bluuebunny/crossref_metadata_2025 huggingface dataset:
Increasing the Number of Aluminum Atoms in T3 Sites of a Mordenite Zeolite by Low‐Pressure SiCl4 Treatment to Catalyze Dimethyl Ether Carbonylation
Authors: Liu Rongsheng , Fan Benhan , Zhang Wenna , Wang Linying , Qi Liang , Wang Yingli , Xu Shutao , Yu Zhengxi , Wei Yingxu , Liu Zhongmin
Published: February 2022

Controlling the location of aluminum atoms in a zeolite framework is critical for understanding structure–performance relationships of catalytic reaction systems and tailoring catalyst design. Herein, we report a strategy to preferentially relocate mordenite (MOR) framework Al atoms into the desired T3 sites by low‐pressure SiCl4 treatment (LPST). High‐field 27Al NMR was used to identify the exact location of framework Al for the MOR samples. The results indicate that 73 % of the framework Al atoms were at the T3 sites after LPST under optimal conditions, which leads to controllably generating and intensifying active sites in MOR zeolite for the dimethyl ether (DME) carbonylation reaction with higher methyl acetate (MA) selectivity and much longer lifetime (25 times). Further research reveals that the Al relocation mechanism involves simultaneous extraction, migration, and reinsertion of Al atoms from and into the parent MOR framework. This unique method is potentially applicable to other zeolites to control Al location.
Near‐Infrared Light‐Activatable Spherical Nucleic Acids for Conditional Control of Protein Activity
Authors: Zhang Jingfang , Zhao Peng , Li Wenzhe , Ye Ling , Li Lele , Li Zhengping , Li Mengyuan
Published: February 2022

Optical control of protein activity represents a promising strategy for precise modulation of biological processes. We report rationally designed, aptamer‐based spherical nucleic acids (SNAs) capable of noninvasive and programmable regulation of target protein activity by deep‐tissue‐penetrable near‐infrared (NIR) light. The photoresponsive SNAs are constructed by integrating activatable aptamer modules onto the surface of upconversion nanoparticles. The SNAs remain inert but can be remotely reverted by NIR light irradiation to capture the target protein and thus function as an enzyme inhibitor, while introduction of antidote DNA could further reverse their inhibition functions. Furthermore, we demonstrate the potential of the SNAs as controllable anticoagulants for the NIR light‐triggered regulation of thrombin function. Ultimately, the availability of diverse aptamers would allow the design to regulate the activities of various proteins in a programmable manner.
Cove‐Edged Hexa‐peri‐hexabenzo‐bis‐peri‐octacene: Molecular Conformations and Amplified Spontaneous Emission
Authors: Gu Yanwei , Vega‐Mayoral Victor , Garcia‐Orrit Saül , Schollmeyer Dieter , Narita Akimitsu , Cabanillas‐González Juan , Qiu Zijie , Müllen Klaus
Published: February 2022

The bottom‐up synthesis of an unprecedentedly large cove‐edged nanographene, hexa‐peri‐hexabenzo‐bis‐peri‐octacene (HBPO), is reported in this work. Chiral high‐performance liquid chromatography and density functional theory (DFT) calculations revealed multiple conformations in solution. Two different molecular conformations, “waggling” and “butterfly”, were found in crystals by X‐ray crystallography, and the selectivity of conformations could be tuned by solvents. The optoelectronic properties of HBPO were investigated by UV/Vis absorption and fluorescence spectroscopies, cyclic voltammetry, and DFT calculations. The contorted geometry and branched alkyl groups suppress the aggregation of HBPO in solution, leading to a high fluorescence quantum yield of 79 %. The optical‐gain properties were explored through transient absorption and amplified spontaneous emission spectroscopies, which enrich the choices of edge structures for potential applications in laser cavities.
The SARS‐CoV‐2 Spike Glycoprotein Directly Binds Exogeneous Sialic Acids: A NMR View
Authors: Unione Luca , Moure María J. , Lenza Maria Pia , Oyenarte Iker , Ereño‐Orbea June , Ardá Ana , Jiménez‐Barbero Jesús
Published: February 2022

The interaction of the SARS CoV2 spike glycoprotein with two sialic acid‐containing trisaccharides (α2,3 and α2,6 sialyl N‐acetyllactosamine) has been demonstrated by NMR. The NMR‐based distinction between the signals of those sialic acids in the glycans covalently attached to the spike protein and those belonging to the exogenous α2,3 and α2,6 sialyl N‐acetyllactosamine ligands has been achieved by synthesizing uniformly 13C‐labelled trisaccharides at the sialic acid and galactose moieties. STD‐1H,13C‐HSQC NMR experiments elegantly demonstrate the direct interaction of the sialic acid residues of both trisaccharides with additional participation of the galactose moieties, especially for the α2,3‐linked analogue. Additional experiments with the spike protein in the presence of a specific antibody for the N‐terminal domain and with the isolated receptor binding and N‐terminal domains of the spike protein unambiguously show that the sialic acid binding site is located at the N‐terminal domain.
Dynamic Full‐Color Tuning of Organic Chromophore in a Multi‐Stimuli‐Responsive 2D Flexible MOF
Authors: Yao Zhao‐Quan , Wang Kai , Liu Rui , Yuan Yi‐Jia , Pang Jing‐Jing , Li Quan Wen , Shao Tian Yin , Li Zhi Gang , Feng Rui , Zou Bo , Li Wei , Xu Jian , Bu Xian‐He
Published: February 2022

Developing universal stimuli‐responsive materials capable of emitting a broad spectrum of colors is highly desirable. Herein, we deliberately grafted a conformation‐adaptable organic chromophore into the established coordination space of a flexible metal–organic framework (MOF). In terms of the coupled structural transformations and the space confinement, the chromophore in the MOF matrix underwent well‐regulated conformational changes under physical and chemical stimuli, simultaneously displaying thermo‐, piezo‐, and solvato‐fluoro‐chromism with color tunability over the visible range. Owing to the resilient nature and the reduced dimensionality of the selected coordination space, all three color modulations behaved in a sensitive and self‐reversible manner, each following a linear correlation of the emission maximum with stimulus. Single‐crystal X‐ray diffraction of the variable‐temperature structures and solvent‐inclusion crystals elucidated the intricate color varying mechanisms.
Real‐Time Fluorescent Monitoring of Kinetically Controlled Supramolecular Self‐Assembly of Atom‐Precise Cu8 Nanocluster
Authors: Sun Pan‐Pan , Han Bao‐Liang , Li Hong‐Guang , Zhang Cheng‐Kai , Xin Xia , Dou Jian‐Min , Gao Zhi‐Yong , Sun Di
Published: February 2022

Kinetically stable and long‐lived intermediates are crucial in monitoring the progress and understanding of supramolecular self‐assembly of diverse aggregated structures with collective functions. Herein, the complex dynamics of an atomically precise CuI nanocluster [Cu8(tBuC6H4S)8(PPh3)4] (Cu8a) is systematically investigated. Remarkably, by monitoring the aggregation‐induced emission (AIE) and electron microscopy of the kinetically stable intermediates in real time, the directed self‐assembly (DSA) process of Cu8a is deduced. The polymorphism and different emission properties of Cu NCs aggregates were successfully captured, allowing the structure–optical property relationship to be established. More importantly, the utilization of a mathematical “permutation and combination” ideology by introducing a heterogeneous luminescent agent of a carbon dot (CD) to Cu8a aggregates enriches the “visualization” fluorescence window, which offers great potential in real time application for optical sensing of materials.
Proton‐Assisted Aqueous Manganese‐Ion Battery Chemistry
Authors: Bi Songshan , Zhang Yan , Deng Shenzhen , Tie Zhiwei , Niu Zhiqiang
Published: February 2022

Aqueous manganese‐ion batteries (MIBs) are promising energy storage systems because of the distinctive merits of Mn metal, in terms of high abundance, low cost, nontoxicity, high theoretical capacity and low redox potential. Conventional MIBs are based on the Mn2+ ion storage mechanism, whereas the capacity in cathode materials is generally limited due to the high charge density and large solvated ionic radius of Mn2+ ions in aqueous electrolytes. Herein, proton intercalation chemistry is introduced in aqueous MIBs, in which the layered Al0.1V2O5⋅1.5 H2O (AlVO) cathode exhibits a consequent Mn2+ and H+ ion intercalation/extraction process. Such an energy storage mechanism contributes to enhanced electrochemical performance, including high capacity, fast reaction kinetics and stable cycling behavior. Benefiting from this proton intercalation chemistry, the aqueous Mn||AlVO cells could deliver high specific energy and power simultaneously. This work provides a route for the design of high‐performance aqueous MIBs.
Divergent Total Synthesis of Four Kopsane Alkaloids: N‐Carbomethoxy‐10,22‐dioxokopsane, Epikopsanol‐10‐lactam, 10,22‐Dioxokopsane, and N‐Methylkopsanone
Authors: Qin Bo , Lu Zhepei , Jia Yanxing
Published: February 2022

We have achieved the divergent total synthesis of four kopsane alkaloids which share a complex heptacyclic caged ring system. Key transformations include an asymmetric Diels–Alder reaction to assemble the central bicyclo[2.2.2]octane moiety and the quaternary stereocenter at C20, a SmI2‐mediated cascade reduction/aldol reaction to construct the five‐membered ring and the quaternary stereocenter at C7, and a late‐stage cascade reductive amination/cyclization to establish the highly strained caged ring system.
Self‐assembly of Gold Nanoparticles into an Adjustable Plasmonic 3D Lattice using Janus‐type Forked Mesogenic Ligands
Authors: Zhao Yang‐yang , Cao Yu , Siligardi Giuliano , Mehl Georg H. , Liu Feng , Ungar Goran
Published: February 2022

We report the formation of a 3D body‐centred self‐assembled superlattice of gold nanoparticles whose interparticle gap, and hence its plasmonic properties, are adjustable exclusively in the xy‐plane. Thus, even though the particles are spherical, their anisotropic packing generates tailorable plasmonic dichroism. The gold nanoparticles are coated with forked ligands containing two mesogens: either two cholesterols (“twin”), one cholesterol and one azobenzene (“Janus”), or a mixture of the two. Beside the body‐centered arrangement of gold nanoparticles, the structure also contains unusual two‐dimensionally x‐y dual undulated (eggbox‐like) smectic‐like layers of mesogens. Moreover, the presence of azobenzene mesogens allows the superlattice to be melted through UV‐induced photo‐isomerization; the process is reversible displaying low fatigue on repeated cycling.
A Rhodol‐based Fluorescent Probe with a Pair of Hydrophilic and Rotatable Wings for Sensitively Monitoring Intracellular Polarity
Authors: Wasim Afzal Muhammad , Duan Kaixuan , Zhang Yanhui , Gao Ying , Qin Bo , Wang Guangwei , Lei Lin , Tang Haoyang , Guo Yuan
Published: February 2022

Cell polarity, as a vital intracellular microenvironment characteristic, has immense effects on numerous pathological and biological processes. Therefore, the tracking of polarity variations is highly essential to explore the role and mechanism of the polarity in pathophysiological processes. Herein, we designed and synthesized a novel rhodol‐based fluorescent probe (RDS) sensitive to polarity by introducing a bis(2‐hydroxyethylthio)methyl group, like a pair of hydrophilic and rotatable wings, into the rhodol skeleton. This unique design makes RDS adopt the colorless and non‐fluorescent spirocyclic form in a low‐polarity medium while the colored and fluorescent ring‐open form is present in a high‐polarity system, resulting in a positive‐correlation response of fluorescence intension to polarity. Importantly, RDS was successfully applied to monitor the polarity changes in living cells including cancer cells, healthy cells and senescent healthy cells, visualizing that the polarity of cancer cells is lower than that of healthy cells in which the more senescent ones have higher polarity.
Detection of cellular metabolites by redox enzymatic cascades
Authors: Tinikul Ruchanok , Trisrivirat Duangthip , Chinantuya Wachirawit , Wongnate Thanyaporn , Watthaisong Pratchaya , Phonbuppha Jittima , Chaiyen Pimchai
Published: February 2022

Detection of cellular metabolites that are disease biomarkers is important for human healthcare monitoring and assessing prognosis and therapeutic response. Accurate and rapid detection of microbial metabolites and pathway intermediates is also crucial for the process optimization required for development of bioconversion methods using metabolically engineered cells. Various redox enzymes can generate electrons that can be employed in enzyme‐based biosensors and in the detection of cellular metabolites. These reactions can directly transform target compounds into various readout signals. By incorporating engineered enzymes into enzymatic cascades, the readout signals can be improved in terms of accuracy and sensitivity. This review critically discusses selected redox enzymatic and chemoenzymatic cascades currently employed for detection of human‐ and microbe‐related cellular metabolites including, amino acids, d‐glucose, inorganic ions (pyrophosphate, phosphate, and sulfate), nitro‐ and halogenated phenols, NAD(P)H, fatty acids, fatty aldehyde, alkane, short chain acids, and cellular metabolites.
Simulated confluence on micropatterned substrates correlates responses regulating cellular differentiation
Authors: Berent Zachary T. , Jain Ishita , Underhill Gregory H. , Wagoner Johnson Amy J.
Published: February 2022

While cells are known to behave differently based on the size of micropatterned islands, and this behavior is thought to be related to cell size and cell−cell contacts, the exact threshold for this difference between small and large islands is unknown. Furthermore, while cell size and cell−cell contacts can be easily manipulated on small islands, they are harder to measure and continually monitor on larger islands. To investigate this size threshold, and to explore cell size, cell−cell contacts, and differentiation, we use a previously established simulation to plan experiments and explain results that we could not explain from experiments alone. We use five seeding densities covering three orders of magnitude over 25−500 µm diameter islands to examine markers of proliferation and differentiation in bone marrow‐derived mesenchymal cells (cell line). We show that osteogenic markers are most accurately described as a function of confluence for larger islands, but a function of time for smaller islands. We further show, using results of the simulation, that cell size and cell‐cell contacts are also related to confluence on larger islands, but only cell−cell contacts are related to confluence on small islands. This study uses simulations to explain experimental results that could not be explained from experiments alone. Together, the simulations and experiments in this study show different differentiation patterns on large and small islands, and this simulation may be useful in planning future studies related to this study.
Synthesis, Antimicrobial Evaluation, and Molecular Modeling Studies of New Thiosemicarbazide‐Triazole Hybrid Derivatives of (S)‐Naproxen
Authors: Han M. İhsan , Ince Ufuk , Gündüz Miyase Gözde , Küçükgüzel Ş. Güniz
Published: February 2022

The discovery of new antimicrobial molecules is crucial for combating drug‐resistant bacterial and fungal infections that pose a dangerous threat to human health. In the current research, we applied a molecular hybridization approach to synthesize original thiosemicarbazide‐triazole derivatives starting from (S)‐naproxen (7a–7k). After structural characterization using FT‐IR, 1H‐NMR, 13C‐NMR, and HR‐MS, the obtained compounds were screened for their antimicrobial activities against Staphylococcus aureus ATCC 29213, Escherichia coli ATCC 25922, Candida albicans ATCC 10231 and their isolates, as well. Although all compounds were found to be moderate antimicrobial agents, in general, their antibacterial activities were better than antifungal effects. Among the tested compounds, 7j carrying nitrophenyl group on the thiosemicarbazide functionality represented the best MIC value against S. aureus isolate. Finally, molecular docking studies were performed in the active pocket of S. aureus flavohemoglobin to rationalize the obtained biological data.
Principles of Amino‐Acid‐Nucleotide Interactions Revealed by Binding Affinities between Homogeneous Oligopeptides and Single‐Stranded DNA Molecules
Authors: Wang Pengyu , Fang Xiaocui , Du Rong , Wang Jiali , Liu Mingpeng , Xu Peng , Li Shiqi , Zhang Kaiyue , Ye Siyuan , You Qing , Yang Yanlian , Wang Chen
Published: February 2022

We have determined the binding strengths between nucleotides of adenine, thymine, guanine and cytosine in homogeneous single stranded DNAs and homo‐octapeptides consisting of 20 common amino acids. We use a bead‐based fluorescence assay for these measurements in which octapeptides are immobilized on the bead surface and ssDNAs are in solutions. Comparative analyses of the distribution of the binding energies reveal unique binding strength patterns assignable to each DNA nucleotide and amino acid originating from the chemical structures. Pronounced favorable (such as Arg‐G, etc.) and unfavorable (such as Ile‐T, etc.) binding interactions can be identified in selected groups of amino acid and nucleotide pairs that could provide basis to elucidate energetics of amino‐acid‐nucleotide interactions. Such interaction selectivity, specificity and polymorphism establish the contributions from DNA backbone, DNA bases, as well as main chain and side chain of the amino acids.
The effect of all‐trans retinoic acid on the mitochondrial function and survival of cardiomyoblasts exposed to local photodamage
Authors: Kurekova Simona , Sevcikova Tomaskova Zuzana , Andelova Natalia , Macejova Dana , Cervienkova Michaela , Brtko Julius , Ferko Miroslav , Grman Marian , Mackova Katarina
Published: February 2022

Using H9C2 cardiomyoblasts, we have shown that all‐trans retinoic acid (ATRA), the biologically active metabolite of vitamin A, affects mitochondrial dynamics and functions. The low dose (10 nM) ATRA stimulates the expression of nuclear retinoid receptors and induces mechanisms that are protective against severe local damage caused by laser irradiation at the mitochondrial level. These changes include increased density of the mitochondrial network, higher number of mitochondrial junctions, and enhanced mitochondrial velocity. Moreover, the treated cells had lower basal level of reactive oxygen species (ROS) and could maintain mitochondrial potential (ΔΨm) after photodamage. Cells treated with 10 nM ATRA had significantly better survival rate after photodamage in comparison to control cells. Cells treated with pharmacological concentration of ATRA (1 µM) expressed higher mitochondrial connectivity without increased motility, which did not lead to better survival or decreased ROS level as was in the case of low‐dose ATRA. The proteomics analysis showed changes in proteins related to cellular metabolism (glycolysis) and respiration in ATRA‐treated cells. The l‐lactate assay confirmed the shift to anaerobic glycolysis in cells treated with 1 µm ATRA, whereas the 10 nM ATRA decreased the level of lactate in medium. The increased levels of cytochrome c or peroxiredoxins 5 level and also lower expression of retinoid and rexinoid receptors were observed in cells treated with 1 µM ATRA. The effect of ATRA is concentration‐dependent; the increased mitochondrial dynamics and slower metabolism at 10 nM ATRA contributed significantly to the chance of survival of the cells after photodamage whereas the higher concentration of ATRA overrode the protective effect and led to the unfavorable ones.
Modified safety techniques for transcatheter repair of superior sinus venosus defects with partial anomalous pulmonary venous drainage using a 100‐mm Optimus‐CVS® covered XXL stent
Authors: Haddad Raymond N. , Bonnet Damien , Gewillig Marc , Malekzadeh‐Milani Sophie
Published: February 2022

We report the first use of a single 100‐mm long custom‐made version of the Optimus‐CVS® balloon‐expandable PTFE‐covered XXL (15‐Zig) stent (AndraTec, GmbH) to eliminate sinus venosus defect left‐to‐right shunt and redirect anomalous right pulmonary veins blood flow through a new walled channel to the left atrium. Anatomical feasibility and strategy decision were guided by ex‐vivo procedure simulation on the patient‐specific 3D printed heart model and in‐vivo balloon interrogation. Modified procedural and implantation techniques are detailed. Immediate and one‐month follow‐up showed excellent outcomes.
Probing the Potential of Hitherto Unexplored Base‐Stabilized Borylenes in Dinitrogen Binding
Authors: Fantuzzi Felipe , Moral Rubi , Dewhurst Rian D. , Braunschweig Holger , Phukan Ashwini K.
Published: February 2022

Computational investigations were carried out to probe the potential of several dicoordinate, singly base‐stabilized borylenes of the form [L→BR] (L=neutral Lewis base) in dinitrogen binding. The calculated reaction free energies and activation barriers associated with the formation of mono‐ and diborylene‐N2 adducts suggest the presence of thermally surmountable kinetic barriers towards their possible isolation. Our results show that the exergonicity of dinitrogen activation and fixation is linearly dependent on the natural charge at the boron center, which can be tuned to design novel boron‐based compounds with potential applications to small‐molecule activation. EDA‐NOCV analysis reveals strong binding of dinitrogen to these base‐stabilized borylenes.
Biological applications of chiral inorganic nanomaterials
Authors: Fan Yuan , Ou‐yang Shaobo , Zhou Dong , Wei Junchao , Liao Lan
Published: February 2022

Chirality is common in nature and plays the essential role in maintaining physiological process. Chiral inorganic nanomaterials with intense optical activity have attracted more attention due to amazing properties in recent years. Over the past decades, many efforts have been paid to the preparation and chirality origin of chiral nanomaterials; furthermore, emerging biological applications have been investigated widely. This review mainly summarizes recent advances in chiral nanomaterials. The top‐down and bottom‐up preparation methods and chirality origin of chiral nanomaterials are introduced; besides, the biological applications, such as sensing, therapy, and catalysis, will be introduced comprehensively. Finally, we also provide a perspective on the biomedical applications of chiral nanomaterials.
Non‐vitamin K oral anticoagulants versus vitamin K antagonists in post transcatheter aortic valve replacement patients with clinical indication for oral anticoagulation: A meta‐analysis
Authors: Chen Yi‐feng , Liu Fei , Li Xi‐wen , Zhang Hou‐jing , Liu Yi‐ge , Lin Lu
Published: February 2022

Background

Current guidelines recommend oral anticoagulation (OAC) following transcatheter aortic valve replacement (TAVR) in patients with clinical indication, but the optimal antithrombotic regimen remains uncertain. We aimed to compare the efficacy and safety of non‐vitamin K oral anticoagulants (NOACs) versus vitamin K antagonists (VKAs) in patients undergoing TAVR with concomitant indication of OAC.

Hypothesis

Comparing with VKAs therapy, NOACs are similar in reducing the all‐cause mortality and major bleeding in post‐TAVR patients requiring OAC medication.

Methods

We searched the databases of PubMed, Embase, and Cochrane library databases to identify studies that investigated NOACs versus VKAs after TAVR in patients with another indication of OAC, which were published before 28th September 28, 2021. The effectiveness of outcomes was all‐cause mortality and stroke or systemic embolism, while the main safety outcome was major and/or life‐threatening bleeding. The hazard ratio (HR) with 95% confidence interval (CI) was used as a measure of treatment effect.

Results

Our search identified eight studies. We included 4947 post‐TAVR patients with another indication of OAC allocated to the NOAC (n = 2146) or VKA groups (n = 2801). There were no significant differences in the all‐cause mortality (HR: 0.91, 95% CI: 0.77–1.08, p = .29, I2 = 47%), stroke or systemic embolism (HR: 0.96, 95% CI: 0.68–1.37, p = .84, I2 = 0%), and major and/or life‐threatening bleeding (HR: 1.09, 95% CI: 0.89–1.32, p = .40, I2 = 30%) in both groups.

Conclusion

Among post‐TAVR patients who required OAC therapy, NOACs therapy compared to VKAs is similar in reducing the all‐cause mortality, stroke or systemic embolism, and major and/or life‐threatening bleeding events.
Substituent Effects in π‐Hole Regium Bonding Interactions Between Au(p‐X‐Py)2Complexes and Lewis Bases: Anab initioStudy
Authors: De las Nieves Piña María , Burguera Sergi , Buils Jordi , Àngel Crespí Miquel , Ernesto Morales Julian , Pons Jordi , Bauzá Antonio , Frontera Antonio
Published: February 2022

Long range substituent effects in regium bonding interactions involving Au(I) linear complexes are investigated for the first time. The Au(I) atom is coordinated to twopara‐substituted pyridine ligands. The interaction energy (RI‐MP2/def2‐TZVP level of theory) of the π‐hole regium bonding assemblies is affected by the pyridine substitution. The Hammett's plot representations for several sets of Lewis bases have been carried out and, in all cases, good regression plots have been obtained (interaction energiesvs. Hammett's σ parameter). The Bader's theory of “atoms‐in‐molecules” has been used to evidence that the electron density computed at the bond critical point that connects the Au‐atom to the electron donor can be used as a measure of bond order in regium bonding. Several X‐ray structures retrieved from the Cambridge Structural Database (CSD) provide experimental support to the existence of π‐hole regium bonding in [Au(Py)2]+derivatives.
Selective Catalytic Transfer Hydrogenation of Lignin to Alkyl Guaiacols Over NiMo/Al‐MCM‐41
Authors: Lu Xinyu , Guo Haoquan , Chen Jiajia , Wang Duoying , Lee Adam F. , Gu Xiaoli
Published: February 2022

Efficient deoxygenation of lignin‐derived bio‐oils is central to their adoption as precursors to sustainable liquid fuels in place of current fossil resources. In‐situ catalytic transfer hydrogenation (CTH), using isopropanol and formic acid as solvent and in‐situ hydrogen sources, was demonstrated over metal‐doped and promoted MCM‐41 for the depolymerization of oxygen‐rich (35.85 wt%) lignin from Chinese fir sawdust (termed O‐lignin). A NiMo/Al‐MCM‐41 catalyst conferred an optimal lignin‐derived oil yield of 61.6 wt% with a comparatively low molecular weight (Mw=542 g mol−1, Mn=290 g mol−1) and H/C ratio of 1.39. High selectivity to alkyl guaiacols was attributed to efficient in‐situ hydrogen transfer from isopropanol/formic acid donors, and a synergy between surface acid sites in the Al‐doped MCM‐41 support and reducible Ni/Mo species, which improved the chemical stability and quality of the resulting lignin‐derived bio‐oils.
Ecosystem restoration and belowground multifunctionality: A network view
Authors: Tian Dashuan , Xiang Yangzhou , Seabloom Eric , Chen Han Y. H. , Wang Jinsong , Yu Guirui , Deng Ye , Li Zhaolei , Niu Shuli
Published: February 2022

Ecological restoration is essential to reverse land degradation worldwide. Most studies have assessed the restoration of ecosystem functions individually, as opposed to a holistic view. Here we developed a network‐based ecosystem multifunctionality (EMF) framework to identify key functions in evaluating EMF restoration. Through synthesizing 293 restoration studies (2900 observations) following cropland abandonment, we found that individual soil functions played different roles in determining the restoration of belowground EMF. Soil carbon, total nitrogen, and phosphatase were key functions to predict the recovery of belowground EMF. On average, abandoned cropland recovered ~19% of EMF during 18 years. The restoration of EMF became larger with longer recovery time and higher humidity index, but lower with increasing soil depth and initial soil carbon. Overall, this study presents a network‐based EMF framework, effectively helping to evaluate the success of ecosystem restoration and identify the key functions.
Functional differences in scavenger communities and the speed of carcass decomposition
Authors: Wenting Elke , Rinzema Salomé C. Y. , van Langevelde Frank
Published: February 2022

Carcass decomposition largely depends on vertebrate scavengers. However, how behavioral differences between vertebrate scavenger species, the dominance of certain species, and the diversity of the vertebrate scavenger community affect the speed of carcass decomposition is poorly understood. As scavenging is an overlooked trophic interaction, studying the different functional roles of vertebrate species in the scavenging process increases our understanding about the effect of the vertebrate scavenger community on carcass decomposition. We used motion‐triggered infrared camera trap footages to profile the behavior and activity of vertebrate scavengers visiting carcasses in Dutch nature areas. We grouped vertebrate scavengers with similar functional roles. We found a clear distinction between occasional scavengers and more specialized scavengers, and we found wild boar (Sus scrofa) to be the dominant scavenger species in our study system. We showed that these groups are functionally different within the scavenger community. We found that overall vertebrate scavenger diversity was positively correlated with carcass decomposition speed. With these findings, our study contributes to the understanding about the different functional roles scavengers can have in ecological communities.
Insights into the species evolution of Calanus copepods in the northern seas revealed by de novo transcriptome sequencing
Authors: Lizano Apollo Marco , Smolina Irina , Choquet Marvin , Kopp Martina , Hoarau Galice
Published: February 2022

Copepods of the zooplankton genus Calanus play a key role in marine ecosystems in the northern seas. Although being among the most studied organisms on Earth, due to their ecological importance, genomic resources for Calanus spp. remain scarce, mostly due to their large genome size (from 6 to 12 Gbps). As an alternative to whole‐genome sequencing in Calanus spp., we sequenced and de novo assembled transcriptomes of five Calanus species: Calanus glacialis, C. hyperboreus, C. marshallae, C. pacificus, and C. helgolandicus. Functional assignment of protein families based on clusters of orthologous genes (COG) and gene ontology (GO) annotations showed analogous patterns of protein functions across species. Phylogenetic analyses using maximum likelihood (ML) of 191 protein‐coding genes mined from RNA‐seq data fully resolved evolutionary relationships among seven Calanus species investigated (five species sequenced for this study and two species with published datasets), with gene and site concordance factors showing that 109 out of 191 protein‐coding genes support a separation between three groups: the C. finmarchicus group (including C. finmarchicus, C. glacialis, and C. marshallae), the C. helgolandicus group (including C. helgolandicus, C. sinicus, and C. pacificus) and the monophyletic C. hyperboreus group. The tree topology obtained in ML analyses was similar to a previously proposed phylogeny based on morphological criteria and cleared certain ambiguities from past studies on evolutionary relationships among Calanus species.
Dung beetle community composition affects dung turnover in subtropical US grasslands
Authors: Stanbrook Roisin , King Joshua R.
Published: February 2022

An important service in many ecosystems is the turnover and degradation of dung deposited by cattle. Dung beetles are the primary group of insects responsible for dung turnover, and factors affecting their abundance and distribution thus impact dung degradation. Lands lost to grazing due to dung buildup and pasture contamination total millions of acres per year in US pastures.

We evaluated the structural differences in dung beetle assemblages in natural grasslands versus a managed agroecosystem in subtropical southeastern Florida (USA). We measured the direct effect of dung longevity when dung beetle fauna normally inhabiting dung pats were excluded.

Our results indicate dung beetle abundance, functional diversity, and species richness have a substantial impact on the rate of dung turnover in subtropical pastoral lands with ~70% of dung removed from the soil surface after three months. Functional diversity and evenness did not have a significant positive effect on dung removal in managed, versus natural grasslands demonstrating a strong relationship between dung beetle assemblage composition and delivery of a key ecological process, dung degradation.

We suggest the importance of trees, which provide a thermal refuge for beetles, should be dispersed within matrixes of open pasture areas and within proximity to adjacent closed‐canopy hammocks to facilitate the exchange of dung beetles between habitats and therefore maintain the provisioning of dung degradation services by dung beetle assemblages.
Sex and habitat drive hantavirus prevalence in marsh rice rat populations impacted by the Deepwater Horizon oil spill
Authors: Pérez‐Umphrey Anna A. , Jonsson Colleen B. , Bonisoli‐Alquati Andrea , Snider Allison M. , Stouffer Philip C. , Taylor Sabrina S.
Published: February 2022

Bayou orthohantavirus (BAYV) is one of several hantaviruses in the United States that cause hantavirus pulmonary syndrome in humans. Its host reservoir, the marsh rice rat (Oryzomys palustris), inhabits coastal saltmarshes of Louisiana, a region extensively impacted by anthropogenic disturbances, such as the 2010 Deepwater Horizon (DWH) oil spill. The oil spill presents an opportunity to investigate how a large‐scale ecological disturbance can influence the hantavirus host–pathogen dynamic by examining BAYV presence in its reservoir host species in areas with different oiling histories. Here, we: (1) quantify BAYV prevalence in the rice rat in coastal saltmarshes of Louisiana; (2) assess whether prevalence is driven by rice rat demographics, seasonality, or association with habitat characteristics; and (3) determine whether these factors differ by marsh oiling history. We collected mark–recapture data and blood and tissue samples over 5 years (2013–2017) at oiled, unoiled, and reference sites. Testing of the samples for BAYV revealed an antibody and RNA prevalence of 13.7%. Logistic regression analysis found that prevalence varied seasonally and inter‐annually, and in July of 2016 reached 30.8%. Sex (male) and increasing cover of Sporobolus alterniflorus and open water compared to Juncus roemerianus and bare ground were the strongest predictors of hantavirus prevalence. Abundance estimates derived from Huggins closed‐capture models were greatest at oiled sites, but oiling treatment had no residual influence on BAYV prevalence, and abundance and prevalence were not correlated. This study supports the hypothesis that habitat is a main driver of hantavirus prevalence in the host and implies that continued and future disturbances in the region will likely impact the rice rat–BAYV dynamic by altering plant communities and landscape structure.
Navigating the trade‐offs between environmental DNA and conventional field surveys for improved amphibian monitoring
Authors: Moss Wynne E. , Harper Lynsey R. , Davis Mark A. , Goldberg Caren S. , Smith Matthew M. , Johnson Pieter T. J.
Published: February 2022

The need for efficient, accurate biodiversity monitoring is growing, especially for globally imperiled taxa, such as amphibians. Environmental DNA (eDNA) analysis holds enormous potential for enhancing monitoring programs, but as this tool is increasingly adopted, it is imperative for users to understand its potential benefits and shortcomings. We conducted a comparative study to evaluate the efficacy of two eDNA methodologies (quantitative (q)PCR and metabarcoding) and conventional field sampling approaches (seining, dipnetting, and visual encounter surveys) in a system of 20 ponds containing six different amphibian species. Using an occupancy modeling framework, we estimated differences in detection sensitivity across methods, with a focus on how eDNA survey design could be further optimized. Overall, both metabarcoding and qPCR were competitive with or improved upon conventional methods. Specifically, qPCR (species‐specific approach) was the most effective technique for detecting two rare species, the California tiger salamander (Ambystoma californiense) and California red‐legged frog (Rana draytonii), with a detection probability of >0.80 per survey. Metabarcoding (community approach) estimated amphibian diversity with comparable rates to field techniques on average, and detected an additional 41 vertebrate taxa. However, for two abundant species (western toads, Anaxyrus boreas, and Pacific chorus frogs, Pseudacris regilla), field techniques outperformed metabarcoding, especially as individuals metamorphosed. Our results indicate that eDNA approaches would be most effective when paired with visual encounter surveys to detect terrestrial life stages, and that more optimization, specifically primer choice and validation, is needed. By comparing methods across a diverse set of ponds and species, we provide guidance for future studies integrating eDNA approaches into amphibian monitoring.
Multiport converter integrating automatic current balancing interleaved PWM converter and DAB converter with improved transformer utilization for electric vehicles
Authors: Sato Motoki , Uno Masatoshi , Tada Yoshiya
Published: February 2022

Multiport converters (MPCs) that integrate multiple converters into a single unit have been proposed to reduce the converter count in electric vehicle power systems where multiple batteries are employed. However, conventional MPCs comprising a dual active bridge (DAB) converter and an interleaved PWM converter require feedback control loops and current sensors to balance the inductor currents. Furthermore, the transformer utilization decreases as the duty cycle of the interleaved PWM converter drifts away from 0.5. This paper proposes a novel MPC that integrates a DAB converter and an interleaved PWM converter with an automatic current balancing capability and improved transformer utilization. A 1‐kW prototype with a half‐bridge or full‐bridge circuit on the high‐voltage side was built for the experimental verification, and loss analysis was performed. The results demonstrated the automatic current balancing capability, improved transformer utilization, and flexible power exchange among three ports.
Intriguing Second‐Order NLO Switches Based on New DTE Compounds
Authors: Boixel Julien , Colombo Alessia , Fagnani Francesco , Matozzo Paola , Dragonetti Claudia
Published: February 2022

Two new photochromic compounds bearing a dithienylethene unit have been designed, synthesized, and well characterized. The first contains a platinum dialkynyl moiety whereas the second bears a simple phenyl‐dimethylamino fragment. Both compounds have demonstrated an excellent photochromic behavior. This efficient photochromism is the springboard for a significant photomodulation of the second‐order nonlinear optical properties, determined in dichloromethane solution by means of the Electric Field Induced Second Harmonic generation technique. The results are of interest for the design of reversible NLO switches as a tool for emerging photonic technologies.
A Concise and Safe Synthesis of 1,2,3‐Propanetriamine (PTA)
Authors: Travagin Fabio , Giovenzana Giovanni B.
Published: February 2022

1,2,3‐Propanetriamine (PTA) is the simplest aliphatic vicinal triamine, a key compound in coordination chemistry and for the preparation of polymers and for many other important applications. Despite its simple structure and its sesquicentennial history, the preparations of PTA have always been elaborate, hazardous, and low yielding. In this article a concise, safe and inexpensive synthesis of PTA is presented. PTA is prepared by a nitro‐Mannich reaction between dibenzylamine, nitromethane and paraformaldehyde, followed by a catalytic reduction‐debenzylation with Pearlman's catalyst leading to the desired triamine in 73 % yield over two steps. The procedure is amenable for larger‐scale preparations.
N‐Alkylation of α‐Amino Esters and Amides through Hydrogen Borrowing
Authors: Coomber Charlotte E. , Diorazio Louis J.
Published: February 2022

The iridium catalysed N‐alkylation of α‐amino esters and amides using alcohols through hydrogen borrowing has been developed. The protocol can be applied to both the free base and hydrochloride salts of the amines and produces water as the only by‐product. This transformation can provide easy access to chiral N‐alkyl amines from readily available starting materials in a simple one step reaction.
Moisture contents and product quality prediction of Pu‐erh tea in sun‐drying process with image information and environmental parameters
Authors: Chen Cheng , Zhang Wuyi , Shan Zhiguo , Zhang Chunhua , Dong Tianwu , Feng Zhouqiang , Wang Chengkang
Published: February 2022

In this study, moisture contents and product quality of Pu‐erh tea were predicted with deep learning‐based methods. Images were captured continuously in the sun‐drying process. Environmental parameters (EP) of air humidity, air temperature, global radiation, wind speed, and ultraviolet radiation were collected with a portable meteorological station. Sensory scores of aroma, flavor, liquor color, residue, and total scores were given by a trained panel. Convolutional neural network (CNN) and gated recurrent unit (GRU) models were constructed based on image information and EP, which were selected in advance using the neighborhood component analysis (NCA) algorithm. The evolved models based on deep‐learning methods achieved satisfactory results, with RMSE of 0.4332, 0.2669, 0.7508 (also with R2 of .9997, .9882, .9986, with RPD of 53.5894, 13.1646, 26.3513) for moisture contents prediction in each batch of tea, tea at different sampling periods, the overall samples, respectively; and with RMSE of 0.291, 0.2815, 0.162, 0.1574, 0.3931 (also with R2 of .9688, .9772, .9752, .9741, .8906, with RPD of 5.6073, 6.5912, 6.352, 6.1428, 4.0045) for final quality prediction of aroma, flavor, liquor color, residue, total score, respectively. By analyzing and comparing the RMSE values, the most significant environmental parameters (EP) were selected. The proposed combinations of different EP can also provide a valuable reference in the development of a new sun‐drying system.
Genome‐wide association study of multiethnic nonsyndromic orofacial cleft families identifies novel loci specific to family and phenotypic subtypes
Authors: Mukhopadhyay Nandita , Feingold Eleanor , Moreno‐Uribe Lina , Wehby George , Valencia‐Ramirez Luz Consuelo , Restrepo Muñeton Claudia P. , Padilla Carmencita , Deleyiannis Frederic , Christensen Kaare , Poletta Fernando A. , Orioli Ieda M. , Hecht Jacqueline T. , Buxó Carmen J. , Butali Azeez , Adeyemo Wasiu L. , Vieira Alexandre R. , Shaffer John R. , Murray Jeffrey C. , Weinberg Seth M. , Leslie Elizabeth J. , Marazita Mary L.
Published: February 2022

Nonsyndromic orofacial clefts (OFCs) are among the most common craniofacial birth defects worldwide, and known to exhibit phenotypic and genetic heterogeneity. Cleft lip plus cleft palate (CLP) and cleft lip only (CL) are commonly combined together as one phenotype (CL/P), separately from cleft palate alone. In comparison, our study analyzes CL and CLP separately. A sample of 2218 CL and CLP cases, 4537 unaffected relatives of cases, and 2673 pure controls with no family history of OFC were selected from the Pittsburgh Orofacial Cleft (Pitt‐OFC) multiethnic study.genome‐wide association studies were run for seven specific phenotypes created based on the cleft type(s) observed within these families, as well as the combined CL/P phenotype. Five novel genome‐wide significant associations, 3q29 (rs62284390), 5p13.2 (rs609659), 7q22.1 (rs6465810), 19p13.3 (rs628271), and 20q13.33 (rs2427238), and nine associations (p ≤ 1.0E−05) within previously confirmed OFC loci—PAX7, IRF6, FAM49A, DCAF4L2, 8q24.21, ARID3B, NTN1, TANC2 and the WNT9B:WNT3 gene cluster—were observed. We also found that single nucleotide polymorphisms within a subset of the associated loci, both previously known and novel, differ substantially in terms of their effects across cleft‐ or family‐specific phenotypes, indicating not only etiologic differences between CL and CLP, but also genetic heterogeneity within each of the two OFC subtypes.
Intratumoral Microbiome of Human Primary Liver Cancer
Authors: Qu Dingding , Wang Yi , Xia Qingxin , Chang Jing , Jiang Xiangnan , Zhang He
Published: February 2022

Primary liver tumors (PLCs) and liver metastasis currently represent the leading cause of cancer‐related deaths worldwide due to poor outcomes, high incidence, and postsurgical recurrence. Hence, novel diagnostic markers and therapeutic strategies for PLCs are urgently needed. The human microbiome can directly or indirectly impact cancer initiation, progression, and response to therapy, including cancer immunotherapy; however, the roles of the microbiota in the tumor microenvironment are not clear and require more investigation. Here, we investigated intratumoral microbial community profiling on formalin‐fixed paraffin‐embedded tissue samples of patients with PLC by 16S ribosomal RNA using the MiSeq platform. We characterized the microbial communities in different histopathological subtypes and in the different prognoses of patients with PLC. The study revealed microbial population differences not only in carcinoma tissue and the matched adjacent nontumor tissue but in different histopathological subtypes, even in patients with PLC with different prognoses. Interestingly, the abundance of certain bacteria that have antitumor effects at family and genus level, such as Pseudomonadaceae, decreased in tumor tissue and was linearly associated with prognosis of patients with PLC. Conclusion: We provide a potential novel diagnostic biomarker and therapeutic strategy for early clinical diagnosis and treatment of PLC.
The role of microglia in Alzheimer's disease and progress of treatment
Authors: Guan Yi‐Huan , Zhang Ling‐Jing , Wang Shi‐Ya , Deng Ya‐Dan , Zhou Hong‐Su , Chen Dong‐Qing , Zhang Lan‐Chun
Published: February 2022

Microglia are permanent immune cells of the central nervous system. Microglia play an important role in the pathological process of Alzheimer's disease (AD). They are mainly involved in the uptake and clearance of amyloid‐β (Aβ), as well as the formation of neuroinflammation. We found that overactivated microglia increase Aβ and Tau, and Aβ and Tau in turn act as activators of microglia. Additionally, various cytokines and proteins, high cholesterol, and telomere shortening are all associated with microglia activation. More activated microglia induce the release of inflammatory and anti‐inflammatory factors to regulate inflammation, while microglia express multiple homologous receptors that bind to neuroimmunomodulators to prevent microglia overactivation. Moreover, aging of the body promotes neuroinflammation by increasing the response to IFN‐γ (interferon‐γ), and aging of the microglia themselves promotes AD by inducing the accumulation of large amounts of iron and reducing autophagy by regulating protein levels. Cognitive dysfunction occurs when activated microglia induce an increase in beta oligomers, promoting the production of pro‐inflammatory factors that alter the shape, composition, and density of synapses. Based on their correlation, microglia‐mediated AD therapy as well as the corresponding targets and drugs are discussed. In contrast to similar reviews, this article also summarizes some novel microglia‐mediated AD treatment methods over the recent years.