Introducing the penicillamine moiety into a metallopeptide mimicking the NiSOD enzyme: electronic and kinetic effects

The novel NiSOD related metallopeptide incorporates penicillamine moiety in the active center which alters both the electronic and kinetic features.

Characterization of Orientation Correlation Kinetics: Chiral-mesophase Domains in Suspensions Charged DNA-rods

Bacteriophage DNA fd-rods are long and stiff rod-like particles which are known to exhibit a rich equilibrium phase behavior. Due to their helical molecular structure, they form the stable chiral nematic (N*) mesophases. Very little is known about the kinetics of forming various phases with orientations. The present study addresses the kinetics of chiral-mesophases and N*-phase, by using a novel image-time correlation technique. Instead of correlating time-lapsed real-space microscopy images, the corresponding Fourier images are shown for time-correlated averaged orientations. This allows to unambiguously distinguish to detect the temporal evolution of orientations on different length scales, such as domain sizes (depending on their relative orientations), and the chiral pitch within the domains. Kinetic features are qualitatively interpreted in terms of replica symmetry breaking of elastic deformations in the orthogonal directional axes of chiral-mesophase domains, as well by the average twist angle and the order parameter. This work can be interesting for characterizing other types of charged rods, mimicking super-cooled liquids and orientation glasses.

A Ratiometric Calcium Reporter CGf Reveals Calcium Dynamics Both in the Single Cell and Whole Plant Levels Under Heat Stress

Land plants evolved to quickly sense and adapt to temperature changes, such as hot days and cold nights. Given that calcium (Ca2+) signaling networks are implicated in most abiotic stress responses, heat-triggered changes in cytosolic Ca2+ were investigated in Arabidopsis leaves and pollen. Plants were engineered with a reporter called CGf, a ratiometric, genetically encoded Ca2+ reporter with an mCherry reference domain fused to an intensiometric Ca2+ reporter GCaMP6f. Relative changes in [Ca2+]cyt were estimated based on CGf’s apparent KD around 220 nM. The ratiometric output provided an opportunity to compare Ca2+ dynamics between different tissues, cell types, or subcellular locations. In leaves, CGf detected heat-triggered cytosolic Ca2+ signals, comprised of three different signatures showing similarly rapid rates of Ca2+ influx followed by differing rates of efflux (50% durations ranging from 5 to 19 min). These heat-triggered Ca2+ signals were approximately 1.5-fold greater in magnitude than blue light-triggered signals in the same leaves. In contrast, growing pollen tubes showed two different heat-triggered responses. Exposure to heat caused tip-focused steady growth [Ca2+]cyt oscillations to shift to a pattern characteristic of a growth arrest (22%), or an almost undetectable [Ca2+]cyt (78%). Together, these contrasting examples of heat-triggered Ca2+ responses in leaves and pollen highlight the diversity of Ca2+ signals in plants, inviting speculations about their differing kinetic features and biological functions.

MECHANODESTRUCTION OF ISOPRENE RUBBER. PART 3. KINETICS OF OXIDATIVE DESTRUCTION

Continuation of studies of changes in molecular parameters, in particular, the molecular weight (MM) during the plasticization (P) of SKI-3 isoprene rubber. The kinetics of oxidative destruction (OD) in the temperature range (T) 30-130 °C and time (t) 30–600 s were studied in detail. Plasticization of rubber, as before, was carried out in a laboratory rubber mixer of the company «NFM», and gel chromatographic studies were carried out on a gel chromatograph of the company «Waters». The speed constant OD K0 decreases in absolute value with a decrease in T and an increase in t. The calculated effective activation energy of OD Eeff decreases from 24,4 to 13 kJ/mol in the studied t range. The influence of the oxygen diffusion process on the kinetic features of the OD of SKI-3 at Р is pointed out.

Ultrafast Photoconversion Dynamics of the Knotless Phytochrome SynCph2

The family of phytochrome photoreceptors contains proteins with different domain architectures and spectral properties. Knotless phytochromes are one of the three main subgroups classified by their distinct lack of the PAS domain in their photosensory core module, which is in contrast to the canonical PAS-GAF-PHY array. Despite intensive research on the ultrafast photodynamics of phytochromes, little is known about the primary kinetics in knotless phytochromes. Here, we present the ultrafast Pr ⇆ Pfr photodynamics of SynCph2, the best-known knotless phytochrome. Our results show that the excited state lifetime of Pr* (~200 ps) is similar to bacteriophytochromes, but much longer than in most canonical phytochromes. We assign the slow Pr* kinetics to relaxation processes of the chromophore-binding pocket that controls the bilin chromophore’s isomerization step. The Pfr photoconversion dynamics starts with a faster excited state relaxation than in canonical phytochromes, but, despite the differences in the respective domain architectures, proceeds via similar ground state intermediate steps up to Meta-F. Based on our observations, we propose that the kinetic features and overall dynamics of the ultrafast photoreaction are determined to a great extent by the geometrical context (i.e., available space and flexibility) within the binding pocket, while the general reaction steps following the photoexcitation are most likely conserved among the red/far-red phytochromes.

Electrosynthesis and characterization of lead dioxide–perfluorobutanesulfonate composite

The effect of potassium perfluorobutanesulfonate on the kinetic features of electrodeposition of lead dioxide from methanesulfonate electrolytes has been investigated. The introduction of C4F9SO3K into the lead dioxide deposition electrolyte leads to insignificant inhibition of the Pb2+ electrooxidation process, while the mechanism of the process does not change. A composite coating is formed upon deposition of coatings from electrolytes containing surfactants. The surface of a composite material consists of a mixture of clearly expressed large crystalline blocks with sharp angles and small crystals. Energy dispersive X-ray analysis revealed the satisfactory distribution of modifying elements in the entire sample bulk, and not only on the coating surface. It was shown that the electrocatalytic activity of lead dioxide–perfluorobuthanesulfonate composite differs from the undoped sample. The oxygen evolution reaction slightly decelerates on a PbO2–C4F9SO3K composite. The Tafel slopes in 1 M HClO4 calculated from these curves plotted in semilogarithmic coordinates are 136 and 145 mV dec–1 for undoped sample and lead dioxide-surfactant composite, respectively. The reaction of electrochemical oxidation of p-chlorophenol is characterized by the pseudo-first order kinetics with respect to the initial compound. The use of doped C4F9SO3K lead dioxide as an anode leads to the inhibition of the process of oxygen evolution and an almost one and a half higher rate of electrochemical conversion of 4-chlorophenol to aliphatic compounds.

Synthesis and Investigation of pH-Switchable RAFT Agent in Polymerization of Styrene

pH-switchable chain transfer agent 1-cyano-1-methylethyl (phenyl)(pyridin-4-yl)-carbamodithioate (CMPC) was synthesized and reversible addition-fragmentation chain-transfer (RAFT) polymerization of styrene in presence of CMPC was studied. It was shown that presence of CMPC affects molar mass distribution and kinetic features and realizes supposed mechanism of RAFT polymerization. Different effect of CMPC on polymerization of styrene in presence of protic acids was studied.

Evaluation of the Effect of Sizing Compositions on the Properties of Hydrated Cellulose Technical Yarn

The influence of sizing compositions on the reinforcing properties of hydrated cellulose technical yarns has been investigated. The optimal mode of modification of hydrated cellulose yarns has been determined. The evaluation of the structural properties of the modified yarns has been carried out. The kinetic features of the modified yarns wetting by an epoxy oligomer have been studied.