Sergei G. Kazarian

Molecular states of water in room temperature ionic liquids

ATR and transmission IR spectroscopy have been used to investigate the state of water in room temperature ionic liquids (RTILs) based on the 1-alkyl-3-methylimidazolium cation with the anions: [PF6]−, [SbF6]−, [BF4]−, [ClO4]−, [CF3SO3]−, [(CF3SO2)2N]−, [NO3]− and [CF3CO2]−. It has been shown that in these RTILs water molecules absorbed from the air are present mostly in the “free” (not self-associated) state, bound via H-bonding with [PF6]−, [BF4]−, [SbF6]−, [ClO4]−, [CF3SO3]−, [(CF3SO2)2N]− with the concentrations of dissolved water in the range 0.2–1.0 mol dm−3. It has been concluded that most of the water molecules at these concentrations exist in symmetric 1 : 2 type H-bonded complexes: anion...HOH...anion. Additional evidence that the preferred sites of interaction with water molecules are the anions has been obtained from the experiments with RTILs of the 1-butyl-2,3-dimethylimidazolium and 1-butyl-2,3,4,5-tetramethylimidazolium cations. Water molecules can also form associated liquid-like formations in RTILs with anions of stronger basicity such as [NO3]− and [CF3CO2]−. When these RTILs are exposed to air the water concentrations exceed 1.0 mol dm−3. The strength of H-bonding between water molecules and anions increases in the order [PF6]− < [SbF6]− < [BF4]− < [(CF3SO2)2N]− < [ClO4]− < [CF3SO3]− < [NO3]− < [CF3CO2]−. The energies of this H-bonding were estimated from spectral shifts, with the resulting enthalpies being in the range 8–13 kJ mol−1. ATR-IR spectroscopy has also been used to study H-bonding between methanol and RTILs.

Spectroscopy of polymer/drug formulations processed with supercritical fluids: in situ ATR–IR and Raman study of impregnation of ibuprofen into PVP

In situ ATR (attenuated total reflectance)-IR spectroscopy has been used to study poly(vinylpyrrolidone) (PVP) films subjected to a solution of ibuprofen in supercritical CO2. The process of impregnation of ibuprofen into PVP has been monitored in situ. It has been shown that the supercritical fluid impregnation process results in ibuprofen being molecularly dispersed in a polymer matrix with ibuprofen molecules interacting with the C=O group of PVP. Raman spectra of ibuprofen impregnated into PVP from supercritical fluid solution have also been measured and compared with the Raman spectra of crystalline ibuprofen. ATR-IR spectroscopy has also revealed specific interactions between the C=O groups of PVP and CO2. Impregnation of ibuprofen into PVP makes the C=O groups of PVP less available for interactions with CO2. It has also been demonstrated that the presence of ibuprofen in PVP also affects sorption of water into PVP.

ATR-FTIR spectroscopic imaging: recent advances and applications to biological systems.

Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopic imaging is a highly versatile, label free and non-destructive chemical imaging method which can be applied to study a wide range of samples and systems. This review summarises some of the recent advances and applications of this imaging method in the area of biomedical studies, including examples of section of aorta, skin tissue and live cells. Two of the major advantages of measuring in ATR mode are the opportunity to measure samples that absorb strongly in the IR spectrum, such as aqueous systems, without significant sample preparation and the ability to increase the spatial resolution of the measured image. The implications of these advantages as well as some limitations of this imaging approach are discussed and a brief outlook at some of the possible future developments in this area is provided.

The use of murine embryonic stem cells, alginate encapsulation, and rotary microgravity bioreactor in bone tissue engineering

The application of embryonic stem cells (ESCs) in bone tissue engineering and regenerative medicine requires the development of suitable bioprocesses that facilitate the integrated, reproducible, automatable production of clinically-relevant, scaleable, and integrated bioprocesses that generate sufficient cell numbers resulting in the formation of three-dimensional (3D) mineralised, bone tissue-like constructs. Previously, we have reported the enhanced differentiation of undifferentiated mESCs toward the osteogenic lineage in the absence of embryoid body formation. Herein, we present an efficient and integrated 3D bioprocess based on the encapsulation of undifferentiated mESCs within alginate hydrogels and culture in a rotary cell culture microgravity bioreactor. Specifically, for the first 3 days, encapsulated mESCs were cultured in 50% (v/v) HepG2 conditioned medium to generate a cell population with enhanced mesodermal differentiation capability followed by osteogenic differentiation using osteogenic media containing ascorbic acid, beta-glycerophosphate and dexamethasone. 3D mineralised constructs were generated that displayed the morphological, phenotypical, and molecular attributes of the osteogenic lineage, as well mechanical strength and mineralised calcium/phosphate deposition. Consequently, this bioprocess provides an efficient, automatable, scalable and functional culture system for application to bone tissue engineering in the context of macroscopic bone formation.

New Opportunities in Micro- and Macro-Attenuated Total Reflection Infrared Spectroscopic Imaging: Spatial Resolution and Sampling Versatility

New opportunities exist to obtain chemical images using attenuated total reflection infrared (ATR-IR) spectroscopy. This paper shows the feasibility of obtaining FT-IR images with a spatial resolution of at least 3–4 μm using a Ge ATR objective coupled with an infrared microscope. The improved spatial resolution compared to FT-IR images obtained by the transmission method is due to the high refractive index of the ATR crystal, which gives a high numerical aperture and hence, a higher spatial resolution. FT-IR imaging with a conventional diamond ATR accessory has been investigated. This is the first time that FT-IR imaging is reported using such a versatile accessory based on a diamond ATR crystal. These results showed that a spatial resolution up to 13 μm can be achieved without the use of infrared microscope objectives. One advantage of the diamond element is that it allows pressure to be applied and hence, good contact to be obtained over the whole field of view.

Micro- and Macro-Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Imaging

Fourier transform infrared (FT-IR) spectroscopic imaging has become a very powerful method in chemical analysis. In this review paper we describe a variety of opportunities for obtaining FT-IR images using the attenuated total reflection (ATR) approach and provide an overview of fundamental aspects, accessories, and applications in both micro- and macro-ATR imaging modes. The advantages and versatility of both ATR imaging modes are discussed and the spatial resolution of micro-ATR imaging is demonstrated. Micro-ATR imaging has opened up many new areas of study that were previously precluded by inadequate spatial resolution (polymer blends, pharmaceutical tablets, cross-sections of blood vessels or hair, surface of skin, single live cells, cancerous tissues). Recent applications of ATR imaging in polymer research, biomedical and forensic sciences, objects of cultural heritage, and other complex materials are outlined. The latest advances include obtaining spatially resolved chemical images from different depths within a sample, and surface-enhanced images for macro-ATR imaging have also been presented. Macro-ATR imaging is a valuable approach for high-throughput analysis of materials under controlled environments. Opportunities exist for chemical imaging of dynamic aqueous systems, such as dissolution, diffusion, microfluidics, or imaging of dynamic processes in live cells.

Swellable, Water- and Acid-Tolerant Polymer Sponges for Chemoselective Carbon Dioxide Capture

To impact carbon emissions, new materials for carbon capture must be inexpensive, robust, and able to adsorb CO2 specifically from a mixture of other gases. In particular, materials must be tolerant to the water vapor and to the acidic impurities that are present in gas streams produced by using fossil fuels to generate electricity. We show that a porous organic polymer has excellent CO2 capacity and high CO2 selectivity under conditions relevant to precombustion CO2 capture. Unlike polar adsorbents, such as zeolite 13x and the metal-organic framework, HKUST-1, the CO2 adsorption capacity for the hydrophobic polymer is hardly affected by the adsorption of water vapor. The polymer is even stable to boiling in concentrated acid for extended periods, a property that is matched by few microporous adsorbents. The polymer adsorbs CO2 in a different way from rigid materials by physical swelling, much as a sponge adsorbs water. This gives rise to a higher CO2 capacities and much better CO2 selectivity than for other water-tolerant, nonswellable frameworks, such as activated carbon and ZIF-8. The polymer has superior function as a selective gas adsorbent, even though its constituent monomers are very simple organic feedstocks, as would be required for materials preparation on the large industrial scales required for carbon capture.

Combining ionic liquids and supercritical fluids: in situ ATR-IR study of CO2 dissolved in two ionic liquids at high pressures

An in situ ATR (attenuated total reflectance)-IR study of CO2 dissolved in two ionic liquids at high pressures has demonstrated the effects of the anionic species of the ionic liquids on the molecular state of the dissolved CO2.

Chemical Imaging of Live Cancer Cells in the Natural Aqueous Environment

Chemical imaging with Fourier transform infrared (FT-IR) spectroscopy allows the visualization of the distribution of chemical components in cells without the need for labels or added dyes. However, obtaining such images of living cells is difficult because of the strong absorption of water in the mid-infrared region. We report the use of attenuated total reflection (ATR) FT-IR spectroscopic imaging to study live human cancer cells in an aqueous environment, on a single cell level. Two complementary approaches have been used, providing flexibility with field of view and spatial resolution: (1) micro-ATR FT-IR imaging using a microscope objective with a Ge crystal, and (2) single-reflection diamond ATR-FT-IR imaging. Using both approaches, the ATR-FT-IR spectroscopic signatures allow the differentiation between several cellular organelles, e.g., the nucleus and the endoplasmic reticulum (ER). The overall cell shape can be defined by the distribution of the amide II band in the measured image, while the DNA-rich nucleus and glycogen-rich ER could be imaged using the spectral bands at 1084 cm−1 and 1023 cm−1, respectively. We also demonstrate the potential of ATR-FT-IR spectroscopic imaging for unraveling the details of the dynamics of biological processes, which are not accessible from cell ensemble studies, with high molecular specificity and satisfactory spatial resolution.

Membrane transport of hydrocortisone acetate from supersaturated solutions; the role of polymers

Permeation of hydrocortisone acetate (HA) from supersaturated solutions was studied across a model silicone membrane. Supersaturated solutions were prepared using the cosolvent technique with propylene glycol and water (or aqueous polymer solutions) as the cosolvents. In the absence of the polymer, the flux of HA was similar at all degrees of saturation and was not significantly different from the value obtained for a saturated solution. Flux enhancement, as a result of supersaturation, was observed with all the polymers. The flux increased with increasing polymer concentration, reached a maximum and decreased at higher polymer percentages. The amount of polymer required for maximum enhancement differed for each polymer. The decrease of flux at high polymer concentrations is attributed to changes in microviscosity and a marginal increase in solubility. The infrared spectroscopic and differential scanning calorimetry data suggest that HA-polymer interactions occurred through hydrogen bonding thus explaining the proposed mechanism of the anti-nucleant properties of the polymers.