Alexey V. Markin

New Surface-Enhanced Raman Scattering Platforms: Composite Calcium Carbonate Microspheres Coated with Astralen and Silver Nanoparticles

Surface-enhanced Raman scattering (SERS) microspectroscopy is a very promising label-free, noncontact, and nondestructive method for real-time monitoring of extracellular matrix (ECM) development and cell integration in scaffolds for tissue engineering. Here, we prepare a new type of micrometer-sized SERS substrate, core-shell microparticles composed of solid carbonate core coated with silver nanoparticles and polyhedral multishell fullerene-like structure, astralen. Astralen has been assembled with polyallylamine hydrochloride (PAH) by the layer-by-layer manner followed by Ag nanoparticle formation by means of a silver mirror reaction, giving the final structure of composite particles CaCO3(PAH/astralen)x/Ag, where x = 1-3. The components of the microparticle carry multiple functionalities: (i) an easy identification by Raman imaging (photostable astralen) and (ii) SERS due to a rough surface of Ag nanoparticles. A combination of Ag and astralen nanoparticles provides an enhancement of astralen Raman signal by more than 1 order of magnitude. Raman signals of commonly used scaffold components such as polylactide and polyvinyl alcohol as well as ECM component (hyaluronic acid) are significantly enhanced. Thus, we demonstrate that new mechanically robust and easily detectable (by astralen signal or optically) core-shell microspheres based on biocompatible CaCO3 can be used as SERS platform. Particle design opens many future perspectives for fabrication of SERS platforms with multiple functions for biomedical applications, for example, for theranostic.

Synthesis of magnetite hydrosols in inert atmosphere

A setup is described for magnetite hydrosol synthesis in inert atmosphere via coprecipitation of bi- and trivalent iron salts in the presence of a base with the formation of nanoparticles having desired sizes and chemical composition. The size of nanoparticles is estimated based on analysis of light-scattering and transmission-electron-microscopy data. The chemical composition of magnetite nanoparticles is monitored by Raman spectroscopy.

Thermodynamic Properties of Carbosilane Dendrimers of the Sixth Generation with Ethylene Oxide Terminal Groups.

The temperature dependences of heat capacities of carbosilane dendrimers of the sixth generation with ethyleneoxide terminal groups, denoted as G6[(OCH2CH2)1OCH3]256 and G6[(OCH2CH2)3OCH3]256, were measured in the temperature range from T = (6 to 520) K by precision adiabatic calorimetry and differential scanning calorimetry (DSC). In the above temperature range the physical transformations, such as glass transition and high-temperature relaxation transition, were detected. The standard thermodynamic characteristics of the revealed transformations were determined and analyzed. The standard thermodynamic functions, namely, heat capacity Cp°(T), enthalpy H°(T) - H°(0), entropy S°(T) - S°(0), and Gibbs energy G°(T) - H°(0) for the range from T → 0 to 520 K, and the standard entropies of formation ΔfS° of the investigated dendrimers in the devitrified state at T = 298.15 K, were calculated per corresponding moles of the notional structural units. The standard thermodynamic properties of dendrimers under study were discussed and compared with literature data for carbosilane dendrimers with different functional terminal groups.

Thermodynamic characteristics of triphenylantimony bis(acetophenoneoximate)

The temperature dependence of heat capacity Cp° = f(T) of triphenylantimony bis(acetophenoneoximate) Ph3Sb(ONCPhMe)2 was measured for the first time in an adiabatic vacuum calorimeter in the range of 6.5–370 K and a differential scanning calorimeter in the range of 350–463 K. The temperature, enthalpy, and entropy of fusion were determined. Treatment of low-temperature (20 K ≤ T ≤ 50 K) heat capacity was performed on the basis of Debye’s theory of the heat capacity of solids and its multifractal model and, as a consequence, a conclusion was drawn on the type of structure topology. Standard thermodynamic functions Cp°(T), H°(T) — H°(0), S°(T), and G°(T) — H°(0) were calculated according to the experimental data obtained for the compound mentioned in the crystalline and liquid states for the range of T → 0–460 K. The standard entropy of the formation of crystalline Ph3Sb(ONCPhMe)2 was determined at T = 298.15 K.

Thermodynamics of G-3(D-4) and G-6(D-4) carbosilanecyclosiloxane dendrimers

Temperature dependences of the heat capacity of G-3(D4) and G-6(D4) carbosilanecyclosiloxane dendrimers are studied for the first time by precision adiabatic vacuum and differential scanning calorimetry in the range of 6 to 350–450 K. Physical transformations in the investigated temperature range are observed and their standard thermodynamic characteristics are determined and discussed. Standard thermodynamic functions for a mole unit are calculated from the experimental data: Cp○(T), H○(T), − H○(0), S○(T) − S○(0), and G○(T) − H○(0) in the range of T → 0 to (350–449) K and standard entropies of formation at 298.15 K. Low-temperature (T ≤ 50 K) heat capacity is analyzed using the Debye theory of heat capacity of solids and the multifractal model. The values of fractal dimensionality D are determined and some conclusions on the topology of the investigated structures are drawn. The corresponding thermodynamic properties of the investigated carbosilanecyclosiloxane dendrimers under study are compared.

Nanoencapsulated and microencapsulated SERS platforms for biomedical analysis.

The problems of layer-by-layer-based surface enhancement Raman scattering (SERS)-sensor application for pharmaceutical analysis were discussed. Layer-by-layer (LbL) method allows fabrication of encapsulated SERS platforms with high reproducibility of enhancement factor and increased signal/noise ratio of Raman scattering. LbL encapsulation approach opens an avenue to implement a novel type of theranostic systems combining SERS based sensing and drug delivery in one entity. The area of encapsulation development toward smart multifunctional theranostic systems could bring benefits for personalized medicine and should minimize costs and resources at preclinical and clinical study in pharmacology while testing new bioactive compounds.

Thermodynamic characteristics of triphenylantimony diacrylate

The heat capacity of triphenylantimony diacrylate Ph3Sb(O2CCH=CH2)2 was studied in an adiabatic vacuum calorimeter at 6–350 K and differential scanning calorimeter at 330–450 K. Melting was revealed at these temperatures; the melting point was estimated at 428.4 ± 0.5 K. It was accompanied by the partial decomposition of the substance. The low-temperature (20 K ≤ T ≤ 50 K) heat capacity was treated using the Debye theory of the heat capacity of solids and its multifractal model. The type of the structure topology was determined. The standard thermodynamic functions Cpo(T), Ho(T) − Ho(0), So(T), and Go(T) − Ho(0) of the compound in the crystal state were calculated from the obtained experimental data in the range from T → 0 to 428 K. The standard entropy of the formation of the crystalline compound Ph3Sb(O2CCH=CH2)2 at T = 298.15 K was determined.

Thermodynamics of a seventh generation carbosilane dendrimer with phenylic substituent on the initial branching center and terminal butyl groups

The temperature dependence of the heat capacity of carbosilane dendrimer of the seventh generation of series 3 × 3 with phenylic substituent on the initial branching center and terminal butyl groups was studied by the methods of precision adiabatic vacuum calorimetry and differential scanning calorimetry over the temperature range T = 7–580 K for the first time. Physical transformations in the above temperature range were detected and their standard thermodynamic characteristics estimated and analyzed. The experimental results were used to calculate standard thermodynamic functions Cp∘(T), H∘(T)-H∘(0), S∘(T)-S∘(0), and G∘(T)-H∘(0) (0) over the range T → 0–580 K and standard entropy of formation of dendrimer at T = 298.15 K. The thermodynamic properties of carbosilane dendrimers of the seventh generation of series 4 × 3 with terminal butyl groups and the samples studied in this work were compared.

The thermodynamic properties of bis(η6-ethoxybenzene)chromium fulleride from T → 0 to 340 K

The temperature dependence of the heat capacity of crystalline bis-(η6-ethoxybenzene)chromium fulleride [(η6-(EtOPh))2Cr]·+[C60]·− was studied for the first time by adiabatic vacuum calorimetry over the temperature range 6–340 K with errors of ±0.2%. The temperature dependence of the EPR signal parameters of bis-(η6-ethoxybenzene)chromium fulleride was studied for the first time from 120 to 340 K. A reversible endothermic transformation was observed between 160 and 250 K during heating; it was caused by the dissociation of the [(C60)2]2− dimer and the formation of the [(η6-(EtOPh))2Cr]·+[C60]·− fulleride; its standard thermodynamic characteristics were estimated and analyzed. The experimental data were used to calculate the standard thermodynamic functions, including the heat capacity, enthalpy, entropy, and Gibbs function of the fulleride dimer from T → 0 to 160 K and the [(η6-(EtOPh))2Cr]·+[C60]·− monomeric complex over the temperature range 250–340 K. The standard thermodynamic properties of the fulleride studied, fullerides studied earlier, and fullerite C60 were compared.

Detection of sulfonamide drug in urine using liquid-liquid extraction and surface-enhanced Raman spectroscopy

In this article we have applied liquid-liquid extraction (LLE) as a sample preparation technique for detection of sulfadimethoxine (one of sulfonamide drugs) in urine using surface-enhanced Raman spectroscopy (SERS). SERS substrate based on silver nanoparticles has been prepared by citrate reduction of silver nitrate. Obtained calibration curve (SERS intensity vs. sulfadimethoxine concentration) has been used for detection of sulfadimethoxine in human urine samples artificially contaminated by sulfadimethoxine. Three different solvents (ethyl acetate, diethyl ether, chloroform) have been used for LLE performance tests. Chloroform being found as the most effective one based on calculation of recoveries after SERS measurements. Thus we would like to propose fast (less than 20 minutes), simple and sensitive (detection limit up to 1 μg/ml) test for detecting sulfa drugs in urine using a combination of SERS with LLE with sample volume as low as 100 μL. Such test can be applied for evaluation of the degree of drug extraction from human body and half-life of such drug applied in the course of therapeutic treatments of certain diseases.