bluuebunny/crossref_metadata_2025_split huggingface dataset:
Physico-chemical Characterization of Some Metal Complexes Formed by Substituted Thiourea
Authors: Swarnabala G. , Khatavkar S. B. , Sadana G. S. , Bharadwaj Anahita 
Published: October 2022

In view of unique physico-chemical observations affecting the geometry and various properties of the substituted thiourea complexes in literature along with several biological activities, N-(hydroxy)-N,N-diphenyl thiourea was taken up for study. Complexes with geometries of high spin octahedral for iron(II), cobalt(II); tetrahedral & square planar for nickel(II); and dimeric square planar for copper chloride, copper perchlorate, copper acetate and distorted octahedral for copper nitrate were synthesized and characterized based on magnetic moments, visible spectra, diffuse reflectance spectra, electron spin resonance, infrared spectral studies, and thermal analysis.
Interestingly, the nature of anion influenced the geometry, the complex from copper nitrate salt resulted in a distorted octahedral structure and complexes formed from copper chloride, copper perchlorate, copper acetate exhibited sub-normal magnetic moments, highly insoluble in the most common organic solvents and water. Based on these and spectral data, polymeric or square-planar dimeric geometry with sulfur bridging between copper atoms is proposed. It was confirmed by the application of Bleaney-Bower’s equation for magnetic susceptibility, applicable to dimeric copper complexes.
The overall thermal behavior of the ligand and complexes were observed and the detailed calculations interestingly lead to confirmation of the above proposed geometrical structures.
A general optimal adaptive framework for managing a threatened species
Authors: Nicol Sam , Ferrer‐Mestres Jonathan , Lloyd Hannah , Brazill‐Boast James , Gorrod Emma , Chades Iadine 
Published: October 2022

AbstractManagers must determine which interventions best protect threatened species when the outcomes of interventions are uncertain. Adaptive management is a dynamic optimization approach that generates optimal management actions based on current knowledge while learning to improve future management outcomes. Although adaptive management theory is well‐developed, uptake has been impeded by its complexity and a tendency to develop bespoke solutions with high implementation costs for problem‐specific returns.To increase uptake of adaptive management and improve threat management for species recovery, we developed a general adaptive management decision model, framed as a Mixed Observability Markov Decision process. We embraced principles of generality, simplicity and interpretability to overcome previous implementation challenges. We created a general model structure that is applicable to any species–threat combination, thus avoiding the need to develop customized models for every species. Simplicity was achieved by minimizing states to reduce the information requirements for parameterization. To improve interpretability, we implemented our method as a Shiny application and employed a recent artificial intelligence approach to simplify the optimal strategy. We applied our approach to a case study of fox impacts on a threatened marsupial.Our case study shows that when one management action is robust to uncertainty, the value of information of optimal adaptive management may be low. Cases like these highlight species–threat combinations where investment in adaptive management is not required.Our tool provides a rapid prototype adaptive management approach with minimal cost to management agencies. Our simple yet general model structure improves efficiency for implementing adaptive management for large numbers of threatened species, improving the effectiveness of conservation investments.
Oral Complications of Cancer and Their Treatment
Authors: Sonis Stephen T. , Yuan Anna , Villa Alessandro 
Published: October 2022

OverviewThe oral cavity is uniquely heterogeneous relative to tissue types, microbiome, immunology, and fluidic environment which make it a sentinnental site for manifestations of both acute and late cancer regimen‐related toxicities. The rapid turnover of its non‐keratinized mucosa is subject to a radiation and chemotherapy initiated biological cascade that results in dramatic epithelial injury. Osteonecrosis of the jaws is associated with bisphosphonate and radiation. A diverse and shifting microflora parallels myelosuppressive treatment or drug‐ and radiation‐induced xerostomia resulting in secondary infections and a bacterial repository for bacteremia and sepsis. Exacerabation of dental caries and periodontal disease is a common consequence of treatment. Virtually every form of current cancer treatment from conventional cytotoxic regimens to the most innovative forms of targeted and immunotherapy are associated with the risk of toxic manifestations in the mouth. Preventive and management strategies can be helpful in attenuating risk and modulating the severity of these complications. Given the potential disproportionate impact of oral complications on patient outcomes, it is incumbent on providers to assure that the mouth is not overlooked in the overall management of the patient being treated for cancer.
Unexpected Redispersion Effect of Au Nanoclusters for Enormous Enhancement of Electrocatalytic Stability and Activity
Authors: Xiao Xiang‐Yu , Song Zong‐Yin , Xie Huanyu , Zhao Yong‐Huan , Chen Shi‐Hua , Li Yong‐Yu , Yang Meng , Li Pei‐Hua , Ji Hengxing , Huang Xing‐Jiu 
Published: October 2022

AbstractThe irreconcilable conflict between stability and excellent electrocatalytic activity of Au nanoclusters greatly limits their application. Extensive efforts are devoted to fabricating various substrates to immobilize Au nanoclusters while it is still challenging to maintain its electrocatalytic activities for long term tasks due to the highly reactive environments that the Au nanoclusters encounter in electrocatalytic reactions. Herein, an unexpected “redispersion effect” is discovered when Au25 nanoclusters are loaded on the nanocomposites of black phosphorus and N‐doped graphene (AuCs/BP‐NG), forming the sandwich configuration with the enhanced stability. The size of Au nanoclusters reduce from 1.56 ± 0.5 to 1.04 ± 0.2 nm, leading to improved catalytic ability. Such redispersion effect yields a super‐high electrocatalytic performance of the AuCs/BP‐NG toward Cr(VI) sensing that the detection sensitivity achieved 0.414 µA ppb−1, which is two orders of magnitude higher than the state‐of‐the‐art value. Compared with BP‐NG and Au nanoparticles (AuNPs) loaded on BP‐NG (AuNPs/BP‐NG), the lowest reaction barrier in the rate‐determining steps of H2CrO4 reduction is observed. The findings provide an opportunity to develop a superior electrocatalyst in the community of energy and environment‐related electrocatalysis.
Engineering Pore Nanostructure of Carbon Cathodes for Zinc Ion Hybrid Supercapacitors
Authors: Jian Wenbin , Zhang Wenli , Wei Xueer , Wu Bingchi , Liang Wanling , Wu Ying , Yin Jian , Lu Ke , Chen Yanan , Alshareef Husam N. , Qiu Xueqing 
Published: October 2022

AbstractZinc ion hybrid supercapacitors (ZIHCs) with both high power density and high energy density have tremendous potential for energy storage applications such as hybrid electric vehicles and renewable energy storage. However, the large radius of hydrated Zn2+ ions hampers their efficient storage in micropores with limited pore sizes, resulting in the limited gravimetric specific capacitance and inferior rate capability of ZIHCs. Therefore, it is critically important to understand to what extent pore size influences the storage of hydrated Zn2+ ions in the pores with limited sizes. Herein, porous carbon nanosheets with different pore architectures are prepared using an ammonium chloride molten salt carbonization strategy. The influence of pore size on hydrated Zn2+ ion storage in nanostructured carbon with divergent pore architectures is analyzed by electrochemical methods and molecular dynamic simulation. Micropores smaller than 6.0 Å obstruct the diffusion of hydrated Zn2+ ions, while micropores larger than 7.5 Å exhibit a low diffusion energy barrier for the hydrated Zn2+ ions. Mesopores improve capacitance and rate capability by exposing the electrochemically active sites and enhancing the diffusion of the hydrated Zn2+ ions.
Donor End‐Capped Alkyl Chain Length Dependent Non‐Radiative Energy Loss in All‐Small‐Molecule Organic Solar Cells
Authors: Zhang Lili , Sun Rui , Zhang Ziqi , Zhang Jianqi , Zhu Qinglian , Ma Wei , Min Jie , Wei Zhixiang , Deng Dan 
Published: October 2022

AbstractA critical bottleneck for further efficiency breakthroughs in organic solar cells (OSCs) is to minimize the non‐radiative energy loss (eΔVnr) while maximizing the charge generation. With the development of highly emissive low‐bandgap non‐fullerene acceptors, the design of high‐performance donors becomes critical to enable the blend with the electroluminescence quantum efficiency to approach or surpass the pristine acceptor. Herein, by shortening the end‐capped alkyl chains of the small‐molecular donors from hexyl (MPhS‐C6) to ethyl (MPhS‐C2), the material obtained aggregation that was insensitive to thermal annealing (TA) along with condensed packing simultaneously. The former leads to small phase separation and suppressed upshifts of the highest occupied molecular orbital energy level during TA, and the latter facilitates its efficient charge‐transport at aggregation‐less packing. Hence, the ΔVnr decreases from 0.242 to 0.182 V, from MPhS‐C6 to MPhS‐C2 based OSCs. An excellent PCE of 17.11% is obtained by 1,8‐diiodoctane addition due to almost unchanged high Jsc (26.6 mA cm−2) and Voc (0.888 V) with improved fill factor, which is the record efficiency with the smallest energy loss (0.497 eV) and ΔVnr (0.192 V) in all‐small‐molecule OSCs. These results emphasize the potential material design direction of obtaining concurrent TA‐insensitive aggregation and condensed packing to maximize the device performances with a super low ΔVnr.
Decatungstate‐Photocatalyzed Acylation of Single‐Walled Carbon Nanotubes
Authors: Canton‐Vitoria Ruben , Quintana Mildred , Malliaros Nikitas G. , Tagmatarchis Nikos 
Published: October 2022

AbstractAlthough the functionalization and modification of single‐walled carbon nanotubes (SWCNTs) has been advanced for two decades, their chemical transformation via catalytic processes has yet to be explored and further facilitate their industrial utility. Here, the decatungstate‐photocatalyzed acylation is described of semiconducting (7,6)SWCNTs and the scope of the reaction is investigated by employing alkyl, aromatic, and organometallic aldehydes. The success of the methodology is confirmed by diverse spectroscopic, thermal, microscopy imaging, and redox techniques. The developed catalytic process for the functionalization of SWCNTs is environmetal friendly, since the catalyst and unreacted aldehydes can be recovered and reused, while the modified SWCNTs can be easily isolated and purified by membrane filtration. It is believed that the current findings will open new avenues for the catalytic functionalization of SWCNTs and the approach is intended to extend for modifying 2D nanomaterials.
Interface Engineering Enabled Low Temperature Growth of Magnetic Insulator on Topological Insulator
Authors: Bhattacharjee Nirjhar , Mahalingam Krishnamurthy , Will‐Cole Alexandria , Wei Yuyi , Fedorko Adrian , Bowers Cynthia T. , Page Michael , McConney Michael , Heiman Don , Sun Nian Xiang 
Published: October 2022

AbstractCombining topological insulators (TIs) and magnetic materials in heterostructures is crucial for advancing spin‐based electronics. Magnetic insulators (MIs) can be deposited on TIs using the spin‐spray process, which is a unique nonvacuum, low‐temperature growth process. TIs have highly reactive surfaces that oxidize upon exposure to atmosphere, making it challenging to grow spin‐spray ferrites on TIs. In this work, it is demonstrated that a thin titanium capping layer on TI, followed by oxidation in atmosphere to produce a thin TiOx interfacial layer, protects the TI surface, without significantly compromising spin transport from the magnetic material across the TiOx to the TI surface states. First, it is demonstrated that in Bi2Te3/TiOx/Ni80Fe20 heterostructures, TiOx provides an excellent barrier against diffusion of magnetic species, yet maintains a large spin‐pumping effect. Second, the TiOx is also used as a protective capping layer on Bi2Te3, followed by the spin‐spray growth of the MI, NixZnyFe2O4 (NZFO). For the thinnest TiOx barriers, Bi2Te3/TiOx/NZFO samples have antiferromagnetic (AFM) disordered interfacial layer because of diffusion. With increasing TiOx barrier thickness, the diffusion is reduced, but still maintains strong interfacial magnetic exchange‐interaction. These experimental results demonstrate a novel method of low‐temperature growth of magnetic insulators on TIs enabled by interface engineering.
Stable Transgenic Mouse Strain with Enhanced Photoactivatable Cre Recombinase for Spatiotemporal Genome Manipulation
Authors: Li Huiying , Wu Yingyin , Qiu Yuhao , Li Xinru , Guan Yuting , Cao Xiya , Liu Meizhen , Zhang Dan , Huang Sijie , Lin Longnian , Hui Lijian , Ma Xueyun , Liu Mingyao , Zhang Xueli , Wang Liren , Li Dali 
Published: October 2022

AbstractOptogenetic genome engineering is a powerful technology for high‐resolution spatiotemporal genetic manipulation, especially for in vivo studies. It is difficult to generate stable transgenic animals carrying a tightly regulated optogenetic system, as its long‐term expression induces high background activity. Here, the generation of an enhanced photoactivatable Cre recombinase (ePA‐Cre) transgenic mouse strain with stringent light responsiveness and high recombination efficiency is reported. Through serial optimization, ePA‐Cre is developed to generate a transgenic mouse line that exhibits 175‐fold induction upon illumination. Efficient light‐dependent recombination is detected in embryos and various adult tissues of ePA‐Cre mice crossed with the Ai14 tdTomato reporter. Importantly, no significant background Cre activity is detected in the tested tissues except the skin. Moreover, efficient light‐inducible cell ablation is achieved in ePA‐Cre mice crossed with Rosa26‐LSL‐DTA mice. In conclusion, ePA‐Cre mice offer a tightly inducible, highly efficient, and spatiotemporal‐specific genome engineering tool for multiple applications.
Gossypol Broadly Inhibits Coronaviruses by Targeting RNA‐Dependent RNA Polymerases
Authors: Wang Wenjing , Li Wenkang , Wen Zhiyuan , Wang Chong , Liu Weilong , Zhang Yufang , Liu Juncheng , Ding Tianze , Shuai Lei , Zhong Gongxun , Bu Zhigao , Qu Lingbo , Ren Maozhi , Li Fuguang 
Published: October 2022

AbstractOutbreaks of coronaviruses (CoVs), especially severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2), have posed serious threats to humans and animals, which urgently calls for effective broad‐spectrum antivirals. RNA‐dependent RNA polymerase (RdRp) plays an essential role in viral RNA synthesis and is an ideal pan‐coronaviral therapeutic target. Herein, based on cryo‐electron microscopy and biochemical approaches, gossypol (GOS) is identified from 881 natural products to directly block SARS‐CoV‐2 RdRp, thus inhibiting SARS‐CoV‐2 replication in both cellular and mouse infection models. GOS also acts as a potent inhibitor against the SARS‐CoV‐2 variant of concern (VOC) and exerts same inhibitory effects toward mutated RdRps of VOCs as the RdRp of the original SARS‐CoV‐2. Moreover, that the RdRp inhibitor GOS has broad‐spectrum anti‐coronavirus activity against alphacoronaviruses (porcine epidemic diarrhea virus and swine acute diarrhea syndrome coronavirus), betacoronaviruses (SARS‐CoV‐2), gammacoronaviruses (avian infectious bronchitis virus), and deltacoronaviruses (porcine deltacoronavirus) is showed. The findings demonstrate that GOS may serve as a promising lead compound for combating the ongoing COVID‐19 pandemic and other coronavirus outbreaks.
A novel MTX2 gene splice site variant resulting in exon skipping, causing the recently described mandibuloacral dysplasia progeroid syndrome
Authors: Yeter Doğan Burcu , Günay Neslihan , Ada Yasin , Doğan Muhammet Ensar 
Published: October 2022

AbstractUntil recently, mandibuloacral dysplasia (MAD) with type A and type B lipodystrophy was the first to come to mind in the association of mandibular hypoplasia, lipodystrophy, and acro‐osteolysis. However, it has recently been added to the differential diagnosis of MAD, a newly defined syndrome, called MDPS. MDPS is a skeletal dysplasia characterized by postnatal growth retardation, hypotonia, generalized lipodystrophy, skin changes, progeroid traits, and dysmorphic facial features, including prominent eyes, long pinched nose, mandibular hypoplasia, and a small mouth. Biallelic null variants of the MTX2 gene are responsible for this syndrome. We performed whole‐exome sequencing (WES) in a 6‐year‐old patient with skeletal dysplasia. WES revealed a novel homozygous c.543+1G>T splice site variant in the MTX2 gene. We also extracted total RNA from peripheral blood and used reverse transcription‐polymerase chain reaction to generate cDNA. Sanger sequencing from cDNA showed that exon 8 of MTX2 was skipped. This study adds to the genetics and phenotype of MDPS and underlines the importance of comprehensive clinical and molecular research.
Light‐Induced Divergent Cyanation of Alkynes Enabled by Phosphorus Radicals
Authors: Zhang Yanyan , Han Yunhong , Zhu Shengqing , Qing Feng‐Ling , Xue Xiao‐Song , Chu Lingling 
Published: October 2022

AbstractA photochemically induced selective and divergent cyanation reaction of alkynes, enabled by phosphorus radicals, is described. With the use of simple triarylphosphine as a co‐catalyst, three cyanation reactions, including di‐hydrocyanation, anti‐Markovnikov hydrocyanation, and domino hydrocyanation/reduction, can be divergently achieved, furnishing a wide array of alkyl dinitriles, alkenyl nitriles, and alkyl nitriles under mild conditions. Terminal and internal alkynes are applicable with high efficiency and excellent selectivity. Synthetic applications for biologically active agents and preliminary experimental and computational mechanistic studies are reported.
Ambient Electrosynthesis of Urea with Nitrate and Carbon Dioxide over Iron‐Based Dual‐Sites
Authors: Geng Jing , Ji Sihan , Jin Meng , Zhang Chao , Xu Min , Wang Guozhong , Liang Changhao , Zhang Haimin 
Published: October 2022

AbstractThe development of efficient electrocatalysts to generate key *NH2 and *CO intermediates is crucial for ambient urea electrosynthesis with nitrate (NO3−) and carbon dioxide (CO2). Here we report a liquid‐phase laser irradiation method to fabricate symbiotic graphitic carbon encapsulated amorphous iron and iron oxide nanoparticles on carbon nanotubes (Fe(a)@C‐Fe3O4/CNTs). Fe(a)@C‐Fe3O4/CNTs exhibits superior electrocatalytic activity toward urea synthesis using NO3− and CO2, affording a urea yield of 1341.3±112.6 μg h−1 mgcat−1 and a faradic efficiency of 16.5±6.1 % at ambient conditions. Both experimental and theoretical results indicate that the formed Fe(a)@C and Fe3O4 on CNTs provide dual active sites for the adsorption and activation of NO3− and CO2, thus generating key *NH2 and *CO intermediates with lower energy barriers for urea formation. This work would be helpful for design and development of high‐efficiency dual‐site electrocatalysts for ambient urea synthesis.
Porous Liquids Responsive to Light**
Authors: Dinker Manish Kumar , Zhao Kan , Dai Zhengxing , Ding Lifeng , Liu Xiao‐Qin , Sun Lin‐Bing 
Published: October 2022

AbstractA porous liquid is a unique liquid medium that combines the cavity of porous solids with the fluidity of liquids. This special characteristic offers potential in various applications. Here we report a type II photoresponsive porous ionic liquid (PPIL) from dissolving a photoresponsive metal‐organic polyhedron (PMOP, constructed from dicopper and azobenzene‐containing carboxylate) in a polyethylene‐glycol‐functionalized bulky ionic liquid (IL). Owing to favorable ion interactions, bulky IL molecules encircle outside PMOP, and the inter cavities are maintained. The azobenzene moieties can be isomerized freely in the PPILs to expose and shelter active sites upon visible and UV light irradiation. Hence, the adsorption capacity of PPILs is controllable by light irradiation, and the change in CO2 uptake is up to 30 % compared to neat IL. This study may inspire the development of new adsorption process regulated by light instead of pressure and temperature swing adsorption.
Host Spin‐Crossover Thermodynamics Indicate Guest Fit
Authors: Zheng Jieyu , von Krbek Larissa K. S. , Ronson Tanya K. , Nitschke Jonathan R. 
Published: October 2022

AbstractSpin‐crossover (SCO) metal‐organic cages capable of switching between high‐spin and low‐spin states have the potential to be used as magnetic sensors and switches. Variation of the donor strength of heterocyclic aldehyde subcomponents in imine‐based ligands can tune the ligand field for a FeIIcenter, which results in both homoleptic and heteroleptic cages with diverse SCO behaviors. The tetrahedral SCO cage built from 1‐methyl‐1H‐imidazole‐2‐carbaldehyde is capable of encapsulating various guests, which stabilize different cage spin states depending on guest size. Conversely, the SCO tetrahedron exhibits different affinities for guests in different spin states, which is inferred to result from subtle structural differences of the cavity caused by the change in metal center spin state. Examination of SCO thermodynamics across a series of host–guest complexes enabled sensitive probing of guest fit to the host cavity, providing information complementary to binding‐constant determination.
Control the Single‐, Two‐, and Three‐Photon Excited Fluorescence of Atomically Precise Metal Nanoclusters
Authors: Pan Peiyao , Liu Lingling , Zhang Lidi , Wei Xiao , Tian Yupeng , Kang Xi , Zhang Qiong , Zhu Manzhou 
Published: October 2022

AbstractIt remains challenging to control the single‐, two‐, and three‐photon excited fluorescence of metal nanoclusters. In this work, the control over the non‐linear optics of metal nanoclusters as single‐, two‐, and three‐photon excited fluorescence has been accomplished via exploiting the solvent effect. An emissive nanocluster, Au9Ag6(SPhtOMe)4(DPPOE)3Cl3, was synthesized and structurally determined. The solvent effect can not only control the fluorescence of this nanocluster, but more significantly, it can also regulate the photoluminescence nature of the cluster as single‐, two‐, and three‐photon excited fluorescence. We concluded that the increased solution polarity, improved dipole moment, enlarged HOMO–LUMO energy gap, and reduced solution viscosity of the cluster in solutions endow them with excellent high‐order multiphoton excited fluorescence. The results provide an intriguing cluster template that enables us to manipulate the linear and nonlinear optics at the atomic level.