bluuebunny/crossref_metadata_2025 huggingface dataset:
Rayleigh LIDAR and satellite (HALOE, SABER, CHAMP and COSMIC) measurements of stratosphere-mesosphere temperature over a southern sub-tropical site, Reunion (20.8° S; 55.5° E): climatology and comparison study
Authors: Sivakumar V. , Vishnu Prasanth P. , Kishore P. , Bencherif H. , Keckhut P.
Published: April 2011

Abstract. For the first time, climatology of the middle atmosphere thermal structure is presented, based on 14 years of LIDAR and satellite (HALOE, SABER, CHAMP and COSMIC) temperature measurements. The data is collected over a southern sub-tropical site, Reunion Island (20.8° S; 55.5° E), for the height range between 30 and 60 km. The overall monthly mean temperature shows a maximum of 265–270 K at the stratopause height region from ~44–52 km and peaks during the months of March and November. Furthermore, the temperature profiles are compared with different satellite datasets (HALOE, CHAMP, COSMIC and SABER) and the results are found to be in reasonable agreement with each other, although a relative difference in temperature of ± 5 to 6 K is noticed. In comparison, LIDAR shows higher/lower temperatures for the lower mesosphere/upper stratosphere height region. The differences in temperature measured by the LIDAR and satellite measurements are analogous with previous results available elsewhere. Long-term temperature measurements are used to further study seasonal oscillations, especially annual, semi-annual and quasi-biennial oscillations. In comparison with SAO, the measured spectral amplitudes of AO shows dominant amplitudes in both the upper stratosphere and lower mesosphere height regions. Using LIDAR and the other satellite measurements, the quasi-biennial oscillation was found to be approximately 26 months. The spectral amplitudes are comparable to the results reported earlier by other researchers.
A Case Study on the Selection of Materials for Eye Lenses
Authors: Findik Fehim
Published: April 2011

A case study on the selection of materials for eye lenses is reported by means of Ashby's materials selection diagrams. In this study, 6 polymer materials of PMMA, PC, PS, PVC, PET, and PA are reviewed and their properties are found from the selection diagrams of Ashby and compared in a table. The final results confirmed that PMMA (acrylic) is the best material for eye lenses. The outcome also showed that the present material is environmental friendly being nontoxic and recyclable.
Potassium Hydroxide Impregnated Alumina (KOH-Alumina) as a Recyclable Catalyst for the Solvent-Free Multicomponent Synthesis of Highly Functionalized Substituted Pyridazines and/or Substituted Pyridazin-3(2H)-ones under Microwave Irradiation
Authors: Mecadon Hormi , Myrboh Bekington
Published: April 2011

The work described herein employs potassium hydroxide impregnated alumina (KOH-alumina) as a mild, efficient, and recyclable catalyst for a one-pot solvent-free and environmentally safer synthesis of 3,4,6-triarylpyridazines and some substituted pyridazines from active methylene carbonyl species, 1,2-dicarbonyls, and hydrazine hydrate by microwave (MW) irradiation. The method offers highly convergent, inexpensive, and functionality-tolerable procedure for rapid access to important pyridazine compounds in good yields.
Patient Preference Assessment Reveals Disease Aspects Not Covered by Recommended Outcomes in Polymyositis and Dermatomyositis
Authors: Alemo Munters Li , van Vollenhoven Ronald F. , Alexanderson Helene
Published: April 2011

Objectives. Polymyositis (PM) and dermatomyositis (DM) are characterized by impaired muscle function with a majority of patients developing sustained disability. The aim of this study was to evaluate the patient’s individual priorities (patient preference) of disabilities most important to improve in PM/DM using the MacMaster Toronto Arthritis Patient Preference Disability Questionnaire (MACTAR), to correlate the MACTAR to myositis outcomes and to evaluate its test-retest reliability. Methods. Twenty-eight patients with PM/DM performed recommended outcomes as well as the MACTAR, which was performed twice with one week apart. Results. Sexual activity, walking, biking, social activities, and sleep constituted the predominating disabilities. Seventy-two and 33% of the identified disabilities were not covered by items of the Health Assessment Questionnaire and the Myositis Activities Profile. Correlations between the MACTAR and health-related quality of life measures were = −0.67–0.73, correlations with measures of activities of daily living and participation in society were = 0.51–0.60 with lower correlations for other outcomes. Intraclass correlation (ICC) and weighted Kappa () coefficients were 0.83 and 0.68, respectively, for test-retest reliability of the MACTAR. Conclusions. The MACTAR interview had promising measurement properties and identified patient preference disabilities in PM/DM that were not covered by recommended outcomes.
Neurodevelopment and Metabolism in the Maternal-Placental-Fetal Unit
Authors: Parenti Mariana , Schmidt Rebecca J. , Tancredi Daniel J. , Hertz-Picciotto Irva , Walker Cheryl K. , Slupsky Carolyn M.
Published: May 2024

Importance

Disturbances in maternal, placental, and fetal metabolism are associated with developmental outcomes. Associations of maternal, placental, and fetal metabolism with subsequent neurodevelopmental outcomes in the child are understudied.

Objective

To investigate the metabolic associations within the maternal-placental-fetal unit and subsequent neurodevelopmental outcomes in younger siblings of children with autism spectrum disorder (ASD).

Design, Setting, and Participants

This cohort study was conducted within a subset of the Markers of Autism Risk in Babies, Learning Early Signs (MARBLES) cohort. MARBLES is a prospective birth cohort of younger siblings of children with ASD assessed for neurodevelopmental outcomes at approximately age 36 months. Participants in MARBLES were recruited through the UC Davis MIND Institute. This subset of the MARBLES cohort included younger siblings born between 2009 and 2015. Maternal third trimester serum, placental tissue, and umbilical cord serum samples were collected from participants. Only pregnancies with at least 2 of these sample types were included in this analysis. Data analysis was conducted from March 1, 2023, to March 15, 2024.

Exposures

Quantitative metabolomics analysis was conducted on maternal third trimester serum, as well as placental tissue and umbilical cord serum collected at delivery.

Main Outcomes and Measures

Using the Autism Diagnostic Observation Schedule and Mullen Scales of Early Learning, outcomes were classified as ASD, other nontypical development (non-TD), and typical development (TD).

Results

This analysis included 100 maternal serum samples, 141 placental samples, and 124 umbilical cord serum samples from 152 pregnancies (median [IQR] maternal age, 34.6 [30.8-38.3] years; median [IQR] gestational age, 39.0 [38.6-39.7] weeks; 87 [57.2%] male infants). There was no evidence that the maternal third trimester serum metabolome was significantly associated with the other metabolomes. The placental and cord serum metabolomes were highly correlated (first latent variate pair: R2 = 0.75; P < .001) and the variate scores for each tissue were significantly associated with reduced risk of non-TD (placenta: relative risk [RR], 0.13; 95% CI, 0.02-0.71; cord: RR, 0.13; 95% CI, 0.03-0.70) but not ASD (placenta: RR, 1.09; 95% CI, 0.42-2.81; cord: RR, 0.63; 95% CI, 0.23-1.73) compared with the TD reference group.

Conclusions and Relevance

In this cohort study of children with high familial risk of ASD, placental and cord serum metabolism at delivery were highly correlated. Furthermore, placental and cord serum metabolic profiles were associated with risk of non-TD.
Tuning Lubrication Performance of Phase‐Changing Emulsion‐Filled Gels by Sugar Alcohols
Authors: Lu Yao , Araiza‐Calahorra Andrea , Gao Yanxiang , Mao Like , Sarkar Anwesha
Published: May 2024

Lubrication by hydrogels is an emerging area in surface science. Although oil‐driven friction reduction is predominant in literature, emulsion gel‐based lubrication has attracted very little attention to date. We hypothesize that an interplay of viscoelasticity and oil volume fraction may modulate the lubricity of emulsion‐filled gels. Herein, phase‐change gelatin‐based emulsion‐filled gels with different sugar alcohols and oil droplet concentrations (0–30 wt%) are tested for their lubrication performance. The rheological and tribological tests are analyzed in conjunction with spectroscopic and structural characterizations to reveal structure–function relationship. Structural characterizations demonstrate that hydrogen bonding is enhanced in pure gelatin gels with the increase of sugar alcohol (glycerol)‐replacement time, which enhance the storage modulus (G′) of the gel networks. Emulsified droplets serve as active fillers further strengthening the G′ and strikingly the presence of glycerol reduced the thermoresponsiveness of the emulsion‐filled gels. Emulsion‐filled gels containing sugar alcohols, irrespective of their type, can greatly reduce the friction coefficients (μ) between hydrophobic surfaces in the boundary and mixed regimes versus the systems without sugar alcohols. In the hydrodynamic regime, the friction coefficient of the system is proportional to the second plateau shear viscosity, regulated by the oil content.
Enhancing Osmotic Energy Harvesting Through Supramolecular Design of Oxygen‐Functionalized MXene with Biomimetic Ion Channels
Authors: Ren Ziqi , Zhang Qixiang , Yin Jianyu , Jia Peixue , Lu Wenzhong , Yao Qianqian , Deng Mingfang , Gao Yihua , Liu Nishuang
Published: May 2024

Reverse electrodialysis (RED) technology, relying on ion‐selective permeability membranes (ISPM), offers a direct means of harnessing osmotic energy from the salinity difference between seawater and freshwater. Critical technical challenges include limitations in ISPM's immobile charge carriers, transmembrane ionic internal resistance, and durability in water. Drawing inspiration from the subunit structure of the epithelial sodium channel (ENaC), an ISPM assembled using a supramolecular engineering strategy is introduced. This innovative approach enables the synergistic action of multiple molecular building blocks to mimic the distribution of ENaC subunit structures, strategically planning the placement of immobile charge carriers on nanofluidic channels. The design incorporates nano‐confined oxygen‐rich functionalized MXene (O‐MXene) and high‐strength polymer backbone aramid fibers to construct 3D nanofluidic channels with a high surface charge density. Enhanced by a bonding network of sodium carboxymethylcellulose, the ISPM achieved an exceptional output power density of 21.7 W m−2 and 46.0% energy conversion efficiency in a RED half‐cell system using natural seawater and river water, surpassing current technologies. This research not only advances RED technology but also provides biomimetic customization concepts for ISPM design across various applications, including flow batteries, fuel cells, and related fields.
High Mobility n‐Type Imide‐Based Semiconductor with Unusual Single‐Crystal Packing Structure in Solution‐Processed Thin Film
Authors: Liu Miao , Shih Yen‐Han , Yu Xinyu , Yu Ming‐Hsuan , Sun Xianglang , Chueh Chu‐Chen , Li Zhong'an
Published: May 2024

Solid‐state molecular arrangement has been recognized as the most important role in the charge transport properties of organic semiconductors. Although highly ordered molecular stacking is achieved in single crystals, maintaining single‐crystal molecular packing in solution‐processed thin films remains a significant challenge. Herein, a new type of n‐type organic semiconductors based on an asymmetric fluoranthene imide unit is reported, whose intermolecular packing and aggregation behavior in the thin film state can be effectively controlled by regulating the cyano substitution sites and alkyl chain types in the imide group. F10 with cyano groups at 4,9‐sites and branched 2‐ethylhexyl chain encouragingly shows a highly ordered single‐crystal‐like molecular packing in solution‐processed thin film after thermal annealing, and thus the resulting organic field‐effect transistors exhibit impressive charge transport performance, with the electron mobility as high as 0.116 cm2 V−1 s−1. This work opens a new avenue for developing high‐performance solution‐processed n‐type semiconductors.
Mechanically Robust Photonic‐Ionic Skin Cross‐Linked by Metal–Imidazole Interactions
Authors: Sun Yudong , Wang Xiaocheng , Li Hongyu , Zhang Shufen , Niu Wenbin
Published: May 2024

Photonic‐ionic skins (PI‐skins) featuring multi‐signal synergistic outputs exhibit fascinating interactive sensing potential in flexible iononics. However, the existing ones are susceptible to irreversible damage in usage due to their poor toughness and deficiency in self‐healing. Herein, a novel tough mechanochromic PI‐skin is ingeniously constructed, from both molecular engineering and nanostructural engineering perspectives, via integrating the ordered photonic array and robust metal‐imidazole cross‐linked network. The PI‐skin displays synchronous structural color variation and sensitive electrical response under strain. Notably, the synergy of dense physical cross‐linking network and microphase‐separation structure achieved by strong metal‐imidazole coordination greatly promotes energy dissipation. PI‐skin possesses a combination of exceptional properties, including high fracture strength (8.22 MPa), remarkable toughness (10.23 MJ m−3), and robust adhesion behavior (2.30 MPa). Furthermore, favorable self‐healing capability at room temperature is realized thanks to the dynamic topological rearrangement of metal‐imidazole coordination. The PI‐skin demonstrates promising uses as a visually interactive wearable device for human motion monitoring and remote communication. This work not only broadens design considerations for the development of high‐performance artificial skins but also offers a general optical platform for high‐level interactive wearable devices.
Interphase‐Designable Additive‐Enabled Ethylene Carbonate‐Free Electrolyte for Wide‐Temperature, Long‐Cycling, High‐Voltage Lithium Metal Batteries
Authors: Huang Junda , Li Yong , Liu Jiandong , Liu Quanhui , Alodhayb Abdullah N. , Ma Jianmin
Published: May 2024

Increasing the upper cut‐off voltage of the LiNixCoyMn1‐x‐yO2 (NCM)‐based lithium‐metal batteries (LMBs) is highly pursued for achieving high battery energy density. However, the cycling stability of high‐voltage LMBs, which is associated with ethylene carbonate electrolytes, remains greatly challenging. Herein, an interphase‐designable additive‐enabled ethylene carbonate‐free electrolyte strategy is proposed for achieving 4.6 V Li||NCM811 battery with long cycling life from 55 to −30 °C. The solvent characteristics of ethyl methyl carbonate endow LMBs with potential merits in high voltage, wide temperature, and cycling stability, which are further strengthened by the additive, 1,5‐difluoro‐2,4‐dinitrobenzene (FNB), for optimizing electrode electrolyte interphases. The sturdy LiF‐rich and LiNxOy‐contained electrode/electrolyte interphase on cathode/anode surfaces can protect two electrodes well from electrolyte corrosion and also reduce excessive electrolyte decomposition. As expected, the Li||NCM811 batteries can maintain 70% capacity retention after 500 cycles with superior high‐temperature and low‐temperature performance (from 55 to −30 °C). The 6.8Ah pouch cells with this electrolyte can achieve a high energy density of up to 505 Wh kg−1.
Ultrathin 2D Alloyed Cu−Ga−Zn−S Curved Nanobelts for Boosting Visible‐Light Photocatalytic Hydrogen Evolution
Authors: Li Yu , Ma Mengmeng , Yi Ding , Zhou Qi , Chen Jie , Bian Yangyang , Niu Wentao , Yang Chunhe , Yin Zhe , Wang Zhijie , Tang Aiwei
Published: May 2024

2D semiconductor nanomaterials have received significant attention as photocatalysts for solar‐to‐hydrogen conversion due to their robust light absorption capacity, large specific surface area, and superior electron transport characteristics. Nevertheless, it is challenging to develop 2D quaternary copper‐based sulfides (QCSs) with functional integration of conducive structural features for photocatalysis from multiple elements and intricate control conditions. Herein, ultrathin 2D alloyed Cu−Ga−Zn−S (CGZS) curved nanobelts (NBs) are fabricated by using a facile one‐pot colloidal method. Subsequently, the derived Cu31S16‐CGZS Janus heterostructures are designed by increasing Cu concentrations. The formation mechanism of 2D curved alloys and Janus heterostructures is systematically investigated. Without cocatalysts, curved alloyed CGZS NBs demonstrated superior photocatalytic activities of 1264.2 µmol g−1 h−1 compared to Janus heterostructured Cu31S16−CGZS (463.1 µmol g−1 h−1) under visible light (> 400 nm). Experimental and theoretical results unveiled that the improved photocatalytic activities of curved CGZS NBs can be attributed to enhanced charge–carrier separation efficiency resulting from high crystallinity and ultrathin 2D structure, abundant active sites from curved structure, high‐active (0001) crystal facet with the lowest reaction Gibbs energy, work function, and metal‐like properties. This work offers new insights into functional integration into ultrathin 2D QCSs with enhanced visible‐light photocatalytic performance.
Nanoclay Mediated Self‐Promoted Reactive Oxygen Species Releasing Enables Efficient Antimicrobial
Authors: Ji Huichao , Yu Kun , Wang Hao , Yang Huaming
Published: May 2024

Reactive oxygen species (ROS) releasing materials are increasingly used in nanomedicines due to their effectiveness against a broad spectrum of microbes. However, most ROS‐releasing materials rely on external stimuli such as photoirradiation, either through photodynamic or photocatalytic processes, which limits their practical applications. Herein, this work presents a novel nanoclay mediated self‐promoted ROS releasing material called oxygen vacancies‐rich ZnO/kaolinite (Ov‐rich ZnO/Kaol). Both experiments and density functional theory (DFT) calculations reveal that the introduction of kaolinite increases the content of Ov in ZnO, and the change in the electronic structure promotes the process of oxygen adsorption and activation, resulting in the generation of ·O2−through oxygen reduction without photoirradiation. Molecular dynamics simulations confirm that Ov enhances the interaction between the material and bacterial membrane, promoting the bacterial‐killing effect of ·O2−. More importantly, Ov‐rich ZnO/Kaol is successfully prepared on a pilot scale and used to manufacture antibacterial gauze, which showed at least 99% antibacterial activity against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) in the absence of light. The as‐prepared material also exhibited satisfactory biocompatibility and biosafety. This method can offer a more benign approach to address the limitations of traditional photoirradiation‐dependent photosensitizers for antimicrobial gauze.
Cobalt‐based zeolitic imidazole framework derived hollow Co3S4 nanopolyhedrons for supercapacitors
Authors: Zhu Maiyong , Yang Yu , Zhang Xun , Liang Yiming , Tang Jingjing
Published: May 2024

Transition metal sulfides with designed nanostructures are expected to provide superior electrochemical performance when used as electrode materials for pseudocapacitors compared to their oxide counterparts. In this paper, hollow Co3S4 dodecahedra were successfully prepared using cobalt‐based zeolite imidazolium skeleton (ZIF‐67) as the precursor and thioacetamide (TAA) as the sulfur source combined with a facile one‐step vulcanization process. The hollow cavity structure not only shortens the carrier transport distance but also provides a higher specific surface area and abundant active sites, which promotes an efficient mass transfer process. In addition, the one‐step synthesis of hollow Co3S4 has greater advantages than the one‐step synthesis in terms of cost control and process simplification. The specific capacitance of the produced hollow Co3S4 nanopolyhedra was 668 F/g at 1 A/g and remained at 353 F/g at 10 A/g when used as a pseudocapacitor electrode, demonstrating its superior multiplication capability. In addition, the capacitance retention is 86.4% after 5000 cycles at 4 A/g, indicating its long cycle stability. Notably, employing commercial activated carbon as negative electrode and the as‐prepared hollow Co3S4 polyhedrons as positive electrode, the assembled asymmetry supercapacitor device delivers a high energy density of 20.7 Wh/kg at a power density of 716 kW/kg. The capacitance value of the device remains up to 81.4% after 2000 charging/discharging cycles. The simple synthesis process opens new opportunities to develop advanced hollow nanostructures exhibiting potential for various applications.
Salvia hispanica L. (chia) seed improves redox state and reverts extracellular matrix collagen deposition in skeletal muscle of sucrose‐rich diet‐fed rats
Authors: Illesca Paola G. , Ferreira María del R. , Benmelej Adriana , D'Alessandro María Eugenia
Published: May 2024

Skeletal muscle (SkM) is a plastic and dynamic tissue, essential in energy metabolism. Growing evidence suggests a close relationship between intramuscular fat accumulation, oxidative stress (OS), extracellular matrix (ECM) remodeling, and metabolic deregulation in SkM. Nowadays natural products emerge as promising alternatives for the treatment of metabolic disorders. We have previously shown that chia seed administration reverts SkM lipotoxicity and whole‐body insulin resistant (IR) in sucrose‐rich diet (SRD) fed rats. The purpose of the present study was to assess the involvement of OS and fibrosis in SkM metabolic impairment of insulin‐resistant rats fed a long‐term SRD and the effects of chia seed upon these mechanisms as therapeutic strategy. Results showed that insulin‐resistant SRD‐fed rats exhibited sarcopenia, increase in lipid peroxidation, altered redox state, and ECM remodeling‐increased collagen deposition and lower activity of the metalloproteinase 2 (MMP‐2) in SkM. Chia seed increased ferric ion reducing antioxidant power and glutathione reduced form levels, and the activities of glutathione peroxidase and glutathione reductase enzymes. Moreover, chia seed reversed fibrosis and restored the MMP‐2 activity. This work reveals a participation of the OS and ECM remodeling in the metabolic alterations of SkM in our experimental model. Moreover, current data show novel properties of chia seed with the potential to attenuate SkM OS and fibrosis, hallmark of insulin‐resistant muscle.
Engineering the Substrate Specificity of (S)‐β‐Phenylalanine Adenylation Enzyme HitB
Authors: Wang Dawei , Miyanaga Akimasa , Chisuga Taichi , Kudo Fumitaka , Eguchi Tadashi
Published: May 2024

Adenylation enzymes catalyze the selective incorporation of aminoacyl building blocks in the biosynthesis of nonribosomal peptides and related natural products. Although β‐amino acid units are one of the important aminoacyl building blocks in natural product biosynthesis, very little is known about the engineering of β‐amino acid adenylation enzymes. In this study, we engineered the substrate specificity of the (S)‐β‐phenylalanine adenylation enzyme, HitB, involved in the biosynthesis of macrolactam polyketide hitachimycin. Based on the previously determined structure of HitB wild‐type, we mutated Phe328 and Ser293, which are located near the meta and ortho position of the (S)‐β‐phenylalanine moiety, respectively. As a result, the HitB F328V and F328L mutants efficiently activated meta‐substituted (S)‐β‐phenylalanine analogs, and the HitB T293G and T293S mutants efficiently activated ortho‐substituted (S)‐β‐phenylalanine analogs. Structural analysis of the HitB F328L and T293G mutants with the corresponding nonhydrolyzable intermediate analogs revealed an enlarged substrate binding pocket for (S)‐β‐phenylalanine analogs, providing detailed insights into the structural basis for creating enzyme substrate promiscuity. Our findings may be useful for production of various β‐amino acid‐containing natural product analogs.
Self‐Assembly of Discrete Multi‐Chromophoric Systems
Authors: Daniel Jomol , Satheesh Ashwin P , Kartha Kalathil Krishnan
Published: May 2024

Self‐assembly of chromophoric systems is a prerequisite to create well‐ordered, processable nanomaterials with multiple functionalities. In the past two decades, the field of functional organic materials has primarily focused on systems featuring only one type of dye/π‐conjugated unit. Consequently, many reports with mechanistic insights on the self‐assembly of the dyes featuring different molecular packing have been reported. Subsequently, we have witnessed several attempts to organize the multi‐chromophoric systems in solution and solid‐state via different approaches using self‐assembly as a tool. Incorporation of more than one dye is important in creating materials with tuneable optoelectronic properties. Consequently, self‐assembly of more than one chromophoric systems have been investigated to some extent. This review aims to discuss the self‐assembled materials derived from discrete π‐conjugated systems comprising more than one dye units connected through covalent bonding (multi‐chromophoric systems). Molecular design of various multi‐chromophoric systems leading to the formation of crystals, liquid crystals and supramolecular polymers have been correlated with corresponding properties. We envisage that classification of self‐assembled multi‐chromophoric systems, with a note on tuneable optoelectronic properties, can provide a deeper understanding on the molecular design strategies, which is important in the fabrication of functional organic materials with optimum performances.
Enhanced Co‐Adsorption of Alcohols and Amines for Visible Light Driven Oxidative Condensation Using Iron‐Based MOF
Authors: Zhang Kai , Huang Yu , Zhang Dongsheng , Wu Jianghua , Mai Yuanqiang , Cai Nengjun , Wang Chao , Yue Huiyu , Liang Wenting , Su Ren
Published: May 2024

Imines are essential intermediates in organic transformations, and is generally produced by dehydrogenative condensation of alcohols and amines with the assist of specialized catalysts and additives. Heterogeneous photocatalysis provides a sustainable platform for such process without the using of toxic oxidants, yet a functionalized photocatalyst with optimized co‐adsorption of reactants needs to be developed to promote the stoichiometric oxidative condensation under ambient conditions. Here, we show that benzyl alcohol and aniline adsorb non‐interferingly on the Fe node and the linker sites of the MIL‐53(Fe) metal organic frameworks (MOFs), respectively. The co‐adsorption of both reactants barely influences the reduction of molecular oxygen to generate oxygen radicals, resulting in efficient formation of benzaldehyde under visible light. Additionally, the weak adsorption of water together with surface acidity of the MIL‐53(Fe) promote a rapid condensation of benzaldehyde with aniline and the depletion of generated water, achieving an efficient C−N bond creation for a wide range of substrates.
Prebiotic Formation of Peptides Through Bubbling and Arc Plasma
Authors: Wei Wei , Chu Fengjian , Chen Guanru , Zhou Shiwen , Sun Cuirong , Feng Hongru , Pan Yuanjiang
Published: May 2024

The abiotic synthesis of peptides, widely regarded as one of the key chemical reactions on the prebiotic Earth, is thermodynamically constrained in solution. Herein, a simulation of the lightning phenomenon on the sea surface using bubble bursting and arc plasma under ambient conditions enables dipeptide formation of six amino acids with conversion ratios ranging from 2.6 % to 25.5 %. Additionally, we observed the formation of biologically active tripeptides and investigated the stereoselectivity of the dipeptide formation reaction. By utilizing a mixture of 20 amino acids in the reaction, 102 possible dipeptides were generated. These results establish experimental constructions to mimic achievable prebiotic conditions and provide a credible pathway for endogenous biopolymer synthesis on prebiotic Earth.
Protecting oil storage tanks against floods: Natech risk assessment with imprecise probabilities
Authors: Dehghanisanij Alireza , Khakzad Nima , Salzano Ernesto , Amyotte Paul
Published: May 2024

Natechs are technological accidents that are triggered by natural disasters. The increase in the frequency and severity of climatic natural disasters along with the growth of industrialization has accelerated the demand for development of dedicated methodologies for risk assessment and management of Natechs. Due to a lack of accurate and sufficient data, risk assessment of Natechs has largely been based on subjective assumptions and imprecise probabilities, making the assessed risks and the subsequent risk management strategies deficient in terms of cost‐effectiveness. In the present study, evidence theory, as an effective technique for dealing with imprecise probabilities, and Bayesian network, as an effective tool for reasoning under uncertainty, are combined to develop a methodology for risk analysis of Natechs based on imprecise probabilities with no attempt to increase the precision of the input data but the accuracy and cost‐effectiveness of the outcomes. Flotation of oil tanks during floods has been considered to exemplify the methodology. The methodology is demonstrated to outperform conventional approaches where average probabilities or generic probability distributions are used instead of interval probabilities for risk assessment and management.
Formation of Methanol via Fischer‐Tropsch Catalysis by Cosmic Iron Sulphide
Authors: Martinez‐Bachs Berta , Anguera‐Gonzalez Alexia , Pareras Gerard , Rimola Albert
Published: May 2024

Chemical reactions in the gas phase of the interstellar medium face significant challenges due to its extreme conditions (i. e., low gas densities and temperatures), necessitating the presence of dust grains to facilitate the synthesis of molecules inaccessible in the gas phase. While interstellar grains are known to enhance encounter rates and dissipate energy from exothermic reactions, their potential as chemical catalysts remain less explored. Here, we present mechanistic insights into the Fischer‐Tropsch‐type methanol (FTT‐CH3OH) synthesis by reactivity of CO with H2 and using cosmic FeS surfaces as heterogeneous catalysts. Periodic quantum chemical calculations were employed to characterize the potential energy surface of the reactions on the (011) and (001) FeS surfaces, considering different Fe coordination environments and S vacancies. Kinetic calculations were also conducted to assess catalytic capacity and allocate reaction processes within the astrochemical framework. Our findings demonstrate the feasibility of FeS‐based astrocatalysis in the FTT‐CH3OH synthesis. The reactions and their energetics were elucidated from a mechanistic standpoint. Kinetic analysis demonstrates the temperature dependency of the simulated processes, underscoring the compulsory need of energy sources considering the astrophysical scenario. Our results provide insights into the presence of CH3OH in diverse regions where current models struggle to explain its observational quantity.
Velocity Map Imaging Photoelectron Spectroscopy of Silver Iodide Aerosol Particles
Authors: Danilović Danijela , Nahon Laurent , Garcia Gustavo A. , Milosavljević Aleksandar R. , Vukmirović Nenad , Dojčilović Radovan , Tošić Dragana , Djoković Vladimir , Božanić Dušan K.
Published: May 2024

The valence band electronic structure of isolated silver iodide nanoparticles (AgI NP) was investigated by vacuum‐ultraviolet aerosol photoelectron spectroscopy using the velocity map imaging technique (VUV VMI‐PES). The VUV VMI‐PES results were obtained for polydisperse aerosol produced by aggregation of hydrocolloid of silver iodide particles 8–15 nm in size. The ionization energy of the AgI particles was found to be 6.0±0.1 eV with respect to the vacuum level. The DFT calculations showed that the main contribution to the density of AgI electronic states in the valence region originates from I 5p orbitals. The dependence of the asymmetry parameter on the electron energy showed that the value of the characteristic energy loss of excited photoelectrons was 2.7 eV, which coincided with the band gap of the nanomaterial.
Janus Cr2BN Monolayer with Ferroelectricity and Room‐Temperature Ferromagnetism
Authors: Yan Xu , Wang Junyuan , Liu Yong , Yang Guochun
Published: May 2024

Janus monolayers, a special kind of two‐dimensional materials, offer an exciting platform for the development of novel electronic/spintronic devices because of their out‐of‐plane asymmetry. Herein, we propose a sandwich liked Janus tetragonal Cr2BN monolayer with ferroelectricity and ferromagnetism through first‐principles calculations. The predicted magnetic moment is up to ~3.0 μB/Cr originating from the distorted square crystal field induced by out‐of‐plane asymmetry. The Cr2BN monolayer possesses an intrinsic ferromagnetism with a high Curie temperature of 383 K and a sizeable magnetic anisotropy energy of 171 μeV/Cr. Its robust ferromagnetism, dominating by the multi‐anion mediated super‐exchange interactions, can even resist −5 % ~5 % biaxial strain. Its large cohesive energy and high dynamical/thermal stability provide a strong feasibility for experimental synthesis. These intriguing properties render the Cr2BN monolayer a promising material for nanoscale spintronic devices.
Inhibition of HDAC2 sensitises antitumour therapy by promoting NLRP3/GSDMD‐mediated pyroptosis in colorectal cancer
Authors: Guan Xin , Liu Ruiqi , Wang Bojun , Xiong Ruxin , Cui Luying , Liao Yuanyu , Ruan Yuli , Fang Lin , Lu Xiaolin , Yu Xuefan , Su Dan , Ma Yue , Dang Tianjiao , Chen Zhuo , Yao Yuanfei , Liu Chao , Zhang Yanqiao
Published: May 2024

Background

Although numerous studies have indicated that activated pyroptosis can enhance the efficacy of antitumour therapy in several tumours, the precise mechanism of pyroptosis in colorectal cancer (CRC) remains unclear.

Methods

Pyroptosis in CRC cells treated with antitumour agents was assessed using various techniques, including Western blotting, lactate dehydrogenase release assay and microscopy analysis. To uncover the epigenetic mechanisms that regulate NLRP3, chromatin changes and NLRP3 promoter histone modifications were assessed using Assay for Transposase‐Accessible Chromatin using sequencing and RNA sequencing. Chromatin immunoprecipitation‒quantitative polymerase chain reaction was used to investigate the NLRP3 transcriptional regulatory mechanism. Additionally, xenograft and patient‐derived xenograft models were constructed to validate the effects of the drug combinations.

Results

As the core molecule of the inflammasome, NLRP3 expression was silenced in CRC, thereby limiting gasdermin D (GSDMD)‐mediated pyroptosis. Supplementation with NLRP3 can rescue pyroptosis induced by antitumour therapy. Overexpression of HDAC2 in CRC silences NLRP3 via epigenetic regulation. Mechanistically, HDAC2 suppressed chromatin accessibility by eliminating H3K27 acetylation. HDAC2 knockout promotes H3K27ac‐mediated recruitment of the BRD4‐p‐P65 complex to enhance NLRP3 transcription. Inhibiting HDAC2 by Santacruzamate A in combination with classic antitumour agents (5‐fluorouracil or regorafenib) in CRC xenograft‐bearing animals markedly activated pyroptosis and achieved a significant therapeutic effect. Clinically, HDAC2 is inversely correlated with H3K27ac/p‐P65/NLRP3 and is a prognostic factor for CRC patients.

Conclusion

Collectively, our data revealed a crucial role for HDAC2 in inhibiting NLRP3/GSDMD‐mediated pyroptosis in CRC cells and highlighted HDAC2 as a potential therapeutic target for antitumour therapy.

Highlights

Silencing of NLRP3 limits the GSDMD‐dependent pyroptosis in colorectal cancer.

HDAC2‐mediated histone deacetylation leads to epigenetic silencing of NLRP3.

HDAC2 suppresses the NLRP3 transcription by inhibiting the formation of H3K27ac/BRD4/p‐P65 complex.

Targeting HDAC2 activates pyroptosis and enhances therapeutic effect.
Human metabolism of the semi‐synthetic cannabinoids hexahydrocannabinol, hexahydrocannabiphorol and their acetates using hepatocytes and urine samples
Authors: Lindbom Karin , Norman Caitlyn , Baginski Steven , Krebs Lucas , Stalberga Darta , Rautio Tobias , Wu Xiongyu , Kronstrand Robert , Gréen Henrik
Published: May 2024

Hexahydrocannabinol (HHC), hexahydrocannabiphorol (HHCP) and their acetates, HHC‐O and HHCP‐O, respectively, are emerging in Europe as alternatives to tetrahydrocannabinol (THC). This study aimed to elucidate the metabolic pathways of the semi‐synthetic cannabinoids HHC, HHCP, HHC‐O and HHCP‐O from incubation with human hepatocytes. The metabolites of HHC were also identified in authentic urine samples. HHC, HHCP, HHC‐O and HHCP‐O were incubated with primary human hepatocytes for 1, 3 and 5 h. Authentic urine samples from cases screened positive for cannabis in blood using ELISA but confirmed negative were analysed both non‐hydrolysed and hydrolysed for HHC metabolites. Potential metabolites were identified using ultra‐high performance liquid chromatography (UHPLC) coupled to a quadrupole time‐of‐flight mass spectrometer (QToF‐MS). HHC and HHCP were primarily metabolised through monohydroxylation (monoOH), followed by oxidation to a carboxylic acid metabolite. HHC‐O and HHCP‐O were rapidly metabolised to HHC and HHCP, respectively. In authentic urine samples, 18 different metabolites were identified, and 99.3% of hydroxylated metabolites were glucuronidated. 11‐OH‐HHC, 5′OH‐HHC and another metabolite with a monoOH on the side chain were the only metabolites present in all 16 urine samples. The metabolism of HHC and HHCP were similar, although the longer alkyl side chain of HHCP (heptyl) led to greater hydroxylation on the side chain than HHC (pentyl). The use of HHC and HHCP can be differentiated from the use of THC and other phytocannabinoids, but the use of the acetate analogues may not be differentiable from their non‐acetate analogues.
Aboveground biomass determines canopy rainfall interception loss in Semiarid Grassland Communities
Authors: Luo Yang , Yang Quan , Zhou Junjie , Jian Chunxia , Chen Zhifei , Xiong Peifeng , Palta Jairo A. , Xu Bingcheng
Published: May 2024

Canopy rainfall interception is one key hydrological process, affecting rainwater redistribution and effectiveness in semiarid regions. Canopy rainfall interception loss is jointly influenced by meteorology, vegetation and topography. The canopy water storage capacity (S), rainfall interception depth (Im) and ratio (I%) and vegetation characteristics, together with topographic factors of three grassland communities (dominated by Bothriochloa ischaemum, Lespedeza davurica and Artemisia gmelinii, respectively) were investigated on the Loess Plateau of China during the main growing season (June to September). Results showed that Im ranged from 0.55 to 0.89 mm and I% ranged from 6.14% to 12.1%, with the maximum values occurring in August for three communities, and A. gmelinii community had the largest Im (0.89 mm) and I% (12.1%). The Im and I% were positively correlated with aboveground biomass (AGB), coverage (Cov), leaf area index (LAI), community‐weighted mean height (CWMH) and altitude (Alt), but negatively correlated with slope degree and rainfall intensity (RI). Hierarchical partitioning analysis (HPA) showed that AGB had the highest contribution for Im (20.3%), while Alt had the highest contribution for I% (18.2%). The regression models based on forward selection could effectively predict the values of Im (R2 = 0.802, RMSE = 0.049) and I% (R2 = 0.546, RMSE = 1.434). Topographic factors (altitude, slope degree and aspect) indirectly influenced both Im and I% by modulating vegetation characteristics (AGB, Cov, etc.). All these indicated that aboveground biomass mainly determines grassland community rainfall interception loss in the semiarid Loess Plateau.
2024 update in heart failure
Authors: Beghini Alberto , Sammartino Antonio Maria , Papp Zoltán , von Haehling Stephan , Biegus Jan , Ponikowski Piotr , Adamo Marianna , Falco Luigi , Lombardi Carlo Mario , Pagnesi Matteo , Savarese Gianluigi , Metra Marco , Tomasoni Daniela
Published: May 2024

In the last years, major progress has occurred in heart failure (HF) management. The 2023 ESC focused update of the 2021 HF guidelines introduced new key recommendations based on the results of the last years of science. First, two drugs, sodium–glucose co‐transporter‐2 (SGLT2) inhibitors and finerenone, a novel nonsteroidal, selective mineralocorticoid receptor antagonist (MRA), are recommended for the prevention of HF in patients with diabetic chronic kidney disease (CKD). Second, SGLT2 inhibitors are now recommended for the treatment of HF across the entire left ventricular ejection fraction spectrum. The benefits of quadruple therapy in patients with HF with reduced ejection fraction (HFrEF) are well established. Its rapid and early up‐titration along with a close follow‐up with frequent clinical and laboratory re‐assessment after an episode of acute HF (the so‐called ‘high‐intensity care’ strategy) was associated with better outcomes in the STRONG‐HF trial. Patients experiencing an episode of worsening HF might require a fifth drug, vericiguat. In the STEP‐HFpEF‐DM and STEP‐HFpEF trials, semaglutide 2.4 mg once weekly administered for 1 year decreased body weight and significantly improved quality of life and the 6 min walk distance in obese patients with HF with preserved ejection fraction (HFpEF) with or without a history of diabetes. Further data on safety and efficacy, including also hard endpoints, are needed to support the addition of acetazolamide or hydrochlorothiazide to a standard diuretic regimen in patients hospitalized due to acute HF. In the meantime, PUSH‐AHF supported the use of natriuresis‐guided diuretic therapy. Further options and most recent evidence for the treatment of HF, including specific drugs for cardiomyopathies (i.e., mavacamten in hypertrophic cardiomyopathy and tafamidis in transthyretin cardiac amyloidosis), device therapies, cardiac contractility modulation and percutaneous treatment of valvulopathies, with the recent finding from the TRILUMINATE Pivotal trial, are also reviewed in this article.
Pro‐ and antitumorigenic functions of γδ T cells
Authors: Fiala Gina J. , Lücke Jöran , Huber Samuel
Published: May 2024

γδ T cells are a subset of T cells that are characterized by the expression of a TCR‐γδ instead of a TCR‐αβ. Despite being outnumbered by their αβ T cell counterpart in many tissues, studies from the last 20 years underline their important and non‐redundant roles in tumor and metastasis development. However, whether a γδ T cell exerts pro‐ or antitumorigenic effects seems to depend on a variety of factors, many of them still incompletely understood today. In this review, we summarize mechanisms by which γδ T cells exert these seemingly contradictory effector functions in mice and humans. Furthermore, we discuss the current view on inducing and inhibiting factors of γδ T cells during cancer development.
Fracture evaluation of the plutonic basement in the Upper Magdalena Basin: Implications for the development of naturally fractured reservoirs in the Northern Andes
Authors: Rodríguez‐Cuevas Maryi , Cardona Agustín , Monsalve Gaspar , Zapata Sebastián , Valencia‐Gómez Juan Camilo
Published: May 2024

Plutonic rocks typically have negligible matrix porosity and permeability. However, fractures and mineral alterations create storage space and flow pathways that turn plutonic rocks into fluid reservoirs. Despite significant hydrocarbon discoveries, naturally fractured reservoirs in plutonic rocks have been poorly studied. In most Colombian basins, the crystalline basement has undergone multiple deformational events and is thrust over the Cretaceous to Cenozoic source and reservoir rocks of the conventional petroleum system. This structural configuration is ideal for the migration of oil into a fractured basement. A multiscale fracture analysis, including field, petrographical and petrophysical techniques was conducted on the Permian and Jurassic plutonic basement of Upper Magdalena Basin in order to understand the controls on brittle deformation, the development of fracture networks and their potential to form hydrocarbon reservoirs. The results indicate that protolith textures and structures, including magmatic and mylonitic foliation, favours fracturing. Dykes exhibit higher fracture density (7–48 fractures/m), porosity (mean = 0.4%) and permeability (mean = 125,818.75 mD) than the host rock (2–25 fractures/m; 0.23%; 12,066.09 mD). Intersection zones from regional faults, are characterized by the highest fracture and lineament intensity. Our results suggest that dyke swarms and interacting damage zones can significantly enhance the reservoir quality of plutonic rocks by providing storage in fractures and fluid pathways to the host rock.
Socio‐demographic and infrastructural variables influencing maternal risk concentration among ever‐married women of reproductive age in rural West Bengal, India
Authors: Ghosh Alokananda , Mistri Biswaranjan
Published: May 2024

Background

The risk of a woman dying as a result of pregnancy or childbirth during her lifetime is about one in six in the poorest parts of the world.

Objectives

The present study aims to determine prevalence of maternal risk and the influencing variables among ever‐married women belonging to the reproductive age group (15–49) of Birbhum district, West Bengal.

Methods

A cohort‐based retrospective cross‐sectional study was carried out among the sample of 229 respondents through a purposive stratified random sampling method and a pre‐designed semi‐structured questionnaire. The ordinal logistic regression (OLR) model was taken as a tool of assessment. Before developing the proportional OLR model, we have checked the multicollinearity effect among the predictors and the first‐order effect modifier was evaluated as well. We performed data analysis using SPSS version 26.

Results

The result shows that illiterate women (Odds ratios [OR] = 2.81, 95% CI, 0.277–1.791), from lower standard of living (OR = 1.14, 95% CI, −0.845–1.116), married before the age of 15 years (OR = 21.96, 95% CI, −0.55–6.73) and between the age of 15–18 years (OR = 24.51. 95% CI, −0.45–6.85) are more likely to be affected by the higher concentration of maternal risk. Other important predictor is the time of pregnancy registration. Considering the transport and related en‐route causalities, the result portraying a clear picture where the distance and travel time becoming significant factors in determining the concentration of maternal risk.

Conclusion

Incidences of child marriages should be restricted. Eradicating factors influencing an individual's decision to seek care would be an essential contribution in excluding the dominant maternal risk factors.