bluuebunny/crossref_metadata_2025 huggingface dataset:
The Indian Lessons to be Learnt from COVID-19 Pandemic
Authors: Wavare Sonali , Dhengare Archana
Published: January 2022

Emerging pandemics indicate that people are not infallible and that communities need to be prepared. Coronavirus COVID-19 outbreak was first identified in late 2019, and has now been declared a World Health Organization pandemic. Countries around the world are reacting to the virus outbreak differently. On the other hand, several other nations have put in place successful measures to control the virus, reporting a relatively limited number of cases since the pandemics started. Restrictive steps such as social distancing, lockdown, case identification, isolation, touch monitoring and exposure quarantine had shown the most effective acts to monitor the spread of the disease. This review will help readers understand that this invisible and ‘omnipresent’ virus has taught a lesson for the first time in human history that whatever human power might have, it could not subjugate every living being in this world. This has been confirmed once again by the recent invasion of this human virus. Difference in the answers of the different countries and their outcomes,  based on that country's experience, India responded accordingly to the pandemic. Only time will tell how well India comes up against the outbreak. We also propose the potential approaches the global community will take in handling and minimizing the emergency.
Is the Urine Analysis, a Diagnostic Value in COVID-19 Patients?
Authors: Sulochana Sonti , Asokan Lakshmi Priya , Mathesh . , Srinivasan Chitra
Published: January 2022

Background: Severe acute respiratory syndrome coronavirus 2 (SARS CoV-2), a novel coronavirus causing Coronavirus disease 19 (COVID-19) in December 2019, is now a pandemic infectious disease, primarily affecting the respiratory tract. To date, many investigations are available for the diagnosis of SARS-CoV-2. A viral nucleic acid test has been used for the diagnosis of COVID-19, and some hematological indicators have been used in the auxiliary diagnosis and identification of the severity of COVID-19. There are very few studies available in routine urine biochemical parameters and their relation with Covid-19 patients.

Aim: This study is aimed to study the changes in urine parameter values in COVID-19 disease and to predict the severity of the disease with the changes in urine parameters.

Materials and Methods: A total of 150 patients with COVID-19 were admitted at Saveetha Medical College and Hospital during the study period. All cases tested positive for SARS-CoV-2 by RT-PCR test done on nasopharyngeal swabs during the study period were included. Patients who tested negative by RT-PCR test were considered as controls. The relationship between the results of urine biochemical parameters and the severity of COVID-19 were analysed by Descriptive statistics, Chi-squared test.

Results: The positive rates of proteinuria (PRO) and leucocytes were more significant in COVID-19 patients than in healthy controls. The urine specific gravity (SG) value was highly significant (p <0.001) while the blood, nitrites in urine, and  potential of hydrogen (pH) value was insignificant.

Conclusion: There were some considerable changes in few urine biochemical parameters between patients with the SARS-CoV-2 and healthy controls. So from this study we conclude, proteinuria is helpful for predicting COVID-19 severity and kidney function.
Covid Shielding (Preventive Measures of COVID-19)
Authors: Upadhyay Pranjal , Jain Pradip , Patel Praful
Published: January 2022

COVID-19 had a lot of lessons to tell, and one of the most interesting was how difficult it is to manage a deadly, fast-moving disease in a community that is closely tied together by mass transportation, mass consumption, and mass media. As the largest pandemic to have occurred in the “digital-mass society” period, COVID-19 demonstrates how quickly a virus can spread through the "masses" despite the many steps taken by public health authorities to limit its spread. The primary measure most in use by health officials during COVID-19 pandemic is preventing person to person spread of disease by creating a firewall between uninfected and infected masses. COVID-19 had a lot of lessons to tell, and one of the most interesting was how difficult it is to manage a deadly, fast-moving disease in a community that is closely tied together by mass transportation, mass consumption, and mass media. As the largest pandemic to have occurred in the “digital-mass society” era, COVID-19 offers an insight on how quickly a virus can spread through the "masses" despite the many steps taken by public health authorities to limit its spread. The material required for the review was taken from the databases of Pub Med, Web of science, the from the website of World Health Organization and the patients data of SMHRC and DMMC Wanadongari Nagpur.
Oral Submucous Fibrosis with and without Associated Oral Squamous Cell Carcinoma
Authors: Masoud Ahmad , Shafique Muzzamil , Arif Faiza
Published: January 2022

Introduction: Oral submucous fibrosis (OSF) is a potentially malignant disorder of the oral cavity.

Aims and Objectives: The core objective of the study is to analyze the oral submucous fibrosis with and without associated oral squamous cell carcinoma (OSCC).

Materials and Methods: This cross sectional study was conducted in Baqai Dental College Karachi during October 2020 to June 2021. The data was collected from 100 patients of both genders who were confirmed with OSF on the basis of history and clinical examinations were included in the study. Demographic and clinical information were recorded.

Results: The data were collected from 100 patients of both females and males. The age distribution of the sample was analyzed. The patients were mostly above 50 years of age in both categories. However, the number of patients who were with OSCC at an age below 50 was greater in the OSF-positive group (23.8% vs. 21.9%). Similarly, the mean age of OSF + OSCC patients was 57.5 years while this value was 59.5 years for those without.

Conclusion: It is concluded that tumors show well-differentiated histology and less lymph node involvement. However, a statistical significance was not observed among these variables, when comparing the OSCC patients with OSF to those who are without.
Effectiveness of Perioperative Local Use of Anesthetics and Antiseptics in Patients with Purulent-necrotic Lesions of Lower Extremities in Diabetes Mellitus
Authors: Babina Yuliana , Dmyrtriiev Dmytro , Nazarchuk Oleksandr , Hormash Pavlo , Vernyhorodskyi Serhii
Published: January 2022

Background: Every second patient with the diabetes mellitus (DM) needs surgery due to purulent-necrotic changes in the feet.

The aim of the study was comparative morphological examination of the course of the wound process in purulent-necrotic lesions of the lower extremities of patients with DM with different approaches to local treatment in the perioperative period.

Materials and Methods: We investigated changes in the histological structure and the nature of the reactions of skin tissues, muscles and fascia during the healing of an ulcer in patients with the diabetes mellitus after various types of local treatment. Then the specimens were photographed and analyzed using the OLIMPUS BX 41 light microscope.

Results: In the first comparison group, which used standard anesthesia techniques and locally antiseptic povidon-iodine - granulation tissue was characterized by the complete absence of fibrous structures and the presence of a small number of small-sized neoplastic vessels with swollen endothelium. And in patients of the II observation group who received locally decamethoxin and infiltration anesthesia with a 2% solution of lidocaine after surgery during the study of histological preparations of the affected tissues, a significant decrease in signs of pathological vascular reaction was established compared with the comparison group.

Conclusions: In group 1 (control) healing of wounds on the third-seventh day is characterized by somewhat slow regeneration. Wound healing was most favorable in patients of the second group, where infiltration anesthesia was used by local anesthetic and antiseptic decamethoxin.
Epitope Based Vaccine Peptide Predictions for fimH gene of Acinetobacter baumannii
Authors: Devika B. , Girija A. S. Smiline , Ganesh P. Sankar , Priyadharsini J. Vijayashree
Published: January 2022

Background: Acinetobacter baumannii is an opportunistic bacterial pathogen that is primarily associated with hospital-acquired infections. Recently, there is a dramatic increase in the incidence of multidrug-resistant (MDR) strains, which has significantly raised the profile of this emerging opportunistic pathogen. MDR is often associated with the formation of biofilms and various other virulence factors. Amidst all the genes, fimH gene is our area of interest in this research, because it is an important virulence factor in A. baumannii which encodes the Type 1 fimbriae, that helps bacteria bind to the surface of host cells initiating further infection.

Aim: The aim of this study was to assess the epitope based vaccine epitope peptide predictions for the fimH protein of A. baumannii.

Materials and Methods: The fimH gene for epitope prediction was selected. Druggability and physico-chemical properties were analysed. Antigenicity was predicted. Epitope mapping of T-cell MHC class 1, Class 1 immunogenicity, conservancy and toxicity analysis was done. T-cell class II epitopes were further mapped together with the immuno-dominant B-cell epitopes. 

Results: From the selected 20 epitopes, 2 best epitopes (AALVASVCL and YSSGANAFT) were selected after analysing their antigenicity and allergenicity. The epitope YSSGANAFT showed better values in association with HLA alleles - HLA-DP, HLA-DQ, HLA-DR and TLR-2.

Conclusion: The finding of the study documents a single immunodominant peptide (sequence) as a promising vaccine candidate to treat infections caused by A. baumannii. However further experimental analysis must be performed to assess the immunological memory and response of the peptide in both in-vitro and in-vivo studies.
Assessment of Oral Health Care Needs among Fishermen Living in North Chennai, India – A Cross Sectional Study
Authors: Nithya V. R. , Krithika Chandrasekaran , Sridhar Chitathoor , Arumugam A. Edeinton
Published: January 2022

Introduction: Studies conducted among fishermen shows that there was a high prevalence rate in Oral mucosal lesions. However, data on oral health care needs among fisherman is scarce. Hence this was undertaken to obtain a data that can be used to plan programmes for the prevention and treatment of such oral mucosal lesions in the fishermen.

Materials and Methods: A study was carried out among 71 fishermen after obtaining clearance from the institutional ethical committee and concerned authorities. A self administered questionnaire is distributed among the study group comprising questions relating to personal history and deleterious habits. Clinical examination was carried out using mouth mirror, explorer and under proper illumination.  Oral health examination was   done using WHO Basic Oral health Assessment proforma, 2013. Data collected and analysed statistically using SPSS software.

Results: Among the 71 fishermen, 56(78.9%) were males and 15 (21.1 %) were females. In the study population, 44(62%) were tobacco chewers, 39(54.9%) were snuff users, 24(33.8%) were alcohol consumers and 19(26.8%) were smokers. Smokeless tobacco (41.5%) was the most common deleterious habit after which by alcohol consumption (33.8%) and smoking (26.8%).The prevalence of oral mucosal lesions was 20.8%.It was found that statistically significant association existed between the deleterious habits and leukoplakia.

Conclusion: According to the our study, the prevalence of oral mucosal lesions was 20.8% among the fishermen who had a clear association with deleterious habits such as tobacco chewing, smoking, alcohol consumption and snuff.
High‐Resolution Erasable “Live” Patterns Based on Controllable Ink Diffusion on the 3D Blue‐Phase Liquid Crystal Networks
Authors: Meng Fanshu , Zheng Chenglin , Yang Wenjie , Guan Bo , Wang Jingxia , Ikeda Tomiki , Jiang Lei
Published: January 2022

Colorful blue phase liquid crystal (BPLC) patterns have attracted wide research attention owing to their intriguing and advantageous properties and promising applications. However, it remains a challenge to develop novel and high‐resolution patterns from BPLC owing to the complicated synthetic procedure for the functional molecules. This study reports a high‐resolution “live” pattern by well‐designed diffusion of 5CB ink on the wettability‐modified BPLC networks. Interestingly, the shape and color of the as‐prepared pattern change with time, which results in unique spectra change of the printed pattern, “first red‐shift and subsequent blue‐shift of the stopband position” and “continuous growth in reflectivity intensity” with time. The hydrophobic substrate greatly suppresses the random spreading and diffusion of ink, contributing to high‐resolution patterns. The promising applications of live patterns for program display and active labels are demonstrated. Various high‐resolution erasable colorful patterns are obtained. The structure reconfiguration of the writing and erasing processes is proved by transmitted electronic microscope images and Kossel diffraction diagrams, which ensures the reversible writing/erasing of the pattern on the membrane. This work is of significance for the development of novel rewritable paper and high‐quality optic devices based on BPLC materials.
Patterning All‐Inorganic Halide Perovskite with Adjustable Phase for High‐Resolution Color Filter and Photodetector Arrays
Authors: Kim Woosik , Kim Su‐Kyung , Jeon Sanghyun , Ahn Junhyuk , Jung Byung Ku , Lee Sang Yeop , Shin Chanho , Seong Tae‐Yeon , Jeong Sohee , Jang Ho Seong , Ng TSe Nga , Oh Soong Ju
Published: January 2022

Perovskite has been actively studied for optoelectronic applications, such as photodetectors and light‐emitting diodes (LEDs), because of its excellent optoelectronic properties. However, ionic bonds of the perovskite structure are vulnerable to chemicals, which makes perovskite incompatible with photolithography processes that use polar solvents. Such incompatibility with photolithography hinders perovskite patterning and device integration. Here, an all‐solution based cesium lead halide perovskite (CsxPbyBrz) patterning method is introduced in which PbBr2 is patterned and then synthesized into CsxPbyBrz. Each step of the top‐down patterning process (e.g., developing, etching, and rinsing) is designed to be compatible with existing photolithography equipment. Structural, chemical, and optical analyses show that the PbBr2 pattern of (10 µm)2 squares is successfully transformed into CsPbBr3 and Cs4PbBr6 with excellent absorption and emission properties. High‐resolution photoconductor arrays and luminescent pattern arrays are fabricated with CsPbBr3 and Cs4PbBr6 on various substrates, including flexible plastic films, to demonstrate their potential applications in image sensors or displays. The research provides a fundamental understanding of the properties and growth of perovskite and promotes technological advancement by preventing degradation during the photolithography process, enabling the integration of perovskite arrays into image sensors and displays.
Peritoneum‐Inspired Janus Porous Hydrogel with Anti‐Deformation, Anti‐Adhesion, and Pro‐Healing Characteristics for Abdominal Wall Defect Treatment
Authors: Liang Weiwen , He Wenyi , Huang Rongkang , Tang Youchen , Li Shimei , Zheng Bingna , Lin Yayu , Lu Yuheng , Wang Hui , Wu Dingcai
Published: January 2022

Implantable meshes used in tension‐free repair operations facilitate treatment of internal soft‐tissue defects. However, clinical meshes fail to achieve anti‐deformation, anti‐adhesion, and pro‐healing properties simultaneously, leading to undesirable surgery outcomes. Herein, inspired by the peritoneum, a novel biocompatible Janus porous poly(vinyl alcohol) hydrogel (JPVA hydrogel) is developed to achieve efficient repair of internal soft‐tissue defects by a facile yet efficient strategy based on top‐down solvent exchange. The densely porous and smooth bottom‐surface of JPVA hydrogel minimizes adhesion of fibroblasts and does not trigger any visceral adhesion, and its loose extracellular‐matrix‐like porous and rough top‐surface can significantly improve fibroblast adhesion and tissue growth, leading to superior abdominal wall defect treatment to commercially available PP and PCO meshes. With unique anti‐swelling property (maximum swelling ratio: 6.4%), JPVA hydrogel has long‐lasting anti‐deformation performance and maintains high mechanical strength after immersion in phosphate‐buffered saline (PBS) for 14 days, enabling tolerance to the maximum abdominal pressure in an internal wet environment. By integrating visceral anti‐adhesion and defect pro‐healing with anti‐deformation, the JPVA hydrogel patch shows great prospects for efficient internal soft‐tissue defect repair.
2D FeP Nanoframe Superlattices via Space‐Confined Topochemical Transformation
Authors: Deng Yuwei , Xi Xiangyun , Xia Yan , Cao Yangfei , Xue Shuqing , Wan Siyu , Dong Angang , Yang Dong
Published: January 2022

Self‐assembled nanocrystal superlattices represent an emergent class of designer materials with potentially programmable functionalities. The ability to construct hierarchically structured nanocrystal superlattices with tailored geometry and porosity is critical for extending their applications. Here, 2D superlattices comprising monolayer FeP nanoframes are synthesized through a space‐confined topochemical transformation approach induced by the Kirkendall effect, using carbon‐coated Fe3O4 nanocube superlattices as a precursor. The particle shape and the close‐packed nature of Fe3O4 nanocubes as well as the interconnected carbon layer network contribute to the topochemical transformation process. The resulting 2D FeP nanoframe superlattices possess several unique and advantageous structural features that are unavailable in conventional 3D nanocrystal superlattices, which make them particularly attractive for catalytic applications. As a proof of concept, such 2D FeP nanoframe superlattices are harnessed as highly efficient and durable electrocatalysts for the hydrogen evolution reaction, the performance of which is superior to that of most FeP‐based catalysts reported previously. This topochemical transformation approach is scalable and general, representing a new route of designing hierarchical superlattices with highly open features that cannot be accessible by traditional self‐assembly methods.
Tris(pentafluorophenyl)borane‐Catalyzed Oxygen Insertion Reaction of α‐Diazoesters (α‐Diazoamides) with Dimethyl Sulfoxide
Authors: Wu Xiao‐Yang , Gao Wen‐Xia , Zhou Yun‐Bing , Liu Miao‐Chang , Wu Hua‐Yue
Published: January 2022

A tris(pentafluorophenyl)borane‐catalyzed oxidation reaction of α‐diazoesters (α‐diazo amides) with dimethyl sulfoxide has been developed. The reaction proceeds under metal free conditions to afford a series α‐ketoesters and α‐ketoamides. The synthetic utility of this protocol is demonstrated through synthetic transformations and scaled‐up synthesis.

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The impact of crop insurance on farm financial outcomes
Authors: DeLay Nathan D. , Brewer Brady , Featherstone Allen , Boussios David
Published: January 2022

We use data from the Kansas Farm Management Association to estimate the impact of crop insurance liability and insurance indemnities on farm debt. Subsidized crop insurance may increase farms' financial risk through a mechanism known as “risk balancing.” Previous findings in support of risk balancing may suffer from bias due to unobservable farm characteristics and simultaneity in insurance and debt decisions. Employing a simultaneous equations model with farm fixed effects, we find no statistical relationship between crop insurance liability and debt, calling into question the risk balancing hypothesis in federal crop insurance. We show that large insurance indemnity payments reduce farms' reliance on short‐term debt, but leave the total debt level unchanged.
Perceived utility and disutility of genomic sequencing for pediatric patients: Perspectives from parents with diverse sociodemographic characteristics
Authors: Halley Meghan C. , Young Jennifer L. , Fernandez Liliana , Kohler Jennefer N. ,   Undiagnosed Diseases Network, Bernstein Jonathan A. , Wheeler Matthew T. , Tabor Holly K.
Published: January 2022

Given the limited therapeutic options for most rare diseases diagnosed through genomic sequencing (GS) and the proportion of patients who remain undiagnosed even after GS, it is important to characterize a broader range of benefits and potential harms of GS from the perspectives of families with diverse sociodemographic characteristics. We recruited parents of children enrolled in the Undiagnosed Diseases Network. Parents completed an in‐depth interview, and we conducted a comparative content analysis of the data. Parents (n = 30) were demographically diverse, with 43.3% identifying as Hispanic, 33.3% primarily Spanish‐speaking, and widely variable household income and education. Parents reported minimal changes in their child's health status following GS but did report a range of other forms of perceived utility, including improvements in their child's healthcare management and access, in their own psychological well‐being, and in disease‐specific social connections and research opportunities. Parents who received a diagnosis more frequently perceived utility across all domains; however, disutility also was reported by both those with and without a diagnosis. Impacts depended on multiple mediating factors, including parents' underlying expectations and beliefs, family sociodemographic characteristics, individual disease characteristics, and prior healthcare access. Our study suggests that the perceived utility of GS varies widely among parents and may depend on multiple individual, sociodemographic, and contextual factors that are relevant for pre‐ and post‐GS counseling, for value assessment of GS, and for policymaking related to access to new genomic technologies.
Ethical Perspectives on Treatment Options with Spinal Muscular Atrophy Patients
Authors: Yeo Crystal J. J. , Simmons Zachary , De Vivo Darryl C. , Darras Basil T.
Published: January 2022

Since 2016, 3 innovative therapies for spinal muscular atrophy (SMA) have changed the face of the disease. Although these therapies often result in remarkable improvements in infants and children, benefits in adults are modest and treatment is not curative. Concerns have been raised about the enormous costs of these medications, the ultimate burden to taxpayers, and the costs to society of withholding treatments and sacrificing or disadvantaging some individuals. Physicians are best positioned to serve our patients by carefully considering the costs, benefits, implications for quality of life (QOL), and the interplay of these factors within the framework of core ethical principles that guide clinical care. ANN NEUROL 2022;91:305–316
Study on structural and functional properties of porous SiO2 core‐shell construction/polyethylene nanocomposites with enhanced interfacial interaction
Authors: Zhang Chuying , Zhao Hang , Yang Fan , Zhang Na , Zhu Tongguang , Leng Kunyue , Bai Jinbo
Published: January 2022

The addition of inorganic particles can endow polymer matrices with different new features, thereby realizing an optimization to the structural and functional properties of composite. The overall properties of composites are greatly influenced by both fillers dispersion and fillers‐polymer interfacial interaction. However, to simultaneously improve these mentioned two issues is still a critical challenge in the field of polymer‐based nanocomposite. Herein, a typical core‐shell structured mesoporous silica‐coated silica (SiO2@mSiO2) construction was successfully synthesized by using a bi‐phase method. The SiO2@mSiO2 filled polyethylene (PE) nanocomposite was fabricated through a precisely controlled melt‐mixing approach. Benefiting from the additional mesoporous SiO2 shell, both the dispersion of SiO2@mSiO2 and the SiO2@mSiO2‐PE matrix interfacial interaction are improved. Moreover, the stress–strain behavior, temperature‐dependent mechanical property, thermal stability, and electrical insulating property of SiO2@mSiO2/PE composite were studied in detail. It is found that SiO2@mSiO2 core‐shell nanoparticles are capable of not only making a balance between the strength and toughness of the PE‐based composite, but also improving the thermal stability of the composite. In addition, the SiO2@mSiO2/PE composite exhibited an enhanced breakdown strength (256.4 MV·m−1) when filled with as small as 1 wt% SiO2@mSiO2, which is 108% higher than neat PE. All these optimized features are attributed to the well‐designed core‐shell structure. These experimental results provide a promising way to design and fabricate future advanced composite with excellent structural and functional properties in the future.
Solventless solid‐phase extraction using Zn ion‐imprinted polymer detected by colorimetric method
Authors: Lee Yelin , Ahn Soyoung , Cho Hansang , Ogunro Vincent , Bae Sunyoung
Published: January 2022

Ion‐imprinted polymers attract a lot of attention and are actively studied because of easy preparation and their high selectivity. Zn is known to be essential mineral in human body; however, when it is absorbed into our body, it is hardly discharged completely and causes various disease or side effects. To suggest new method for selective Zn extraction, Zn ion‐imprinted polymer (ZIIP) was synthesized by bulk polymerization and NZIIP (non‐ZIIP) was prepared as a control. Then, ZIIP and NZIIP were characterized by Fourier‐transform infrared spectroscopy, Scanning electron microscope, and X‐ray photoelectron spectroscopy to investigate structural changes during polymerization. Adsorption isotherm studies indicated that sigmoidal Langmuir isotherm equation was fitted well and the maximum adsorption capacity and affinity of Zn on ZIIP was superior to NZIIP. Dithizone was used to chelate with Zn in supernatant for colorimetric determination. ZIIP‐solid‐phase extraction potentially used as Zn ion filter was investigated showing good removal efficiency.
Determination, residue analysis, dietary risk assessment, and processing of flupyradifurone and its metabolites in pepper under field conditions using LC–MS/MS
Authors: Feng Yizhi , Zhang Aijuan , Bian Yanli , Liang Lin , Zuo Bojun
Published: January 2022

An effective method based on LC–MS/MS was established to determine the concentrations of flupyradifurone, difluoroacetic acid, and 6‐chloronicotinic acid in pepper. On the basis of this method, the dissipation, processing factor, and dietary risk of flupyradifurone in pepper were investigated. The results show that the half‐life of flupyradifurone in peppers was 2.6–3.8 days. The terminal residual concentration of flupyradifurone in the supervised trials was not higher than the maximum residue limit (MRL) for pepper in the Codex Alimentarius Commission (CAC) (0.9 mg kg−1) with the highest residual values of 0.53 mg kg−1. The national estimated daily intake of flupyradifurone was 0.00094 mg kg−1, based on the dietary structure of Chinese consumers and the terminal residues under field conditions. The risk quotient for flupyradifurone was 0.012, which was significantly < 1. The processing factor of flupyradifurone in dried pepper was 10.9–14.2, which indicated that drying increased the residual amounts of flupyradifurone in dried pepper, but the residual concentration was still lower than its MRL of 9 mg kg−1 established by CAC.
Ionic Liquid Modified Active Edge‐Rich Antimonene Nanodots for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction
Authors: Wang Jingkun , Wang Chengqiang , Song Yanhui , Sha Wenbo , Wang Zhiyuan , Cao Hailiang , Zhao Min , Liu Peizhi , Guo Junjie
Published: January 2022

Two‐dimensional (2D) monoelemental antimonene has aroused great research interest since it emerged as a promising electrocatalyst for the hydrogen evolution reaction (HER). Nevertheless, the catalytic efficiency of the reported antimonene catalysts has been limited by their poor conductivity and low‐density of exposed active sites. Herein, the active edge sites engineering is adopted to expose abundant catalytically active edge sites by decreasing the size of antimonene nanosheets to ultrasmall‐sized antimonene nanodots (AMNDs). Meanwhile, the synergy effect of the surface modulation strategy by decorating the base surface of AMNDs using the ionic liquid benefits the mass transfer during the HER process. Impressively, the ionic liquid modified AMNDs (noted as IL‐AMNDs) achieve a low overpotential of 116 mV at the current density of 10 mA cm−2 and excellent long‐term durability, even superior to many other previously reported 2D catalysts. This work spreads the way out for the development of highly active and efficient hydrogen production catalysts.
Enhanced Electroconversion CO2‐to‐Formate by Oxygen‐Vacancy‐Rich Ultrasmall Bi‐Based Catalyst Over a Wide Potential Window
Authors: Wang Xueli , Zhang Lu‐Hua , Chen Datong , Zhan Jiayu , Guo Jiangyi , Zhang Zisheng , Yu Fengshou
Published: January 2022

Bi‐based materials quickly rise as promising candidates for electrochemical CO2‐to‐formate conversion. However, most of them only display a narrow potential range for the desired formate selectivity. Herein, we designed an oxygen‐vacancy‐rich ultrasmall bismuth subcarbonate supported on reduced graphene oxide composite (Vo‐BOC/G) for electrochemical CO2‐to‐formate conversion. The Vo‐BOC/G exhibits an outstanding formate selectivity up to 100 % at −1.2 V vs. RHE and an impressive partial current density of 38 mA cm−2 in 0.1 M KHCO3. More importantly, the considerable formate selectivity (>80 %) was obtained over an impressively wide potential range of 600 mV, superior over most of reported Bi‐based electrocatalysts under the same conditions. Theoretical results show the abundant Vo defects significantly lower energy barrier for *CO2 formation, resulting in high formate selectivity over a wider potential window. This work may pave the way for Bi‐based materials application in different renewable energy‐conversion devices.
Inhibition of p‐Nitrothiophenol Catalytic Hydrogenation on Ag‐Containing AgAu/Pd/TiO2 Plasmonic Catalysts Probed in situ by SERS
Authors: Lopes Douglas S. , Vono Lucas L. R. , Miranda Ester V. , Ando Rômulo A. , Corio Paola
Published: January 2022

Compositional variations of surface‐enhanced Raman scattering (SERS)‐active catalysts play an essential role and can drastically affect the reaction pathway, rate, and product selectivity. Here, the Pd‐catalyzed p‐nitrothiophenol (PNTP) to p‐aminothiophenol (PATP) hydrogenation and the surface plasmon resonance (SPR) mediated p‐aminothiophenol (PATP) to p,p‐dimercaptoazobenzene (DMAB) oxidation catalytic activities over TiO2‐supported AgAu/Pd NPs (AgAu/Pd/TiO2) are investigated as a function of the Ag to Au ratio using in situ SERS. The results showed that as the PNTP hydrogenation rates grew exponentially with decreased Ag mole fraction, the yield of the PATP to DMAB conversion rapidly diminishes in the opposite trend. The observed variations in catalytic performance can be explained by the formation of surface Ag oxides in Ag‐containing substrates, leading to the inhibition of PNTP catalytic hydrogenation on Ag/Pd/TiO2 while favoring the PATP to DMAB oxidation. This work provides a concrete example of how oxidized Ag can significantly affect the catalytic activity of bifunctional substrates and can guide the rational design of SERS‐active catalysts.
Revisiting the Fundamental Nature of Metal‐Ligand Bonding: An Impartial and Automated Fitting Procedure for Angular Overlap Model Parameters
Authors: Buchhorn Moritz , Deeth Robert J. , Krewald Vera
Published: January 2022

The properties and reactivities of transition metal complexes are often discussed in terms of Ligand Field Theory (LFT), and with ab initio LFT a direct connection to quantum chemical wavefunctions was recently established. The Angular Overlap Model (AOM) is a widely used, ligand‐specific parameterization scheme of the ligand field splitting that has, however, been restricted by the availability and resolution of experimental data. Using ab initio LFT, we present here a generalised, symmetry‐independent and automated fitting procedure for AOM parameters that is even applicable to formally underdetermined or experimentally inaccessible systems. This method allows quantitative evaluations of assumptions commonly made in AOM applications, for example, transferability or the relative magnitudes of AOM parameters, and the response of the ligand field to structural or electronic changes. A two‐dimensional spectrochemical series of tetrahedral halido metalates ([MIIX4]2−, M=Mn−Cu) served as a case study. A previously unknown linear relationship between the halide ligands’ chemical hardness and their AOM parameters was found. The impartial and automated procedure for identifying AOM parameters introduced here can be used to systematically improve our understanding of ligand–metal interactions in coordination complexes.
d‐Orbital Reconstructions Forced by Double Bow‐Shaped Deformations and Second Coordination Sphere Effects of Cu(II) Heme Analogs in HER**
Authors: Liu Qiuhua , Ren Wanjie , Zhang Siwei , Huang Yang , Chen Dilong , Zeng Wennan , Zhou Zaichun , He Lin , Guo Wenping , Li Jianfeng
Published: January 2022

Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes (4‐, 3‐, 2‐ and 1‐Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis‐ortho) to give double bow‐shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d‐orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1‐Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow‐shaped architecture and the strong saddle porphyrin core in 1‐Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation.
Weak Antiferromagnetic Exchange and Ferromagnetic Alignment of FeII (S=2) Spins in Differently Charged {HAT ⋅ (FeIICl2)3}n (n=2‐ and 3‐) Assemblies of Hexaazatriphenylenes (HAT)
Authors: Mikhailenko Maxim V. , Khasanov Salavat S. , Shestakov Alexader F. , Kuzmin Aleksey V. , Otsuka Akihiro , Yamochi Hideki , Kitagawa Hiroshi , Konarev Dmitri V.
Published: January 2022

Hexaazatrianthracene (HATA) and hexaazatriphenylenehexacarbonitrile {HAT(CN)6} are reduced by metallic iron in the presence of crystal violet (CV+)(Cl−). Anionic ligands are produced, which simultaneously coordinate three FeIICl2 to form (CV+)2{HATA ⋅ (FeIICl2)3}2− ⋅ 3 C6H4Cl2 (1) and (CV+)3{HAT(CN)6. (FeIICl2)3}3− ⋅ 0.5CVCl ⋅ 2.5 C6H4Cl2 (2). High‐spin (S=2) FeII atoms in both structures are arranged in equilateral triangles at a distance of 7 Å. An antiferromagnetic exchange is observed between FeII in {HATA ⋅ (FeIICl2)3}2− (1) with a Weiss temperature (Θ) of −80 K, the PHI estimated exchange interaction (J) is −4.7 cm−1. The {HAT(CN)6 ⋅ (FeIICl2)3}3− assembly is obtained in 2. The formation of HAT(CN)6.3− is supported by the appearance of an intense EPR signal with g=2.0037. The magnetic behavior of 2 is described by a strong antiferromagnetic coupling between the FeII and HAT(CN)6.3− spins with J1=−164 cm−1 (−2 J formalism) and by a weaker antiferromagnetic coupling between the FeII spins with J2=−15.4 cm−1. The stronger coupling results in the spins of the three FeIICl2 units to be aligned parallel to each other in the assembly. As a result, an increase of the χMT values is observed with the decrease of temperature from 9.82 at 300 K up to 15.06 emu ⋅ K/mol at 6 K, and the Weiss temperature is also positive being at +23 K. Thus, a change in the charge and spin state of the HAT‐type ligand to ⋅3− results in ferromagnetic alignment of the FeII spins, yielding a high‐spin (S=11/2) system. DFT calculations showed that, due to the high symmetry and nearly degenerated LUMO of both HATA and HAT(CN)6, their complexes with FeIICl2 have a variety of closely lying excited high‐spin states with multiplicity up to S=15/2.
An Adaptive Hydrogen‐Bonded Organic Framework for the Exclusive Recognition of p‐Xylene
Authors: Ma Li , Xie Yi , Khoo Rebecca Shu Hui , Arman Hadi , Wang Bin , Zhou Wei , Zhang Jian , Lin Rui‐Biao , Chen Banglin
Published: January 2022

Separation of xylene isomers is one of the most important but most challenging and energy‐intensive separation processes in the petrochemical industry. Here, we report an adaptive hydrogen‐bonded organic framework (HOF‐29) constructed from a porphyrin based organic building block 4,4′,4′′,4′′′‐(porphyrin‐5,10,15,20‐tetrayl) tetrabenzonitrile (PTTBN), exhibiting the exclusive molecular recognition of p‐xylene (pX) over its isomers of o‐xylene (oX) and m‐xylene (mX), as clearly demonstrated in the single crystal structure transformation and 1H NMR studies. Single crystal structure studies show that single‐crystal‐to‐single‐crystal transformation from the as‐synthesized HOF‐29 to the pX exclusively included HOF‐29⊃pX is triggered by the encapsulation of pX molecules, accompanied by sliding of the 2D layers and local distortion of the ligand, which provides multiple C−H⋅⋅⋅π interactions.
Revealing Functional Significance of Interleukin‐2 Glycoproteoforms Enabled by Expressed Serine Ligation
Authors: Zhao Jie , Liu Jiazhi , Liu Xinnan , Cao Qi , Zhao Hongbo , Liu Lizhen , Ye Farong , Wang Can , Shao Hong , Xue Dongxiang , Tao Houchao , Li Bin , Yu Biao , Wang Ping
Published: January 2022

Comprehensive Summary

Naturally occurring interleukin‐2 (IL‐2) is a pleiotropic glycoprotein that regulates immune responses by controlling the differentiation and homeostasis of T cells. Non‐glycosylated IL‐2 has been used in clinical settings for three decades. However, the function of the O‐glycan of native IL‐2 remains elusive. Herein, to stress this issue, we report a highly efficient semi‐synthesis of homogeneous glycosylated IL‐2 with various glycoproteoforms on a multi‐milligram scale. The glycopeptide fragment was prepared by chemical synthesis and then merged with recombinant fragment via a serine ligation to generate the desired glycoprotein in a single operation. Biological evaluation of the homogenous glycoprotein library reveals that the activity of IL‐2 in activating individual T cell subset is glycan dependent, thus highlighting the possibility of further improving current clinical medicine.
Aggregative Growth of Oligopeptide‐Protected Gold Nanoclusters into Plasmonic Particles
Authors: Zheng Zhiren , Hu Yanyan , Lv Ying , Liu Lu , Fan Daoqing , Zhang Lichao , Chen Ling , Yu Haizhu , Zhu Manzhou
Published: January 2022

The stimuli response of nanomaterials represents a highly appealing characteristic, whereas the practical applications (in catalysis, biosensing etc.) are largely restricted by the limited understanding on the recognition mechanism. Herein, we report a pH‐regulated size evolution from atomically precise Au nanoclusters (NCs) to plasmonic nanoparticles (NPs). The spectral monitoring demonstrates a three‐stage aggregative growth pathway. First, the non‐covalent interactions among the exterior oligopeptide ligands are gradually enhanced with the increased alkalinity, and then the Au−S bonding is partially disrupted, with the exposed Au atoms aggregating to form relatively larger, polydisperse clusters under weak alkaline conditions. Finally, size‐redistribution occurs slowly under strong alkaline conditions to form the plasmonic particles. The controllable transition sheds light on the transition characteristics from molecular state to metallic state of Au nanomaterials.
Role of minimally invasive surgery in the treatment of gallbladder metastatic melanoma. A review of the literature and a case report
Authors: Bangeas Petros Ioannis , Bekiaridou Alexandra , Tsolakidis Alexandros , Efthymiadis Kostantinos Georgios , Drevelegkas Kostantinos , Giakoustidis Dimitris , Giakoustidis Alexandros , Alexidis Petros , Papadopoulos Vassileios Nikolaos
Published: January 2022

Background

Primary and secondary gallbladder melanomas are rare, and only 58 cases have been reported in scientific literature to date. This paper aimed to explore the role of minimally invasive surgery in the management of gallbladder metastatic melanomas.

Case

Herein, we present the case of a 68‐year‐old man with metastatic gallbladder melanoma who was treated with laparoscopic cholecystectomy. Our case management was then compared with that of other cases reported in the literature.

Conclusion

Currently, metastatic melanomas can be considered as a potentially curable disease. Palliation of symptoms and fast recovery following minimally invasive procedures could be beneficial for these patients. Particularly, laparoscopic procedures appear to prolong the survival of gallbladder melanoma patients.
Identification of Cooperative Reaction Sites in Metal−Organic Framework Catalysts for High Yielding Lactic Acid Production from d‐Xylose
Authors: Rungtaweevoranit Bunyarat , Chaipojjana Kawisa , Junkaew Anchalee , Thongratkaew Sutarat , Impeng Sarawoot , Faungnawakij Kajornsak
Published: January 2022

Determining the roles of surface functionality of heterogeneous acid catalysts is important for many industrial catalysts. In this study, the decisive structure of metal−organic frameworks (MOFs) is utilized to identify important features for the effective conversion of d‐xylose into lactic acid. Several acidic MOFs are tested and the combination of Lewis acidity and adjacent hydroxy sites is found to be critical to attain high lactic acid yields. This hypothesis is corroborated experimentally by modification of the MOF to increase such sites, which affords an enhanced lactic acid yield of 79 %, and investigation of the acidity by using in situ FTIR spectroscopy. Density functional theory calculations disclose the cooperative behavior of Lewis acid sites and hydroxy groups in promoting the Cannizzaro reaction, a key step in the production of lactic acid.
Diastereodivergent Synthesis of (+)‐α‐Conhydrine and (−)‐β‐Conhydrine from a η,γ‐Dibromo‐β‐ketosulfoxide
Authors: Salom‐Roig Xavier J.
Published: January 2022

Diastereodivergent syntheses of the enantiopure hemlock alkaloid (+)‐α‐conhydrine and its diastereomer (−)‐β‐conhydrine are reported. Our approach relies on efficient Crystallization‐Induced Diastereomer Transformation (CIDT) of an epimeric mixture of a η,γ‐dibromo‐β‐ketosulfoxide, optically pure only at the sulfur atom, that provided a stable α‐bromoketone, and diastereoselective β‐ketosulfoxide reduction that led to the corresponding anti and syn‐bromohydrins with high level of asymmetric induction.
Petrography and geochemistry of the Middle Jurassic Fort Member Sandstone, Jaisalmer Formation, Western India: Implications for weathering, provenance, and tectonic setting
Authors: Ahmad Faiz , Amir Mohd , Adnan Quasim Mohammad , Absar Nurul , Masood Ahmad Abul Hasnat
Published: January 2022

Detrital mineralogy, major oxides, trace, and rare earth elements (REE) were examined in the Middle Jurassic Fort Member Sandstone (FMS) of the Jaisalmer Formation in Western India to understand palaeoweathering, provenance of sediments, and to decipher the tectonic setting. The sandstones are classified as arkose to sub‐litharenite types according to their relative percentages of quartz, feldspar, and lithic fragments, and major elemental ratios. The values of Chemical Index of Alteration (67–85), Plagioclase Index of Alteration (78–97) and Chemical Index of Weathering (83–97) along with A‐CN‐K diagram suggest moderate to intense chemical weathering in the source region. Presence of fresh feldspars and dominance of monocrystalline quartz, showing both parallel and undulose extinction, indicate plutonic and volcanic felsic igneous provenance. Contribution from metamorphic orogen sources is indicated by the lithic fragment population. Various geochemical parameters such as Th/Sc, Cr/Th, Ti/Zr, and Eu/Eu* support a dominant felsic provenance. Higher Zr/Sc ratios relative to the magmatic Zr/Sc‐Th/Sc trend, higher Zr and Hf concentrations in the FMS indicate some extent of sedimentary recycling and zircon sorting. LREE enrichment, flat HREE pattern, negative Eu anomaly and trace element ratios, in conjunction with palaeocurrent data, indicate a likely sediment contribution from basement source terrains including Erinpura‐Mount Abu‐Sirohi granites, Malani Igneous Suite, and Aravalli‐Delhi orogens. The major and trace element tectonic setting discrimination diagrams for the FMS indicate a passive margin setting.
The relationship between social isolation and anxiety in people with cognitive impairment in the United States
Authors: Hwang Yeji , Massimo Lauren , Aryal Subhash , Hodgson Nancy A.
Published: January 2022

Objectives

Social isolation among older adults with cognitive impairment is understudied. The purpose of this study is to examine the relationship between social isolation and anxiety in people with cognitive impairment in the United States.

Methods/Design

Secondary data analyses were conducted using the National Social Life, Health, and Aging Project (NSHAP) Wave 2 (2010–2011) dataset which includes a nationally representative sample of American older adults living at home. A total of 1343 people who had probable cognitive impairment measured by a Montreal Cognitive Assessment (MoCA) score of 22 or less were selected. Anxiety was measured using the anxiety measure of Hospital Anxiety and Depression Scale (HADS‐A) and social isolation was measured using Perceived Social Isolation Scale. A weighted multivariable linear regression analysis and weighted F tests were used to examine the relationship between social isolation and anxiety.

Results

We observed that greater social isolation was related to increased anxiety in people with cognitive impairment (coefficients = 0.7242, t = 2.51, p = 0.015), adjusting for severity of cognitive impairment, race, pain, depression, activities of daily living, and instrumental activities of daily living. Weighted F tests showed that persons with clinically significant anxiety (HADS‐A ≥ 8) had higher levels of loneliness, including feeling a lack of companionship, feeling left out, and greater social isolation.

Conclusions

The results of our study suggest that people with cognitive impairment can feel social isolation and it may contribute to their anxiety. Health care professionals, family, and friends of people with cognitive impairment should pay greater attention to social isolation of their loved ones.