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The use of anti-relaxation coatings in alkali vapor cells yields substantial performance improvements compared to a bare glass surface by reducing the probability of spin relaxation in wall collisions by several orders of magnitude. Some of the most effective anti-relaxation coating materials are alpha-olefins, which (as in the case of more traditional paraffin coatings) must undergo a curing period after cell manufacturing in order to achieve the desired behavior. Until now, however, it has been unclear what physicochemical processes occur during cell curing, and how they may affect relevant cell properties. We present the results of nondestructive Raman-spectroscopy and magnetic-resonance investigations of the influence of alkali metal vapor (Cs or K) on an alpha-olefin, 1-nonadecene coating the inner surface of a glass cell. It was found that during the curing process, the alkali metal catalyzes migration of the carbon-carbon double bond, yielding a mixture of cis- and trans-2-nonadecene.

Recycled carbon fibers (rCF) represent an inexpensive alternative to virgin carbon fibers (CF) but the mechanical improvement brought by rCF to polymer composites is noticeably lower than that from CF. In this article we evaluate two methods of coating rCF by single walled carbon nanotubes (SWCNTs), wet and dry, and demonstrate that extremely low concentrations of SWCNTs, ∼0.03%, are sufficient to measurably improve the strength (by 16%), modulus (by 38%), and Izod impact strength (by 52%) of thermoplastic crystalline polyamide polyxylylene adipamide (MXD6) with 30% rCF. The dry method with grinding of rCF and SWCNTs works better than the wet (dip coating) method and the rCF with residual epoxy is better than purified by pyrolysis rCF. We link this improvement of the mechanical properties to the enhanced crystallization rate caused by SWCNTs, which is observed in differential scanning calorimetry (DSC). Graphical Abstract [ABSTRACT FROM AUTHOR]

Chemical investigation of the hydnoid fungus Sarcodontia setosa resulted in the isolation of five compounds, including two new sarcodontic acid derivatives - setosic acid ( 1 ) and 7,8-dehydrohomosarcodontic acid ( 2 ) along with three known benzoquinone pigments - sarcodontic acid ( 3 ), 4,5-dehydrosarcodontic acid ( 4 ) and dihydrosarcodontic acid ( 5 ). The structures were elucidated using spectroscopic methods (UV, NMR and HR-ESIMS). The biosynthetic relationship of the isolated compounds is proposed and discussed. Antibacterial activity screening of compounds 1 - 5 against ESKAPE bacterial strains in vitro with zones of inhibition was performed and MIC values were established for the most active compounds ( 3 and 5 ).

Two previously undescribed isoquinoline alkaloids, bracteatinine (1) and isogroenlandicine (2), together with four known alkaloids - coptisine (3), dehydrocorydaline (4), palmatine (5) and jatrorrhizine (6) were isolated from the aerial parts of Corydalis bracteata (Steph. Ex. Willd.) Pers. The structures of the compounds were elucidated using 1D and 2D NMR data along with HRESI-MS. The isolated new compounds bracteatinine and isogroenlandicine are close structural derivatives and isomers of corgoine and groenlandicine, respectively. Bracteatinine is also notable, being a representative of the rare 2-benzylisoquinoline alkaloids. Many natural products isolated from different plants are used as adjuvants, in addition to standard chemotherapy, in treatment of different cancers. Cancer-associated thrombosis remains a common complication and leading cause of mortality for cancer patients. Because platelets play the key role in thrombotic complications, we investigated effects of the isolated alkaloids 1-6 on platelet reactivity and showed that they did not significantly affect platelet function., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Ethnopharmacological Relevance: Ziziphora clinopodioides subsp. bungeana (Juz.) Rech.f. is a subshrub that is widely distributed in China, Kazakhstan, Kyrgyzstan, Mongolia, Russia, Tajikistan, Turkmenistan, and Uzbekistan. The species is used in traditional medicine for the relief of symptoms connected to cardiovascular diseases like coronary heart disease or hypertension., Aim of the Study: was to validate traditional use of Z. clinopodioides subsp. bungeana for the treatment of coronary hearth diseases using in vivo models and to find active compounds responsible for the activity., Materials and Methods: Multiple extracts were obtained from the aerial parts of Z. clinopodioides subsp. bungeana using maceration, liquid-liquid extraction, CO2 extraction and ultrasound-assisted extraction. Preliminary screening studies for the evaluation of the efficacy of Z. clinopodioides subsp. bungeana extracts on the model of hemic hypoxia were performed. The most effective samples were selected and included in the main study. Stage 2 of the study evaluated the cardiotropic activity of the selected extracts on a model of chronic heart failure. Preparations were administered to animals intragastrically once a day for 28 days. For the isolation of individual compounds plant material was extracted with 96% ethanol. The obtained crude extract was sequentially extracted with n-hexane and dichloromethane and separated by chromatography on a Diaion HP-20 column. The obtained fractions were further subjected to Sephadex LH-20 column chromatography and eluted isocratically with 96% ethanol (EtOH) to yield subfractions, which were further separated by preparative HPLC to obtain 13 individual compounds., Results: Extracts obtained from Ziziphora clinopodioides subsp. bungeana (Juz.) Rech.f. herb were subjected to pharmacological screening for the evaluation of their efficacy on hemic hypoxia. Based on the obtained results, out of the sixteen tested extracts two (AR and US 60%) were selected for further evaluation of their cardiotropic activity. Modeling of chronic heart failure was carried out in accordance with the following stages: 1) anesthesia with chloral hydrate at a dose of 450 mg/kg, intraperitoneally, 2) artificial ventilation of the lungs, 3) thoracotomy, 4) modeling of permanent ischemic or ischemic-reperfusion damage. Both extracts effected the indicators of contraction and output, comparable to the reference drug - Monopril. Based on the extraction methods used to obtain RAF and US60 and data from the literature, it can be assumed that they contain compounds with medium polarity, including polyphenols and terpenoids. At the next stage three previously undescribed monoterpenoid derivatives - Ziziphoric acid (1), Ziziphoroside D (2) and 6'-malonylziziphoroside A (3), along with two previously described megastigmane glucosides - blumenol C glucoside (4), blumenol C 9-O-(6'-O-malonyl-beta-D-glucopyranoside (5) and two previously described monoterpenoids 7a-hydroxymintlactone (6), 7-hydroxypiperitone (7) together with six polyphenols - pinocembrine-7-O-rutinoside (8), chrysine-7-O-rutinoside (9), acacetin-7-O-rutinoside (10), luteolin-7-O-rutinoside (11), rutin (12) and rosmarinic acid (13) were isolated from Z. clinopodioides subsp. bungeana extracts., Conclusion: Our results support the traditional use of Z. clinopodioides subsp. bungeana for the treatment of coronary diseases. As a result of Z. clinopodioides subsp. bungeana extracts screening in vivo, two extracts were selected as potential cardiotropic agents. Phytochemical analysis of the plant material led to the isolation of five terpenoid derivatives, two megastigmane glycosides, five flavonoids and one cinnamic acid derivative, which could be responsible for the reported biological activity. Future experiments are required to understand the mechanisms of action for the isolated compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Aqueous dispersions of single-walled carbon nanotubes (SWCNTs) with a surfactant were studied by using a combination of differential sedimentation and dynamic light scattering methods. When applied to elongated particles like SWCNTs, the differential sedimentation method makes it possible to measure their diameters in dispersions, while the dynamic light scattering method allows to measure their lengths. Both methods have logarithmic dependence on the ratio between the length and diameter of the particles, and their simultaneous use improves the accuracy of measuring particles' dimensions. It was shown that sonication of dispersions leads not only to unbundling of agglomerates into individual nanotubes but also to a decrease in their lengths and the appearance of new defects detectable in increasing the D/G ratio in the Raman spectra. Unbundling into individual nanotubes occurs after exposure to 1 kWh/L energy density, and the single nanotube diameter with SDBS is ca. 3.3 nm larger than that of the naked nanotubes. Conductivity of thin SWCNT films made out of individual nanotubes demonstrates a power law dependence with the exponent close to the theoretical one for rigid rods., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Chemical investigation of the polypore fungus Fistulina hepatica resulted in the isolation of five compounds, including four new polyacetylenic fatty acid derivatives - isocinnatriacetin B (1), isocinnatriacetin A (2), cinna-triacetin C (3) and ethylcinnatriacetin A (4) together with one known polyacetylene fatty acid derivative - cinnatriacetin A (5). The structures were elucidated using spectroscopic methods (UV, NMR, HR-ESIMS) along with comparison to literature data. Antibacterial activity screening of compounds 1-5 against ESKAPE bacterial strains in vitro with zones of inhibition (ZOI) was performed and MIC values were established for the most active compounds (3 and 4). Together with that morphological and growth parameters under solid-phase cultivation were also researched.

Two undescribed ( 1 - 2) and five known cyclic diarylheptanoids ( 3 - 7 ) were isolated from the false heartwood of white birch ( Betula pubescens Ehrh.). All structures were elucidated through extensive 1D and 2D NMR experiments and HR-ESI-MS data, along with comparison of their spectroscopic data with those reported in the literature. The two new cyclic diarylheptanoids are betuladiol ( 1 ) and betulondiol ( 2 ). Extracts from false heartwood were evaluated for their antimicrobial activity against Klebsiella pneumoniae , Escherichia coli , Proteus mirabilis, Staphylococcus aureus and Cutibacterium acnes together with their antifungal activity against Candida albicans and Candida glabrata .

A new dihydrochalcone, 2',4'-dimethoxydihydrochalcone ( 1 ), together with 7 known compounds, 2',4'-dihydroxydihydrochalcone ( 2 ), 2'-hydroxy-4'-methoxydihydrochalcone ( 3 ), 2'-hydroxy-4'-methoxychalcone ( 4 ), 1-(3,5-dihydroxy-4-methoxyphenyl)-2-(3-hydroxyphenyl) ethane ( 5 ), 2,3,4,7-tetramethoxy-9,10-dihydrophenanthrene ( 6 ), 5-hydroxy-2,3,4-trimethoxy-9,10-dihydrophenanthrene ( 7 ) and 5,7-dihydroxy-6,8-dimethyl flavanone ( 8 ) were isolated from the shoots of Empetrum nigrum L. The structures of these compounds were elucidated using 1D and 2D NMR experiments along with HR-ESI-MS. Compound 6 is reported for the genus Empetrum for the first time.[Formula: see text].

Background and Objective: A novel dual-stage method for active laser drug delivery (DSLADD) in the treatment of nail diseases is being presented. This method includes sequentially performed microporation of the nail with submillisecond pulses of Er:YLF laser radiation through a layer of an aqueous solution of drug deposited on the nail surface (Stage 1) and exposure this layer to the same laser radiation to deliver drug under the nail plate (Stage 2). The delivery of methylene blue (MB) as one of the possible drugs in the treatment of nail diseases is investigated. The influence of the thickness of the MB layer, as well as the energy and number of applied laser pulses, on the rate of active laser delivery is discussed. To illustrate the possible effect of delivery on the drug delivered, special attention is paid to the deformation of the extinction spectrum of MB solution after laser irradiation., Study Design/materials and Methods: Diode-pumped Er:YLF laser was used for DSLADD. The process of DSLADD under the nail plate was investigated using digital video microscopy. For different values of the thickness of MB solution layer applied to the nail plate and the energy of laser pulses, the number of laser pulses required to create a single through a microchannel in the nail plate and the number of laser pulses required to deliver the solution to the ventral side of the nail plate after its microporation were registered. The mass and the dose of MB solution penetrated under the nail plate, and the rate of MB solution delivery through a single microchannel was determined. Investigation of the influence of Er:YLF laser radiation parameters on the extinction spectrum of the drug was performed using a fiber spectrometer. The extinction spectra of the 0.001% aqueous solution of MB were recorded before and after exposure to a different number of Er:YLF laser pulses with the energy of 1-4 mJ., Results: It was found that the minimum number of laser pulses required for active Er:YLF laser drug delivery under the nail corresponds to the MB layer thickness of 100 μm and the laser pulse energy of 4 mJ. It is shown that in this case, the rate of active laser delivery of MB solution reaches 0.26 ± 0.03 mg/pulse. The radiation of the Er:YLF laser affects the shape of the extinction spectrum of the aqueous solution of MВ, which is associated with the transition of the dye from the monomeric to dimeric state. Depending on the laser pulse energy, the fraction of a certain conformational state in the aqueous MB solution can decrease or increase, stimulating a possible change in its photodynamic and antiseptic activity., Conclusion: For the first time, a novel DSLADD through the nail has been described and investigated in vitro. It was demonstrated that at Er:YLF laser pulse repetition rate of f = 30 Hz, microporation of the nail plate and drug delivery through a single microchannel will be about 1.5 s. Lasers Surg. Med. © 2021 Wiley Periodicals LLC., (© 2021 Wiley Periodicals LLC.)

Proton exchange membranes are at the heart of various technologies utilizing electrochemical storage of intermittent energy sources and powering electrical devices. Current state of the art membranes are based on perfluorosulfonic acid, introduced more than a half century ago. Low specificity to protons accompanied by permeance by other species is one of the main impediments for various promising applications in green technologies in an energy sustainable economy. Here we present composite membranes that are exclusively proton selective and do not allow crossover of any ionic or molecular species other than protons. Membranes have high proton conductivity and exceptional mechanical and chemical stability and thus may significantly improve performance of hydrogen-based technologies such as electrolyzers, various kinds of fuel cells, and flow batteries in the future.

Inspired by recent reports on possible proton conductance through graphene, we have investigated the behavior of pristine graphene and defect engineered graphene membranes for ionic conductance and selectivity with the goal of evaluating a possibility of its application as a proton selective membrane. The averaged conductance for pristine chemical vapor deposited (CVD) graphene at pH1 is ∼4 mS/cm 2 but varies strongly due to contributions from the unavoidable defects in our CVD graphene. From the variations in the conductance with electrolyte strength and pH, we can conclude that pristine graphene is fairly selective and the conductance is mainly due to protons. Engineering of the defects with ion beam (He + , Ga + ) irradiation and plasma (N 2 and H 2 ) treatment showed improved areal conductance with high proton selectivity mostly for He-ion beam and H 2 plasma treatments, which agrees with primarily vacancy-free type of defects produced in these cases confirmed by Raman analysis.

Active Er-laser drug delivery under the nail plate using a drug-impregnated gel containing liquid methylene blue clusters is demonstrated for the first time. The effect of the agar-agar concentration in the gel and the gel plate thickness on the number of Er:YLF-laser pulses required for formation of a through microhole in the gel and in the nail plate with subsequent active drug delivery is discussed. The influence of the laser pulse energy, the gel plate thickness, and the external pressure applied to the gel on the rate of delivery of methylene blue under the nail plate through a single microhole in it is investigated. It is shown that with a laser pulse energy of 4.0 ± 0.1 mJ, the delivery rate can reach 0.024 ± 0.004 mg/pulse., Competing Interests: The authors declare that there are no conflicts of interest related to this article.

In the current study, we evaluated the solubility of a number of organometallic species and showed that it is noticeably improved in diiodomethane when compared to other haloalkane solvents. The better solvation properties of CH 2 I 2 were associated with the substantially better σ-hole-donating ability of this solvent, which results in the formation of uniquely strong solvent-(metal complex) halogen bonding. The strength of the halogen bonding is attenuated by the introduction of additional halogen atoms in the organometallic species owing to the competitive formation of more favourable intermolecular complex-complex halogen bonding. The exceptional solvation properties of diiodomethane and its inertness towards organometallic species make this solvent a good candidate for NMR studies, in particular, for the acquisition of spectra of insensitive spins., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

There is a demand for the manufacture of two-dimensional (2D) materials with high-quality single crystals of large size. Usually, epitaxial growth is considered the method of choice 1 in preparing single-crystalline thin films, but it requires single-crystal substrates for deposition. Here we present a different approach and report the synthesis of single-crystal-like monolayer graphene films on polycrystalline substrates. The technological realization of the proposed method resembles the Czochralski process and is based on the evolutionary selection 2 approach, which is now realized in 2D geometry. The method relies on 'self-selection' of the fastest-growing domain orientation, which eventually overwhelms the slower-growing domains and yields a single-crystal continuous 2D film. Here we have used it to synthesize foot-long graphene films at rates up to 2.5 cm h -1 that possess the quality of a single crystal. We anticipate that the proposed approach could be readily adopted for the synthesis of other 2D materials and heterostructures.

Vaska-type complexes, i.e. trans-[RhX(CO)(PPh3)2] (X is a halogen or pseudohalogen), undergo a range of reactions and exhibit considerable catalytic activity. The electron density on the Rh(I) atom in these complexes plays an important role in their reactivity. Many cyanotrihydridoborate (BH3CN(-)) complexes of Group 6-8 transition metals have been synthesized and structurally characterized, an exception being the rhodium(I) complex. Carbonyl(cyanotrihydridoborato-κN)bis(triphenylphosphine-κP)rhodium(I), [Rh(NCBH3)(CO)(C18H15P)2], was prepared by the metathesis reaction of sodium cyanotrihydridoborate with trans-[RhCl(CO)(PPh3)2], and was characterized by single-crystal X-ray diffraction analysis and IR, (1)H, (13)C and (11)B NMR spectroscopy. The X-ray diffraction data indicate that the cyanotrihydridoborate ligand coordinates to the Rh(I) atom through the N atom in a trans position with respect to the carbonyl ligand; this was also confirmed by the IR and NMR data. The carbonyl stretching frequency ν(CO) and the carbonyl carbon (1)JC-Rh and (1)JC-P coupling constants of the Cipso atoms of the triphenylphosphine groups reflect the diminished electron density on the central Rh(I) atom compared to the parent trans-[RhCl(CO)(PPh3)2] complex.

A simple sensor for viral particles based on ionic conductivity through anodized alumina membranes was demonstrated using MS2 bacteriophage as an example. A facile two-point measuring scheme is geared toward realization using a computer's sound card input/output capabilities suitable for a fast and inexpensive point of care testing. The lowest detection concentration down to ~7 pfu/mL and a large dynamic range up to ~2000 pfu/mL were obtained due to physical optimization that included proper length and diameter for the pores, removing the oxide layer at the electrode, as well as the chemical optimization of covalent binding of antibodies to the pore's walls.

The noncovalent intermolecular interactions (π-π stacking, metallophilic bonding) of the cyclometalated complexes [Pt(NCN)L](+)X(-) (NCN = dipyridylbenzene, L = pyridine (1), acetonitrile (2)) are determined by the steric properties of the ancillary ligands L in the solid state and in solution, while the nature of the counterion X(-) (X(-) = PF6(-), ClO4(-), CF3SO3(-)) affects the molecular arrangement of 2·X in the crystal medium. According to the variable-temperature X-ray diffraction measurements, the extensive Pt···Pt interactions and π-stacking in 2·X are significantly temperature-dependent. The variable concentration (1)H and diffusion coefficients NMR measurements reveal that 2·X exists in the monomeric form in dilute solutions at 298 K, while upon increase in concentration [Pt(NCN)(NCMe)](+) cations undergo the formation of the ground-state oligomeric aggregates with an average aggregation number of ∼3. The photoluminescent characteristics of 1 and 2·X are largely determined by the intermolecular aggregation. For the discrete molecules the emission properties are assigned to metal perturbed IL charge transfer mixed with some MLCT contribution. In the case of oligomers 2·X the luminescence is significantly red-shifted with respect to 1 and originates mainly from the (3)MMLCT excited states. The emission energies depend on the structural arrangement in the crystal and on the complex concentration in solution, variation of which allows for the modulation of the emission color from greenish to deep red. In the solid state the lability of the ligands L leads to vapor-induced reversible transformation 1 ↔ 2 that is accompanied by the molecular reorganization and, consequently, dramatic change of the photophysical properties. Time-dependent density functional theory calculations adequately support the models proposed for the rationalization of the experimental observations.

By creating nanoscale pores in a layer of graphene, it could be used as an effective separation membrane due to its chemical and mechanical stability, its flexibility and, most importantly, its one-atom thickness. Theoretical studies have indicated that the performance of such membranes should be superior to state-of-the-art polymer-based filtration membranes, and experimental studies have recently begun to explore their potential. Here, we show that single-layer porous graphene can be used as a desalination membrane. Nanometre-sized pores are created in a graphene monolayer using an oxygen plasma etching process, which allows the size of the pores to be tuned. The resulting membranes exhibit a salt rejection rate of nearly 100% and rapid water transport. In particular, water fluxes of up to 10(6) g m(-2) s(-1) at 40 °C were measured using pressure difference as a driving force, while water fluxes measured using osmotic pressure as a driving force did not exceed 70 g m(-2) s(-1) atm(-1).

Ten formally symmetric anionic OHO hydrogen bonded complexes, modeling Asp/Glu amino acid side chain interactions in nonaqueous environment (CDF(3)/CDF(2)Cl solution, 200-110 K) have been studied by (1)H, (2)H, and (13)C NMR spectroscopy, i.e. intermolecularly H-bonded homoconjugated anions of acetic, chloroacetic, dichloroacetic, trifluoroacetic, trimethylacetic, and isobutyric acids, and intramolecularly H-bonded hydrogen succinate, hydrogen rac-dimethylsuccinate, hydrogen maleate, and hydrogen phthalate. In particular, primary H/D isotope effects on the hydrogen bond proton signals as well as secondary H/D isotope effects on the (13)C signals of the carboxylic groups are reported and analyzed. We demonstrate that in most of the studied systems there is a degenerate proton tautomerism between O-H···O(-) and O(-)···H-O structures which is fast in the NMR time scale. The stronger is the proton donating ability of the acid, the shorter and more symmetric are the H-bonds in each tautomer of the homoconjugate. For the maleate and phthalate anions exhibiting intramolecular hydrogen bonds, evidence for symmetric single well potentials is obtained. We propose a correlation between H/D isotope effects on carboxylic carbon chemical shifts and the proton transfer coordinate, q(1) = ½(r(OH) - r(HO)), which allows us to estimate the desired OHO hydrogen bond geometries from the observed (13)C NMR parameters, taking into account the degenerate proton tautomerism.

Hydrophobicity is a fundamental property that is responsible for numerous physical and biophysical aspects of molecular interactions in water. Peculiar behavior is expected for water in the vicinity of hydrophobic structures, such as nanopores. Indeed, hydrophobic nanopores can be found in two distinct states, dry and wet, even though the latter is thermodynamically unstable. Transitions between these two states are kinetically hindered in long pores but can be much faster in shorter pores. As it is demonstrated for the first time in this paper, these transitions can be induced by applying a voltage across a membrane with a single hydrophobic nanopore. Such voltage-induced gating in single nanopores can be realized in a reversible manner through electrowetting of inner walls of the nanopores. The resulting I-V curves of such artificial hydrophobic nanopores mimic biological voltage-gated channels., (© 2011 American Chemical Society)

The (1)H and (13)C NMR spectra of 17 OHN hydrogen-bonded complexes formed by CH(3)(13)COOH(D) with 14 substituted pyridines, 2 amines, and N-methylimidazole have been measured in the temperature region between 110 and 150 K using CDF(3)/CDF(2)Cl mixture as solvent. The slow proton and hydrogen bond exchange regime was reached, and the H/D isotope effects on the (13)C chemical shifts of the carboxyl group were measured. In combination with the analysis of the corresponding (1)H chemical shifts, it was possible to distinguish between OHN hydrogen bonds exhibiting a single proton position and those exhibiting a fast proton tautomerism between molecular and zwitterionic forms. Using H-bond correlations, we relate the H/D isotope effects on the (13)C chemical shifts of the carboxyl group with the OHN hydrogen bond geometries.

(1)H, (2)H, (19)F and (15)N NMR spectra of a strongly hydrogen-bonded anionic cluster, CNHF(-), as an ion pair with a tetrabutylammonium cation dissolved in CDF(3)-CDF(2)Cl mixture were recorded in the slow exchange regime at temperatures down to 110 K. The fine structure due to spin-spin coupling of all nuclei involved in the hydrogen bridge was resolved. H/D isotope effects on the chemical shifts were measured. The results were compared with those obtained earlier for a similar anion, FHF(-), and interpreted via ab initio calculations of magnetic shielding as functions of internal vibrational coordinates, namely an anti-symmetric proton stretching and a doubly-degenerate bending. The values of primary and secondary isotope effects on NMR chemical shifts were estimated using a power expansion of the shielding surface as a function of vibrational coordinates. A positive primary isotope effect was explained as a result of the decrease of the hydron stretching amplitude upon deuteration. We show that the proton shielding surface has a minimum close to the equilibrium geometry of the CNHF(-) anion, leading to the positive primary H/D isotope effect in a rather asymmetric hydrogen bond. We conclude that caution should be used when making geometric estimations on the basis of NMR data, since the shapes of the shielding functions of the internal vibrational coordinates can be rather exclusive for each complex.

The consequences of photoexcitation of a platinum diimine bisacetylide complex and its triads with phenothiazine species (McGarrah, J. E.; Eisenberg, R. Inorg. Chem. 2003, 42, 4355-4365) were investigated by the photoinduced transient displacement current (PTDC) method, with the aim of understanding the role of solvent in defining the nature and extent of intratriad electron transfer. PTDC enables reports on the distance of charge separation in photoexcited states. Photoexcition of the triad, Pt(dbbpy)(CCC(6)H(4)CH(2)(PTZ))(2) (where dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine), leads to formation of the (3)MLCT excited state, which in CH(2)Cl(2) is intramolecularly quenched by PTZ to form a charge-separated (CS) state, Pt(dbbpy(*-))(CCC(6)H(4)CH(2)(PTZ) CCC(6)H(4)CH(2)(PTZ(*+)); the CS state features a dipole moment oriented in essentially the opposite direction to that of the ground state. In toluene the last step of charge separation is shut down. In THF these two transient states are equilibrated, approximately as a 1:1 mixture of (3)MLCT and CS states, causing a complex, but instructive, PTDC response. The PTDC response for Pt(dbbpy)(CCC(6)H(5))(2), on the other hand, is similar in all solvents and shows a negative signal corresponding to a long-lived, and comparatively nonpolar, (3)MLCT state. The ground-state dipole moment, mu(g), weakly increases with solvent polarity, from approximately 11.5 D in toluene to approximately 15.5 D in THF and CH(2)Cl(2).

Surface-assisted photoinduced transient displacement charge (SPTDC) technique was developed in order to study light-induced charge transfer in surface-bound molecules and applied to investigation of self-assembled monolayers of 7-diethylaminocoumarin and 2,4-dinitrophenylamine. The dipole moment change measured by SPTDC correlates reasonably well with that measured in solution by standard PTDC technique and with semiempirical calculations. Shortening of the excited-state lifetime of surface-immobilized coumarin due to stimulated emission was observed in both fluorescence and dipole measurements. The dipole signal decline in low-polarity solvents indicates the importance of dipole-dipole interaction that causes reorientation of molecules upon photoexcitation.

Surface-assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to an oxide surface in the atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of the gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to half of that for the collision rate.

Circadian rhythm of DNA synthesis, mitotic activity, and duration of mitosis in rat liver were studied on days 3, 7, and 12 of life. Age-associated differences in the rhythmic parameters of these characteristics were detected. Epidermal growth factor plays an important role in the formation of cell proliferation rhythm in the early postnatal ontogeny and in the formation of proliferative hepatocyte pool.

Circadian rhythms of DNA synthesis, mitotic activity, and duration of mitosis in rat liver were studied on postnatal days 3, 7, and 12. Some age-related peculiarities of these rhythms were revealed. Epidermal growth factor was found to play an important role in the formation of cell proliferation rhythm during the early postnatal ontogeny and in the regulation of the pool of proliferating hepatocytes.

In this paper, equations are proposed which relate various NMR parameters of OHN hydrogen-bonded pyridine-acid complexes to their bond valences which are in turn correlated with their hydrogen-bond geometries. As the valence bond model is strictly valid only for weak hydrogen bonds appropriate empirical correction factors are proposed which take into account anharmonic zero-point energy vibrations. The correction factors are different for OHN and ODN hydrogen bonds and depend on whether a double or a single well potential is realized in the strong hydrogen-bond regime. One correction factor was determined from the known experimental structure of a very strong OHN hydrogen bond between pentachlorophenol and 4-methylpyridine, determined by the neutron diffraction method. The remaining correction factors which allow one also to describe H/D isotope effects on the NMR parameters and geometries of OHN hydrogen bond were determined by analysing the NMR parameters of the series of protonated and deuterated pyridine- and collidine-acid complexes. The method may be used in the future to establish hydrogen-bond geometries in biologically relevant functional OHN hydrogen bonds.

1H, (2)H, and (13)C NMR spectra of enriched CH(3)(13)COOH acid without and in the presence of tetra-n-butylammonium acetate have been measured around 110 K using a liquefied Freon mixture CDF(3)/CDF(2)Cl as a solvent, as a function of the deuterium fraction in the mobile proton sites. For comparison, spectra were also taken of the adduct CH(3)(13)COOH.SbCl(5) 1 and of CH(2)Cl(13)COOH under similar conditions, as well as of CH(3)(13)COOH and CH(3)(13)COO(-) dissolved in H(2)O and D(2)O at low and high pH at 298 K. The low temperatures employed allowed us to detect several well-known and novel hydrogen-bonded complexes in the slow hydrogen bond exchange regime and to determine chemical shifts and coupling constants as well as H/D isotope effects on chemical shifts from the fine structure of the corresponding signals. The measurements show that self-association of both carboxylic acids in Freon solution gives rise exclusively to the formation of cyclic dimers 2 and 3 exhibiting a rapid degenerate double proton transfer. For the first time, a two-bond coupling of the type (2)J(CH(3)COOH) between a hydrogen-bonded proton and the carboxylic carbon has been observed, which is slightly smaller than half of the value observed for 1. In addition, the (1)H and (2)H chemical shifts of the HH, HD, and the DD isotopologues of 2 and 3 have been determined as well as the corresponding HH/HD/DD isotope effects on the (13)C chemical shifts. Similar "primary", "vicinal", and "secondary" isotope effects were observed for the novel 2:1 complex "dihydrogen triacetate" 5 between acetic acid and acetate. Another novel species is the 3:1 complex "trihydrogen tetraacetate" 6, which was also characterized by a complex degenerate combined hydrogen bond- and proton-transfer process. For comparison, the results obtained previously for hydrogen diacetate 4 and hydrogen maleate 7 are discussed. Using an improved (1)H chemical shift-hydrogen bond geometry correlation, the chemical shift data are converted into hydrogen bond geometries. They indicate cooperative hydrogen bonds in the cyclic dimers; i.e., widening of a given hydrogen bond by H/D substitution also widens the other coupled hydrogen bond. By contrast, the hydrogen bonds in 5 are anticooperative. The measurements show that ionization shifts the (13)C signal of the carboxyl group to low field when the group is immersed in water, but to high field when it is embedded in a polar aprotic environment. This finding allows us to understand the unusual ionization shift of aspartate groups in the HIV-pepstatin complex observed by Smith, R.; Brereton, I. M.; Chai, R. Y.; Kent, S. B. H. Nature Struct. Biol. 1996, 3, 946. It is demonstrated that the Freon solvents used in this study are better environments for model studies of amino acid interactions than aqueous or protic environments. Finally, a novel correlation of the hydrogen bond geometries with the H/D isotope effects on the (13)C chemical shifts of carboxylic acid groups is proposed, which allows one to estimate the hydrogen bond geometries and protonation states of these groups. It is shown that absence of such an isotope effect is not only compatible with an isolated carboxylate group but also with the presence of a short and strong hydrogen bond.

The low-temperature (1)H, (19)F, and (15)N NMR spectra of mixtures of collidine-(15)N (2,4,6-trimethylpyridine-(15)N, Col) with HF have been measured using CDF(3)/CDF(2)Cl as a solvent in the temperature range 94-170 K. Below 140 K, the slow proton and hydrogen bond exchange regime is reached where four hydrogen-bonded complexes between collidine and HF with the compositions 1:1, 2:3, 1:2, and 1:3 could be observed and assigned. For these complexes, chemical shifts and scalar coupling constants across the (19)F(1)H(19)F and (19)F(1)H(15)N hydrogen bridges have been measured which allowed us to determine the chemical composition of the complexes. The simplest complex, collidine hydrofluoride ColHF, is characterized at low temperatures by a structure intermediate between a molecular and a zwitterionic complex. Its NMR parameters depend strongly on temperature and the polarity of the solvent. The 2:3 complex [ColHFHCol](+)[FHF](-) is a contact ion pair. Collidinium hydrogen difluoride [ColH](+)[FHF](-) is an ionic salt exhibiting a strong hydrogen bond between collidinium and the [FHF](-) anion. In this complex, the anion [FHF](-) is subject to a fast reorientation rendering both fluorine atoms equivalent in the NMR time scale with an activation energy of about 5 kcal mol(-)(1) for the reorientation. Finally, collidinium dihydrogen trifluoride [ColH](+)[F(HF)(2)](-) is an ionic pair exhibiting one FHN and two FHF hydrogen bonds. Together with the [F(HF)(n)()](-) clusters studied previously (Shenderovich et al., Phys. Chem. Chem. Phys. 2002, 4, 5488), the new complexes represent an interesting model system where the evolution of scalar couplings between the heavy atoms and between the proton and the heavy atoms of hydrogen bonds can be studied. As in the related FHF case, we observe also for the FHN case a sign change of the coupling constant (1)J(FH) when the F.H distance is increased and the proton shifted to nitrogen. When the sign change occurs, that is, (1)J(FH) = 0, the heavy atom coupling constant (2)J(FN) remains very large, of the order of 95 Hz. Using the valence bond order model and hydrogen bond correlations, we describe the dependence of the hydrogen bond coupling constants, of hydrogen bond chemical shifts, and of some H/D isotope effects on the latter as a function of the hydrogen bond geometries.

Combined local and general ozone therapy was used in 30 patients with local sluggish pyoinflammatory diseases of the maxillofacial soft tissues. The results were compared to those in 33 patients administered no ozone therapy. Ozone therapy decreased the duration of treatment more than 2-fold due to antibacterial effect and stimulation of nonspecific and immunological reactivity. Lack of obvious contraindications and selective activity and universal immunocorrective effect recommend ozone therapy for wide use in this patient population irrespective of the type of inflammatory reaction.

Sixty-three patients with local sluggish suppurative inflammations of maxillofacial soft tissues were examined. Medical ozone was added to the treatment protocols of 30 of these patients. Before treatment peripheral blood leukocyte phagocytic activity was decreased in 54 patients, which corresponded to clinical form of a sluggish inflammation. Traditional therapy did not appreciably change the level of phagocytosis. Addition of medical ozone exposure to therapy promoted normalization of leukocyte phagocytic activity and accelerated liquidation of inflammation.

Central hemodynamics, diastolic and pumping functions of the heart, myocardial reactivity, microcirculation and biological age of cardiovascular system were studied in 66 elderly patients suffering from hypertension and ischemic heart disease. The patients received systemic magnetotherapy which produced a geroprotective effect as shown by improved microcirculation, myocardial reactivity, central hemodynamics reducing biological age of cardiovascular system and inhibiting its ageing.

The 1H and 13C NMR of trypsin stabilized by chemical modification with a hydrophilic polymer have been obtained in a wide range of pH (1.0-11.0). The spectral features referred to some nuclei of the "catalytic triad" have been identified using different NMR techniques as well as chemical modification with selective reagents. It was found that the monoprotonation of this system results in a quasi-symmetrical hydrogen bond formed between the basic groups which provided explanation for the discrepancies between the experimental findings obtained by different authors concerning the protonation site in this catalytic system. Simulation of the catalytic triad by a 15N-labelled low molecular model suggests that an increase in the OH-group acidity is unaccompanied by a discrete double proton transfer; however, a smooth shift of the bridging protons from one basic atom to another occurs with quasi-symmetrical hydrogen bonds formed in intermediate cases. On the basis of experimental data a new concept has been proposed for the mechanism of acid-base catalysis performed by pains of weak basic groups, such as His-Im and Asp(Glu)-COO- (pKa = 3-7) which are not capable of proton abstraction from alcoholic or water OH-groups (pKa > 13). The catalysis may consist in changing the charge densities on the reacting groups due to strong H-bonding and, on the other hand, in facilitating the free movement of a proton in the field of several basic atoms when going along the reaction coordinate. The energy of very strong hydrogen bonds thus formed diminishes the activation energy of the reaction.

G1- and G2-chalone effects of pig's stomach mucosa extract were registered in mice stomach gland epithelium. The inhibitory activity of chalones on cell's proliferation reduced following increased level of thyroid hormones. Local (chalones) and organism (thyroid hormones) factors cooperate in control of gland epithelial cell proliferation.

The control effects of thyroid hormones were registered in mice stomach gland epithelium. The growth fraction, rhythm, activity of proliferation changed differently in fundal and pyloric epithelium following increased level of thyroid hormones.

The mutant pEG1 of R-factor RP4 with temperature-sensitive defect in replication, carrying a transposable ampicillin resistance element Tn1 was used to define the frequency of insertion of this element into Escherichia coli K-12 chromosome and some other plasmids. Our results indicate that the frequency of colony forming by bacteria with pEG1-factor on ampicillin medium in non-permissive conditions corresponds to the frequency of Tn1 insertion into bacterial chromosome or some other plasmid (in case when the strains are carrying a second plasmid). The frequency of Tn1 insertion into the chromosome is about 4.10(-4). The defect in recA gene produce no serious change in the frequency of Tn1 insertion into the bacterial chromosome. The translocation of Tn1 element from pEG1-factor to R483, R6 and ColE1 plasmids occurs at 10 to 100-fold-higher frequency than from the plasmid to the chromosome. The insertion of Tn1 into the F'-factor KLF10 and R-factor R64-11 occurs at far lower frequency than that to plasmids R6, R483, or ColE1.