Search Results (17)

Disaccharide trehalose has been proven in many cases to be particularly effective in preserving the functional and structural integrity of biological macromolecules. In this work, we studied its effect on the electron transfer reactions that occur in the chromatophores of the photosynthetic bacterium Cereibacter sphaeroides. In the presence of a high concentration of trehalose, following the activation of the photochemistry by flashes of light, a slowdown of the electrogenic reactions related to the activity of the photosynthetic reaction center and cytochtome (cyt) bc₁ complexes is observable. The kinetics of the third phase of the electrochromic carotenoid shift, due to electrogenic events linked to the reduction in cyt b_H heme via the low-potential branch of the cyt bc₁ complex and its oxidation by quinone molecule on the Q_i site, is about four times slower in the presence of trehalose. In parallel, the reduction in oxidized cyt (c₁ + c₂) and high-potential cyt b_H are strongly slowed down, suggesting that the disaccharide interferes with the electron transfer reactions of the high-potential branch of the bc₁ complex. A slowing effect of trehalose on the kinetics of the electrogenic protonation of the secondary quinone acceptor Q_B in the reaction center complex, measured by direct electrometrical methods, was also found, but was much less pronounced. The direct detection of carbohydrate content indicates that trehalose, at high concentrations, permeates the membrane of chromatophores. The possible mechanisms underlying the observed effect of trehalose on the electron/proton transfer process are discussed in terms of trehalose’s propensity to form strong hydrogen bonds with its surroundings. Full article

In our study, we investigated the accelerated aging process of PLA under 253.7 nm UV-C irradiation with the use of the GPC, NMR, FTIR, and DSC methods and formal kinetic analysis. The results of GPC and DSC indicated a significant degree of destructive changes in the PLA macromolecules, while spectroscopic methods NMR and FTIR showed maintenance of the PLA main structural elements even after a long time of UV exposure. In addition to that, the GPC method displayed the formation of a high molecular weight fraction starting from 24 h of irradiation, and an increase in its content after 144 h of irradiation. It has been shown for the first time that a distinctive feature of prolonged UV exposure is the occurrence of intra- and intermolecular radical recombination reactions, leading to the formation of a high molecular weight fraction of PLA decomposition products. This causes the observed slowdown of the photolysis process. It was concluded that photolysis of PLA is a complex physicochemical process, the mechanism of which depends on morphological changes in the solid phase of the polymer under UV radiation. Full article

In this paper, the interactions of low-energy muons (E < 10 MeV) with natural silicon, the basic material of microelectronics, are studied by Geant4 and SRIM simulation. The study is circumscribed to muons susceptible to slowdown/stop in the target and able to transfer sufficient energy to the semiconductor to create single events in silicon devices or related circuits. The capture of negative muons by silicon atoms is of particular interest, as the resulting nucleus evaporation and its effects can be catastrophic in terms of the emission of secondary ionizing particles ranging from protons to aluminum ions. We investigate in detail these different nuclear capture reactions in silicon and quantitatively evaluate their relative importance in terms of number of products, energy, linear energy transfer, and range distributions, as well as in terms of charge creation in silicon. Finally, consequences in the domain of soft errors in microelectronics are discussed. Full article

This paper analyzes the potential spillovers of a slowdown in Chinese growth to the United States and the rest of the world. Through a combination of structural VAR and DSGE analyses, we find that (1) spillovers from China to the rest of the world have grown significantly in the past decade; (2) the negative growth spillovers to the United States are more modest than to emerging market economies—particularly for commodity exporters—or other advanced economies, primarily because the latter group has larger direct exposure in trade to China; and (3) although the United States has limited direct financial exposure to China, the negative spillovers to the U.S. economy are amplified significantly if the negative Chinese growth shock leads to adverse global risk sentiment and monetary policy in the United States is constrained in its reaction. Full article

Following the emergence of COVID-19, nations around the world implemented effective restrictions that limited people’s movements and economic activity, which reportedly led to environmental improvements. The lowering of air emissions is one environmental indicator that has been connected to the pandemic. The diurnal temperature range (DTR) is one environmental indicator that has been linked to air pollution. In this study, it was hypothesized that because of the pandemic restrictions and slowdowns, the DTR in 2020 for a country that implemented major restrictive measures in reaction to the pandemic would be higher than in previous years, despite or in addition to background climatic forcings. Based on information from weather stations in the contiguous United States of America (USA), the DTR for the year 2020 was compared to the five years before it as a test of this hypothesis. It was verified that the annual mean DTR of 2020 was higher than the three years prior (2017–2019), but lower than the DTR of 2015 and 2016. Compared to historical trends (since 1911), the DTR change in 2020 is within past mean DTR variations that occurred over approx. 12-year cycles, linked to sunspot activity (Schwabe solar cycle). Moreover, climatic effects such as El Niño, La Niña and the prolonged trend of global warming reduce the confidence in the perceived effect of the pandemic. To determine if or how anthropogenic and environmental factors can magnify the impact of the COVID-19 restrictions on the regional mean DTR, five other parameters (annual snowfall quantities, gross domestic product per capita, population density, latitude (northern/southern), and longitude (coastal/inner)) were also examined against changes in DTR from 2015 to 2020. This analysis pointed to the environmental and industrial factors being more strongly correlated with short-term climate changes than societal factors and geographical location. Full article

Reactive thermoplastics matrices offer ease of processing using well-known molding techniques (such as Resin Transfer Molding) due to their initially low viscosity. For Polyamide 6 (PA6)/glass composites, the hydroxyl groups on the glass surface slow down the anionic ring-opening polymerization (AROP) reaction, and can ultimately inhibit it. This work aims to thoroughly control the hydroxyl groups and the surface chemistry of glass particulates to facilitate in situ AROP-an aspect that has been barely explored until now. A model system composed of a PA6 matrix synthesized by AROP is reinforced with calcinated and silanized glass microparticles. We systematically quantify, by TGA and FTIR, the complete particle surface modification sequence, from the dehydration, dehydroxylation and rehydroxylation processes, to the silanization step. Finally, the impact of the particle surface chemistry on the polymerization and crystallization of the PA6/glass composites was quantified by DSC. The results confirm that a careful balance is required between the dehydroxylation process, the simultaneous rehydroxylation and silane grafting, and the residual hydroxyl groups, in order to maintain fast polymerization and crystallization kinetics and to prevent reaction inhibition. Specifically, a hydroxyl concentration above 0.2 mmol OH·g⁻¹ leads to a slowdown of the PA6 polymerization reaction. This reaction can be completely inhibited when the hydroxyl concentration reaches 0.77 mmol OH·g⁻¹ as in the case of fully rehydroxylated particles or pristine raw particles. Furthermore, both the rehydroxylation and silanization processes can be realized simultaneously without any negative impact on the polymerization. This can be achieved with a silanization time of 2 h under the treatment conditions of the study. In this case, the silane agent gradually replaces the regenerated hydroxyls. This work provides a roadmap for the preparation of reinforced reactive thermoplastic materials. Full article

Since rising temperature (T) will enhance biochemical reactions and coastal marine sediments are hotspots of carbon cycling, marine heatwaves’ (MHWs’) intensification caused by climate change will affect coastal biogeochemistry. We investigated the effects of MHWs on sediment organic matter (OM) in a nearshore locality (NW Sardinia, Mediterranean Sea) receiving an artificial warm water plume generating T anomalies of 1.5–5.0 °C. Sediments were collected before and after 3 and 11 weeks from the initial plume release. Both MHWs influenced sedimentary OM quantity, composition, and degradation rates, with major effects associated with the highest T anomaly after 3 weeks. Both MHWs enhanced sedimentary OM contents, with larger effects associated with the highest T anomaly. Phytopigment contents increased in the short term but dropped to initial levels after 11 weeks, suggesting the occurrence of thermal adaptation or stress of microphytobenthos. In the longer term we observed a decrease in the nutritional quality of OM and a slowdown of its turnover mediated by extracellular enzymes, suggestive of a decreased ecosystem functioning. We anticipate that intensification of MHWs will affect benthic communities not only through direct effects on species tolerance but also by altering benthic biogeochemistry and the efficiency of energy transfer towards higher trophic levels. Full article

Proteasomes hydrolyze most cellular proteins. The standard reaction to determine proteasome activity in cellular lysate or elsewhere contains AMC-conjugated peptide substrate, ATP, Mg²⁺, and DTT. ATP and Mg²⁺ are included to maintain 26S proteasome functionality. However, most cellular proteasomes are 20S proteasomes, and the effects of ATP on the turnover of fluorogenic substrates by 20S complexes are largely unknown. Here, we evaluated the effect of ATP alone or in combination with Mg²⁺ on the degradation of AMC-conjugated fluorogenic substrates by purified 20S proteasomes. Degradation of substrates used to determine chymotrypsin-, caspase- and trypsin-like proteasome activities was gradually decreased with the rise of ATP concentration from 0.25 to 10 mM. These effects were not associated with the blockage of the proteasome catalytic subunit active sites or unspecific alterations of AMC fluorescence by the ATP. However, ATP-induced peptide degradation slowdown was rescued by the addition of Mg²⁺. Moreover, the substrate degradation efficacy was proportional to the Mg²⁺/ATP ratio, being equal to control values when equimolar concentrations of the molecules were used. The obtained results indicate that when proteasome activity is assessed, the reciprocal effects of ATP and Mg²⁺ on the hydrolysis of AMC-conjugated fluorogenic substrates by the 20S proteasomes should be considered. Full article

Implantation of composite scaffolds could be potentially associated with the risk of hemostatic disturbances in a recipient. However, there is a lack of information on possible alterations in clotting mechanisms resulting from such a procedure. The aim of the present work was to investigate changes in hemostatic parameters in sheep implanted with a scaffold composed of poly(ε-caprolactone) and hydroxyapatite and tricalcium phosphate (9:4.5:4.5), settled previously with mesenchymal stem cells stimulated by fibroblast growth factor-2 and bone morphogenetic protein-2. Nine Merino sheep were examined for 7 days, and measurements of clotting times (PT, aPTT), activities of antithrombin, protein C and clotting factors II-XII, and concentrations of fibrinogen and D-dimer were carried out before and 1 h, 24 h, 3 days and 7 days after scaffold implantation. The introduction of scaffold initially resulted in a slowdown of the clotting processes (most evident 24 h after surgery); PT and aPTT increased to 14.8 s and 33.9 s, respectively. From the third day onwards, most of these alterations began to return to normal values. The concentration of fibrinogen rose throughout the observation period (up to 8.4 g/L), mirroring the ongoing inflammatory reaction. However, no signals of significant disturbances in hemostatic processes were detected in the sheep tested. Full article

We present a critical analysis of the mechanism of $reversible$ hydrogen evolution reaction based on thermodynamics of hydrogen processes considering atomic and ionic species as intermediates. Clear distinction between molecular hydrogen evolution/oxidation (H${}_2$ER and H${}_2$OR) and atomic hydrogen evolution/oxidation (HER and HOR) reactions is made. It is suggested that the main reaction describing $reversible$ H${}_2$ER and H${}_2$OR in acidic and basic solutions is: ${\mathrm{H}}_3{\mathrm{O}}^{+}+2e^{-}\stackrel{{\left({\mathrm{H}}_2^{+}\right)}_{ad}}{\rightleftharpoons }{\mathrm{H}}_2+{\mathrm{OH}}^{-}$ and its standard potential is $E^0$ = −0.413 V (vs. standard hydrogen electrode, SHE). We analyse experimentally reported data with models which provide a quantitative match (R.J.Kriek et al., Electrochem. Sci. Adv. e2100041 (2021)). Presented analysis implies that $reversible$ H₂ evolution is a two-electron transfer process which proceeds via the stage of adsorbed hydrogen molecular ion H${}_2^{+}$ as intermediate, rather than H${}_{\mathrm{ad}}$ as postulated in the Volmer-Heyrovsky-Tafel mechanism. We demonstrate that in theory, two slopes of $potential$ vs. $\lg \left(current\right)$ plots are feasible in the discussed reversible region of H₂ evolution: $2.3RT/F\approx 60$ mV and $2.3RT/2F\approx 30$ mV, which is corroborated by the results of electrocatalytic hydrogen evolution studies reported in the literature. Upon transition to $irreversible$ H${}_2$ER, slowdown of H${}_2^{+}$ formation in the first electron transfer stage manifests, and the slope increases to $2.3RT/0.5F\approx 120$ mV; $R,F,T$ are the universal gas, Faraday constants and absolute temperature, respectively. Full article

Mixed-matrix membranes (MMMs) are membranes that are composed of polymers embedded with inorganic particles. By combining the polymers with the inorganic fillers, improvements can be made to the permeability compared to the pure polymer membranes due to new pathways for gas transport. However, the fillers, such as hyper cross-linked polymers (HCP), can also help to reduce the physical aging of the MMMs composed of a glassy polymer matrix. Here we report the synthesis of two novel HCP fillers, based on the Friedel–Crafts reaction between a tetraphenyl methane monomer and a bromomethyl benzene monomer. According to the temperature and the solvent used during the reaction (dichloromethane (DCM) or dichloroethane (DCE)), two different particle sizes have been obtained, 498 nm with DCM and 120 nm with DCE. The change in the reaction process also induces a change in the surface area and pore volumes. Several MMMs have been developed with PIM-1 as matrix and HCPs as fillers at 3% and 10wt % loading. Their permeation performances have been studied over the course of two years in order to explore physical aging effects over time. Without filler, PIM-1 exhibits the classical aging behavior of polymers of intrinsic microporosity, namely, a progressive decline in gas permeation, up to 90% for CO₂ permeability. On the contrary, with HCPs, the physical aging at longer terms in PIM-1 is moderated with a decrease of 60% for CO₂ permeability. ¹³C spin-lattice relaxation times (T1) indicates that this slowdown is related to the interactions between HCPs and PIM-1. Full article

During the preparative synthesis of 2-fluorocordycepin from 2-fluoroadenosine and 3′-deoxyinosine catalyzed by E. coli purine nucleoside phosphorylase, a slowdown of the reaction and decrease of yield down to 5% were encountered. An unknown nucleoside was found in the reaction mixture and its structure was established. This nucleoside is formed from the admixture of 2′,3′-anhydroinosine, a byproduct in the preparation of 3-′deoxyinosine. Moreover, 2′,3′-anhydroinosine forms during radical dehalogenation of 9-(2′,5′-di-O-acetyl-3′-bromo- -3′-deoxyxylofuranosyl)hypoxanthine, a precursor of 3′-deoxyinosine in chemical synthesis. The products of 2′,3′-anhydroinosine hydrolysis inhibit the formation of 1-phospho-3-deoxyribose during the synthesis of 2-fluorocordycepin. The progress of 2′,3′-anhydroinosine hydrolysis was investigated. The reactions were performed in D₂O instead of H₂O; this allowed accumulating intermediate substances in sufficient quantities. Two intermediates were isolated and their structures were confirmed by mass and NMR spectroscopy. A mechanism of 2′,3′-anhydroinosine hydrolysis in D₂O is fully determined for the first time. Full article

Drought stress, especially during the seedling stage, seriously limits the growth of maize and reduces production in the northeast of China. To investigate the molecular mechanisms of drought response in maize seedlings, proteome changes were analyzed. Using an isotopic tagging relative quantitation (iTRAQ) based method, a total of 207 differentially accumulated protein species (DAPS) were identified under drought stress in maize seedlings. The DAPS were classified into ten essential groups and analyzed thoroughly, which involved in signaling, osmotic regulation, protein synthesis and turnover, reactive oxygen species (ROS) scavenging, membrane trafficking, transcription related, cell structure and cell cycle, fatty acid metabolism, carbohydrate and energy metabolism, as well as photosynthesis and photorespiration. The enhancements of ROS scavenging, osmotic regulation, protein turnover, membrane trafficking, and photosynthesis may play important roles in improving drought tolerance of maize seedlings. Besides, the inhibitions of some protein synthesis and slowdown of cell division could reduce the growth rate and avoid excessive water loss, which is possible to be the main reasons for enhancing drought avoidance of maize seedlings. The incongruence between protein and transcript levels was expectedly observed in the process of confirming iTRAQ data by quantitative real-time polymerase chain reaction (qRT-PCR) analysis, which further indicated that the multiplex post-transcriptional regulation and post-translational modification occurred in drought-stressed maize seedlings. Finally, a hypothetical strategy was proposed that maize seedlings coped with drought stress by improving drought tolerance (via. promoting osmotic adjustment and antioxidant capacity) and enhancing drought avoidance (via. reducing water loss). Our study provides valuable insight to mechanisms underlying drought response in maize seedlings. Full article

N-lipidated short peptides and amino acids immobilized on the cellulose were used as catalysts cleaved amide bonds under biomimetic conditions. In order to select catalytically most active derivatives a library of 156 N-lipidated amino acids, dipeptides and tripeptides immobilized on cellulose was obtained. The library was synthesized from serine, histidine and glutamic acid peptides N-acylated with heptanoic, octanoic, hexadecanoic and (E)-octadec-9-enoic acids. Catalytic efficiency was monitored by spectrophotometric determination of p-nitroaniline formed by the hydrolysis of a 0.1 M solution of Z-Leu-NP. The most active 8 structures contained tripeptide fragment with 1-3 serine residues. It has been found that incorporation of metal ions into catalytic pockets increase the activity of the synzymes. The structures of the 17 most active catalysts selected from the library of complexes obtained with Cu²⁺ ion varied from 16 derivatives complexed with Zn²⁺ ion. For all of them, a very high reaction rate during the preliminary phase of measurements was followed by a substantial slowdown after 1 h. The catalytic activity gradually diminished after subsequent re-use. HPLC analysis of amide bond splitting confirmed that substrate consumption proceeded in two stages. In the preliminary stage 24–40% of the substrate was rapidly hydrolysed followed by the substantially lower reaction rate. Nevertheless, using the most competent synzymes product of hydrolysis was formed with a yield of 60–83% after 48h under mild and strictly biomimetic conditions. Full article

The thermal degradation related to stability in long-term storage of a carbon nanotube-based biosensor has been investigated. The effect of storage temperature on detachment and denaturation of glucose oxidase (GOx) biocatalyst has been proved. The carbon nanotubes (CNTs) coated with polyethyleneimine (PEI) as entrapping polymer to attract more GOx to form a durable and layered CNT/PEI/GOx structure is used for long-term storage to minimize GOx detachment from the structure and minimize the possibility of enzyme and protein denaturation. After 120 days, the glucose response of the CNT/PEI/GOx biosensor stored under 4°C is preserved up to 66.7% of its initial value, while under a 25 °C storage the response is maintained up to 41.7%. The enzyme coverage activity of CNT/PEI/GOx stored at 4 °C and 25 °C has decreased by 31.1% and 51.4%, respectively. Denaturation and detachment of GOx are the common causes of thermal degradation in biosensors under improper storage temperatures, but the presence of PEI in the structure can slow-down these phenomena. Moreover, the electrons transfer constant of CNT/PEI/GOx biocatalyst stored at 4 °C and 25 °C were 7.5 ± 0.5 s⁻¹ and 6.6 ± 0.3 s⁻¹, respectively, indicating that also electrons mobility is damaged by detachment and denaturation of enzyme protein and the detection of glucose from the glucose oxidation reaction (GOR) is compromised. Full article