bluuebunny/crossref_metadata_2025 huggingface dataset:
Evaluation of the Strength at Home Group Intervention for Intimate Partner Violence in the Veterans Affairs Health System
Authors: Creech Suzannah K. , Benzer Justin K. , Bruce LeAnn , Taft Casey T.
Published: March 2023

Importance

Intimate partner violence (IPV) is a serious and prevalent public health issue that is interconnected with experiences of trauma, mental and physical health difficulties, and health disparities. Strength at Home (SAH) is a group intervention for persons using IPV in their relationships. Although previous studies have provided evidence of SAH’s effectiveness in reducing IPV, its patient outcomes as implemented within organized health care have not been examined.

Objective

To evaluate patient outcomes from implementation of SAH in the Department of Veterans Affairs (VA) health system.

Design, Setting, and Participants

This quality improvement study evaluated patient outcomes from a national implementation and training program conducted between December 11, 2015, and September 24, 2021. Data were collected as part of treatment and submitted by clinicians at 73 VA health care facilities. Patients were 1754 veterans seeking care aimed at addressing and/or preventing their use of aggression in intimate relationships. They completed 1 pretreatment assessment and 1 follow-up assessment in the immediate weeks after group completion.

Intervention

Strength at Home is a 12-week trauma-informed and cognitive behavioral group intervention to address and prevent the use of IPV in relationships.

Main Outcomes and Measures

Changes in IPV were measured with the Centers for Disease Control and Prevention 2010 National Intimate Partner and Sexual Violence Survey. Changes in posttraumatic stress disorder (PTSD) symptoms were measured with the PTSD Checklist for DSM-5, and alcohol misuse was measured with the Alcohol Use Disorders Identification Test.

Results

The study included 1754 participants (mean [SD] age, 44.3 [13.0] years; 1421 men [81%]), of whom 1088 (62%) were involved with the criminal legal system for IPV charges. Analyses indicate that SAH was associated with reductions in use of physical IPV (odds ratio, 3.28; percentage difference from before to after treatment, –0.17 [95% CI, −0.21 to −0.13]) and psychological IPV (odds ratio, 2.73; percentage difference from before to after treatment, –0.23 [95% CI, −0.27 to −0.19]), coercive control behaviors (odds ratio, 3.19; percentage difference from before to after treatment, –0.18 [95% CI, –0.22 to –0.14), PTSD symptoms (mean change, −4.00; 95% CI, 0.90-7.09; Hedges g = 0.10), and alcohol misuse (mean change, 2.70; 95% CI, 1.54-3.86; Hedges g = 0.24).

Conclusions and Relevance

In this quality improvement study of the patient outcomes after implementation of SAH, results suggested that the program was associated with reductions in IPV behaviors, PTSD symptoms, and alcohol misuse. Results also suggest that IPV intervention in routine health care at VA health care facilities was successful; extension to other organized health care systems could be warranted.
Bullying involvement and the transition to high school: A brief report
Authors: Vaillancourt Tracy , Brittain Heather , Farrell Ann H. , Krygsman Amanda , Vitoroulis Irene
Published: March 2023

School transitions are common educational experiences for children and adolescents and many of them worry about being bullied during this type of major life‐changing point. In a sample of 701 Canadians assessed yearly from grade 5 (age 10) to grade 12 (age 18), we examined heterogeneous patterns of bullying involvement while statistically accounting for the transition into high school. Gender differences were also examined. Results indicated that on average, bullying victimization declined over time with a significant drop noted between grade 8 and grade 9 (the transition into high school), with few differences between girls and boys. Bullying perpetration also declined for most students (no gender differences), with a notable drop found at the transition into high school. However, for a subset of adolescents, the transition into high school was accompanied by an increase in bullying perpetration. These varied experiences highlight the need to model heterogeneity when examining the impact of school transitions on bullying, a neglected focus of inquiry to date. Our results suggest that moving into high school is beneficial for most adolescents involved in bullying, but not for all.
Quasistatic Compression Properties of Fiber Hybrid Ceramic Matrix Composites with Different Hybrid Ratios and Fiber Dispersions
Authors: Hu Peili , Shan Zhongde , Zang Yong , Wu Xiaochuan , Sun Zheng
Published: March 2023

Fiber hybrid composites can give full play to the performance advantages of different component fibers, and hybrid weaving is one of the effective methods to improve the properties of composite materials. Herein, based on the flexible‐oriented 3D woven technology, fiber hybrid ceramic matrix composites (FHCMCs) with different hybrid ratios and fiber dispersions are designed and fabricated, and their quasistatic compression properties, failure modes, and hybrid effects are studied. The results show that the reasonable hybrid of carbon (C) fiber and silicon carbide (SiC) fiber can make up for the shortcoming of single‐fiber composites and improve the compression properties of FH‐CMCs. The compressive failure modes of the FH‐CMCs are mainly the crushing failure in the C fiber layers and shear failure of the specimen. For the compressive failure deformation, the positive hybrid effect gradually becomes obvious with the increase of fiber dispersion, but the compressive strength shows a negative hybrid effect as a whole. The improved rule of mixture by introducing different parameters has a better prediction effect for the compressive strength of the FH‐CMCs. The research results provide experimental and theoretical reference for the high‐performance manufacturing of hybrid composites in the future.
3D Biomimetic Models to Reconstitute Tumor Microenvironment In Vitro: Spheroids, Organoids, and Tumor‐on‐a‐Chip
Authors: Li Wenxiu , Zhou Zhihang , Zhou Xiaoyu , Khoo Bee Luan , Gunawan Renardi , Chin Y. Rebecca , Zhang Liang , Yi Changqing , Guan Xinyuan , Yang Mengsu
Published: March 2023

Decades of efforts in engineering in vitro cancer models have advanced drug discovery and the insight into cancer biology. However, the establishment of preclinical models that enable fully recapitulating the tumor microenvironment remains challenging owing to its intrinsic complexity. Recent progress in engineering techniques has allowed the development of a new generation of in vitro preclinical models that can recreate complex in vivo tumor microenvironments and accurately predict drug responses, including spheroids, organoids, and tumor‐on‐a‐chip. These biomimetic 3D tumor models are of particular interest as they pave the way for better understanding of cancer biology and accelerating the development of new anticancer therapeutics with reducing animal use. Here, the recent advances in developing these in vitro platforms for cancer modeling and preclinical drug screening, focusing on incorporating hydrogels are reviewed to reconstitute physiologically relevant microenvironments. The combination of spheroids/organoids with microfluidic technologies is also highlighted to better mimic in vivo tumors and discuss the challenges and future directions in the clinical translation of such models for drug screening and personalized medicine.
Distribution pattern of major crops and their cultivation intensity indicated by soil phosphorus concentrations in Europe
Authors: Szigeti Nóra , Hermann Tamás , Juhos Katalin , Tóth Gergely
Published: March 2023

The sowing area and yield of crops are primarily determined by climatic suitability and modified by terrain conditions. This study presents the actual sowing area of 10 major crops in Europe and reveals the spatial pattern of available soil phosphorus (P) concentrations between and within the sowing areas of the crops, based on the Land Use/Land Cover Area Frame Survey (LUCAS) database. A great variance in cropping pattern over Europe was observed, especially for crops with a broad climatic tolerance. Results show significant differences between soil phosphorus concentrations under different agricultural crops, indicating the differences in management intensities of major crops. A strong relationship between high yields and P‐fertilizer use was found, as indicated by soil P concentration. In the context of environmental zones, P‐concentration values were higher in northern zones, medium in the zones in central Europe, and lower in the Mediterranean zones. The more suitable the climate is for growing crops, the more it pays to apply P fertilizers. Consequently, soil P‐concentration is a good indicator of crop cultivation intensity, land productivity, P‐fertilizer use, and the total P demand of plants. Among the most commonly cultivated crops, maize seems to be the most dependent crop for the level of P‐concentration of soil or the P inputs. For more sustainable P use in Europe, further research is needed to calculate how the P‐requirements of yields compare to the P‐fertilizer use in the case of different crop types.
Athletes in sporting events with upper‐body gripping movements have greater handgrip strength than those in sporting events that prioritize the lower body
Authors: Abe Takashi , Kohmura Yoshimitsu , Suzuki Koya , Someya Yuki , Loenneke Jeremy P. , Machida Shuichi , Naito Hisashi
Published: March 2023

Objective

Evidence suggests that acquiring a high level of handgrip strength early in life and maintaining that strength throughout life may be important for health. In addition, it is thought that sports activities performed during the developmental period are effective in improving handgrip strength, but it is unknown what types of sports are more effective. As a first step, we conducted a cross‐sectional study to compare handgrip strength across different sports (upper‐body gripping sports vs. lower body) in early adulthood.

Methods

We used the Juntendo Fitness Plus Study data from 1973 to 2018 and selected two types of sporting events with matching physiques (soccer, baseball, and kendo) but different degrees of gripping. Data on 7344 male first‐year sports university students included 1127 soccer, 297 Kendo, and 698 baseball players.

Results

Those in the lower body‐only (soccer) sports had −3.78 (95% CI: −4.27, −3.29) kg lower handgrip strength than those in the lower + upper (kendo and baseball). Comparing each individual sport found that each sport was different from each other with Kendo > Baseball > Soccer (between each sport, p < .001). In addition, the difference between sports has become greater across time.

Conclusions

In early adulthood, handgrip strength is greatest in those participating in sports with upper‐body movements compared to those participating in sports that mainly involved lower‐body movements. The three sports we selected are natural activities that do not directly train handgrip strength. Therefore, sport may be one potential method to improve low handgrip strength in children/adolescents during the developmental period.
Breakpoint analysis for cytogenetically balanced translocation revealed unexpected complex structural abnormalities and suggested the position effect for MEF2C
Authors: Tamura Takeaki , Shimojima Yamamoto Keiko , Imaizumi Taichi , Yamamoto Hisako , Miyamoto Yusaku , Yagasaki Hiroshi , Morioka Ichiro , Kanno Hitoshi , Yamamoto Toshiyuki
Published: March 2023

Many disease‐causing genes have been identified by determining the breakpoints of balanced chromosomal translocations. Recent progress in genomic analysis has accelerated the analysis of chromosomal translocation‐breakpoints at the nucleotide level. Using a long‐read whole‐genome sequence, we analyzed the breakpoints of the cytogenetically balanced chromosomal translocation t(5;15)(q21;26.3), which was confirmed to be of de novo origin, in a patient with a neurodevelopmental disorder. The results showed complex rearrangements with seven fragments consisting of five breakpoint‐junctions (BJs). Four of the five BJs showed microhomologies of 1–3‐bp, and only one BJ displayed a signature of blunt‐end ligation, indicating chromothripsis as the underlying mechanism. Although the BJs did not disrupt any disease‐causing gene, the clinical features of the patient were compatible with MEF2C haploinsufficiency syndrome. Complex rearrangements were located approximately 2.5‐Mb downstream of MEF2C. Therefore, position effects were considered the mechanism of the occurrence of MEF2C haploinsufficiency syndrome.
Engineering an Oxygen‐Binding Protein for Photocatalytic CO2Reductions in Water
Authors: Deng Yunling , Dwaraknath Sudharsan , Ouyang Wenhao O. , Matsumoto Cory J. , Ouchida Stephanie , Lu Yi
Published: March 2023

While native CO2‐reducing enzymes display remarkable catalytic efficiency and product selectivity, few artificial biocatalysts have been engineered to allow understanding how the native enzymes work. To address this issue, we report cobalt porphyrin substituted myoglobin (CoMb) as a homogeneous catalyst for photo‐driven CO2to CO conversion in water. The activity and product selectivity were optimized by varying pH and concentrations of the enzyme and the photosensitizer. Up to 2000 TON(CO) was attained at low enzyme concentrations with low product selectivity (15 %), while a product selectivity of 74 % was reached by increasing the enzyme loading but with a compromised TON(CO). The efficiency of CO generation and overall TON(CO) were further improved by introducing positively charged residues (Lys or Arg) near the active stie of CoMb, which demonstrates the value of tuning the enzyme secondary coordination sphere to enhance the CO2‐reducing performance of a protein‐based photocatalytic system.
Decrypting the Controlled Product Selectivity over Ag−Cu Bimetallic Surface Alloys for Electrochemical CO2 Reduction
Authors: Wei Daixing , Wang Yiqing , Dong Chung‐Li , Zhang Zhengqi , Wang Xinyu , Huang Yu‐Cheng , Shi Yuchuan , Zhao Xiaoli , Wang Jialin , Long Ran , Xiong Yujie , Dong Fan , Li Mingtao , Shen Shaohua
Published: March 2023

Electrochemical CO2 reduction reaction (ECO2RR) with controlled product selectivity is realized on Ag−Cu bimetallic surface alloys, with high selectivity towards C2 hydrocarbons/alcohols (≈60 % faradaic efficiency, FE), C1 hydrocarbons/alcohols (≈41 % FE) and CO (≈74 % FE) achieved by tuning surface compositions and applied potentials. In situ spectral investigations and theoretical calculations reveal that surface‐composition‐dependent d‐band center could tune *CO binding strengths, regulating the *CO subsequent reaction pathways and then the product selectivity. Further adjusting the applied potentials will alter the energy of participated electrons, which leads to controlled ECO2RR selectivity towards desired products. A predominant region map, with an indicator proposed to evaluate the thermodynamic predominance of the *CO subsequent reactions, is then provided as a reliable theoretical guidance for the controllable ECO2RR product selectivity over bimetallic alloys.
Structurally Simple Osmium(II) Polypyridyl Complexes as Photosensitizers for Photodynamic Therapy in the Near Infrared**
Authors: Mani Asma , Feng Tao , Gandioso Albert , Vinck Robin , Notaro Anna , Gourdon Lisa , Burckel Pierre , Saubaméa Bruno , Blacque Olivier , Cariou Kevin , Belgaied Jamel‐Eddine , Chao Hui , Gasser Gilles
Published: March 2023

Five osmium(II) polypyridyl complexes of the general formula [Os(4,7‐diphenyl‐1,10‐phenanthroline)2L]2+ were synthesized as photosensitizers for photodynamic therapy by varying the nature of the ligand L. Thanks to the pronounced π‐extended structure of the ligands and the heavy atom effect provided by the osmium center, these complexes exhibit a high absorption in the near‐infrared (NIR) region (up to 740 nm), unlike related ruthenium complexes. This led to a promising phototoxicity in vitro against cancer cells cultured as 2D cell layers but also in multicellular tumor spheroids upon irradiation at 740 nm. The complex [Os(4,7‐diphenyl‐1,10‐phenanthroline)2(2,2′‐bipyridine)]2+ was found to be the most efficient against various cancer cell lines, with high phototoxicity indexes. Experiments on CT26 tumor‐bearing BALB/c mice also indicate that the OsII complexes could significantly reduce tumor growth following 740 nm laser irradiation. The high phototoxicity in the biological window of this structurally simple complex makes it a promising photosensitizer for cancer treatment.
Design of Drug Efficacy Guided by Free Energy Simulations of the β2‐Adrenoceptor
Authors: Panel Nicolas , Vo Duc Duy , Kahlous Nour Aldin , Hübner Harald , Tiedt Stephanie , Matricon Pierre , Pacalon Jody , Fleetwood Oliver , Kampen Stefanie , Luttens Andreas , Delemotte Lucie , Kihlberg Jan , Gmeiner Peter , Carlsson Jens
Published: March 2023

G‐protein‐coupled receptors (GPCRs) play important roles in physiological processes and are modulated by drugs that either activate or block signaling. Rational design of the pharmacological efficacy profiles of GPCR ligands could enable the development of more efficient drugs, but is challenging even if high‐resolution receptor structures are available. We performed molecular dynamics simulations of the β2 adrenergic receptor in active and inactive conformations to assess if binding free energy calculations can predict differences in ligand efficacy for closely related compounds. Previously identified ligands were successfully classified into groups with comparable efficacy profiles based on the calculated shift in ligand affinity upon activation. A series of ligands were then predicted and synthesized, leading to the discovery of partial agonists with nanomolar potencies and novel scaffolds. Our results demonstrate that free energy simulations enable design of ligand efficacy and the same approach can be applied to other GPCR drug targets.
Enantioselective Reductive (Hetero)Arylation of Cyclic N‐Sulfonyl Imines by Cobalt Catalysis
Authors: Xiao Jieshuai , Wang Minyan , Yin Xuwen , Yang Shuo , Gu Pei , Lv Xueli , Zhao Yue , Shi Zhuangzhi
Published: March 2023

Transition‐metal‐catalyzed enantioselective addition of aryl organometallic reagents to imines has emerged as one of the most powerful tools for the formation of optically active diarylmethylamines. Here, we report the first asymmetric reductive (hetero)arylations of imines using aryl and heteroaryl halides enabled by a chiral cobalt‐bisphosphine catalyst. This approach shows good functional group compatibility and complements the reported strategy without use of organometallic reagents. Mechanistic investigations supported that aryl‐cobalt, instead of an arylzinc reagent, was formed in situ in this reductive aryl‐addition event.
Nachhaltiger Eisen‐Photokatalysator auf Holzbasis für vielfältige Anwendungen mit Sonnenlicht: Wasseraufbereitung und radikalische Photopolymerisation
Authors: Guo Xiaolin , Zhao Xinpeng , Luo Xiongfei , Pang Yulian , Tian Bing , Liu Shouxin , Li Shujun , Li Jian , Strehmel Bernd , Chen Zhijun
Published: March 2023

Durch Behandlung von Holz und Eisenoxid wurde ein nachhaltiger Photokatalysator für vielfältige Verwendungzwecke hergestellt, welcher demethyliertes Lignin (Fe3O4@D‐wood) enthält. Die Charakterisierung erfolgte mittels XRD, UV/Vis, Photostromunterschungen und elektrochemischen Messungen. Dieses Material wurde zum Gegenstand photokatalytischer Untersuchungen für die Wasseraufbereitung und die Materialsynthese mittels radikalischer Photopolymerisation. Die Bestrahlung vonFe3O4@D‐woodmit künstlichem Sonnenlicht zeigte eine verbesserte Aktivität bei der photochemischen Oxidation von organischen Schadstoffen in Gegenwart von H2O2. Die effiziente Erzeugung reaktiver Radikale ermöglichte bei diesem System auch die Photopolymerisation. Hier können Radikale, die auf reaktiven Sauerstoffspezies (ROS) basieren und in dem katalytischen Zyklus erzeugt werden, als die dominierenden Spezies zur Initiierung der radikalischen Polymerisation angesehen werden. Eine Mischung ausUDMAundTPGDAzeigte eine gute Reaktivität mit Cumolhydroperoxid (CHP). Der für die Wasseraufbereitung verwendete Photokatalysator ermöglicht die Wiederverwendung für die Photopolymerisation.
Palladium‐Catalyzed Direct Carbonylation of Bromoacetonitrile to Synthesize 2‐Cyano‐N‐acetamide and 2‐Cyanoacetate Compounds
Authors: Bao Zhi‐Peng , Wu Xiao‐Feng
Published: March 2023

Nitrile compounds containing ester and amide groups are important functionalized chemicals in synthetic and medicinal chemistry. In this article, an efficient and convenient palladium‐catalyzed carbonylative procedure toward 2‐cyano‐N‐acetamide and 2‐cyanoacetate compounds has been developed. The reaction proceeds under mild conditions via radical intermediate which is suitable for late‐stage functionalization. Gram‐scale experiment was performed successfully under low catalyst loading and gave the target product in excellent yield. Additionally, this transformation can be performed under atmospheric pressure and provide alternative routes to 7 drug precursors.
Polydopamine as a Visible‐Light Photosensitiser for Photoinitiated Polymerisation
Authors: Bailey Christopher G. , Nothling Mitchell D. , Fillbrook Lucy L. , Vo Yen , Beves Jonathon E. , McCamey Dane R. , Stenzel Martina H.
Published: March 2023

Polydopamine (PDA) is a synthetic model for melanin and has a wide range of opto‐electronic properties that underpin its utility in applied and biological settings, from broadband light absorbance to possessing stable free radical species. Here, we show that PDA free radicals are photo‐responsive under visible light irradiation, enabling PDA to serve as a photo‐redox catalyst. Steady‐state and transient electron spin resonance spectroscopy reveals a reversible amplification in semiquinone radical population within PDA under visible light. This photo‐response modifies the redox potential of PDA and supports sensitisation of exogenous species via photoinduced electron transfer (PET). We demonstrate the utility of this discovery by employing PDA nanoparticles to photosensitise a common diaryliodonium photoinitiator and initiate free‐radical polymerisation (FRP) of vinylic monomers. In situ 1H nuclear magnetic resonance spectroscopy reveals an interplay between PDA‐driven photosensitising and radical quenching during FRP under blue, green, and red light. This work provides crucial insights into the photoactive free radical properties of melanin‐like materials and reveals a promising new application for polydopamine as a photosensitiser.
Single‐Benzene Dual‐Emitters Harness Excited‐State Antiaromaticity for White Light Generation and Fluorescence Imaging
Authors: Kim Younghun , Kim Heechan , Son Jung Bae , Filatov Michael , Choi Cheol Ho , Lee Nam Ki , Lee Dongwhan
Published: March 2023

Molecular emitters simultaneously generating light at different wavelengths have wide applications. With a small molecule, however, it is challenging to realize two independent radiative pathways. We invented the first examples of dual‐emissive single‐benzene fluorophores (SBFs). Two emissive tautomers are generated by synthetic modulation of the hydrogen bond acidity, which opens up pathways for excited‐state proton transfer. White light is produced by a delicate balance between the energy and intensity of the emission from each tautomer. We show that the excited‐state antiaromaticity of the benzene core itself dictates the proton movements driving the tautomer equilibrium. Using this simple benzene platform, a fluorinated SBF was synthesized with a record high solubility in perfluorocarbon solvents. White light‐emitting devices and multicolor imaging of perfluorocarbon nanodroplets in live cells demonstrate the practical utility of these molecules.
Electrochemical Reactors Enable Divergent Site Selectivity in the C−H Carboxylation of N‐Heteroarenes
Authors: Wang Peng‐Zi , Xiao Wen‐Jing , Chen Jia‐Rong
Published: March 2023

Catalytic and switchable C−H functionalization of N‐heteroarenes under easily tunable conditions is a robust but challenging tool for the construction of biologically relevant compounds. Recently, a general electrochemical strategy has been developed for the direct C−H carboxylation of N‐heteroarenes with CO2, and by simply choosing different types of cell setups, carboxylated products are furnished with excellent and tunable site selectivity. This study also paves the way for regulating the reactivity modes in electrochemical synthesis.
Towards Automated Microfluidic‐based Platforms: Optimizing Hydrogenation Efficiency of Nitrobenzene through π–π Interactions in Pd Nanoparticles on Covalent Organic Frameworks
Authors: Deng Juan , Cai Yueji , Chen Jingsheng , Wang Qing , Lu Jun , Chen Xiao , Zhang Wuxiang , Wu Kangjie , Wang Weikang , Wei Lingfei , Yang Fu , Yuan Aihua , Pang Huan , Yu Chao
Published: March 2023

Microplatform with timed automata has been leveraged for guiding the preparation of molecules, whereas the requirement of handling expertise and sophisticated instrument is inevitable in combination with heterogeneous catalysis. Here we report a microfluidic‐based autolab with open structures, called Put & Play Automated Microplatform (PPAM). It shows the efficient hydrogenation performance of palladium nanoparticles on the triphenylene‐based covalent organic frameworks (Pd/TP‐COFs) in which the π–π interactions of TP rings in the vicinity of Pd is optimized by easy change‐over of catalyst and simple tuning of reactor geometries in PPAM. Using experiment/simulation of the Pd/TP‐COFs coating (PCC) and mixing (PCM) across PPAM with different channel sizes, the turnover frequencies are 60 times the commonly used batch reactor, and aniline productivity of 8.8 g h−1 is achieved in 0.09 cm3. This work will raise awareness about the benefits of the catalyst‐loaded microplatform in future materials performance campaigns.
Rational Utilization of Black Phosphorus Nanosheets to Enhance Palladium‐Mediated Bioorthogonal Catalytic Activity for Activation of Therapeutics
Authors: Rong Mingjie , Liu Jian , Sun Zhen , Li Tong , Li Yang , Jiang Chunhuan , Lu Lehui
Published: March 2023

Pd‐catalyzed chemistry has played a significant role in the growing subfield of bioorthogonal catalysis. However, rationally designing Pd nanocatalysts that show outstanding catalytic activity and good biocompatibility poses a great challenge. Herein, we propose an innovative strategy through exploiting black phosphorous nanosheets (BPNSs) to enhance Pd‐mediated bioorthogonal catalytic activity. Firstly, the electron‐donor properties of BPNSs enable in situ growth of Pd nanoparticles (PdNPs) on it. Meanwhile, due to the superb capability of reducing PdII, BPNSs can act as hard nucleophiles to accelerate the transmetallation in the decaging reaction process. Secondly, the lone pair electrons of BPNSs can firmly anchor PdNPs on their surface via Pd−P bonds. This design endows Pd/BP with the capability to retard tumor growth by activating prodrugs. This work proposes new insights into the design of heterogeneous transition‐metal catalysts (TMCs) for bioorthogonal catalysis.
A Dynamic Defect Generation Strategy for Efficient Enzyme Immobilization in Robust Metal‐Organic Frameworks for Catalytic Hydrolysis and Chiral Resolution
Authors: Feng Yifan , Shi Ruixuan , Yang Mingfang , Zheng Yunlong , Zhang Zhenjie , Chen Yao
Published: March 2023

Enzyme immobilization has been demonstrated to be a favorable protocol for promoting the industrialization of bioactive molecules, but still with formidable challenge. Addressing this challenge, we create a dynamic defect generation strategy for enzyme immobilization by using the dissociation equilibrium of metal‐organic frameworks (MOFs) mediated by enzymes. Enzymes can act as “macro ligands” to generate competitive coordination against original ligands, along with the release of metal clusters of MOFs to generate defects, hence promoting the gradual transport of enzymes from the surface to inside. Various enzymes can be efficiently immobilized in MOFs to afford composites with good enzymatic activities, protective performances and exceptional reusabilities. Moreover, multienzyme bioreactors capable of efficient cascade reactions can also be generated. This study provides new opportunities to construct highly efficient biocatalysts incorporating different types of enzymes.
Main anatomical characteristics of the hominin fossil humeri from the Sima de los Huesos Middle Pleistocene site, Sierra de Atapuerca, Burgos, Spain: An update
Authors: Carretero José‐Miguel , García‐González Rebeca , Rodríguez Laura , Arsuaga Juan‐Luis
Published: March 2023

Some of the Sima de los Huesos (SH) humeri have been previously studied and described elsewhere. Here we present an updated inventory and a review of the specimens recovered to the present day. The morphological key traits of the adult and subadult specimens are described, discussed, and illustrated. The SH humeri share with Neandertals many traits usually considered to be Neandertal specializations, thus, most of this morphological pattern is not exclusive to them. The variation found within fossil samples stresses the frequential nature of all these traits and in the specific case of the SH humeri, most of the traits considered as phylogenetically relevant are retained by their descendants, the Neandertals. Some traits are plesiomorphic for the entire genus Homo or are present in European hominins since the early Pleistocene. Finally, some other traits display high variability within the SH sample or different hominin samples and are of uncertain phylogenetic value. Altogether, this evidence is consistent with the hypothesis based on the overall cranial and postcranial morphology that the SH hominins are a sister group to the later Neandertals.
Comparative analysis of the two suborders of Thysanoptera and characterization of the complete mitochondrial genome of Thrips parvispinus
Authors: Pakrashi Avas , Patidar Abhishek , Singha Devkant , Kumar Vikas , Tyagi Kaomud
Published: March 2023

Thrips parvispinus is a serious sucking pest on a number of economically important crops in the oriental region. It has gained importance recently for its drastic range extension distribution as an invasive pest. Here, the complete mitochondrial genome (15,067 bp) of Thrips parvispinus was sequenced and characterized. It possesses 37 genes and the putative noncoding region is duplicated. Comparative analyses of nucleotide diversity, skewness, codon usage bias, and selection pressure in mitochondrial protein‐coding genes of the available 31 thrips mitogenomes (24 Terebrantia + 7 Tubulifera) were performed. Phylogenetic analysis showed a sister relationship of T. parvispinus to the clade (T. florum + T. hawaiiensis). Phylogenetic analyses formed the monophyly of subfamilies Phlaeothripinae and Idolothripinae within the family Phlaeothripidae (Suborder Tubulifera). Low nucleotide diversity was indicative of reversal of strand asymmetry in the Tubulifera. Neutrality analysis showed that directional mutation plays a major role in shaping codon usage bias in both suborders. Principal component analysis indicated distinct codon usage patterns in each suborder. Our data suggested weaker selection constrains on Terebrantia than in the Tubulifera. More tubuliferan mitogenomes are required to resolve previous classification hypotheses and elucidate genome evolution in these two suborders.
Preclinical evaluation of the Versius surgical system: A next‐generation surgical robot for use in minimal access prostate surgery
Authors: Vasdev Nikhil , Charlesworth Philip , Slack Mark , Adshead Jim
Published: March 2023

Objectives

To evaluate the Versius surgical system for robot‐assisted prostatectomy in a preclinical cadaveric model using varying system setups and collect surgeon feedback on the performance of the system and instruments, in line with IDEAL‐D recommendations.

Materials and methods

Procedures were performed in cadaveric specimens by consultant urological surgeons to evaluate system performance in completing the surgical steps required for a prostatectomy. Procedures were conducted using either a 3‐arm or 4‐arm bedside unit (BSU) setup. Optimal port placements and BSU layouts were determined and surgeon feedback collected. Procedure success was defined as the satisfactory completion of all steps of the procedure, according to the operating surgeon.

Results

All four prostatectomies were successfully completed; two were completed with a 3‐arm BSU setup and two using a 4‐arm BSU setup. Small adjustments were made to the port and BSU positioning, according to surgeon preference, in order to complete the surgical steps. The surgeons noted some instrument difficulties with the Monopolar Curved Scissor tip and the Needle Holders, which were subsequently refined between the first and second sessions of the study, in line with surgeon feedback. Three cystectomies were also successfully completed, demonstrating the capability of the system to perform additional urological procedures.

Conclusions

This study provides a preclinical assessment of a next‐generation surgical robot for prostatectomies. All procedures were completed successfully, and port and BSU positions were validated, thus supporting the progression of the system to further clinical development according to the IDEAL‐D framework.
Online practical assessment in biochemistry designed on Bloom's taxonomy to assess the student's competency: Prior exposure of the students to online tools beneficial
Authors: Kempegowda Swetha Nagarahalli , Ramachandra Shobha Chikkavaddaragudi , Arun Brunda , Devaraju Abhijith , Shivashankar Kusuma Kasapura , Raghunathachar Sahana Kabbathy , Bettadapura Anjalidevi Shankarrao , Puttalingaiah Sujatha , Devegowda Devananda , Vishwanath Prashant , Nataraj Suma Maduvanahalli , Prashant Akila
Published: March 2023

Online assessments are needed during the prevailing pandemic situation to continue educational activities while ensuring safety. After conducting the online practical assessment (OPrA) in Biochemistry, we analyzed the students' responses. The blueprint of the OPrA was prepared by the faculty, referring to the various levels and domains of Bloom's taxonomy. Four components were chosen for the online assessment: digital spotters, enumerating the steps of objective structured practical examination, interpretation of quantitative estimation, and case discussion. Each faculty assessed about 12–13 students in separate breakout rooms over 15–20 min on all four components. Feedback on the conduct of the examination was collected from the students and faculty anonymously and analyzed. Out of the 200 students who attended the online assessment, only one scored less than 50%, majority of them scored between 71% and 90%. Under the individual exercises, the average score of students in “Spotters” was 9.8 out of 10; in “OSPE,” 8.7 out of 10; in “Quantitative experiments,” 15.2 out of 20 and in “Case discussion,” 22.4 out of 30. Around 20% had previous experience attending the OPrA. They differed in their opinion from the rest of the students on five aspects; time allotted for the assessment (p value = 0.02, χ2 = 5.07), students using unfair means during the online viva (p value = 0.02, χ2 = 5.57), their computing skills (p value = 0.001, χ2 = 19.82), their performance (p value = 0.001, χ2 = 8.84), and overall conduct of the examination (p value = 0.001, χ2 = 15.55). OPrA tools may be designed referring to Bloom's taxonomy, and prior exposure to the online tools may benefit the students.
Application of QbD‐based approach to the development and validation of an RP‐HPLC method for simultaneous estimation of pregabalin and naringin in dual‐drug loaded liposomes
Authors: Gupta Isha , Adin Syeda Nashvia , Aqil Mohd. , Mujeeb Mohd. , Akhtar Mohd.
Published: March 2023

The current work delineates the development of a novel, rugged and sensitive stability‐indicating risk‐based HPLC method based on an analytical quality‐by‐design (QbD) approach for the concurrent estimation of naringin and pregabalin in dual‐drug‐loaded nanopharmaceuticals. Preliminary screening trials were conducted, along with systemic risk analysis, in order to identify the critical method attributes, namely injection volume, pH and acetonitrile content, that influence critical quality attributes. The Box–Behnken design was used to optimize the tailing factor as a response to pregabalin and naringin in a short run time. The chromatographic conditions were improved by running 17 experimental runs generated by design expert software. After analysing the optimized zone within the confines of the design space, the following chromatographic conditions were chosen: mobile phase water–acetonitrile adjusted to pH 6.9 with phosphate buffer (80:20, %v/v), at flow rate of 1.0 ml/min using a C18 analytical column at an isobestic wavelength of 212 nm. Furthermore, the optimized method was validated in accordance with International Conference on Harmonization guidelines and was found to be within the prescribed limits. The developed RP‐HPLC method has a high degree of practical utility in in vivo and in vitro studies for the synchronous detection of pregabalin and naringin in pharmaceutical nanodosage forms such as protein‐based nanoparticles, nanocrystals, polymeric nanoparticles and metallic nanoparticles.
Incorporating a Polyethyleneglycol Linker to Enhance the Hydrophilicity of Mitochondria‐Targeted Triphenylphosphonium Constructs
Authors: Uno Shinpei , Harkiss Alexander H. , Chowdhury Roy , Caldwell Stuart T. , Prime Tracy A. , James Andrew M. , Gallagher Brendan , Prudent Julien , Hartley Richard C. , Murphy Michael P.
Published: March 2023

The targeting of bioactive molecules and probes to mitochondria can be achieved by coupling to the lipophilic triphenyl phosphonium (TPP) cation, which accumulates several hundred‐fold within mitochondria in response to the mitochondrial membrane potential (Δψm). Typically, a simple alkane links the TPP to its “cargo”, increasing overall hydrophobicity. As it would be beneficial to enhance the water solubility of mitochondria‐targeted compounds we explored the effects of replacing the alkyl linker with a polyethylene glycol (PEG). We found that the use of PEG led to compounds that were readily taken up by isolated mitochondria and by mitochondria inside cells. Within mitochondria the PEG linker greatly decreased adsorption of the TPP constructs to the matrix‐facing face of the mitochondrial inner membrane. These findings will allow the distribution of mitochondria‐targeted TPP compounds within mitochondria to be fine‐tuned.
Computationally Supported Inversion of Ketoreductase Stereoselectivity
Authors: Delgado‐Arciniega Estela , Wijma Hein J. , Hummel Chantal , Janssen Dick B.
Published: March 2023

Whereas directed evolution and rational design by structural inspection are established tools for enzyme redesign, computational methods are less mature but have the potential to predict small sets of mutants with desired properties without laboratory screening of large libraries. We have explored the use of computational enzyme redesign to change the enantioselectivity of a highly thermostable alcohol dehydrogenase from Thermus thermophilus in the asymmetric reduction of ketones. The enzyme reduces acetophenone to (S)‐1‐phenylethanol. To invert the enantioselectivity, we used an adapted CASCO workflow which included Rosetta for enzyme design and molecular dynamics simulations for ranking. To correct for unrealistic binding modes, we used Boltzmann weighing of binding energies computed by a linear interaction energy approach. This computationally cheap method predicted four variants with inverted enantioselectivity, each with 6–8 mutations around the substrate‐binding site, causing only modest reduction (2‐ to 7‐fold) of kcat/KM values. Laboratory testing showed that three variants indeed had inverted enantioselectivity, producing (R)‐alcohols with up to 99 % enantiomeric excess. The broad substrate range allowed reduction of acetophenone derivatives with full conversion to highly enantioenriched alcohols. The results demonstrate the use of computational methods to control ketoreductase stereoselectivity in asymmetric transformations with minimal experimental screening.
Micro/nano‐wrinkled elastomeric electrodes enabling high energy storage performance and various form factors
Authors: Yoo Changeun , Lee Seokmin , Song Yongkwon , Chang Woojae , Park Moon Kyu , Ko Younji , Cho Jinhan
Published: March 2023

Stretchable elastomer‐based electrodes are considered promising energy storage electrodes for next‐generation wearable/flexible electronics requiring various shape designs. However, these elastomeric electrodes suffer from the limited electrical conductivity of current collectors, low charge storage capacities, poor interfacial interactions between elastomers and conductive/active materials, and lack of shape controllability. In this study, we report hierarchically micro/nano‐wrinkle‐structured elastomeric electrodes with notably high energy storage performance and good mechanical/electrochemical stabilities, simultaneously allowing various form factors. For this study, a swelling/deswelling‐involved metal nanoparticle (NP) assembly is first performed on thiol‐functionalized polydimethylsiloxane (PDMS) elastomers, generating a micro‐wrinkled structure and a conductive seed layer for subsequent electrodeposition. After the assembly of metal NPs, the conformal electrodeposition of Ni and NiCo layered double hydroxides layers with a homogeneous nanostructure on the micro‐wrinkled PDMS induces the formation of a micro/nano‐wrinkled surface morphology with a large active surface area and high electrical conductivity. Based on this unique approach, the formed elastomeric electrodes show higher areal capacity and superior rate capability than conventional elastomeric electrodes while maintaining their electrical/electrochemical properties under external mechanical deformation. This notable mechanical/electrochemical performance can be further enhanced by using spiral‐structured PDMS (stretchability of ~500%) and porous‐structured PDMS (areal capacity of ~280 μAh cm−2).
Synergistic interactions between the charge‐transport and mechanical properties of the ionic‐liquid‐based solid polymer electrolytes for solid‐state lithium batteries
Authors: Agrawal Ashutosh , Yari Saeed , Hamed Hamid , Gouveia Tom , Lin Rongying , Safari Mohammadhosein
Published: March 2023

The performance sensitivity of the solid‐state lithium cells to the synergistic interactions of the charge‐transport and mechanical properties of the electrolyte is well acknowledged in the literature, but the quantitative insights therein are very limited. Here, the charge‐transport and mechanical properties of a polymerized ionic‐liquid‐based solid electrolyte are reported. The transference number and diffusion coefficient of lithium in the concentrated solid electrolyte are measured as a function of concentration and stack pressure. The elastoplastic behavior of the electrolyte is quantified under compression, within a home‐made setup, to substantiate the impact of stack pressure on the stability of the Li/electrolyte interface in the symmetric lithium cells. The results spotlight the interaction between the concentration and thickness of the solid electrolyte and the stack pressure in determining the polarization and stability of the solid‐state lithium batteries during extended cycling.
De‐Risking S‐F Bond Formation: A Gas Cylinder‐Free Strategy to Access S(IV) and S(VI) Fluorinated Compounds**
Authors: Kordnezhadian Reza , Zogu Armir , Borgarelli Carlotta , Van Lommel Ruben , Demaerel Joachim , De Borggraeve Wim M. , Ismalaj Ermal
Published: March 2023

The sulfur‐fluorine partnership occupies a privileged position in fluorine chemistry given the functional versatility that it imparts to organic structures. Despite this, available methodologies to forge S−F bonds are limited compared to C−F bond formation. Here, we describe a synthetic protocol that selectively enables the oxidative halogenation of aliphatic, aromatic, and heteroaromatic thiols to their corresponding SF4Cl, SO2F and SF3 derivatives. Selective oxidation of thiols to either S(IV)‐F or S(VI)‐F compounds is achieved by employing bench‐stable calcium hypochlorite as chlorine surrogate (CLOgen), in the presence of KF as fluoride source. Density functional theory (DFT) calculations provided insight into the mechanistic aspects of the transformation and rationalized the observed isomeric preference towards the SF4Cl derivatives. Ultimately, this glovebox‐free method selectively dispatches three classes of compounds upon reaction condition fine‐tuning. Furthermore, first‐in‐class transformations are reported, including the preparation of aliphatic SF4Cl intermediates, their transformation into aliphatic sulfur pentafluoride analogs, and post‐functionalizations that allow accessing highly complex SF4‐bridged scaffolds.
Adsorption‐Induced In‐Situ Construction of TiO2 Hollow Sphere/UiO‐66‐NH2 Heterostructures with Boosted Photocatalytic Activity toward Cr(VI) Reduction
Authors: Xu Qiankun , Li Yaru , Ji Wen , Mei Jun , Wang Xianbiao
Published: March 2023

Water contamination caused by highly toxic Cr(VI) should be resolved imminently with a more efficient photocatalytic approach. The interaction between photocatalyst heterostructure is critical for charge separation which largely affects the photocatalytic efficiency. Herein, TiO2 hollow sphere/UiO‐66‐NH2 (TiO2/UiO‐66‐NH2) heterostructures were successfully synthesized by an adsorption‐induced in‐situ solvothermal growth strategy. The UiO‐66‐NH2 particles were well dispersed on TiO2 hollow spheres by solvothermal treatment of Zr4+ adsorbed TiO2 hollow spheres with NH2‐BDC ligand. The photocatalytic activities of TiO2/UiO‐66‐NH2 heterostructures were investigated by reduction of Cr(VI) with visible light irradiation. With the introduction of UiO‐66‐NH2, the reduction efficiency toward Cr(VI) by TiO2/UiO‐66‐NH2 heterostructures reached 89% after 180 min of irradiation, which is much higher than those of TiO2 hollow spheres (10%) and UiO‐66‐NH2 crystals (29%). Moreover, the TiO2/UiO‐66‐NH2 heterostructures display good regeneration ability and can still maintain 70% of Cr(VI) removal ability after four cycles. The integration of TiO2 and UiO‐66‐NH2 could construct a type‐II heterojunction to broaden the absorption range of light and suppress the recombination of photoproduced electrons and holes. As a result, such unique composite structure significantly enhance the photocatalytic performance towards Cr(VI) reduction. This work not only inspires a new approach for in‐situ solvothermal synthesis of semiconductor@MOFs composites, but provides a novel photocatalyst for highly efficient removal of Cr(VI) from wastewater.