Exploring Chromophore-Binding Pocket: High-Resolution Solid-State 1H–13C Interfacial Correlation NMR Spectra with Windowed PMLG Scheme

High-resolution two-dimensional (2D) 1H–13C heteronuclear correlation spectra are recorded for selective observation of interfacial 3–5.5 Å contacts of the uniformly 13C-labeled phycocyanobilin (PCB) chromophore with its unlabeled binding pocket. The experiment is based on a medium- and long-distance heteronuclear correlation (MELODI–HETCOR) method. For improving 1H spectral resolution, a windowed phase-modulated Lee–Goldburg (wPMLG) decoupling scheme is applied during the t1 evolution period. Our approach allows for identification of chromophore–protein interactions, in particular for elucidation of the hydrogen-bonding networks and charge distributions within the chromophore-binding pocket. The resulting pulse sequence is tested on the cyanobacterial (Cph1) phytochrome sensory module (residues 1–514, Cph1Δ2) containing uniformly 13C- and 15N-labeled PCB chromophore (u-[13C,15N]-PCB-Cph1Δ2) at 17.6 T

NMR-Based Structural Modeling of Graphite Oxide Using Multidimensional 13C Solid-State NMR and ab Initio Chemical Shift Calculations

Chemically modified graphenes and other graphite-based materials have attracted growing interest for their unique potential as lightweight electronic and structural nanomaterials. It is an important challenge to construct structural models of noncrystalline graphite-based materials on the basis of NMR or other spectroscopic data. To address this challenge, a solid-state NMR (SSNMR)-based structural modeling approach is presented on graphite oxide (GO), which is a prominent precursor and interesting benchmark system of modified graphene. An experimental 2D C-13 double-quantum/single-quantum correlation SSNMR spectrum of C-13-labeled GO was compared with spectra simulated for different structural models using ab initio geometry optimization and chemical shift calculations. The results show that the spectral features of the GO sample are best reproduced by a geometry-optimized structural model that is based on the Lerf-Klinowski model (Lerf, A. et al. Phys. Chem. B 1998, 102, 4477); this model is composed of interconnected sp(2), 1,2-epoxide, and COH carbons. This study also convincingly excludes the possibility of other previously proposed models, including the highly oxidized structures involving 1,3-epoxide carbons (Szabo, I. et al. Chem. Mater. 2006, 18, 2740). C-13 chemical shift anisotropy (CSA) patterns measured by a 2D C-13 CSA/isotropic shift correlation SSNMR were well reproduced by the chemical shift tensor obtained by the ab initio calculation for the former model. The approach presented here is likely to be applicable to other chemically modified graphenes and graphite-based systems

Long-Range Intra-Protein Communication Can Be Transmitted by Correlated Side-Chain Fluctuations Alone

Allosteric regulation is a key component of cellular communication, but the way in which information is passed from one site to another within a folded protein is not often clear. While backbone motions have long been considered essential for long-range information conveyance, side-chain motions have rarely been considered. In this work, we demonstrate their potential utility using Monte Carlo sampling of side-chain torsional angles on a fixed backbone to quantify correlations amongst side-chain inter-rotameric motions. Results indicate that long-range correlations of side-chain fluctuations can arise independently from several different types of interactions: steric repulsions, implicit solvent interactions, or hydrogen bonding and salt-bridge interactions. These robust correlations persist across the entire protein (up to 60 Å in the case of calmodulin) and can propagate long-range changes in side-chain variability in response to single residue perturbations

Study on heat under dynamic loading of rubber

A number of studies on heat buildup in tire rubber surface scan method samples using a thermal imaging camera. Investigated the exothermic chemical reaction mechanical destruction rubber when loading designs permanent cyclic stretching with deformation of the working zone 50%. Percentage of deformation of the working zone was chosen on the basis of the actual data on the stretch-compression zone "Rusk" tires, which is the maximum level difference of deformation during run-in. Experiment plan provided for periodic relaxation samples of at least 72 hours for more accurate simulation of operation process of structural products. Created and processed data on temperature changes in samples for bar and line profile for rubber compounds with the introduction of nanomodificator (fullerene-containing technical carbon) in comparison with the control sample without him. The data obtained reflect the nature of heat depending on the composition of the compound. Identified common patterns of thermal nature of physicochemical process mechanical destruction rubbers. For rubber with nanomodifikatorom there has been an increase in the temperature interval reaction from a minimum to a maximum 2 degrees that is also linked to the rise in the average temperature of the reaction on the histogram also at 2-3 degrees of deformation under the same conditions and the level of cyclic loading. However, the temperature in the control sample that is associated with the beginning of the formation of hardened rubber structures, economies of Mallinza-Petrikeeva, occurs with delay twice compared with modified Fullerenes. Measurement of physic-mechanical indicators selected in the course of testing of samples showed the beginning of formation of structure with increased strength of samples in the sample temperature zone that corresponds to the thermal effect of èndotermičeskomu recombination reactions of macromolecules

STUDY ON HEAT DYNAMIC LOADING OF RUBBER

A number of studies on heat buildup in tire rubber surface scan method samples using a thermal imaging camera. Investigated the exothermic chemical reaction mechanical destruction rubber when loading designs permanent cyclic stretching with deformation of the working zone 50%. Percentage of deformation of the working zone was chosen on the basis of the actual data on the stretch-compression zone "Rusk" tires, which is the maximum level difference of deformation during run-in. Experiment plan provided for periodic relaxation samples of at least 72 hours for more accurate simulation of operation process of structural products. Created and processed data on temperature changes in samples for bar and line profile for rubber compounds with the introduction of nanomodifiers (fulleren technical carbon) in comparison with the control sample without him. The data obtained reflect the nature of heat depending on the composition of the compound. Identified common patterns of thermal nature of physico-chemical process mechanical destruction rubbers. For rubber with nanomodifikatorom there has been an increase in the temperature interval reaction from a minimum to a maximum 2 degrees that is also linked to the rise in the average temperature of the reaction on the histogram also at 2-3 degrees of deformation under the same conditions and the level of cyclic loading. However, the temperature in the control sample that is associated with the beginning of the formation of hardened rubber structures, economies of Mallinz-Petrikeev, occurs with delay twice compared with modified Fullerenes. Measurement of physic-mechanical indicators selected in the course of testing of samples showed the beginning of formation of structure with increased strength of samples in the sample temperature zone that corresponds to the thermal effect of èndotermičeskomu recombination reactions of macromolecules

QUALITY MANAGEMENT AND FORMATION OF A COMPLEX OF PROPERTIES OF POLYMERIC COMPOSITES BY UPDATING BY CARBON NANOMATERIALS

Management of quality indicators of rubbers defining product service life at the expense of updating by a mix fullerenes fractions C50-C92

DEVELOPMENT OF A METHOD STATISTICAL ANALYSIS ACCURACY AND PROCESS STABILITY PRODUCTION OF EPOXY RESIN ED-20

Statistical methods play an important role in the objective evaluation of quantitative and qualitative characteristics of the process and are one of the most important elements of the quality assurance system production and total quality management process. To produce a quality product, one must know the real accuracy of existing equipment, to determine compliance with the accuracy of a selected technological process specified accuracy products, assess process stability. Most of the random events in life, particularly in manufacturing and scientific research, are characterized by the presence of a large number of random factors, is described by a normal distribution, which is the main in many practical studies. Modern statistical methods is quite difficult to grasp and wide practical use without in-depth mathematical training of all participants in the process. When we know the distribution of a random variable, you can get all the features of this batch of products, to determine the mean value and the variance. Using statistical control methods and quality control in the analysis of accuracy and stability of the technological process of production of epoxy resin ED20. Estimated numerical characteristics of the law of distribution of controlled parameters and determined the percentage of defects of the investigated object products. For sustainability assessment of manufacturing process of epoxy resin ED-20 selected Shewhart control charts, using quantitative data, maps of individual values of X and sliding scale R. Using Pareto charts identify the causes that affect low dynamic viscosity in the largest extent. For the analysis of low values of dynamic viscosity were the causes of defects using Ishikawa diagrams, which shows the most typical factors of the variability of the results of the process. To resolve the problem, it is recommended to modify the polymer composition of carbon fullerenes and to use the developed method for the production of epoxy resins