How do nanoparticles heat up?

The function Q(r, t) represents an energy source coming

from light dissipation in NPs:

In the steady-state regime, the local

temperature around a single NP is
described by a simple equation
How do nanoparticles heat up?
 Nanoparticles for PPTT
Gold nanorods (GNR) were synthesized by a
seed-mediated approach and functionalized
with PEG

Geometrical parameters :
L = 41 ± 8 nm
d= 10,2 ± 2 nm
r = 4,03 ± 0,7

Plasmon resonance at the wavelength 820 nm

Transmission electron microscopic image
of gold nanorods

Chumakov et. al. SFM ‘13

 Scheme of experiments

Suspension volume – 1,5 ml

Duration of irraditaion– 5 min
Power density - 1 W/сm2
Wavelength- 810 nm

IRYSYS thermal imager was placed at the

distance 37 cm of the test tube
 Scheme of experiments
Dependence of the temperature increment ∆T on the concentration of gold
nanorods in the suspension after irradiation with laser light (810 nm, 1
W/сm2 ) during 5 min.
 Laboratory animals
Laboratory animals

Female linear mice BALB/с

Age : 3 months
Body mass : 20-22 g

Tumour model :
Ehrlich’s ascites carcinoma

The mean volume of the tumour was

1,7 ± 0,3 см2
 Scheme of experiments
Control group Control group
№1 №2
6 animals
6 animals

Laser irradiation No irradiation

Wavelength - 810 nm
Duration - 5 min
Power Density- 1 W/cm2

2 animals Evaluation of tumor growth 2 animals Evaluation of tumor growth

(AAS) dynamic (4 animals) (AAS) dynamic (4 animals)
 Effect of laser radiation

before laser irradiation 1 min 5 min

 Effect of heat on tissues

The effect of hyperthermia on the induction Hyperthermia induces cell death in the adult testis
of cell death in the adult rat cerebellum.
Sagittal sections of the adult cerebellum
from 15 hours after hyperthermia
dwm, deep white matter; g, granule cell layer; m,
molecular layer; p, Purkinje cellular layer
Cell Stress & Chaperones (2002) 7 (1), 73–90
 Other applications of PPTT

• Destruction of viruses or bacteria

• Controlled localized denaturation

• Cleavage of proteins and nucleic acids,

potentially useful for diagnostic or
therapeutic goals
Adv. Sci. 2019, 6, 1900471
Enhanced permeability and retention effect (EPR)
Molecules of certain sizes (typically liposomes, nanoparticles, and macromolecular drugs)
tend to accumulate in tumor tissue much more than they do in normal tissues

The newly formed tumor

vessels are usually abnormal
in form and architecture.
They are poorly aligned
defective endothelial cells
with wide fenestrations,
lacking a smooth muscle
layer, or innervation with a
wider lumen, and impaired
functional receptors for
angiotensin II. Furthermore,
tumor tissues usually lack
effective lymphatic drainage.
All of these factors lead to
abnormal molecular and
fluid transport dynamics
Targeting tumor through nanoparticles

Mutations that lead to EGFR

overexpression (known as
upregulation) or overactivity
have been associated with a
number of cancers, including
squamous-cell carcinoma of
the lung (80% of cases), anal
cancers, glioblastoma (50%)
and epithelian tumors of the
head and neck (80-100%).

https://doi.org/10.2147/IJN.S55118
 Characterization of nanoparticles

Nanomaterials & Nanostructures are characterized by: -

X-ray diffraction (XRD) –
Various Electron Microscopy (EM)
(i) Scanning Electron Microscopy (SEM)
(ii) Transmission Electron Microscopy (TEM)
(iii) Scanning Probe Microscopy (SPM)

Chemical Characterization Techniques –

Optical Spectroscopy
Electron Spectroscopy
Ionic Spectrometry
Sample Preparation
Holder is made of Beryllium to absorb the hard x-ray background.
Poisonous- so cannot be handled with bare hands.
Types of Grids
Scheme of the preparation for cross-sections
and anisotropic materials. The first steps
involve the embedding of the material,
sandwich formation and its fixation in a
copper pipe with resin
(left side). Disks are cut from this pipe with a
diamond wire saw. Then, the disks are
abraded on both sides and then dimples are
ground. Finally, a hole in the thin center of
the disk is generated by an ion
beam treatment (right side)
Extraction replica technique for sample preparation.
 SIGNALS IN ELECTRON MICROSCOPY

x-rays backscattered e's

composition microstructure

secondary e's
microstructure

inelastically scattered e's elastically scattered e's

composition crystallographic structure

transmitted e's
microstructure
 SEM - scanning electron microscopy

Secondary electron detector - scintillation detector

+ bias mesh needed in front of

detector to attract low energy
electrons

line of sight unnecessary

SEM - scanning electron microscopy
Choose correct detector- topography example

Fracture surface in iron

backscattered electrons secondary electrons

 SEM - scanning electron microscopy

Composition - what elements present at a particular spot in specimen?

Use solid state detector

Do energy scan for fluorescent X-rays
 SEM - scanning electron microscopy
Composition mapping - x-ray fluorescence
Use solid state detector set for X-ray energy for a
particular element in specimen

image X-ray map

 SEM - scanning electron microscopy

Interaction volume

Backscattered electrons
come from whole volume
(high energy)

Secondary electrons come

from neck only (low energy)
 TEM case studies
HRTEM Study of Niobium Tungsten Oxides
Dark-Field Imaging
Scanning Transmission Electron Microscope

Scheme of a scanning (transmission) electron microscope showing

the ray path and the detector arrangement.
• In a conventional SEM, secondary electrons (SE) and back-
scattered electrons (BSE) are collected for image formation on
the upper side of the sample.
• For STEM, detectors are installed below the thin sample: BF:
bright field detector; (HA)ADF: (high angle) annular dark field
detector). The intensity distribution of the electrons scattered
by the sample is indicated by the different grey values. Most
electrons pass a thin sample without any interaction or are
scattered into small angles only. Diffracted beams (black line
symbolizes an example) meet the ADF detector.
(a) HAADF-STEM and (b) SE-STEM image of Au-NPs on TiO2.
Order and Disorder
 Modulated Structures
The modulation of a basic structure can have different reasons: (i) Displacement: Atoms are
displaced from the positions in the basic structure in a periodic way. (ii) Occupation: Empty
positions are occupied or filled positions are occupied by two or more elements in a regular
way. A commensurate modulation gives superstructure reflections besides that of the basic
structure. An example is the structure of Nb8W9O47 that is a threefold superstructure of the basic
TTB type caused by the systematic occupation of 1/3 of the pentagonal channel by M-O strings
 In-Situ Studies
TEM investigation are usually carried out in high vacuum at room temperature. Special
holders allow to perform different experiments like straining tests or electrical measurements.
Even chemical experiments are possible inside the microscope today: the electron beam
interacts with gas or even liquid phase present in thin layers while the high vacuum is
maintained in the rest of the microscope column. The temperature can be changed
either by cooling down or heating up the sample. Cooling beam sensitive samples is often the
only possibility to investigate them. The most important example are biological object; different
cryo-methods are used for their characterization. Phase changes and transitions that occur at
elevated temperature can be observed by heating up a sample.
 Chemistry inside the TEM
Observation of solid-gas reaction in-situ

(i) Differential pumping. Gas is let into the specimen area while the high vacuum other
sections of the microscope is maintained. Additional apertures separate this area from the rest
of the microscope column and additional pumps remove the gas close to the specimen. Such
dedicated microscopes equipped with differential pumping stages are designated as
environmental TEMs (ETEMS).

(ii) Closed cells. The sample is placed between two electron-transparent windows consisting
of a thin film (≤ 40 nm) of light element materials (e.g. SiC, SiN or graphene). The special
construction of the specimen holder allows one or more gases to pass through the space
between the windows to interact with the material. If MEMS chips act as sample carriers, they can be
heated up by an electric current.

The resolution capability of the microscope is of course reduced in both cases

by scattering processes
Scanning electron microscopy (SEM)

https://www.youtube.com/watch?v=uQ1gCIkCbIQ
Basic construction of SEM
Specimen stage
Interaction with electrons
Secondary electrons
Backscattered electrons
Charging and its influence
Ways to prevent charging
Sample preparation
X-Ray Spectroscopy

Energy-dispersive X-ray spectrometers

(EDXS)

Electron energy loss

spectrum (EELS) For the generation of the
inelastic electron-matter interactions described
here, energy is required that is transferred from
an electron in the incoming beam. Consequently,
this electron suffers a loss of energy that is
measured by EELS.
 Analytical Electron Microscopy (AEM)

The ultimate goal of analytical electron microscopy is to characterize the elemental

composition at every site of a specimen with atomic resolution.
 Thermal Analysis

TEGA is a combination high-temperature furnace and mass spectrometer instrument that scientists will use to analyze martian
ice and soil samples. The robotic arm will deliver samples to a hopper designed to feed a small amount of soil and ice into
eight tiny ovens about the size of an ink cartridge in a ballpoint pen. Each of these ovens will be used only once to analyze
eight unique ice and soil samples.

Once a sample is successfully received and sealed in an oven, the temperature is slowly increased at a constant rate, and the
power required for heating is carefully and continuously monitored. This process, called scanning calorimetry, shows the
transitions from solid to liquid to gas of the different materials in the sample: important information needed by scientists to
understand the chemical character of the soil and ice.
 Thermogravimetric analysis

The main function of TGA is the monitoring of the thermal stability of a material by recording
the change in mass of the sample with respect to temperature
 Thermogravimetric analysis
• In thermogravimetric analysis (TGA), a sample is continually weighted while heating, as an inert
gas atmosphere is passed over it.
• Many solids undergo reactions that evolve gaseous byproducts. In TGA, these gaseous byproducts
are removed and changes in the remaining mass of the sample are recorded.

Three variations are commonly employed:

•Dynamic TGA - Temperature continues to increase over time as mass is recorded. This allows simulataneous
identification of how much gas is removed and the temperature at which it occurs.

•Static TGA - Temperature is held constant as the mass is measured. This can be used to gain more information
on a decomposition that happens at a certain temperature or to investigate a material’s ability to withstand a
given temperature.

•Quasistatic TGA - Sample is heated in multiple temperature intervals, and held at those intervals for a time,
often until the mass stabilizes. This is ideal for investigating substances that are known to decompose in various
ways at different temperatures, and better characterizing the way in which they decompose.
Thermogravimetric analysis

• Inside the TGA, there are two pans, a reference pan and a
sample pan. The pan material can be either aluminium or
platinum. As platinum melts at 1760 °C and alumium melts
at 660 °C, platinum pans are chosen when the maximum
temperature exceeds 660 °C.

• Under each pan there is a thermocouple which reads the

temperature of the pan.

• Before the start of each run, each pan is balanced on a

balance arm. The balance arms should be calibrated to
compensate for the differential thermal expansion between
the arms. If the arms are not calibrated, the instrument will
only record the temperature at which an event occurred and
not the change in mass at a certain time.

• To calibrate the system, the empty pans are placed on the

balance arms and the pans are weighed and zeroed.
 Thermogravimetric analysis

• The weight gain (of ca. 5%) at 300 °C is due to

the formation of metal oxide from the
incompletely oxidized catalyst.

• To determine the mass of iron catalyst impurity

in the SWNT, the residual mass must be
calculated. The residual mass is the mass that is
left in the sample pan at the end of the
experiment.

• From this TGA diagram, it is seen that 70% of

the total mass is lost at 400 °C. This mass loss is
attributed to the removal of carbon. The residual
mass is 30%. Given that this is due to both oxide
and oxidized metal, the original total mass of
residual catalyst in raw HiPCO SWNTs is ca.
25%.

The TGA of unpurified HiPco SWNTs under air showing the residual mass associated with the iron
catalyst. Adapted from I. W. Chiang, B. E. Brinson, A. Y. Huang, P. A. Willis, M. J. Bronikowski, J. L. Margrave, R.
E. Smalley, and R. H. Hauge, J. Phys. Chem. B, 2001, 105, 8297. Adapted from Chiang et al, 2001
 The Thermobalance

Thermobalance components. The balance beam is shown as A. The sample cup and holder are B; C is a
counterweight. D is a lamp and photodiodes, E is a magnetic coil, and F is a permanent
magnet. The computer data-acquisition, data-processing, and control systems are components G, H,
and I. Component J is the printer and display unit.
Types of Thermobalances
Schematics of a top-loading balance
 Thermograms of polymeric materials

In polymer studies, thermograms provide information about decomposition mechanisms for various
polymeric preparations. In addition, the decomposition patterns are characteristic
for each kind of polymer and can sometimes be used for identification purposes.
 TGA for compositional analysis

Polyethylene that has been formulated with fine carbon-Black particles to inhibit degradation from
exposure to sunlight. This analysis would be difficult by most other analytical methods.
Recorded thermogram obtained by increasing the temperature of pure
CaC2O4.H2O at a rate of 5°C/min. The clearly defined horizontal regions
correspond to temperature ranges in which the indicated calcium compounds are
stable. This figure illustrates the use of TGA in defining the thermal conditions
needed to produce a pure species.
TGA to the quantitative analysis of a mixture of calcium, strontium, and
barium ions. The three are first precipitated as the monohydrated oxalates.
The mass in the temperature range between 320°C and 400°C is that of the
three anhydrous compounds, CaC2O4, SrC2O4, and BaC2O4, and the mass
between about 580°C and 620°C corresponds to the three carbonates. The
mass change in the next two steps results from the loss of carbon dioxide, as
first CaO and then SrO are formed. Sufficient data are available in the
thermogram to calculate the mass of each of the three elements present in
the sample.

Derivative of the thermogram shown in (a). The derivative curve can

sometimes reveal information that is not detectable in the ordinary
thermogram. For example, the three peaks at 140°C, 180°C, and 205°C suggest
that the three hydrates lose moisture at different temperatures. However, all
appear to lose carbon monoxide simultaneously and thus yield a single sharp
peak at 450°C.
 Differential Thermal Analysis

Differential thermal analysis (DTA) is a technique in which the

difference in temperature between a substance and a reference
material is measured as a function of temperature while the
substance and reference material are subjected to a controlled
temperature program.

The digitized output voltage Es from the sample thermocouple is the input to a computer.
 Differential thermal analysis
In DTA, the temperature of a sample is compared with that of an inert reference material
during a programmed change of temperature. The temperature should be the same until
thermal event occurs, such as melting, decomposition or change in the crystal structure.
Differential thermal analysis

• If an endothermic event takes place within the sample, the

temperature of the sample will lag behind that of the
reference and a minimum will be observed on the curve.

• On the contrary, if an exothermal event takes place, then

the temperature of the sample will exceed that of the
reference and a maximum will be observed on the curve.

• The area under the endotherm or exotherm is related to

the enthalpy of the thermal event, ΔH.
Differential thermal analysis

For many problems, it is advantageous to use both DTA and

TG, because the DTA events can then be classified into
those which do or do not involve mass change.

At the temperature range 500 to 700°Cthere is a change in mass

occurred on the TG curve, which corresponds to dehydration of
Al4(Si4O10)(OH)8,and this dehydration shows up on DTA curve
as an endotherm. At 950 to 980°C, a second DTA effects occurs
but this effect not occurs on the TG curve, because this event
corresponds to recrystallization of the dehydrated kaolin. This
recrystallization process is exothermic.
 Differential Thermal Analysis

The glass transition temperature Tg is the characteristic temperature at which glassy

amorphous polymers become flexible or rubber-like because of the onset of the
concerted motion of large segments of the polymer molecules. When heated to the glass
transition temperature Tg, the polymer changes from a glass to a rubber.
 Differential Thermal Analysis
DTA is also widely used in the ceramics and metals industry. The technique is capable of
studying high-temperature processes (up to 2400°C for some units) and relatively large
sample sizes (hundreds of milligrams). For such materials, DTA is used to study
decomposition temperatures, phase transitions, melting and crystallization points,
and thermal stability.

The DTA method also provides a simple and accurate way

of determining the melting, boiling, and decomposition
points of organic compounds.

Peak at 113°C corresponds to the solid-phase change

from the rhombic to the monoclinic form. The peak at 124°C
corresponds to the melting point of the element. Liquid sulfur
is known to exist in at least three forms, and the peak at 179°C
apparently involves these transitions, whereas the peak at 446°C
corresponds to the boiling point of sulfur.
 Differential Scanning Calorimetry
Differential scanning calorimetry (DSC) is the most often used
thermal analysis method, primarily because of its speed,
simplicity, and availability. In DSC a sample and a reference are
placed in holders in the instrument. Heaters either ramp the
temperature at a specified rate (e.g., 5°C/min) or hold the DSC at
a given temperature.

The basic between DSC and DTA is that DSC is a calorimetric method in which differences in
energy are measured. In contrast, in DTA, differences in temperature are recorded. The
temperature programs for the two methods are similar. DSC is considered to be a
quantitative technique in contrast to DTA.

In power-compensated DSC, the temperatures of the sample and reference

are kept equal to each other while both temperatures are increased or
decreased linearly. The power needed to maintain the sample temperature
equal to the reference temperature is measured.
 Heat-flux DSC

In heat-flux DSC, the difference in heat flow into the sample and reference is
measured while the sample temperature is changed at a constant rate. Both sample
and reference are heated by a single heating unit.

f (T, t) is the kinetic response of the sample in J/mol. We can thus

see that the total heat flow is the sum of two terms, one related to
the heat capacity, and one related to the kinetic response.
DSC scan for a polymeric material
 Glass transition temperatures
Crystallinity and Crystallization Rate
Reaction Kinetics
Protein Stability and Structure

The onset temperature is defined as the temperature at which a line tangent to the baseline intersects
another line tangent to the slope of the transition, as illustrated in Figure 31-15. In some cases
temperatures of transitions, such as the glass transition, are taken as the midpoint of the transition rather
than the onset.
 Microthermal Analysis

Microthermal analysis6 combines thermal analysis with atomic force microscopy. It is actually a family of scanning thermal
microscopy techniques in which thermal properties of a surface are measured as a function of temperature and used to produce
a thermal image. In microthermal analysis the tip of an atomic force microscope is replaced by a thermally sensitive probe such
as a thermistor or thermocouple. The surface temperature can be changed externally or by the probe acting both as a heater and as a
temperature-measuring device.
 Simultaneous Thermal Analysis (STA)
This refers to the application of two or more techniques to a (single) sample at the
same time. A hyphen is used to separate the abbreviations, e.g. simultaneous
thermogravimetric analysis and differential scanning calorimetry (TGA-DSC).

TG-DSC/DTA
Simultaneous mass change and energetic information on
one and the same sample under absolutely identical
measurement conditions
STA Instruments
Scheme of Tungsten furnace
Tungsten furnace provides clean atmospheres
Capillary coupling with Mass Spectrometer
STA – MS – FTIR Coupling
TG – FTIR Measurement of PVC