not bind“; Paul Ehrlich (1906)

2. Die Art der Bindung muss selektiv sein – Gast hat eine zum Wirt komplementäre
Größe oder Form = „molecular recognition“; Emil Fischer (1894)

3. Die Ausbildung der Bindung ist das Resultat von attraktiven / anziehenden Wechsel-
wirkungen zwischen Wirt und Gast; Alfred Werner (1893)

Drei anfänglich völlig unabhängige Konzepte wurden mit der Zeit unter dem Deckmantel
der Supramolekularen Chemie zusammengeführt.

42
What is supramolecular chemistry?

Molecular precursors Molecular chemistry Covalent Molecule:

• Chemical nature
• Shape
+ • Redox properties
• HOMO-LUMO gap
• Vibration/rotation
• Magnetism
• Chirality

Supramolecular chemistry

Specific characteristics:
+ • Function properties
• Recognition
• Catalysis
• Transport
Guest Host
Supramolecule (complex)
degree of order, interactions between subunits,
symmetry of packing, intermolecular interactions

Comparison between the scope of molecular and

43
supramolecular chemistry according to Lehn
What is supramolecular chemistry?

Comparison between the scope of molecular and

supramolecular chemistry according to Lehn
44
(taken from the script of Prof. Kubik / TU Kaiserslautern)
Terms and definitions

Molecular recognition: more or less selective reversible intermolecular interaction of

functional groups, molecules, ions or biomacromolecules

Synthetic receptor, binding site or host molecule: one of the binding partners, typically the
larger one

Self-assembly or self-organization: a sequence of molecular recognition typically involving

many molecules or ions and leading to a certain aggregate

Binding constant K (association constant): equilibrium between host and guest

Thermodynamic selectivity = Kguest1/Kguest2

Kinetic selectivity: related to the rate constants of aggregate formation (one guest
molecule is simply bound faster (not necessary with higher binding affinity))

45
What can we do with supramolecular chemistry?

…taken from the script of Prof. Kubik / TU Kaiserslautern 46

Chemical bonds – type and interaction strength

1000 100 10 1

[kJ/mol]

covalent (~1000 - 100)

C C C C C C I I
839 614 348 151
Ion - ion (350 - 100)

Ion - dipole (200 - 50)

Dipole - dipole (50 - 5)

Hydrogen bonds (120 - 4)

π - π stacking (50 - 1)

(80 - 4)
Cation - π

Van der Waals ( < 5)

J. Howgego, Education in chemistry, 2012, 14-17. 47

Summary of electrostatic interactions

Interactions -∆G [kJ/mol] Ka [M-1, 298 K] Depending on distance

Ion-ion 100-350 > 1017 r-1

Ion-dipole 50-200 > 108 r-2

Dipole-dipole 5-50 101-108 r-3

H-bonding 4-120 5-1021

Cation-π 5-80 101-1014

π-π 0-50 0-108

Dispersion <5 < 101 r-6

- The term “non-covalent” contains an enormous range of attractive and

repulsive effects
- The intermolecular interactions are the driving forces for the formation of
supramolecular structures
- The total inter-molecular force acting between two molecules is the sum of all
the forces they exert on each other

48
Ion-ion interactions

• Strength comparable to covalent bond

(100-350 kJ/mol)
• Long range (1/r)
• A typical ionic solid is sodium chloride
• Active field of research are ionic liquids

[Tris(diazabicyclooctan)]3+
+
[Fe(CN)6]3-

49
Ion-dipole interactions

• Significantly weaker than ion-ion interactions (50-200 kJ/mol)

• Directional forces – can be attractive and repulsive
• Medium range (1/r2)
• Coordinative (dative) bonds with significant covalent components are also often
used in supramolecular assembly

OH2 O N N
H 2O OH2
O O 2+
N Ru N
Na Na
O O N N
H 2O OH2 O
OH2
+ crown ether complex
Na [Ru(bpy)3]
2+

mostly non-covalent covalent contribution

50
Dipole-dipole interactions

• Attractive interactions with energies in the range of 5-50 kJ/mol

• Depends on the geometry – can be attractive and repulsive
• Medium range (1/r3)
• The interaction can be between a single pair of poles on adjacent molecules
(type I) or the opposing alignment of one dipole with another (type II)

-
δ δ+ R
- O C
R δ R R R
R
C δ
+
C O C O
R
O R δ+ δ-
type I type II

51
Hydrogen bonding

„…masterkey interaction in supramolecular chemistry…“

- Dimerisation of carboxylic acids

- Protein folding
- DNA double helix, RNA…
- Increase of boiling points
- Substrate recognition
- …

…taken from the script of Prof. Kubik / TU Kaiserslautern 52

Hydrogen bonding II – a brief history

Pauling – H-bonds in water and ice

First noted by Nernst as weak interactions 1935-
1892 Huggins – hydrogen bridges in organic
between molecules containing OH-groups 1936
compounds

Werner, Hantzsch, and Pfeiffer: Pauling: “Nature of the Chemical Bond” ⇒

1902-
“Nebenvalenz” (near valence) and “Innere 1940 introduction of the concept of hydrogen
1914
Komplexsalzbildung” ⇒ H-bonding bonding to a broader chemical community

"Under certain conditions, an atom of hydrogen is

attracted by rather strong forces to two atoms
Pauling: Hydrogen bonds between water
1931 instead of only one, so that it may be considered to
molecules
be acting as a bond between them. This is called a
hydrogen bond.”

Atkins: “A hydrogen bond is a link formed

Bernal and Huggins proposed the actual
1935 1989 by a hydrogen atom lying between two
term “hydrogen bond”
strongly electronegative atoms”

1) W. Nernst, Z. Phys. Chem. 1892, 8, 110. 2) W. M. Latimer et al., J. Am . Chem. Soc. 1920, 42, 1419-1433. 3) M. L. Huggins, Chemtech, 1980, 422-
429. 4) D. Quane, Bull. Hist. Chem. 1990, 7, 3-13. 5) E. D. Glowacki et al., J. Mater. Chem. B, 2013, 3742-3753.

53
Hydrogen bonding III

A A a) Linear
D H A D H D H
a b c A b) Bent
c) Donating bifurcated
A
A H d) Accepting bifurcated
H
D D H A D A
A e) Trifurcated
H A H
e
A f) Three centre bifurcated
d f

These geometries are termed primary hydrogen interactions → direct interaction

between the donor group and the acceptor group

J. W. Steed, J. L. Atwood, Supramolecular Chemistry, Wiley, 2009 54

Hydrogen bonding IV – secondary interactions

Jorgensen model
• Differences in hydrogen bond stability can be largely attributed to attractive and
repulsive secondary interactions
• Stabilization arises from electrostatic attraction between positively and negatively
polarized atoms in adjacent H-bonds
• Destabilization arises from electrostatic repulsion between two positively or
negatively polarized atoms

D donor
D D D A D D A D A A acceptor
---- primary attractive interaction
A A A D A A D A D ---- secondary attractive interaction
---- secondary repulsive interaction

W. L. Jorgensen et al., J. Am. Chem. Soc. 1990, 112, 2008-2010

W. L. Jorgensen et al., J. Am. Chem. Soc. 1991, 113, 2810-2819 55
Hydrogen bonding V – a satisfactory description?

• The first theoretical models suggested that H-bonding exclusively involves an electrostatic
interaction between the partially positive hydrogen atom of the donor and the lone pair of the
acceptor
• It is generally accepted that H-bonding can be described neither by electrostatic theory nor
by weak covalent bonding alone
• The hydrogen bond can separated in five individual contributions
(Morokuma formalism ∆E = ∆ECOU + ∆EEX + ∆EPOL + ∆ECHT + ∆EDIS)

1) electrostatic or coulomb energy ∆ECOU – attractive

2) exchange repulsion ∆EEX – repulsive
3) polarization energy ∆EPOL – attractive
4) charge-transfer energy or covalent bonding ∆ECHT – attractive
5) dispersion forces ∆EDIS– attractive

L. J. Prins et al., Angew. Chem. Int. Ed. 2001, 40, 2382-2426

K. Morokuma et al., J. Am. Chem. Soc. 1977, 99, 1316-1332 56
Cation - Π interactions

• A cation can interact favorably with the negative charge of a π-system

• The cation should be located near the face of the π-system
• In transition metal complexes such as ferrocene [Fe(C5H5)2] → covalent bonds –
d-orbitals of the metals
• Play a very important role in biological systems

Cation-π interactions with benzene

(gas phase)
Ion - ∆G [kJ/mol]
Li+ 159
Na+ 113
K+ 79
NH4+ 67

J. C. Ma and D. A. Dougherty, Chem. Rev. 1997, 97, 1303-1324

D. A. Dougherty, Acc. Chem. Res. 2013, 46, 885-893
G. W. Gokel et al., Chem. Commun. 2002, 1810-1811. 57
Π - Π interactions

• Aromatic rings where one is relatively electron rich and one is electron poor
• Bond strength 1-50 kJ/mol
• Two general types: face-to-face and edge-to-face → direct overlap is repulsive!!!
• Face-to-face → graphite or DNA;
• Edge-to-face → herringbone packing of benzene in the solid state

Face-to-face Edge-to-face

58
Van der Waals forces

• Arise from the polarization of an electron cloud by the proximity of an adjacent

nucleus → weak electrostatic attraction
• Bond energy is very weak (0.1-5 kJ/mol)
• Non-directional and macroscopic effects
• vdW forces are the general name given to a set of forces characterized by the
same power dependence on distance (1/r6) → the important parameters are the
dipole moment and the atomic polarizability
• Keesom force → electrostatic interactions between charges
• Debye force
• London dispersion force

F. L. Leite et al., Int. J. Mol. Sci. 2012, 13(10), 12773-12856 59

Van der Waals forces II

(a) Permanent Dipole-Permanent Dipole or Keesom forces

(b) Permanent Dipole-Induced Dipole or Debye force
(c) Instantaneous Dipole-Induced Dipole or London forces
(d) Interactions between molecules–temporary and permanent dipoles

F. L. Leite et al., Int. J. Mol. Sci. 2012, 13(10), 12773-12856 60

Hydrophobic effects

The term ‘hydrophobic effect’ refers to the poor solubility of nonpolar substances in
water compared to organic solvents or to polar substances

Hydrophobic interactions are very important in biological systems:

• Creation and maintenance of polynucleotide structures
• Folding of proteins
• Protein-ligand and protein-protein interactions
• Maintenance of phospholipid bilayer cell walls
• Supramolecular complexation of guests with
non-polar parts
•…

61
Hydrophobic effects II

After mixing
• Increase of the surface between
hydrophobic molecules and water
• Loss of conformational entropy
because of strong directional forces
between water molecules ∆S ↓ → ∆G ↑
After Unmixing
• In bulk solution, a water molecule can
rotate and still maintain hydrogen
bonding interactions ∆S ↑, ∆ H ↓ → ∆G ↓

The aggregation of hydrophobic molecules lead to the loss of entropy

→ Minimization of the hydrophobic-water interface

62
…and back to Nanochemistry

- Nanochemistry  so-called „meso-phenomena“ (effects between classical bulk

conditions and molecular length scale)
- Effects often scale with size (i.e. optical properties of Au nanoparticles…)

Ozin, Arsenault, Cademartiri – „Chemistry at the Nanoscale“

Nanomaterial Synthesis
 A short introduction into „Soft Matter“

Credits to:

- Ian W. Hamley, Introduction to Soft Matter, Wiley, 2009

- Script of „Introduction to soft matter“, University of Surrey, Soft matter physics
- …others are explicitly mentioned…
65
What is „Soft matter“?

66
What is „Soft matter“?

• Refers to condensed matter that exhibits characteristics of both solids

and liquids (macroscopic mechanical properties)
• The phrase “soft matter” was used by Pierre de Gennes as the title of his
1991 Nobel Prize acceptance speech.
• Soft matter can flow like liquids (measurable viscosity)
 everything flows (www.thetenthwatch.com)
• Soft matter can bear stress (elastic deformation)
• Lack of long-range 3D order, but local order!
• Viscoelastic behaviour = viscous + elastic
• Examples: rubbers, gels, pastes, creams, paints, soaps, liquid crystals,
proteins, cells…

67
Everything flows?
Rheology is the study of deformation and flow

relatively brittle

Logo of the
Society of Rheology

Pitch drop experiment

68
Examples for „Soft matter“?

https://universe-review.ca/I15-81-softmatter.jpg 69
Characteristics of „Soft matter“?

1) Length scales:
- Structures of ≈10-1000 nm determine the (macroscopic) properties
2) Time scales: processes from 10-12 - 103 s
- Dynamics processes over a wide time scales 10-12 - 103 s
- Very slow processes in non-equilibrium configurations (possible)
3) Weak interactions
- Interactions between molecules and molecular structures ≈ kT
4) Self assembly
- Hierarchical arrangement of structures
- Competition between interaction energy and entropy

70
Origin of surface tension

For example, liquids and gases are separated by a meniscus

Differences in density but not structure (i.e. spatial arrangement of molecules)

• Molecules at an interface experience asymmetric forces

• Molecules are forced below the meniscus to reduce the interfacial area ( different
surrounding)
• Force associated with separating neighbouring molecules = surface tension.

71
Interfacial energy
An interfacial energy Γ is associated with the interface between two
phases (units of Jm-2) (also called interfacial tension: Nm-1)

Γ cos θ = F
d

Interface with air = “surface”

For mercury, Γ = 0.486 N/m
For water, Γ = 0.072 N/m
Naturfotografen-forum.de For ethanol, Γ = 0.022 N/m

http://wps.prenhall.com/wps/media/objects/602/616516/Chapter_10.html
72
Types of „Soft Matter“ - Colloids

• Colloid features sub-mm particles (but not single molecules) of one phase dispersed
in a continuous phase
• The size scale of the dispersed phase is between 1 nm and 1 mm
• The dispersed phase and the continuous phase can consist of either a solid (S), liquid
(L), or gas (G)…

Dispersed Phase Continuous Name Examples

L/S G aerosol fog, hair spray; smoke
G L/S foam beer froth; shaving foam;
poly(urethane) foam
L L (S) emulsion mayonnaise; salad dressing
S L sol latex paint; tooth paste
S S solid suspension pearl; mineral rocks

There is no “gas-in-gas” colloid, because

there is no interfacial tension between gases!

73
…a quick note on beer froth…

2002: Arnd Leike erhält den Ig-Nobelpreis für seine Arbeiten zur
Theorie, dass der Bierschaumzerfall einem exponentiellen Gesetz
folgt. Allerdings ist uns denke ich auch allen klar, dass hier ein Viel-
Faktoren-Problem beschrieben wurde – recht vereinfacht. Das ist
schwer reproduzierbar, hängt auch sehr von der Güte Ihrer
Spülmaschine ab…
Nun, die Forschung von Herrn Leike hat weitere Studien inspiriert,
so zB auch an der Universität Würzburg –hier war die Quintessenz,
dass:
- „…die Beschreibung des Bierschaumzerfalls als Analogon zum
radioaktiven Zerfall problematisch erscheint.“
- „…Bierschaumzerfall ein mögliches Thema für
Seminararbeiten oder Jugend forscht darstellt…“

MC 1.2 / SS2018 / Schacher 74

Types of „Soft Matter“ - Colloids

Surface area (A) / volume (V):

Thus, with smaller particles, the interface

becomes more significant. A greater fraction
of molecules is near the surface.

Consider a 1 cm3 phase dispersed in a continuous medium:

No. particles Particle volume(m3) Edge length (m) Total surface area(m2)
1 10-6 10-2 0.0006
103 10-9 10-3 0.006
106 10-12 10-4 0.06
109 10-15 10-5 0.6
1012 10-18 10-6 6.0
1015 10-21 10-7 60

1018 10-24 10-8 600

75
Types of „Soft Matter“ - surfactants

Typical Γ values for interfaces with water:

carbon tetrachloride: 45 mN/m
benzene: 35 mN/m
octanol: 8.5 mN/m

76
Types of „Soft Matter“ - surfactants

Surfactants:
- Amphiphilic molecules of low molecular weight
- Tendency to adsorb („go to“) at interfaces (interfacially active)
- …never really comfortable in a single solvent…
 Aggregation (minimization of interfacial energy)
 Micro-phase segregation, formation of thermodynamically stable aggregates

Ionic / non-ionic

Phys. Chem. Chem. Phys., 2014,16, 8594-8607 77

Types of „Soft Matter“ – surfactants / examples

78
Types of „Soft Matter“ – surfactants / examples II

79
Types of „Soft Matter“ – surfactants, micellar morphologies

Cécile A. Dreiss, Chapter 1 : Wormlike Micelles: An Introduction, in

Wormlike Micelles: Advances in Systems, Characterisation and Applications, 2017, pp. 1-8

80
Types of „Soft Matter“ – surfactants, micellar morphologies

Morphology also dependant on concentration and temperature (dynamics)

Ian W. Hamley, Introduction to Soft Matter 81

Types of „Soft Matter“ – surfactants – critical micellization concentration

- cmc is not a thermodynamic phase transition, but is defined phenomenologically

(sharp increase of the number of micelles formed)
- …occurs at a fixed temperature T upon increasing amphiphile concentration
- …precise location depends on the technique used for determination
- Often determined using a fluorescent probe (nile red, pyrene, …)

http://www.dataphysics.de/fileadmin/user_upload/Understanding/Schematic_CMCEN.png

82
Types of „Soft Matter“ – surfactants – critical micellization concentration

Many physical properties of such a solution exhibit drastic / abrupt changes upon
crossing the cmc…

Conductivity

Osmotic
pressure
Turbidity
Surface tension

https://csc-iiith.vlabs.ac.in/exp14/fig1.jpg 83
Types of „Soft Matter“ – surfactants – critical micellization concentration

Dependencies of the CMC:

- For most surfactants CMC is independent of the temperature

- CMC is usually lower for non-ionic surfactants if compared to ionic
examples of equal chain length
- Increasing the length of the hydrophobe chain length (variation of the
hydrophilic/lipophilic balance – HLB) favors micellization and leads to an
increase of the CMC
- Addition of salts decreases the CMC for ionic surfactants (screening of the
charges)
- Addition of co-solutes can either increase or decrease CMC, depending on
the co-solute polarity

- BUT: solubility of the surfactant can be drastically influenced by

temperature  Krafft temperature

84
Characteristics of „Soft matter“ – (1) length scales

- Atomic spacing: ~ 0.1 nm

- “Pitch” of a DNA molecule: 3.4 nm

- Diameter of a surfactant micelle: ~6-7 nm

- Radius of a polymer molecule (depends on DP): ~10 nm
- Diameter of a colloidal particle (e.g. in paint): ~200 nm
- Bacteria cell: ~2 mm
- Diameter of a human hair: ~50-70 µm

85
Characteristics of „Soft matter“ – (1) length scales
 Spider silk as an example of hierarchical organization

P. Ball, Nanotechnology 2002, 13, R15-R28 86

Characteristics of „Soft matter“ – (2) dynamics

- Thermal fluctuations
- Brownian motion
- Possibility to equilibrate (in terms of structure, morphology, …)
- Determination of sizes (polymers, colloids)
 light scattering

D diffusion coefficient
k Boltzmann
T temperature
R radius
Η viscosity

Examples:
- Molecules in liquids: 10-9 m2/s
- Polymers in liquids: 10-18 m2/s (or higher, depending on molar mass)
- Micelles in water: 10-11 m2/s (radius of approx. 10 nm)

87
Characteristics of „Soft matter“ – (3) weak interactions

Short-range forces and interfaces are important!

 Combination of many (weak) interactions…

https://sites.psu.edu/siowfa15/2015/11/29/ho
w-is-the-gecko-changing-the-world/

http://rsta.royalsocietypublishing.org/content/366/1870/1575

88
Characteristics of „Soft matter“ – (4) self-assembly processes!

- There is a strong tendency to „self-assemble“ into larger (super-)structures

- Characteristic features beyond the size of the single building block
- Properties of the single „unit“ can be found in the material (hierarchy)

Strands of DNA only bind to those that are

complementary. DNA can be designed so that it
spontaneously creates desired structures.
 DNA Origami

Seeman et al., Biochemistry 2003, 42, 7259-7269 89

Characteristics of „Soft matter“ – (4) self-assembly processes!

Nature Methods 2011, 221-229 90

Characteristics of „Soft matter“ – DNA Origami – underlying principles

Wikipedia Definition: DNA origami is the nanoscale folding of DNA to create

arbitrary two and three dimensional shapes at the nanoscale. The specificity of
the interactions between complementary base pairs make DNA a useful
construction material through design of its base sequences.

Complementary base pairs

(Purin – Pyrimidin)

Adenin - Thymin
Paul W. K. Rothemund
Nature, 2006, 440, 297-303
Caltech Institute

Guanin - Cytosin
91
Characteristics of „Soft matter“ – DNA Origami – underlying principles

92
Nature, 2006, 440, 297-303
Characteristics of „Soft matter“ – DNA Origami – underlying principles

How does this work?

93
Nature, 2006, 440, 297-303
Characteristics of „Soft matter“ – DNA Origami – underlying principles

Assembly of rigid
building blocks

Angew. Chem. Int. Ed.,

2011, 50, 264-267 94
Characteristics of „Soft matter“ – (4) self-assembly processes!

„Colloidosomes“
Colloidal
particles
Liquid
(<1 µm)
B

Liquid A

Dinsmore et al., “Colloidosomes: Selectively Permeable Capsules Composed of Colloidal Particles,”

Science, 298 (2002) p. 1006. 95
Characteristics of „Soft matter“ – (4) self-assembly processes & dynamics

„The secret life of Pickering emulsions?“

100 µm

0h 6h 22 h
5 µm

- Dodecane / myristate in water

- Differently labeled SiO2 NP
- Particle exchange between droplets
357 h

96
Characteristics of „Soft matter“ – (4) self-assembly processes!

Self-assembly / competition of different forces:

- Molecules often segregate at an interface to lower the interfacial energy - leading

to an ordering of the system
 Thermal motion counteracts and disrupts ordering
- Self-assembly usually decreases the entropy, which is not favoured by
thermodynamics
 But there are attractive and repulsive interactions between molecules
that dominate

If free energy decreases (ΔF < 0), then the process is spontaneous.

∆F = ∆U - T∆S
Internal Energy (U) decrease is Entropy (S) increase is favourable
favourable

97
So, finally: what is important about self-assembly?

Whitesides, Grzybowski; „Self-assembly at all scales“, Science 2002, 295, 2418-2421

98
Self-Assembly – a General Concept

Ozin, Arsenault, Cademartiri – „Chemistry at the Nanoscale“

Self-Assembly – a General Concept

Some general considerations:

1) Building block shape and symmetry influences self-assembly, e.g. two nanorods can
either „contact“ at the tip or at the longitudinal side, this is determined by type and
strength of the interactions

2) In general, such a process proceeds to the energetic minimum (static self-assembly),

however, there are situations where an intermediate state is reached and
(meta)stable – sometimes also referred to as „kinetically trapped“

3) Shape and symmetry are also important if several steps are involved, i.e. if
hierarchical structures are formed  determining type and connectivity

4) The structures formed are never perfect  presence of defects

5) Spontaneous self-assembly is not always possible – alternative are „brute force“

methods such as templated self-assembly

Ozin, Arsenault, Cademartiri – „Chemistry at the Nanoscale“

Self-Assembly – Templated

Ozin, Arsenault, Cademartiri – „Chemistry at the Nanoscale“

Self-Assembly – Dynamic

- Developing adaptive systems

- Learning systems which can be turned on/off upon using suitable triggers
Self-Assembly – Dynamic

- Developing adaptive systems

- Learning systems which can be turned on/off upon using suitable triggers
Self-Assembly – The Bio-Nano Interface

Ozin, Arsenault, Cademartiri – „Chemistry at the Nanoscale“

The „Playground“ of Polymer Chemistry

Topology Composition Functionality Molar mass

distribution
X

Microstructure
X
R R R R R R R R R
X X
R R R R
R R R R R
X X X X X X X X X

X X
X X
X X
X X
X X
X X

Material properties
© Axel H. E. Müller, Mainz
Site-specific Incorporation of Metal Nanoparticles within Soft Matter

M. R. Bockstaller, E. L. Thomas, J. Phys. Chem. B 2003, 107, 10017-10024.

Site-specific Incorporation of Metal Nanoparticles within Soft Matter

PS-b-PVP Ligand density on the surface determines location

Au

Au

B. J. Kim, G. H. Fredrickson, E. J. Kramer, Macromolecules 2008, 41, 436-447.

Thin molecular films
thin molecular films
Motivation

Organic electronics

Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)

Mayr, C. et. al. 2014
Movla, H. et. al 2017 110
Motivation

Membranes in living nature

http://en.wikipedia.org/wiki/Cell_membrane
111
Motivation

Membranes in living nature

http://en.wikipedia.org/wiki/Cell_membrane
112
Motivation – Transfer from Nature to Device

1.) Substitute phospholipid with functional amphiphilie, e.g. a dye …

lipophile hydrophile

… that self-assembles at an interface

Layer

113
Motivation – Transfer from Nature to Device

1.) Substitute phospholipid with functional amphiphilie, e.g. a dye …

lipophile hydrophile

… that self-assembles at an interface and can be deposited layer by layer

Layer

114
Introduction – Langmuir Blodgett

115
Langmuir-Blodgett trough

Alternate Trog:
• Standardisiert
• Charakterisierung
vorhanden

Rolle-zu-Rolle Trog:
• Großflächig
• Neu
• Vorcharakterisierung
notwendig
Langmuir-Blodgett trough
Wilhelmy balance
F = σ � 𝐿𝐿 � cos 𝜃𝜃

• to measure force (and contact angle) Pt

plates are frequently used
− inert metal
− large surface free enthalpy, and
consequently 𝜃𝜃 ≈ 0 for most
liquids

• adding a surfactant disrupts hydrogen bonding

network of water molecules at the surface
• change in surface tension
• change in force detected by the Wilhelmy
balance
Langmuir-Blodgett trough – Film deposition
Π(A)-Isotherme
Π(A)-Isotherme

• gaseous phase is formed at large molecular areas, i.e. available area per molecule >> molecular size
• Total area can be extended (infenitely) w/o having a phase transition
Π(A)-Isotherme

• at low surface excess, surface tension decreases linearly with the concentration,
i.e. 𝛾𝛾 = 𝛾𝛾0 − 𝑏𝑏 � 𝑐𝑐, with 𝑏𝑏 depending on solvent and amphiphile;
𝑎𝑎 𝜕𝜕𝜕𝜕
• with Gibbs isotherme, Γ = − 𝑅𝑅𝑅𝑅 � 𝜕𝜕𝜕𝜕 (a is activity) this yields:
𝑐𝑐 𝑑𝑑𝑑𝑑 𝑏𝑏𝑏𝑏
Γ = − 𝑅𝑅𝑅𝑅 � 𝑑𝑑𝑑𝑑 = 𝑅𝑅𝑅𝑅
• with film pressure 𝜋𝜋 ≡ 𝛾𝛾0 − 𝛾𝛾 = 𝛾𝛾0 − 𝛾𝛾0 − 𝑏𝑏 � 𝑐𝑐 = 𝑏𝑏𝑏𝑏
𝜋𝜋
→ Γ = 𝑅𝑅𝑅𝑅 ⇒ 𝜋𝜋 = Γ � 𝑅𝑅𝑅𝑅
𝑁𝑁 1
• with Γ = = ⇒ 𝜋𝜋𝜎𝜎𝐴𝐴 = 𝑘𝑘𝐵𝐵 𝑇𝑇
𝐴𝐴 𝜎𝜎𝐴𝐴
𝑉𝑉
compare to 𝑝𝑝 𝑁𝑁 = 𝑘𝑘𝐵𝐵 𝑇𝑇, i.e. ideal gas!

• gaseous phase is formed at large molecular areas, i.e. available area per molecule >> molecular size
• Total area can be extended (infenitely) w/o having a phase transition
Π(A)-Isotherme

• at low surface excess, surface tension decreases linearly with the concentration,
i.e. 𝛾𝛾 = 𝛾𝛾0 − 𝑏𝑏 � 𝑐𝑐, with 𝑏𝑏 depending on solvent and amphiphile;
𝑎𝑎 𝜕𝜕𝜕𝜕
• with Gibbs isotherme, Γ = − 𝑅𝑅𝑅𝑅 � 𝜕𝜕𝜕𝜕 (a is activity) this yields:
𝑐𝑐 𝑑𝑑𝑑𝑑 𝑏𝑏𝑏𝑏
Γ = − 𝑅𝑅𝑅𝑅 � 𝑑𝑑𝑑𝑑 = 𝑅𝑅𝑅𝑅
• with film pressure 𝜋𝜋 ≡ 𝛾𝛾0 − 𝛾𝛾 = 𝛾𝛾0 − 𝛾𝛾0 − 𝑏𝑏 � 𝑐𝑐 = 𝑏𝑏𝑏𝑏
𝜋𝜋
→ Γ = 𝑅𝑅𝑅𝑅 ⇒ 𝜋𝜋 = Γ � 𝑅𝑅𝑅𝑅
𝑁𝑁 1
• with Γ = = ⇒ 𝜋𝜋𝜎𝜎𝐴𝐴 = 𝑘𝑘𝐵𝐵 𝑇𝑇
𝐴𝐴 𝜎𝜎𝐴𝐴
𝑎𝑎
more realistically: 𝜋𝜋 + 𝜎𝜎2 � 𝜎𝜎𝐴𝐴 − 𝜎𝜎0 = 𝑘𝑘𝐵𝐵 𝑇𝑇
𝐴𝐴

• gaseous phase is formed at large molecular areas, i.e. available area per molecule >> molecular size
• Total area can be extended (infenitely) w/o having a phase transition
Π(A)-Isotherme

• compressing gaseous phase leads to first order phase transition → liquid phase
• characterized by significant lateral interactions of the molecules
Π(A)-Isotherme

• in solid phase the headgroups are largely dehydrated, thus increasing the order of the headgroup
layer
• pressure-area isotherms are linear
• extrapolation to zero-film pressure leads to an area per molecule corresponding to the actual
molecular cross-section
Π(A)-Isotherme
Π(A)-Isotherme as a function of temperature
• before a single liquid phase was discussed
• actually, in most cases, a liquid expanded
and a liquid condensed phase is observed
• these two phases are separated in the
Π 𝐴𝐴 diagram via a plateau at the
coexistence pressure 𝜋𝜋𝐶𝐶
• 𝜋𝜋𝐶𝐶 depends on the temperature
→ see isotherme of van-der-Waals gas
Stability of Molecular Layers

(Hupfer et al. 2017)

Stability of Domain Structures in Magnets

http://hyperphysics.phy-astr.gsu.edu/hbase/Solids/hyst.html
Stability of Domain Structures in Magnets

http://hyperphysics.phy-astr.gsu.edu/hbase/Solids/hyst.html
Stability of Molecular Layers

(Hupfer et al. 2017)

Motivation – Transfer from Nature to Device

… that self-assembles at an interface

Layer

132
 Colored Soaps
Properties of dyes and the resultant monolayers are determined by
• molecular geometry
• amphiphilicity (polar vs. unpolar parts of the molecules)
determines stability of the anchoring
• high molecular extinction coefficient (to yield color)

Quelle: Volkswagen, Wikipedia, Edding, Decathlon Fotolia Water or Substrate

 Colored Soaps
Properties of dyes and the resultant monolayers are determined by
• molecular geometry
• amphiphilicity (polar vs. unpolar parts of the molecules)
determines stability of the anchoring
• high molecular extinction coefficient (to yield color)
• high photostability (no bleaching)
• low costs for applications and device fabriation

HO
O S O

N N O N O CH2
H3 C
H2 C
CH3
O N N O
N N
NH HO S Cl Fe
(III) S OH
(III)
N Cl Fe
O N N O
N N
N
H3 C CH3

O N O

O
O

O
+
N
O- O HO O HO
O O S O

O
O
OH

O
O
Water or Substrate
O
O
Quelle: Volkswagen, Wikipedia, Edding, Decathlon Fotolia
Colored Soaps
Properties of dyes and the resultant monolayers are determined by
• molecular geometry
• amphiphilicity (polar vs. unpolar parts of the molecules)
determines stability of the anchoring
• high molecular extinction coefficient (to yield color)
• high photostability (no bleaching)
• low costs for applications and device fabriation

O N O O N O O N O O N O O N O

O N O O N O O N O O N O O N O

O
Experimental Methods to Characterize Molecular Films

How to measure absorption of molecularly thin films? – Classically (e.g. in solution) one would:
• measure the transmission T
• calculate absorbance A from transmission (assuming e.g. negligible scattering or using an
Ulbricht sphere)
Reminder regarding the Lambert-Beer law:

𝑑𝑑𝑑𝑑 = 𝐼𝐼 � 𝜀𝜀𝜀 𝜆𝜆 � 𝑐𝑐 � 𝑑𝑑𝑑𝑑 → 𝑑𝑑𝑑𝑑�𝐼𝐼 = 𝜀𝜀′ 𝜆𝜆 � 𝑐𝑐 � 𝑑𝑑𝑑𝑑

ln 𝐼𝐼 = 𝜀𝜀′ 𝜆𝜆 � 𝑐𝑐 � 𝑥𝑥 + const.
ln(𝐼𝐼�𝐼𝐼 ) = 𝜀𝜀′ 𝜆𝜆 � 𝑐𝑐 � 𝑥𝑥
0

𝑙𝑙𝑙𝑙𝑙𝑙 𝐼𝐼�𝐼𝐼 = 𝜀𝜀 𝜆𝜆 � 𝑐𝑐 � 𝑥𝑥 = − log 𝑇𝑇 = 𝐴𝐴 ! Please note: If T = 1% = 0,01 ⇒ A = 2

0
𝑙𝑙 This is an opticall super thick sample!
! Note: A is dimensionless, i.e. dim 𝜀𝜀 = 𝑚𝑚𝑚𝑚𝑚𝑚�𝑐𝑐𝑐𝑐
(i) Photothermal Deflection Spectroscopy
(i) Photothermal Deflection Spectroscopy
• film is immersed into an inert solvent with a high
𝑑𝑑𝑑𝑑⁄
𝑑𝑑𝑑𝑑
• film absorbs the incident (monochromatic) light,
the absorbed photon energy is dissipated as heat
→ formation of a thermal lense in vicinity of the
film
• thermal lense leads to the deflection of a probe
laser beam

• PDS is much more sensitive than conventional

transmission-based absorption spectroscopy
• sensitivity can be further enhanced by modulating
the intensity of the monochromatic light and the
use of Lock-In-amplification)
• PDS is a surface-sensitive method
• only the absorbed light contributes to the signal
(reflection and scattering do not contribute)
(i) Photothermal Deflection Spectroscopy

Von Vinzenz Mühlstein at de.wikipedia - Eigenes Werk, Gemeinfrei,

https://commons.wikimedia.org/w/index.php?curid=15269637
(i) Photothermal Deflection Spectroscopy
(ii) Polarization Resolved Fluorescence Spectroscopy
(ii) Polarization Resolved Fluorescence Spectroscopy
(iii) Optical Microscopy
• fluorescence microscopy can be used to study any molecular layer, when a small amount of
amphiphilic fluorescent dye is integrated into the monolayer (typically such dyes are expelled
when the molecular layer is compressed into the condensed liquid or solid phase)
• depending on the phases of the molecular layer spatial variations of dye distribution or
fluorescense quantum yield (and lifetimes, Φ = 𝑘𝑘𝐹𝐹 � 𝜏𝜏) are observed

• domain structure formation depends on the balance of

attractive van-der-Waals forces and repulsive dipole-dipole
interactions
• the molecular dipoles are oriented vertically to the water
surface (by design of the interface) and parallel dipoles repell
each other
• line tension (similar to surface tension) preserves condensed
boundaries of the individual domains

! the presence of a fluorophore in the molecular layer might disturb the native structure of the
molecular layer that is under study
• Brewster angle microscopy solves this problem
(iii) Optical Microscopy
• light shined at a liquid surface is partially
reflected
• the intensity of the reflected light depends on
the angle of incidence

By Jyrkorpela - Own work, CC BY-SA 4.0, https://commons.wikimedia.org/w/

index.php?curid=61463510
• Brewster angle depends on the (index of
Complex phospholipid layer in liquid condensed phase in a Langmuir
Trough, imaged by a Brewster angle microscope
refraction of the) solvent, for H2O it is 53°

⇒ observing water surface at 53° with polarized light yields a dark image
⇒ areas in which the monolayer is formed have different index and hence a slightly different
Brewster angle
⇒ Tthey appear bright in the microscope.
(iv) Infrared Absorption Spectroscopy
• Infrared absorption spectra of thin molecular films can be recorded either by
a. ATR-IR, here the film needs to be transferred to a substrate
b. IRRAS, in which an s-polarized IR beam is directly reflected from the interface

• characteristic molecular structures

cause characteristic absorption
features
2870 and 2955 cm-1: symmetric
and assymetric stretch of CH3
2850 and 2910 cm-1: symmetric
and assymetric stretch of CH2
(v) Sum-Frequency Generation Spectroscopy
• a tunable mid-IR beam is mixed with a
visible pulse
• the signal is resonantly enhanced if the IR
frequency matches a vibrational transition
• VSFG presents a 𝜒𝜒 (2) process, hence the
signal is only generated at positions, at
which the inversion symmetry is broken
⇒ ideal methodology to study thin molecular
layers and interfaces
(v) Sum-Frequency Generation Spectroscopy
(vi) X-Ray Reflection and Diffraction Spectroscopy
• short wavelength of X-rays enable characterization of
molecular order in molecular thin films
• X-ray diffraction: beam is incident at fixed small angle α
and the diffracted beam is detected under various angles
• grazing-incident X-ray diffraction: α is chosen to be
below the critical angle for total internal reflection → all
light can be used for scattering analysis
• for 𝛼𝛼 ≈ 0.1° X-rays penetrate about 5 nm into the
surface → highly surface sensitive method

Now consider X-ray reflection, i.e. 𝜶𝜶 = 𝜶𝜶′ and 𝜷𝜷 = 𝟎𝟎:

• intensity of the directly reflected beam is measured for different angles (typically) up to 5°
• experiments yield information on the electron density (electrons / Å3 ) normal to the surface
• Bragg‘s law: 𝑛𝑛 � 𝜆𝜆 = 2𝑑𝑑 � sin(𝛼𝛼)
(i.e. constructive interference at certain
angles, see also grating)
• typically intensity is not plotted as a function of α
4𝜋𝜋
but of the change in wave vector ∆𝑞𝑞 = 𝜆𝜆 � sin(𝛼𝛼) → 𝑑𝑑 � ∆𝑞𝑞 = 2𝜋𝜋 � 𝑛𝑛
(vi) X-ray Reflection and Diffraction Spectroscopy
(vii) Surface Potential Measurements
• monolayer-forming liquids contain polar groups giving rise to a dipole moment 𝜇𝜇 → net dipole
moment perpendicular to the subphase surface → change in electric potential of the liquid-air
interface
• surface potential 𝝌𝝌𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔 ≡ 𝝌𝝌 − 𝝌𝝌𝟎𝟎 : change of the Volta potential across the liquid surface upon
spreading the monolayer
! sign convention 𝜒𝜒𝑖𝑖 > 0 if electrode in gaseous phase is more positive than electrode in liquid
• surface potential is related to the dipole moment of the molecules normal to the surface 𝜇𝜇⊥ ,
𝜇𝜇⊥
i.e. 𝜒𝜒𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = 𝜎𝜎 �𝜀𝜀�𝜀𝜀
𝐴𝐴 0
Nanomaterial Synthesis

SiO2, Au, …
Synthetic access to Nanomaterials

Dissertation Danial Alexander Kunz, Universität Bayreuth

Synthetic access to Nanomaterials

Solid state techniques:

- Mixing powder reagents, heating, … (limitations: inhomogeneity of starting

materials, mass transport, reactions at particle edges)

- Bulk synthesis, followed by ball milling (size limitations, several steps

necessary in order to achieve narrow size dispersity, …)

Solution techniques:

- Coprecipitation
- Hydrothermal processing
- Solvothermal methods
- Sol-gel chemistry

 Limitations? Scale, waste, …

 Advantages? Atomic level mixing, tool-box, …

Sol-Gel Chemistry

E. Von Ebelmen, Justus Liebigs Annalen der Chemie, 1846, 57, 319f

Origin of sol-gel chemistry:

SiCl4 exposed to air starts to form a gel (hydrolysis to alkoxides)

Liquid precursors  formation of a sol  formation of a gel

Sol-Gel Chemistry

„Sol“: colloidal suspension, dispersion of one phase in another where „the

molecules or polymolecular particles have at least in one direction a dimension
roughly between 1 nm and 1 µm“ (IUPAC); broadly applicable term;

„Gel“: gel state is defined as a non-fluid 3D-network that extends through a fluid
phase; Flory in 1974 defined 4 gel states: ordered lamellar gels (e.g. clays), covalent
networks, physical networks, disordered particulate gels;

„Tube inversion method“

J. Mater. Chem. B, 2017,5, 3217-3229

Sol-Gel Chemistry – Gel types

Mater. Horiz. 2016, 3, 91-112

Sol-Gel Chemistry

General steps of a sol-gel process:

1) Synthesis of the sol from hydrolysis and partial condensation of alkoxides

2) Formation of the gel via polycondensation to form metal-oxo-metal or metal-
hydroxy-metal bonds
3) Syneresis or „ageing“ where condensation continues within the gel network,
often under shrinking and under solvent expulsion
4) Gel drying  „Xerogel“ if the porous network collapses, also „Aerogels“ are
possible
5) Removal of surface M-OH moieties by calcination (if required)

Mater. Horiz. 2016, 3, 91-112

Sol-Gel Chemistry

General steps of a sol-gel process:

1) Synthesis of the sol from hydrolysis and partial condensation of alkoxides

2) Formation of the gel via polycondensation to form metal-oxo-metal or metal-
hydroxy-metal bonds
3) Syneresis or „ageing“ where condensation continues within the gel network,
often under shrinking and under solvent expulsion
4) Gel drying  „Xerogel“ if the porous network collapses, also „Aerogels“ are
possible
5) Removal of surface M-OH moieties by calcination (if required)

Mater. Horiz. 2016, 3, 91-112

Sol-Gel Chemistry

General steps of a sol-gel process:

1) Synthesis of the sol from hydrolysis and partial condensation of alkoxides

2) Formation of the gel via polycondensation to form metal-oxo-metal or metal-
hydroxy-metal bonds
3) Syneresis or „ageing“ where condensation continues within the gel network,
often under shrinking and under solvent expulsion
4) Gel drying  „Xerogel“ if the porous network collapses, also „Aerogels“ are
possible
5) Removal of surface M-OH moieties by calcination (if required)

Mater. Horiz. 2016, 3, 91-112

Sol-Gel Chemistry

General steps of a sol-gel process:

1) Synthesis of the sol from hydrolysis and partial condensation of alkoxides

2) Formation of the gel via polycondensation to form metal-oxo-metal or metal-
hydroxy-metal bonds
3) Syneresis or „ageing“ where condensation continues within the gel network,
often under shrinking and under solvent expulsion
4) Gel drying  „Xerogel“ if the porous network collapses, also „Aerogels“ are
possible
5) Removal of surface M-OH moieties by calcination (if required)

Mater. Horiz. 2016, 3, 91-112

Sol-Gel Chemistry

General steps of a sol-gel process:

1) Synthesis of the sol from hydrolysis and partial condensation of alkoxides

2) Formation of the gel via polycondensation to form metal-oxo-metal or metal-
hydroxy-metal bonds
3) Syneresis or „ageing“ where condensation continues within the gel network,
often under shrinking and under solvent expulsion
4) Gel drying  „Xerogel“ if the porous network collapses, also „Aerogels“ are
possible
5) Removal of surface M-OH moieties by calcination (if required)

Under acidic conditions, first

hydrolysis step often is faster
than the following ones 
condensation begins before
hydrolysis is complete

Mater. Horiz. 2016, 3, 91-112

Stoeber Process – Access to well-defined SiO2 Nanoparticles

Nucleation, nucleus growth, Ostwald ripening (further agglomeration)

Script from Prof. Hintz, University of Magdeburg

Short Excursus – Ostwald Ripening
Ostwald ripening is the process by which components of the discontinuous phase diffuse from smaller
to larger droplets through the continuous phase. It was first described by the German scientist
Wilhelm Ostwald, who is famous for receiving a Noble Prize "in recognition of his work on catalysis
and for his investigations into the fundamental principles governing chemical equilibria and rates of
reaction." Ostwald ripening is different from coalescence in that in coalescence, droplet domains
come into direct contact, while in Ostwald ripening the external phase serves as transfer medium.

http://soft-matter.seas.harvard.edu/index.php/Ostwald_ripening
Short Excursus – Ostwald Ripening

This thermodynamically-driven spontaneous process occurs because larger particles are more
energetically favored than smaller particles. This stems from the fact that molecules on the surface of
a particle are energetically less stable than the ones in the interior.
When Ostwald ripening does occur, initially, the droplet size distribution is dictated by homogenization
conditions, but with time, a steady-state particle distribution is reached. This distribution evolves in
time by increasing in mean size, but keeps a time-independent form. At steady state there is a critical
radius, above which droplets grow and below which droplets shrink. Assuming this radius is
approximately equal to the mean radius, diffusion in the external medium is limiting factor,
inhomogeneities in diffusion are negligible, and that the distances between particles are much larger
than particle size, Lifshitz and Slezov (Kabalnov, 1993) derived a time-evolution equation of the mean
radius.

http://soft-matter.seas.harvard.edu/index.php/Ostwald_ripening
Short Excursus – Ostwald Ripening - Examples

One gastronomical example is in the ouzo effect, where the

droplets in the cloudy microemulsion grow by Ostwald ripening.

Source: Wikipedia
Short Excursus – Ostwald Ripening - Examples

One gastronomical example is in the ouzo effect, where the

droplets in the cloudy microemulsion grow by Ostwald ripening.
Short Excursus – Ostwald Ripening - Examples

Ice Cream:
After warming up, during recrystallization when temperatures decrease again, Ostwald
ripening causes the average crystal size to grow, giving ice-cream an unpleasant texture after
melting and refreezing.

http://soft-matter.seas.harvard.edu/index.php/Ostwald_ripening
Short Excursus – Ostwald Ripening - Examples

In situ TEM heating experiment showing Au nanoparticles at 600°C, which diffuse on an

amorphous carbon support and exhibit Ostwald ripening.
Stoeber Process – Access to well-defined SiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Access to well-defined SiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Access to well-defined SiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Access to well-defined SiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Access to well-defined SiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Access to well-defined SiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Adaptation to well-defined TiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Adaptation to well-defined TiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Adaptation to well-defined TiO2 Nanoparticles

Script from Prof. Hintz, University of Magdeburg

Stoeber Process – Application for Core-Shell Nanomaterials

Step #1: Preparation of a polymer suitable for „grafting to“ reactions

Stoeber Process – Application for Core-Shell Nanomaterials

Step #2: „grafting to“ reactions and subsequent analysis

Stoeber Process – Application for Core-Shell Nanomaterials

Step #3: analysis  graft density, size, ratio …

Excursus – Zeta Potential Measurements

• Electrical double layer of counterions surrounding charged colloids

– Stern layer of firmly bound counterions
– Diffuse layer

• Screening of surface charges through counterions

• Movement of charged particle in solution

→ counterions of diffuse layer are sheared
off at the hydrodynamic slip plane

• Zeta potential = potential at the slip plane

< surface potential

• Zeta potential measurement by electrophoresis

Theory of zeta potential applies to ideal, nonporous and hard spheres!

Excursus – Zeta Potential Measurements – Examples (one that is more applicable)
Excursus – Zeta Potential Measurements – Examples (one that is less applicable)
Excursus – Zeta Potential Measurements – Examples (one that is less applicable)

Reasons? – Polymer coils are different from hard / non-porous spheres, aggregation, …
Au Nanoparticles
Why are Au Nanoparticles of Interest?

Problems: • ligand exchange

• signal loss (particle degradation)
• risk of poisoning (toxic ligands)

Chem. Rev. 2012, 112 (5), 2739-2779

Why are Au Nanoparticles of Interest?

One of the most important properties of gold nanoparticles, especially for their application in
chemical and biological sensing experiments, is their localized surface plasmon resonance
(LSPR). Thereby, light interacts with particles which are much smaller than the incident
wavelength. This leads to a plasmon that oscillates locally around the nanoparticle with a
frequency known as the LSPR. Overall, this is the fundamental effect for surface enhanced
Raman spectroscopy (SERS), on one hand and the UV/Vis absorption of nanoparticle
dispersions on the other. The latter can be correlated to the average particle size. If the size
of the particles remains constant, the position of the UV/Vis absorption band can be used to
characterize the local dielectric environment of the nanoparticles…
(Diploma thesis, C. Hörenz)

Chem. Rev. 2012, 112 (5), 2739-2779

Au Nanoparticles – Colloidal Approach – Turkevich Method

One common method for preparing colloidal gold

nanoparticles employs hydrogen tetrachloroaurate (HAuCl4)
and sodium citrate (Na3C6H5O7) in a dilute solution:

Mechanism: the citrate ions (C6H5O73-) reduce Au3+ to yield

30-40 nm gold particles…

Half reaction equations:

Au3+(aq) + 3e-  Au(s)

C6H5O73-(aq) +H2O(l)  C5H4O42-(aq) + CO2(g) + H3O(aq) + 2e-

https://www.sigmaaldrich.com/technical-documents/articles/materials-science/nanomaterials/gold-nanoparticles.html
Example – Formation of Au Nanoparticles

1. Heat a solution of chloroauric acid (HAuCl4) up to reflux (boiling)

2. Add trisodium citrate as reducing agent.
3. Continue stirring and heating for about 10 minutes.
• During this time, the sodium citrate reduces the gold salt (Au3+) to
metallic gold (Au0).
• The neutral gold atoms aggregate into seed crystals.
• The seed crystals continue to grow and eventually form gold
nanoparticles.

http://mrsec.wisc.edu/Edetc/nanolab/gold/index.html
J. Chem. Ed. 2004, 81, 544A.
Example – Formation of Au Nanoparticles

http://mrsec.wisc.edu/Edetc/nanolab/gold/index.html
J. Chem. Ed. 2004, 81, 544A.
Example – Formation of Au Nanoparticles

Reduction of gold ions: Au(III) + 3e- → Au(0)

Seed Crystal
Nucleation of Au(0) seed crystals: 10’s to 100’s of Atoms

Growth of nanoparticles:
Isotropic Spherical Surface capped
Growth with citrate anions
Nanoparticles
Seed
Adding surfactant to growth solution
Anisotropic Nanorods caps certain crystal faces and promotes
Growth growth only in selected directions.

http://mrsec.wisc.edu/Edetc/nanolab/gold/index.html
J. Chem. Ed. 2004, 81, 544A.
Turkevich Method – more complex than anticipated?
Turkevich Method – more complex than anticipated?
Brust-Schiffrin – Two-Phase Synthesis of Au NP
> 6.000 citations !

TOAB = tetraoctyl ammonium bromide

Brust-Schiffrin – Two-Phase Synthesis of Au NP
> 6.000 citations !
Au NP in the Presence of a Thiol Ligand

Use of alkane thiols as

capping ligands
Au NP in the Presence of a Thiol Ligand
Extension to Functionalized Au NP
Extension to Functionalized Au NP

MUA: 11-mercapto-1-undecanoic
acid

MUDA: 11-
mercaptoundecanamide

AUDDS: azide-terminated undecyl

disulfide
Influence of the Ligand / Au Ratio

UV/Vis: DMAc, 25°C, [Au] = 0.25 mM, [ligand] = 1.14/0.57/0.29/0.14/0.07 mM

Diploma thesis: Christoph Hörenz / 2011
Potential Problem: Ligand Exchange

• Stable dispersion of Au-NPs

• Addition of another ligand
• Exchange of ligands

Diploma thesis: Christoph Hörenz / 2011

Strategy: Crosslinkable Ligands for Au NP

NaBH4
+
SH

SH
Excess
Excess

SH - Toxicity?
- Particle stability?
- Signal loss?
- „Building Block“
AIM: Prevent ligand exchange upon the addition of another Ligand
Strategy: Crosslinkable Ligands for Au NP
Crosslinking Approaches

PEO-b-PAGE-SH:
= = =

PEO-b-PFGE-SH:

= = =
Crosslinking

UV/Vis:
Crosslinking
Proof of Crosslinking

Au@PEO45-b-PFGE7-SH Au@PEO-b-PFGEXL

Au@PEO54-b-PAGE7-SH Au@PEO-b-PAGEXL
Iron Oxide Nanoparticles
Why Magnetic Nanoparticles?
challenges
• secondary aggregation
Why nanoparticles? • circulation times
• immune response
unique properties due to large surface/volume ratio • cell interaction/uptake
• increased chemical reactivity • clearance from organism
• decreased influence of mass forces compared to van der influenced by protein corona
Waals forces or electrostatic interaction and surface chemistry
→ stable dispersions possible
• material-specific properties, e.g. superparamagnetism

Biomedical applications
• contrast agents
• drug delivery
• hyperthermia

Akira Ito et al., J. Biosci. Bioeng, 2005, 100, 1-11

Magnetic Nanoparticles - Properties

Important parameters of
hysteresis loop:
 Saturation magnetisation, Ms
 Remanence, Mr
 Rel. Remanence, Mr/Ms
 Coercivity, Hc
 Loop area (losses)

Lecture slides by Silvio Dutz, TU Ilmenau

Magnetic Nanoparticles - Properties

200

175
superparamagnetic: < 10 nm
150
single domains: 10 to 65 nm
125
coherent rotation of magnetisation
HC [Oe]

100
pseudo single domains:
75 65 to 75 nm
50 multi domains: > 75 nm
25 wall displacement

0
20 40 60 80 100
d [nm]

Lecture slides by Silvio Dutz, TU Ilmenau

The first Ferrofluid

Aim:
A liquid rocket fuel that could be drawn
toward a pump inlet in a weightless
environment by applying a magnetic field

Preparation:
Grinding of 30 µm particles down to 100
nm in presence of a propellant (heptane)
and a dispersing surfactant (oleic acid)
for several days.
Steve Papell invented
ferrofluid for NASA in 1963

Lecture slides by Silvio Dutz, TU Ilmenau

Modern Ferrofluids

Coating: • Stabilization
• Biocompatibility
• Functionalization

Lecture slides by Silvio Dutz, TU Ilmenau

Some Examples
γ-Fe2O3 / Fe3O4 of 5 … 100 nm

Lecture slides by Silvio Dutz, TU Ilmenau

MNP: Preparation Routes

• Biomineralization
• Alkaline Co-Precipitation
• Modified co-precipitation
• Glass crystallization
• Laser evaporation
• Oxidative alkaline hydrolysis of Fe2+ solution
• Polyols synthesis
• Thermal decomposition
• Hydrothermal reactions
• Microemulsion synthesis
• Sol-gel method Variation of:
• …. • Size
• Size distribution
• Shape
Problem with many methods: broad size distribution • Magnetic phase
 Fractionation necessary

Lecture slides by Silvio Dutz, TU Ilmenau

Biomineralization

Preparation of MNP within animals for their sense of direction

(compass), e.g. bacteria, bee, birds, fishes …

resulting mean
particle size:
20 … 100 nm

Lecture slides by Silvio Dutz, TU Ilmenau

Biomineralization
Alkaline Coprecipitation

Fe2+ + 2 Fe3+ + 8 OH- Fe3O4 + 4 H2O

[Khallafalla 1980, Massart 1981]

• Particle size: ≤ 10 nm
• High yield of preparation
• Broad size distribution

Lecture slides by Silvio Dutz, TU Ilmenau

Alkaline Coprecipitation (modified)

FeCl2 + FeCl3 + NaOH Fe3O4 + H2O + NaCl

(Fe2+ / Fe3+ = 1/2)

particle size: 10 … 100 nm

controlled by:
• Temperature
• Concentration
• Chemical kinetics
• pH-value

Lecture slides by Silvio Dutz, TU Ilmenau

Alkaline Coprecipitation (modified)

- Slow precipitation using a weak(er) base

- Formation of primary particles
- Growth / fusion of small primary particles
 Multicore iron oxide nanoparticles

[Dutz et al. JMMM 2007]

Lecture slides by Silvio Dutz, TU Ilmenau

Glass Crystallization

Starting material (α-Fe2O3 in glass: B2O3, CaO)

Melting (1400 °C)

Quenching (104 K/s) Amorphous flakes

Annealing (≈ 600 °C) Crystallization

Dissolution of matrix (acetic acid)

Particles (γ-Fe2O3, Fe3O4), D = 10 … 20 nm

Lecture slides by Silvio Dutz, TU Ilmenau

Laser Evaporation

Exhaust gas

Fan Carrier gas with MNP

Filter

Focused laser
Evaporation chamber
beam

Refill unit

Coating unit

Coating additive
Rotable ring-shaped
heater Carrier gas
channel

Lecture slides by Silvio Dutz, TU Ilmenau

Laser Evaporation
Coating in situ with
different substances,
e.g. stearic acid

resulting mean
particle size:
20 … 100 nm
50 nm
[Kurland et al. 2007]

Lecture slides by Silvio Dutz, TU Ilmenau

Characterization of MNP

Structural characterisation:
• X-ray diffractometry (XRD)
• Transmission electron microscopy (TEM)
• Dynamic light scattering (DLS, also PCS)

Magnetic characterisation:
• Vibrating sample magnetometry (VSM)
• Magnetic field calorimetry (SAR)
• AC-Susceptometry
X-Ray Diffractometry

200
XRD

150

counts
100
Identification of:
• elements 50
• compounds
• foreign phases 0
20 30 40 50 60
2θ [°]

Lecture slides by Silvio Dutz, TU Ilmenau

X-Ray Diffractometry

• phase indentification
MNP, 100 nm
50 MNP, 10 nm γ-Fe2O3 / Fe3O4
40 D ↓ ⇒ γ-Fe2O3
intensity [counts/s]

Maghemite
γ-Fe2O3
30
Magnetite
Fe3O4
• single crystal size:
20

10

62.0 62.5 63.0 63.5 64.0

diffraction angle 2θ [°]

Lecture slides by Silvio Dutz, TU Ilmenau

Surface Modification of MNP
Surface Modification of MNP
Surface Modification of MNP – Shell Characterization
How does a Coating Process proceed in general?

+ several washing steps…

© Paul Wiemuth / Bachelor thesis