The enthalpies of formation of carbon nanomaterials as a key factor for understanding their structural features.

Carbon nanomaterials (CNMs), such as carbon nanotubes (CNTs), carbon nanoflakes (CNFs) and their N-doped derivatives, show sufficient correlations between structure, composition and properties. In this study, the relationships between structure and composition of different types of CNMs as well as their enthalpies of formation are analyzed based on original experimental results and earlier published data. The adiabatic bomb calorimetry technique is used for the determination of these values, together with elemental and thermal analyses, electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy, which are applied for structure and composition analysis. The contributions of surface (ΔfH) and bulk (ΔfH) components in the values of enthalpies of formation ΔfH for different CNMs are estimated for the first time. It is shown that ΔfH is highly influenced by SBET, whereas ΔfH is defined by the number and homogeneity of inner layers conformable to the graphite structure. In the case of nitrogen-doped CNMs, ΔfH is influenced not only by the nitrogen content but also by the coordination of the heteroatom; substitutional nitrogen demonstrates a higher effect compared to pyrrolic and pyridine-like nitrogens.

The role of laser power and pullback velocity in the endovenous laser ablation efficacy: an experimental study.

Endovenous laser ablation is an effective and minimally invasive alternative to surgical removal of incompetent veins. However, many controversies concerning optimal laser parameters usage in this procedure still remain. The purpose of this experimental study was to assess the adequate parameters required for vein wall destruction and to evaluate the role of fiber pullback velocity on vessel wall degradation. Varicose vein segments were treated with 1470-nm diode laser 3 to 9.5 W in power. The fiber moved through the vein at a velocity of 0.7 or 1.5 mm/s; the applied linear endovenous energy density (LEED) was 40-95 J/cm. The temperature of the vein surface in the course of laser irradiation was controlled by IR thermography. The intact collagen in treated vein specimens was studied by differential scanning calorimetry. The increase in the surface temperature with applied energy was found to be about three times slower for the pullback velocity of 0.7 mm/s than that of 1.5 mm/s. The collagen in the tissue was totally denatured in the case of the surface temperature of about 91 °C. The critical values of LEED ensured complete degradation of vein wall were of 53 and 71.5 J/cm for velocities of 1.5 and 0.7 mm/s, respectively. Our experimental study supports the conception that it is laser power and pullback velocity rather than LEED value that determine the temperature as well the collagen framework degradation and therefore the thermal response of procedure.

[Antioxidant Effect on the Growth And Formation of Lipids in the Fungus Lentinus tigrinus Growing on Medium with Lignosulfonate].

The addition of an antioxidant (2-ethyl-6-methyl-3-hydroxypyridine hydrochloride) to a culture of the fungus Lentinus tigrinus growing on a medium with lignosulfonate inhibited growth and changed the composition of cell phospholipids. The ratio of lipid messengers also changed, the phosphatidic acid level decreased, and the content of phosphatidylinositol dramatically increased. The substitution of lignosulfonate with glucose and the addition of an antioxidant increased the biomass yield of L. tigrinus, as well as that of another fungus, Cunninghamella japonica, which was incapable of biodegrading the biopolymer. The obtained results indicate the specificity of growth processes in the presence of lignosulfonate and confirm the role of free radical oxidation reactions in the biodegradation of this biopolymer by L. tigrinus.

[Clinical and epidemiological characteristics of acute myeloid leukemias in adults according to the data of municipal hematology departments in Moscow].

AIM: To estimate the incidence of acute myeloid leukemias (AML) in Moscow adults and to evaluate the efficiency of their treatment. SUBJECTS AND METHODS: Data on Moscow residents who were first diagnosed with AML in 2010 were retrospectively collected. The efficiency of their treatment was evaluated from the rates of complete remissions (CR), recurrences, deaths, and 4-year overall (OS) and relapse-free survival (RFS). The data as of September 1, 2013, were analyzed. RESULTS: According to the 2010 pooled materials of the city's municipal hematology departments, AML (non-M3 types) was diagnosed in 286 patients whose median age at diagnosis was 64.9 years (range, 18.2-92.0 years). The notified incidence rate was 2.9 (3.3 for men and 2.6 for women) cases per 100,000 population. 118 (41%) patients received intensive chemotherapy (ICT); 119 (42%) had chemotherapy with low-dose cytarabine (LDC); 7 (2%) had that with hypomethylating agents (HA); and 42 (15%) had palliative therapy (PT). During first-line therapy, none of the patients underwent allogeneic hematopoietic stem cell transplantation (allo-HSCT). In the entire group, the early (within the first 60 days) mortality rates were 42% (119 deaths); that of patients with primary refractory disease was 32% (90 deaths). CR was achieved in 77 (27%) patients: 57 (48%) on ICT, 17 (14%) on LDC, and 3 (43%) on HA. Recurrences occurred in 37 (48%) of the 77 patients who had achieved CR at a median follow-up of 43.9 months. Four-year OS in all the patients receiving PT was 9.8±1.9% (18.2±3.9% in the patients on ICT versus 4.5±2% in those of LDC; p=0.028); 4-year RFS was 36.1±5.7% (39.6±6.7% inthe patients on ICT versus 31.3±11 .6% in those on LDC; p=0.8). CONCLUSION: High mortality rates in the induction, which are caused by the limited resources of accompanying therapy, poor sanitary conditions, and no own opportunities to perform allo-HSCT, remain a key problem of AML therapy in adults.

[Influence of lignin and oxygen on the growth and the lipid formation of the fungus Lentinus tigrinus].

During cultivation of the filamentous fungus Lentinus tigrinus on a medium containing lignin, a high oxygen content stimulated the growth of the fungus and contributed to the yield of lipids. A high content of phosphatidic acid and a reduction in the level of phosphatidylethanolamine and phosphatidylserine were first detected in the composition of phospholipids. Changes in the composition of neutral lipids, such as variation in the ratio of esterified and free sterols, have occurred; thus, the amount of sterol esters reduced simultaneously with a decrease in the content of free fatty acids. Based on the obtained results, the possible role of phosphatidic acid as a second messenger in the process of the consumption of lignin by the fungus Lentinus tigrinus is discussed.

[Biodiesel fuel production from lipids of filamentous fungi].

The main stages in the production of biodiesel fuel from lipids of filamentous fungi belonging to the order Mucorales are described. Fungi of the family Cunninghamellaceae have been screened; the lipogenic activity of the examined strains has been assessed; and a producer generating up to 50% of lipids, represented by triacylglycerols, has been found. The substitution effect of a source of carbon and nitrogen with less expensive components (in particular, various industrial wastes) has been studied, as well as their influence on the quantity and major characteristics of the final product. An ecologically friendly method for extracting lipids from fungal mycelia, utilizing supercritical technologies, has been used. A correlation between the lipid content in the spore inoculum and the maximal lipid content in biomass has been discovered; this correlation is proposed for optimizing the biotechnology and increasing the yield of final products.

Stabilization of scleral collagen by glycerol aldehyde cross-linking.

The paper aims at the evaluation of prospects for using glyceraldehyde as a cross-linking agent for the scleral tissue. Stability parameters (denaturation temperature, Young's modulus, ultimate tensile stress, proteolytic resistance) and analytical parameter (fluorescence intensity) were determined during the glycation process of isolated rabbit sclera. The analysis of fluorescence spectral characteristic provided information about some glycation products. The glyceraldehyde treatment was resulted in a significant increase in thermal stability, proteolytic resistance and improvement of biomechanical characteristics (Young's modulus, ultimate tensile stress). Unique properties of the reaction between scleral collagen and glyceraldehyde are observed at short cross-linking times. The appearance of intermediate collagen fraction with lowest thermal and proteolytic stability was detected.

[Changes in physicochemical characteristics of rabbit sclera as a result of reinforcement treatment].

It has been shown by biochemical analysis and differential scanning calorimetry that the connective tissue formed around a transplant as a result of sclero-reinforcing interference (capsula) is similar to intact sclera. The main component of newly formed capsules is collagen I whose fibers have a perfect structure and the amount of cross-links sufficient to provide normal thermomechanical properties. A fraction of collagen having thermally labile "immature" cross-links in capsules formed around the transplant impregraned with Panaxal has been detected by differential scanning calorimetry. It was suggested that fibroblasts in tissues of these capsules have a high synthetic activity.

Three-dimensional structure of Serratia marcescens nuclease at 1.7 A resolution and mechanism of its action.

The three-dimensional crystal structure of Serratia marcescens (Sm) nuclease has been refined at 1.7 A resolution to the R-factor of 17.3% and R-free of 22.2%. The final model consists of 3678 non-hydrogen atoms and 443 water molecules. The analysis of the secondary and the tertiary structures of the Sm nuclease suggests a topology which reveals essential inner symmetry in all the three layers forming the monomer. We propose the plausible mechanism of its action based on a concerted participation of the catalytically important amino acid residues of the enzyme active site.

[X-ray structural analysis of magnesium-containing Serratia marcescens endonuclease]. / Rentgenostrukturnyi analiz magniisoderzhashchei éndonukleazy Serratia marcescens.

The three-dimensional crystal structure of the DNA/RNA nonspecific endonuclease from Serratia marcescens was refined at the resolution of 1.07 A to R factor of 12.4% and Rfree factor of 15.3% using the anisotropic approximation. The structure includes 3924 non-hydrogen atoms, 715 protein-bound water molecules, and a Mg2+ ion in each binding site of each subunit of the nuclease homodimeric globular molecule. The 3D topological model of the enzyme was revealed, the inner symmetry of the monomers in its N- and C-termini was found, and the local environment of the magnesium cofactor in the nuclease active site was defined. Mg2+ ion was found to be bound to the Asn119 residue and surrounded by five associated water molecules that form an octahedral configuration. The coordination distances for the water molecules and the O delta 1 atom of Asn119 were shown to be within a range of 2.01-2.11 A. The thermal factors for the magnesium ion in subunits are 7.08 and 4.60 A2, and the average thermal factors for the surrounding water molecules are 11.14 and 10.30 A2, respectively. The region of the nuclease subunit interactions was localized, and the alternative side chain conformations were defined for 51 amino acid residues of the nuclease dimer.

[A comparative structure-function analysis and molecular mechanism of action of endonucleases from Serratia marcescens and Physarum polycephalum]. / Sravnitel'nyi strukturno-funktsional'nyi analiz éndonukleaz Serratia marcescens i Physarum polycephalum i molekuliarnyi mekhanizm ikh deistviia.

Structural and functional characteristics were compared for wild-type nuclease from Serratia marcescens, which belongs to the family of DNA/RNA nonspecific endonucleases, its mutational forms, and the nuclease I-PpoI from Physarum polycephalum, which is a representative of the Cys-His box-containing subgroup of the superfamily of extremely specific intron-encoded homing DNases. Despite the lack of sequence homology and the overall different topology of the Serratia marcescens and I-PpoI nucleases, their active sites have a remarkable structural similarity. Both of them have a unique magnesium atom in the active site, which is a part of the coordinatively bonded water-magnesium complex involved in their catalytic acts. In the enzyme-substrate complexes, the Mg2+ ion is chelated by an Asp residue, coordinates two oxygen atoms of DNA, and stabilizes the transition state of the phosphate anion and 3'-OH group of the leaving nucleotide. A new mechanism of the phosphodiester bond cleavage, which is common for the Serratia marcescens and I-PpoI nucleases and differs from the known functioning mechanism of the restriction and homing endonucleases, was proposed. It presumes a His residue as a general base for the activation of a non-cluster water molecule at the nucleophilic in line displacement of the 3'-leaving group. A strained metalloenzyme-substrate complex is formed during hydrolysis and relaxes to the initial state after the reaction. The English version of the paper.

[Effect of infrared laser radiation on sorption of dry cartilage and connective tissue preparations]. / Vliianie lazernogo izlucheniia infrakrasnogo diapazona na sorptsiiu vody sukhimi preparatami khriashchevoi i soedinitel'noi tkanei.

Cartilaginous and connective tissues were exposed to a moderate-intensity IR laser treatment with IR radiometric temperature control. The isotherms of water sorption by dry preparations of intact and laser-treated tissues were obtained and calculated in terms of well known models. It was shown that the sorption capacity of a monolayer of tissues decreases with increasing temperature during laser treatment. Changes in the supramolecular structure of the extracellular matrix of tissues (loss of regularity) upon IR laser exposure are discussed.

Atomic structure of the Serratia marcescens endonuclease at 1.1 A resolution and the enzyme reaction mechanism.

The three-dimensional crystal structure of Serratia marcescens endonuclease has been refined at 1.1 A resolution to an R factor of 12.9% and an R(free) of 15.6% with the use of anisotropic temperature factors. The model contains 3694 non-H atoms, 715 water molecules, four sulfate ions and two Mg(2+)-binding sites at the active sites of the homodimeric protein. It is shown that the magnesium ion linked to the active-site Asn119 of each monomer is surrounded by five water molecules and shows an octahedral coordination geometry. The temperature factors for the bound Mg(2+) ions in the A and B subunits are 7.08 and 4.60 A(2), respectively, and the average temperature factors for the surrounding water molecules are 12.13 and 10.3 A(2), respectively. In comparison with earlier structures, alternative side-chain conformations are defined for 51 residues of the dimer, including the essential active-site residue Arg57. A plausible mechanism of enzyme function is proposed based on the high-resolution S. marcescens nuclease structure, the functional characteristics of the natural and mutational forms of the enzyme and consideration of its structural analogy with homing endo-nuclease I-PpoI.