Application of IR spectroscopy in the analysis of the woody-fibrous mass in the process of hydrolysis

The possibility has been shown of using IR spectroscopy in the investigation of the changes in the polysaccharide component of wood in the process of acid hydrolysis. The method of determining the relative optical density (ROD) was used for the quantitative evaluation of the changes in the functional groups of the lignocellulose.Deceased.Siberian Scientific Research Institute of Cellulose and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 683–687, September–October, 1990.     

Microscopy in the studies of polymer biodegradation

The goal of the paper is to overview different possibilities of microscopy, which can be helpful in estimating some of the changes undergoing in the materials exposed to the action of micro-organisms. The types of microscopic techniques and methods discussed in the paper are; optical transmission microscopy (OTM), optical transmission microscopy with polarised light (OPTM), optical reflected microscopy (ORM), optical reflected microscopy with polarised light (OPRM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The above methods allow to follow the changes of the surface view, the changes inside the polymer and the changes in birefringence (in the case of semi-crystalline polymers). The results can be compared with other techniques used for monitoring of polymer biodegradation or biostability. The examples from author's studies on different types of polyurethanes and the blends of polyethylene with starch are also described in the paper.     

Unexpected photolysis of the sunscreen octinoxate in the presence of the sunscreen avobenzone

A major concern raised about photostability studies of sunscreen products is that the photodegradation of sunscreens does not readily translate into changes in product performance. This study examines the correlation between photochemical degradation of sunscreen agents and changes in protection provided by sunscreen films. Films of a commercial sunscreen product containing avobenzone, oxybenzone and octinoxate were irradiated using a fluorescent UV-A phototherapy lamp with additional UV-B blocking filter. Periodically, during irradiation the transmittances of the films were measured and samples collected for chemical analysis of the sunscreen agents using high-performance liquid chromatography techniques. The results show that UV-induced changes in UV transmittance of sunscreen films correlate with changes in concentration of sunscreen agents. In a parallel experiment, we also irradiated a thin film of the same product in the cavity of an electron spin resonance (ESR) spectrometer. We report the concomitant photolysis of avobenzone and octinoxate that predominates over expected E/Z photoisomerization and that irradiation of a film of this product produced free radicals detected by ESR spectroscopy that persisted even after exposure had ended.     

Pressure effects on the Raman spectra of proteins: Pressure-induced changes in the conformation of lysozyme in aqueous solutions

The Raman spectrum of pressure-denatured lysozyme in aqueous solution is reported for the first time. Only minor changes occur up to 3.6 kbar. At 5.5 kbar irreversible denaturation and precipitation occurs. The results provide new interpretations for other experimental findings on pressure-induced changes in lysozyme.     

液态水几何构型的分子动力学模拟

利用ＭＣＹＬ势对液态水进行分子动力学模拟，以探求近程和远程相互作用及液体的有序结构对水分子几何构型的影响，并确定对液态中水分子几何构型起作用的主要范围。模拟给出的液态水中原子对径向分布函数和水分子键长键角的变化与实验值能较好地符合。研究结果表明，液态水分子几何构型除与氢键的形成有关外，还与液体的近程有序结构有很大关系。键长的变化对这种近程有序结构虽不敏感，但键角的变化则对此非常灵敏。液态中第二水合     

Change in the rate of decomposition of dioxetanes in sulfolane solutions in the transition from the liquid to the solid phase

Conclusions It has been established that the rate of decompostion of dioxetanes changes in in sulfolane solutions on transition from the liquid to the solid phase, which is explained in terms of structural changes of the molecular complexes dioxetane-sulfolane in the solid phase of the solvent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2238–2243, October, 1988.     

Ultrasonic characterization of the kinetics of water sorption in hydrogels

A complex mechanism characterizes the water uptake kinetics in hydrogels, as a consequence of the strong structural changes occurring in the material during the sorption process. Water acts as a plasticizer, reducing the glass transition temperature of the polymer below the sorption temperature and determining a glass transition in the polymer. In this study the changes in the ultrasonic attenuation and velocity in semicrystalline Poly-vinyl-alcohol (PVA) hydrogel films during water sorption are measured by a pulse-echo system. The ultrasonic wave propagation is applied to monitor the position of the swollen/unswollen fronts and to the measurement of velocity and attenuation. The structural changes in PVA hydrogels, monitored by Wide Angle X-ray Diffractometry (WAXD), performed during the sorption process, are correlated with the ultrasonic data.     

Effect of the increase in temperature on the evolution of the physical and chemical structure of vitrinite

The effect of the progressive increase in temperature (off-line pyrolysis in an open-medium system) on a monomaceralic coal (low rank and pure vitrinite) has been studied on the basis of changes in its chemical and physical structure. The properties of the solid residues and liquid effluents obtained were studied using a wide range of petrographic and geochemical techniques. Results support the validity of this pyrolysis method for following the physico–chemical processes that occur in vitrinite of bituminous coal rank. Of special interest is the information concerning the control of the structure on the vitrinite reflectance parameter in the bituminization stage. The evolution of properties and changes occurring at this stage show that the increase in vitrinite reflectance is strongly related and depends on changes in the chemical structure of this maceral during heating rather than on changes in elemental composition. However, any relationship between reflectance and chemical properties needs to be established empirically. The mechanism during heating consists of a complex mixture of depolymerization and condensation reactions with the progressive homogenisation of the botanical structure of the vitrinite. Moreover, pyrolysis conditions lead to a rapid and massive expulsion of the thermally generated products, causing a significant decrease in the H/C atomic ratio and higher thermostability of the solid residues. The enhancement of cross-linking with the formation of C–O–C bridges, which have high activation energy also contributes to an increase in thermal stability. Results obtained from the production and expulsion of oil suggest that this method is suitable for providing an estimation of the amount of hydrocarbons that might be produced and migrate from coals of similar rank. This is of special interest for coals with significant petroligenous potential or for coals that are gas-prone, depending on their composition and rank.     

Comparison of the water change characteristics between the formation and dissociation of methane hydrate and the freezing and thawing of ice in sand

Hydrate formation and dissociation processes are always accompanied by water migration in porous media, which is similar to the ice. In our study, a novel pF-meter sensor which could detect the changes of water content inside sand was first applied to hydrate formation and dissociation processes. It also can study the water change characteristics in the core scale of a partially saturated silica sand sample and compare the differences of water changes between the processes of formation and dissociation of methane hydrate and freezing and thawing of ice. The experimental results showed that the water changes in the processes of formation and dissociation of methane hydrate were basically similar to that of the freezing and thawing of ice in sand. When methane hydrate or ice was formed, water changes showed the decrease in water content on the whole and the pF values rose following the formation processes. However, there were very obvious differences between the ice thawing and hydrate dissociation.     

醇系溶剂中冠醚与碱金属离子的配位反应

The enthalpy changes, entropy changes and equilibrium constants of coordination reactions of 18-crown-6 with the alkali ions Na+ and K+ at 298.15K were measured by using RD-496 microcalorimeter with methanol, ethanol, n-propanol and n-butanol as solvents respectively. The results indicated that the enthalpy changes △rHm, entropy changes △rSm, and the stability of the complexes are closely related with the polarity of the solvents, and the order of the stability is ethanol>methanol>n-propanol>n-butanol>H2O for the same complex in the solvents investigated. The stability order was reasonably explained by relating the stability constants of the complexes with the dielectric constants of these solvents, and by using the model of solvated-desolvated ions and ion pair in the coordination reactions.     

Changes in the isotropic shielding of the 17O nucleus upon torsion in terminal oxygen systems: a computational study on their origin

We are presenting a computational study on the isotropic shielding, charge, and orbital contributions to the shielding of oxygen in benzaldehydes (Ar-CHO), nitrobenzenes (Ar-NO2), phenyl isocyanates (Ar-NCO), anilides (Ar-NHCOCH3), and N-sulfinylamines (Ar-NSO). In particular, changes upon ortho substitution of the aromatic ring and upon torsion of the unsubstituted parent molecules are examined. The experimentally observed changes in (17)O chemical shift, be they upfield or downfield, upon substitution by ortho-alkyl groups are reproduced well by the calculations. Relaxed torsional scans of the parent systems reveal that (a) charges change as expected from resonance arguments and (b) changes in isotropic shielding are monotonic and in line with changes upon substitution, with N-sulfinylaniline as an exception. In general, the changes in isotropic shieldings are explained in terms of changes in molecular orbitals, their energies, and relative alignments, whose mixing is magnetically active. Thus, for example, the observed deshielding of (17)O upon methyl substitution and upon torsion of benzaldehyde is mainly caused by a contribution from the pi-type oxygen lone pair, yet how these contributions change is fundamentally different. As a consequence, the experimentally observed downfield shift upon methyl substitution cannot be interpreted to imply a change in torsion angle between the phenyl ring and the aldehyde group. For N-sulfinylaniline, the consecutive downfield shifts upon methyl and tert-butyl substitution and the associated changes in torsion angle are in contrast to the 45 degrees maximum in isotropic shielding that is determined from a relaxed torsional scan.     

Determination of the temperature dependence of spherulite growth rate in low-density polyethylene using the small-angle light scattering technique

Small-angle light scattering technique has been used to record changes in spherulite size during non-isothermal crystallization of low-density polyethylene under different cooling conditions. From these changes, the spherulite growth rates at various temperatures in the range 72–91° have been determined. The results are discussed on the basis of the Hoffman Lauritzen theory.     

Use of computerized pattern recognition in the analysis of stress induced changes in coffee aroma

The aim of the study was to evaluate changes in the aroma of coffee that has been exposed to heat for some time. Coffee grinds were extracted with water. The coffee was kept hot and sampled periodically using a continuous gas phase extraction method. Gas chromatography/mass spectrometry was used to follow changes in chromatographic profiles. Data were subjected to pattern recognition. About 20 substances were found that significantly changed when exposed to heat.     

An in situ second harmonic generation study of the electrochemical oxidation of silicon in fluoride media

The electrochemical oxidation of p-type Si in fluoride solutions has been studied by in situ second harmonic generation (SHG) with the SHG signal being recorded simultaneously with the cyclic voltammogram. The SHG signal is shown to change in tandem with the electrochemical response enabling the identification of transition points between different surface conditions such as hydrogen-terminated, hydrated oxide and oxide. Interpretation of the changes in SHG suggests that the initial response is due to the electric field-induced second harmonic (EFISH) due to the electric field gradient at the interface. It then becomes dominated by the variation in the resonant surface non-linear susceptibility as the changes in local bonding affect the response. SHG signals display a much greater sensitivity to surface conditions than the voltammetric response and allow the real-time identification of the potentials at which significant changes take place in the state of the surface.     

On the theory of solute solubility in mixed solvents

A series of equations are developed for the study of the effects of cosolvents on the solubility of a solute in mixed solutions where the solute displays a finite solubility. The equations differ depending on the scale used for the solute (and cosolvent) concentrations. The expressions use Kirkwood-Buff integrals to relate the changes in solubility to changes in the local solution composition around the solute and can be applied to study any type of ternary system including electrolyte cosolvents. The expressions provided here differ from previous approaches because of the use of a semi-open ensemble and the extension to finite solute solubilities.     

Palaeo-variations in the atmospheric concentration of carbon dioxide and the relationship to extinctions

It has been established from geological studies that change in the atmospheric content of carbon dioxide gas commenced about one hundred million years ago. The likely origin of this change is advanced as being the onset of the Brewer circulation caused by the rise in terrain induced by tectonic plate movement. It is demonstrated that tectonic plate movement can be affected by impacts from external bodies which penetrate the crust of the Earth. The consequences of the change in atmospheric concentration of carbon dioxide are proposed as first, extinctions and reductions in animal numbers, including primates, as a result of changes in body chemistry of these animals and second, a change in the rate of weathering of rocks giving rise to changes in the availability of chemicals such as calcium and potassium which are essential for plant and animal life. This latter change contributing to the extinctions and reductions in animal numbers. It is shown that the change in weathering can account for the rise to dominance of angiosperm plants. It is concluded that there were several simultaneous evolutionary environments on Earth which were a function of altitude which gave rise to a vertical variation in atmospheric content of carbon dioxide. This variation disappeared with rise of terrain and the onset of the Brewer circulation. Such changes are advanced and being much more important than any changes in temperature caused by greenhouse effects since the disappearance of atmospheric variations in carbon dioxide allowed animal migration. It is demonstrated that the conditions of extinction could be reintroduced by human activities.     

Indications for chlororespiration in relation to light regime in the marine diatom Thalassiosira weissflogii

The marine diatom Thalassiosira weissflogii was cultured under a light regime simulating the daily rise and fall of the sun. The light regime caused a daily cycle in non-photochemical quenching. Remarkable were the changes in fluorescence directly after a light-to-dark transition that occurred in addition to the changes induced by non-photochemical quenching. A transient non-photochemical reduction of PQ and of Q(A) was indicated by a transient increase in apparent F(o) and by changes in the shape of the fluorescence induction curve. The observed changes developed approximately the first 100-120 s after a light-to-dark transition and could be reversed by the application of far-red illumination. Chlororespiration is thought to cause the reduction of PQ and, as the PQ-pool is in equilibrium with Q(A), also a reduction of Q(A). The function and ecological relevance of chlororespiration are discussed.     

Determination by X-ray absorption spectroscopy of the Fe-Fe separation in the oxidized form of the hydroxylase of methane monooxygenase alone and in the presence of MMOD

The diiron active site in the hydroxylase of Methylococcus capsulatus (Bath) methane monooxygenase (MMOH) has been studied in the oxidized form by X-ray absorption spectroscopy (XAS). Previous investigations by XAS and X-ray crystallography have identified two different distances (3.0 and 3.4 angstroms) between the two Fe atoms in the dinuclear site. The present study has employed a systematic extended X-ray absorption fine structure (EXAFS) fitting methodology, utilizing known and simulated active site and relevant model structures, to determine unambiguously the Fe-Fe separation in the oxidized form of MMOH. Consistent and unique fits were only possible for an Fe-Fe distance of 3.0 angstroms. This methodology was then applied to study potential changes in the active site local structure in the presence of MMOD, a protein of unknown function in multicomponent MMO. Fe K-edge and EXAFS analyses revealed negligible changes in the diiron site electronic and geometric structure upon addition of MMOD to oxidized MMOH.