bluuebunny/crossref_metadata_2025 huggingface dataset:
Use of Social Media for Political Communication among University Students in Bangladesh
Authors: Hassan Razib Mehedy , Tasnim Pinky Farzana
Published: February 2023

The use of social media for political thought and expression has given the study of political communication a new dimension. We endeavored to discover in social media which political topics students found more interesting in conversation. In addition, this study combines communication theories such as uses and gratification and to analyze political interest in social media and the formation of political opinion. Specifically, we attempted to compare the extent of political communication participation based on gender and academic education. A survey reveals that male students are more involved in political communication than female students. And final year students are more engaged in political communication via social media than their first, second, and third-year counterparts. Using the quantitative method of data collection and program language R to analyze them, this study also explores students’ expression of political opinions through social media has a relationship to their political needs. The results here show that freedom of expression given in our constitution if exercised properly, students will be able to engage in political communication.
Detection of Pulmonary Tuberculosis by Gene Xpert Method among HIV Patient in ART Center, Gadarif State, Sudan
Authors: Elbashir Salwa Abdelrahman Hamd , Abakar A. D. , Nour Bakri Y. M.
Published: February 2023

Background: Tuberculosis (TB) is one of the most common and deadly infectious diseases in humans. Due to widespread poverty, inequity, and conflict, suboptimal health services in many countries, and the impact of the HIV/AIDS pandemic, TB/HIV co-infected patients frequently test negative for TB with direct microscopy, posing diagnostic challenges. Traditional HIV-associated TB diagnosis is complex, expensive, time-consuming, and technically demanding because it relies on conventional culture and drug susceptibility testing. The lengthy wait for results has disastrous consequences for patients who go undiagnosed or are diagnosed too late.

Objective: To detect the accuracy of gene X pert® MTB/RIF as a novel automated molecular tool to diagnose   Mycobacterium tuberculosis in HIV patients.

Methods: A cross sectional study was conducted on 70 HIV patients suspected to have Mycobacterium tuberculosis and who were referred to the ART and Tuberculosis Centers at Gadarif state, from June 2022 to December 2022. Sputum samples were tested by two methods involved the Gene X pert (Cepheid, California, United States of America) and direct smear microscopy (SM) stained with ZN stain for detection of acid fast bacilli. Out of 70 sputum samples analyzed for acid fast bacilli, 50(71%) cases were positive using GeneXpert whereas the DM was positive only for 28 (4o %) of the cases. GeneXpert detected another 22 AFB positive cases. Therefore GeneXpert is more accurate. Sensitivity of the GeneXpert was calculated as 93% and the specificity was 43%. The majority of the patients who contributed to (SM) were found to be co-infected with HIV.

Conclusion: GeneXpert demonstrated two-time case detection rate compared to the sputum smear microscopy   so the direct smear showed poor performance tool for evaluation of TB-HIV co-infection. Also The Gene X pert’s sensitivity was found to be high while the specificity was low. Although this was the case, the GeneXpert as compared to DM could greatly reduce false negatives and the wait on treatment initiation can be significantly shortened, minimising premature death and continued transmission.
Immediate Dentin Sealing for Indirect Bonded Restoration: Literature Review
Authors: Omar Sarah , Albelady Waad , Alharbi Yamam , Alzubaidi Tamadher , Shuailah Latifah
Published: February 2023

Objectives: The purpose of this review was to elaborate on the role of the immediate dentinal sealing technique in reducing hypersensitivity after indirect bonded restoration placement.

Materials and Methods: A PubMed literature search was conducted using the search terms “immediate dentin sealing” AND “dual bonding technique” AND “resin coating technique” AND “prehybridization”. The search was restricted to studies published between 1 January 2010 and 1 November 2022. A total of 31 papers were found as a result of the PubMed search. After the exclusion of irrelevant or duplicated articles, 15 articles were included in this review.

Results: The results strongly indicate that the immediate dentine sealing technique (IDS) improves the bonding strength between indirect restoration and tooth as compared to conventional delayed dentinal seal.

Conclusions: IDS is a sealing adhesive technique that reduces post-cementation hypersensitivity and improves adhesion for indirect restoration, especially in those indirect restorations in which hypersensitivity is more common after cementation and retention are difficult to achieve such as porcelain laminated veneer.
Mpox—A Rapidly Evolving Disease
Authors: Cowen Edward W. , Tkaczyk Eric R. , Norton Scott A. , Leslie Kieron S.
Published: February 2023

The 2022 mpox outbreak has rapidly emerged onto the global medical scene while the world continues to grapple with the COVID-19 pandemic. Unlike COVID-19, however, most patients with mpox present with skin findings, the evolving clinical presentation of which may be mistaken for other common skin diseases, particularly sexually transmitted infections. This Special Communication provides an overview of the evolution of mpox skin findings from its initial description in humans in 1970 to the present-day multinational outbreak.
Association of Treatment Strategies and Tumor Characteristics With Overall Survival Among Patients With Anaplastic Thyroid Cancer
Authors: Wu Shannon S. , Lamarre Eric D. , Yalamanchali Anirudh , Brauer Philip R. , Hong Hanna , Reddy Chandana A. , Yilmaz Emrullah , Woody Neil , Ku Jamie A. , Prendes Brandon , Burkey Brian , Nasr Christian , Skugor Mario , Heiden Katherine , Chute Deborah J. , Knauf Jeffrey A. , Campbell Shauna R. , Koyfman Shlomo A. , Geiger Jessica L. , Scharpf Joseph
Published: February 2023

Importance

Survival outcomes for anaplastic thyroid cancer (ATC), the most aggressive subtype of thyroid cancers, have remained poor. However, targeted therapies and immunotherapies present new opportunities for treatment of this disease. Evaluations of survival outcomes over time with new multimodal therapies are needed for optimizing treatment plans.

Objective

To evaluate the association of treatment strategies and tumor characteristics with overall survival (OS) among patients with ATC.

Design, Setting, and Participants

This retrospective case series study evaluated the survival outcomes stratified by treatment strategies and tumor characteristics among patients with ATC treated at a tertiary level academic institution from January 1, 2000, to December 31, 2021. Demographic, tumor, treatment, and outcome characteristics were analyzed. Kaplan-Meier method and log rank test modeled OS by treatment type and tumor characteristics. Data were analyzed in May 2022.

Main Outcomes and Measures

Overall survival (OS).

Results

The study cohort comprised 97 patients with biopsy-proven ATC (median [range] age at diagnosis, 70 [38-93] years; 60 (62%) female and 85 [88%] White individuals; 59 [61%] never smokers). At ATC diagnosis, 18 (19%) patients had stage IVA, 19 (20%) had stage IVB, and 53 (55%) had stage IVC disease. BRAF status was assessed in 38 patients; 18 (47%) had BRAF-V600E variations and 20 (53%), BRAF wild type. Treatment during clinical course included surgery for 44 (45%) patients; chemotherapy, 41 (43%); definitive or adjuvant radiation therapy, 34 (RT; 35%); and targeted therapy, 28 (29%). Median OS for the total cohort was 6.5 (95% CI, 4.3-10.0) months. Inferior OS was found in patients who did not receive surgery (hazard ratio [HR], 2.12; 95% CI, 1.35-3.34; reference, received surgery), chemotherapy (HR, 3.28; 95% CI, 1.99-5.39; reference, received chemotherapy), and definitive or adjuvant RT (HR, 2.47; 95% CI, 1.52-4.02; reference, received definitive/adjuvant RT). On multivariable analysis, age at diagnosis (HR, 1.03; 95% CI, 1.01-1.06), tumor stage IVC (HR, 2.65; 95% CI, 1.35-5.18), and absence of definitive or adjuvant RT (HR, 1.90; 95% CI, 1.01-3.59) were associated with worse OS.

Conclusions and Relevance

This retrospective single-institution study found that lower tumor stage, younger age, and the ability to receive definitive or adjuvant RT were associated with improved OS in patients with ATC.
Machining Properties of Stone‐Plastic Composite Based on an Empirically Validated Finite Element Method
Authors: Wang Jinxin , Buck Dietrich , Tang Qi , Guan Jun , Zhou Xueliang , Wu Zhanwen , Cao Pingxiang , Guo Xiaolei , Zhu Zhaolong
Published: February 2023

High‐cutting performance is an essential metric for improving the suitability of materials for industrial applications. Herein, the machining properties of stone‐plastic composite are assessed through a finite element method to explore orthogonal cutting behavior by diamond cutters. The key aspects examined in this work are the effects of tool geometry and cutting parameters on the cutting force, temperature, chip formation, von Mises stress, and surface quality finish. Primary findings show that chip continuity increases proportionally with increase in rake angle but decreases with cutting speed and depth. Meanwhile, both cutting stability and surface quality are negatively correlated with cutting speed and depth but positively correlated with rake angle. These results support the adoption of cutting conditions using greater rake angle, higher cutting speed, and shallower cutting depth to obtain higher cutting performance, that is, greater cutting stability and surface quality in the finishing machining of stone‐plastic composites.
Influence of Loading Sequence Effect on Cyclic Hysteresis Characteristics of an Al–Mg–Si Alloy
Authors: Li He , Zhou Yifu , Luo Zhong
Published: February 2023

The alloy materials of automotive chassis are subjected to sequential time‐varying loads due to road unevenness. The continuous change of the loading mode and the stress ratio leads to cyclic plasticity of the material, which induces cyclic hardening. The estimation of hardening effects seriously affects the structural's fatigue properties. Therefore, herein, a hardening model and the corresponding fatigue life prediction model are proposed. Then, the loading sequence effect's influence on an Al–Mg–Si alloy's cyclic hysteretic characteristics is analyzed. The steering knuckle is taken as the verification object. The acquired load spectrum is transformed into three sequential forms according to the equivalent damage principle for the verification test. The test results verify the conjecture of the loading sequence effect and confirm the accuracy of the proposed prediction model.
Surface Modification of Fluorine‐Doped Tin Oxide Thin Films Using Femtosecond Direct Laser Interference Patterning: A Study of the Optoelectronic Performance
Authors: Heffner Herman , Soldera Marcos , Ränke Fabian , Lasagni Andrés Fabián
Published: February 2023

Transparent conductive oxides (TCOs) are used in solar cells not only to extract photogenerated carriers but also to allow sunlight to reach the photoactive material. Therefore, controlling the electrical and optical properties of such oxides is crucial for the optimization of the efficiency of solar cells. Herein, direct laser interference patterning (DLIP) method is used to control the surface morphology, optical and electrical properties of fluorine‐doped tin oxide (FTO) by applying femtosecond laser pulses. The topography characterization reveals periodic line‐like microstructures with a period of 3.0 μm and average heights between 20 and 185 nm, depending on the applied laser fluence levels. Laser‐induced periodic surface structures are observed on the valleys of the texture aligned perpendicularly to the laser radiation polarization. A relative increase in the average total and diffuse optical transmittance up to 5% and 500%, respectively, is obtained in the 400–800 nm spectral range as a consequence of the generated micro‐ and nanostructures. Calculations of two figures of merit suggest that the texturing of FTO might enhance the efficiency of solar cells, in particular dye‐sensitized (DSSCs). The findings of this study confirm that DLIP is a convenient technique for structuring electrodes for highly efficient optoelectronic devices.
Nerve‐Fiber‐Inspired Construction of 3D Graphene “Tracks” Supported by Wood Fibers for Multifunctional Biocomposite with Metal‐Level Thermal Conductivity
Authors: Zhang Xilin , Li Jingchao , Gao Qiang , Wang Zhijian , Ye Neng , Li Jianzhang , Lu Yonglai
Published: February 2023

Given the rapid developments in modern electronics, there is an urgent need for polymer composites with excellent heat‐dissipating capabilities to address the cooling problem of these devices. However, designing a highly thermally conductive polymer composite that can outperform metals and ceramics while also exhibiting high processability and low cost remains a challenge. Herein, inspired by the fibrous pathway of human nervous system, natural wood fibers (WFs) are used as the template and coated with graphene nanoplates (GNPs) via a simple electrostatic self‐assembly approach. Subsequent hot‐pressing process yields “core‐sheath” microstructured fibers, wherein the GNPs are compactly contacted face to face and arranged along the surfaces of the fibrous WF “cores”. This WF@G biocomposite consists of highly efficient 3D fibrous “tracks” for heat transmission, resulting in an extremely high thermal conductivity of 134 W (m K)−1, which is at par with those of many metals. It also exhibits several other desirable properties and functionalities, including high mechanical strength and excellent flame resistance as well as remarkable electromagnetic shielding and Joule heating performances, which has significant potential for use as a functional thermal management material (TMM). Hence, this study describes a simple yet scalable manufacturing technique for the development of advanced metal‐level biomass‐based TMMs.
Modulation of Macrophages by In Situ Ligand Bridging
Authors: Kim Seong Yeol , Thangam Ramar , Kang Nayeon , Hong Hyunsik , Kim Chowon , Lee Sungkyu , Son Subin , Lee Hyun‐Jeong , Tag Kyong‐Ryol , Min Sunhong , Jeong Daun , Hwang Jangsun , Kim Kanghyeon , Kim Dahee , Kim Yuri , Joo Jinmyoung , Kim Bong Hoon , Zhu Yangzhi , Park Sung‐Gyu , Song Hyun‐Cheol , Sun Wujin , Ahn Jae‐Pyoung , Jang Woo Young , Paulmurugan Ramasamy , Kim Hong‐Kyu , Kim Jong Seung , Kang Heemin
Published: February 2023

Extracellular matrix (ECM) proteins containing cell‐attachable Arg‐Gly‐Asp (RGD) sequences exhibit variable bridging and non‐bridging in fibronectin‐collagen and laminin‐collagen complexes that can regulate inflammation, tissue repair, and wound healing. In this study, linking molecule‐mediated conjugation of 1D magnetic nanocylinders (MNCs) to material surfaces pre‐decorated with gold nanospheres (GNSs) is performed, thereby yielding RGD‐coated MNCs (RGD‐MNCs) over RGD‐coated GNSs (RGD‐GNSs) in a non‐bridging state. The RGD‐MNCs are drawn closer to the RGD‐GNSs via magnetic field‐mediated compression of the linking molecules to establish the bridging between them. Relative proportion of the RGD‐MNCs to the RGD‐GNSs is optimized to yield effective remote stimulation of integrin binding to variably bridged RGDs similar to that of invariably bridged RGDs used as a control group. Remote manipulation of the RGD bridging facilitates the attachment structure assembly of macrophages that leads to pro‐healing/anti‐inflammatory phenotype acquisition. In contrast, the non‐bridged RGDs inhibited macrophage attachment that acquired pro‐inflammatory phenotypes. The use of various nanomaterials in constructing heterogeneous RGD‐coated materials can further offer various modes in remote switching of RGD bridging and non‐bridging to understand dynamic integrin‐mediated modulation of macrophages that regulate immunomodulatory responses, such as foreign body responses, tissue repair, and wound healing.
A Bimetallic Metal–Organic‐Framework‐Based Biomimetic Nanoplatform Enhances Anti‐Leukemia Immunity via Synchronizing DNA Demethylation and RNA Hypermethylation
Authors: Song Yue , Zhang Lingxiao , Wang Yiqiao , Han Mingda , Wang Zhihua , Wang Ning , Shao Bingru , Li Runan , Cao Kunxia , Song Meiyu , Du Yangyang , Yan Fei
Published: February 2023

Epigenetic‐alterations‐mediated antigenicity reducing in leukemic blasts (LBs) is one of the critical mechanisms of immune escape and resistance to T‐cell‐based immunotherapy. Herein, a bimetallic metal–organic framework (MOF)‐based biomimetic nanoplatform (termed as AFMMB) that consists of a DNA hypomethylating agent, a leukemia stem cell (LSC) membrane, and pro‐autophagic peptide is fabricated. These AFMMB particles selectively target not only LBs but also LSCs due to the homing effect and immune compatibility of the LSC membrane, and induce autophagy by binding to the Golgi‐apparatus‐associated protein. The autophagy‐triggered dissolution of AFMMB releases active components, resulting in the restoration of the stimulator of interferon genes pathway by inhibiting DNA methylation, upregulation of major histocompatibility complex class‐I molecules, and induction of RNA‐methylation‐mediated decay of programmed cell death protein ligand transcripts. These dual epigenetic changes eventually enhance T‐cell‐mediated immune response due to increased antigenicity of leukemic cells. AFMMB also can suppress growth and metastases of solid tumor, which was suggestive of a pan‐cancer effect. These findings demonstrate that AFMMB may serve as a promising new nanoplatform for dual epigenetic therapy against cancer and warrants clinical validation.
Flexible Perovskite X‐Ray Detectors through Interfacial Modification with Perylene Diimide
Authors: Zhao He , Qiu Jian , Hou Bo , Yi Luying , Qin Xian , Liu Xiaogang
Published: February 2023

Flexible direct X‐ray detectors based on perovskites have great potential for X‐ray imaging due to their high sensitivity, low detection limit, low‐cost, and large‐area fabrication. However, these detectors perform inefficiently at X‐ray‐to‐current conversion because of inadequate functional layer thickness and charge‐carrier recombination. Here, the fabrication of an integrated, self‐powered X‐ray detector based on CsPbBr3 quantum dots and a MAPbI3 photoelectric conversion layer embedded with perylene diimide molecules is reported. In addition to optimizing crystal domain formation and charge carrier extraction, the perylene diimide molecules also improve the electron mobility of MAPbI3 films by twofold. The integrated perovskite‐based X‐ray detector has a sensitivity of 143 169 ± 848 µC Gyair−1 cm−2 and a detection limit of 30.77 nGy s−1. The perylene diimide molecule at the grain boundary of MAPbI3 shows defect passivation and charge collection characteristics, leading to stable output over 30 bending cycles. This hybrid molecular approach provides insight into a general method to modify device performance using perylene diimide‐integrated detectors for X‐ray imaging of 3D objects with curved surfaces.
HAT‐Promoted Electrochemical Amination: C(sp2)−H/N−H Cross Dehydrogenative Coupling
Authors: Li Heng , Chen Jiajia , Zhang Juncheng , Liu Ping , Sun Peipei
Published: February 2023

A direct amination of quinoxalin‐2(1H)‐ones via electrochemical C(sp2)−H/N−H cross dehydrogenative coupling was established by using TMSN3as the hydrogen atom transfer (HAT) reagent. Remarkable features of this synthetic strategy include operational simplicity, transition metal‐ and chemical oxidant‐free conditions, and broad functional group tolerance. A wide range of primary, secondary amines and quinoxalinones are tolerated, giving the corresponding secondary and tertiary amination products in good to excellent yields.

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Complement‐targeted therapeutics: An emerging field enabled by academic drug discovery
Authors: Lamers Christina , Ricklin Daniel , Lambris John D.
Published: February 2023

Within a short few years, the number of complement inhibitors that are either approved for therapeutic application or evaluated in late‐stage clinical trials has expanded remarkably. The sudden emergence of this target area in the pipelines of many biotech start‐ups and even large pharmaceutical companies appears even more surprising when considering that the involvement of the complement system in various clinical conditions had long been recognized. In many aspects, however, the complement system is far from being a traditional drug target, which may explain the delayed breakthrough of this therapeutic strategy. While complement modulation is now considered an attractive “platform technology” with applications in a wide spectrum of disorders, the broad yet heterogeneous disease involvement of the complement system has long restricted its placement in traditional drug discovery programs. Concerns about the safety of complement‐targeted interventions, the large number and high plasma concentrations of target proteins, and the complexity of the complement system's engagement in biological processes are among other factors that kept complement off the drug discovery radar for decades. Alongside technical advances and financial incentives, the innovation and persistence of academic and clinical researchers have been the critical driving force to navigate complement therapeutics out of the shadow into the spotlight. In this commentary, we document this remarkable development using select examples and aim to venture some predictions where this promising field may be headed to.
Microwave Synthesis of Pt Clusters on Black TiO2 with Abundant Oxygen Vacancies for Efficient Acidic Electrocatalytic Hydrogen Evolution
Authors: Wu Zexing , Yang Pengfei , Li Qichang , Xiao Weiping , Li Zhenjiang , Xu Guangrui , Liu Fusheng , Jia Baohua , Ma Tianyi , Feng Shouhua , Wang Lei
Published: February 2023

Oxygen vacancies‐enriched black TiO2 is one promising support for enhancing hydrogen evolution reaction (HER). Herein, oxygen vacancies enriched black TiO2 supported sub‐nanometer Pt clusters (Pt/TiO2‐OV) with metal support interactions is designed through solvent‐free microwave and following low‐temperature electroless approach for the first time. High‐temperature and strong reductants are not required and then can avoid the aggregation of decorated Pt species. Experimental and theoretical calculation verify that the created oxygen vacancies and Pt clusters exhibit synergistic effects for optimizing the reaction kinetics. Based on it, Pt/TiO2‐OV presents remarkable electrocatalytic performance with 18 mV to achieve 10 mA cm−2 coupled with small Tafel slope of 12 mV dec−1. This work provides quick synthetic strategy for preparing black titanium dioxide based nanomaterials.
Stable Crystalline Nanohoop Radical and Its Self‐Association Promoted by van der Waals Interactions
Authors: Hou Bingxia , Li Ke , He Huijie , Hu Jinlian , Xu Zhuofan , Xiang Qin , Wang Peng , Chen Xing , Sun Zhe
Published: February 2023

A stable nanohoop radical (OR3) combining the structures of cycloparaphenylene and an olympicenyl radical is synthesized and isolated in the crystalline state. X‐ray crystallographic analysis reveals that OR3 forms a unique head‐to‐tail dimer that further aggregates into a one‐dimensional chain in the solid state. Variable‐temperature NMR and concentration‐dependent absorption measurements indicate that the π‐dimer is not formed in solution. An energy decomposition analysis indicates that van der Waals interactions are the driving force for the self‐association process, in contrast with other olympicenyl derivatives that favor π‐dimerization. The physical properties in solution phase have been studied, and the stable cationic species obtained by one‐electron chemical oxidation. This study offers a new molecular design to modulate the self‐association of organic radicals for overcoming the spin‐Peierls transition, and to prepare novel nanohoop compounds with spin‐related properties.
Programming Super DNA‐Enzyme Molecules for On‐Demand Enzyme Activity Modulation**
Authors: Zhao Haipei , Xiu Xuehao , Li Mingqiang , Dai Shaobo , Gou Mingyang , Tao Leyang , Zuo Xiaolei , Fan Chunhai , Tian Zhongqun , Song Ping
Published: February 2023

Dynamic interactions of enzymes, including programmable configuration and cycling of enzymes, play important roles in the regulation of cellular metabolism. Here, we constructed a super DNA‐enzymes molecule (SDEM) that comprises at least two cascade enzymes and multiple linked DNA strands to control and detect metabolism. We found that the programmable SDEM, which comprises glucose oxidase (GOx) and horseradish peroxidase (HRP), has a 20‐fold lower detection limit and a 1.6‐fold higher reaction rate than free enzymes. An SDEM can be assembled and disassembled using a hairpin structure and a displacement DNA strand to complete multiple cycles. An entropically driven catalytic assembly (catassembly) enables different SDEMs to switch from an SDEM with GOx and HRP cascades to an SDEM with sarcosine oxidase (SOX) and HRP cascades in over six orders of magnitude less time than without the catassembly to detect different metabolisms (GO and sarcosine) on demand.
Ester Reduction with H2 on Bifunctional Metal‐Acid Catalysts: Implications of Metal Identity on Rates and Selectivities
Authors: Berdugo‐Díaz Claudia E. , Manetsch Melissa T. , Sik Yun Yang , Lee Jieun , Luo Jing , Chen Xue , Flaherty David W.
Published: February 2023

Esters reduce to form ethers and alcohols on contact with metal nanoparticles supported on Brønsted acidic faujasite (M‐FAU) that cleave C−O bonds by hydrogenation and hydrogenolysis pathways. Rates and selectivities for each pathway depend on the metal identity (M=Co, Ni, Cu, Ru, Rh, Pd, and Pt). Pt‐FAU gives propyl acetate consumption rates up to 100 times greater than other M‐FAU catalysts and provides an ethyl propyl ether selectivity of 34 %. Measured formation rates, kinetic isotope effects, and site titrations suggest that ester reduction involves a bifunctional mechanism that implicates the stepwise addition of H* atoms to the carbonyl to form hemiacetals on the metal sites, followed by hemiacetal diffusion to a nearby Brønsted acid site to dehydrate to ethers or decompose to alcohol and aldehyde. The rates of reduction of propyl acetate appear to be determined by the H* addition to the carbonyl and by the C−O cleavage of hemiacetal.
Catalytic Asymmetric Conjugate Reduction
Authors: Lonardi Giovanni , Parolin Riccardo , Licini Giulia , Orlandi Manuel
Published: February 2023

Enantioselective reduction reactions are privileged transformations for the construction of trisubstituted stereogenic centers. While these include established synthetic strategies, such as asymmetric hydrogenation, methods based on the enantioselective addition of hydridic reagents to electrophilic prochiral substrates have also gained importance. In this context, the asymmetric conjugate reduction (ACR) of α,β‐unsaturated compounds has become a convenient approach for the synthesis of chiral compounds with trisubstituted stereocenters in α‐, β‐, or γ‐position to electron‐withdrawing functional groups. Because such activating groups are diverse and amenable of further derivatizations, ACRs provide a general and powerful synthetic entry towards a variety of valuable chiral building blocks. This Review provides a comprehensive collection of catalytic ACR methods involving transition‐metal, organic, and enzymatic catalysis since its first versions dating back to the late 1970s.
A Caged In‐Source Laser‐Cleavable MALDI Matrix with High Vacuum Stability for Extended MALDI‐MS Imaging
Authors: Zhou Qiuqin , Rizzo Stefano , Oetjen Janina , Fülöp Annabelle , Rittner Miriam , Gillandt Hartmut , Hopf Carsten
Published: February 2023

Insufficient vacuum stability of matrix chemicals is a major limitation in matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) of large tissue sample cohorts. Here, we designed and synthesized the photo‐cleavable caged molecule 4,5‐dimethoxy‐2‐nitrobenzyl‐2,5‐dihydroxyacetophenone (DMNB‐2,5‐DHAP) and employed it for lipid MALDI‐MSI of mouse brain tissue sections. DMNB‐2,5‐DHAP is vacuum‐stable in a high vacuum MALDI ion source for at least 72 h. Investigation of the uncaging process suggested that the built‐in laser (355 nm) in the MALDI ion source promoted the in situ generation of 2,5‐DHAP. A caging group is used for the first time in designing a MALDI matrix that is vacuum‐stable, uncaged upon laser irradiation during the measurement process, and that boosts lipid ion intensity with MALDI‐2 laser‐induced postionization.
Converting Non‐strained γ‐Valerolactone and Derivatives into Sustainable Polythioesters via Isomerization‐driven Cationic Ring‐Opening Polymerization of Thionolactone Intermediate
Authors: Xia Yongliang , Yuan Pengjun , Zhang Yanping , Sun Yangyang , Hong Miao
Published: February 2023

This contribution reports the efficient conversion of γ‐valerolactone and its derivatives, abundant but unexplored renewable feedstocks, into sustainable and degradable polythioesters via the establishment of the first isomerization‐driven ring‐opening polymerizations (IROPs) of corresponding thionolactone intermediates. The key to this success relies on the development of a new simple and robust [Et3O]+[B(C6F5)4]− cationic initiator which possesses high activity, exclusive selectivity, living nature, and broad scope of thionolactones. A complete inversion of configuration during IROP of enantiopure γ‐thionovalerolactone is also disclosed, affording isotactic semicrystalline polythioesters (Tm=87.0 °C) with mechanical property compared well to the representative commodity polyolefins. The formation of a highly crystalline supramolecular stereocomplex with enhanced thermal property (Tm=117.6 °C) has also been revealed.
Cationic Tetrylene‐Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open‐Shell Iron(−I) Ferrato‐Tetrylenes**
Authors: Keil Philip M. , Soyemi Ademola , Weisser Kilian , Szilvási Tibor , Limberg Christian , Hadlington Terrance J.
Published: February 2023

The open‐shell cationic stannylene‐iron(0) complex 4 (4=[PhiPDippSn⋅Fe⋅IPr]+; PhiPDipp={[Ph2PCH2Si(iPr)2](Dipp)N}; Dipp=2,6‐iPr2C6H3; IPr=[(Dipp)NC(H)]2C:) cooperatively and reversibly cleaves dihydrogen at the Sn−Fe interface under mild conditions (1.5 bar, 298 K), in forming bridging hydrido‐complex 6. The One‐electron oreduction of the related GeII−Fe0 complex 3 leads to oxidative addition of one C−P linkage of the PhiPDipp ligand in an intermediary Fe−I complex, leading to FeI phosphide species 7. One‐electron reduction reaction of 4 gives access to the iron(−I) ferrato‐stannylene, 8, giving evidence for the transient formation of such a species in the reduction of 3. The covalently bound tin(II)‐iron(−I) compound 8 has been characterised through EPR spectroscopy, SQUID magnetometry, and supporting computational analysis, which strongly indicate a high localization of electron spin density at Fe−I in this unique d9‐iron complex.
A High‐Energy NASICON‐Type Na3.2MnTi0.8V0.2(PO4)3 Cathode Material with Reversible 3.2‐Electron Redox Reaction for Sodium‐Ion Batteries
Authors: Hu Ping , Zhu Ting , Cai Congcong , Wang Xuanpeng , Zhang Lei , Mai Liqiang , Zhou Liang
Published: February 2023

Na superionic conductor (NASICON) structured cathode materials with robust structural stability and large Na+ diffusion channels have aroused great interest in sodium‐ion batteries (SIBs). However, most of NASICON‐type cathode materials exhibit redox reaction of no more than three electrons per formula, which strictly limits capacity and energy density. Herein, a series of NASICON‐type Na3+xMnTi1−xVx(PO4)3 cathode materials are designed, which demonstrate not only a multi‐electron reaction but also high voltage platform. With five redox couples from V5+/4+ (≈4.1 V), Mn4+/3+ (≈4.0 V), Mn3+/2+ (≈3.6 V), V4+/3+ (≈3.4 V), and Ti4+/3+ (≈2.1 V), the optimized material, Na3.2MnTi0.8V0.2(PO4)3, realizes a reversible 3.2‐electron redox reaction, enabling a high discharge capacity (172.5 mAh g−1) and an ultrahigh energy density (527.2 Wh kg−1). This work sheds light on the rational construction of NASICON‐type cathode materials with multi‐electron redox reaction for high‐energy SIBs.
Enhancement of Visible‐Light‐Driven Hydrogen Evolution Activity of 2D π‐Conjugated Bipyridine‐Based Covalent Organic Frameworks via Post‐Protonation
Authors: Dai Lu , Dong Anwang , Meng Xiangjian , Liu Huanyu , Li Yueting , Li Pengfei , Wang Bo
Published: February 2023

Photocatalytic hydrogen (H2) evolution represents a promising and sustainable technology. Covalent organic frameworks (COFs)‐based photocatalysts have received growing attention. A 2D fully conjugated ethylene‐linked COF (BTT‐BPy‐COF) was fabricated with a dedicated designed active site. The introduced bipyridine sites enable a facile post‐protonation strategy to fine‐tune the actives sites, which results in a largely improved charge‐separation efficiency and increased hydrophilicity in the pore channels synergically. After modulating the degree of protonation, the optimal BTT‐BPy‐PCOF exhibits a remarkable H2evolution rate of 15.8 mmol g−1 h−1under visible light, which surpasses the biphenyl‐based COF 6 times. By using different types of acids, the post‐protonation is proved to be a potential universal strategy for promoting photocatalytic H2evolution. This strategy would provide important guidance for the design of highly efficient organic semiconductor photocatalysts.
Prevalence of congenital anomalies in the Dutch Caribbean islands of Aruba, Bonaire, and Curaçao
Authors: Verberne Eline A. , Lo‐A‐Njoe Shirley M. , van Ginkel Manon , Zwolsman Jet , Nikkels Sylke , Clement Lauren , de Vroomen Maartje , Wever Maria L. G. , Arends Eric , Holtsema Hilda , Hajenius Petra J. , Moreta Daphne , Ecury‐Goossen Ginette M. , Mannens Marcel M. A. M. , de Walle Hermien E. K. , Bergman Jorieke E. H. , van Haelst Mieke M.
Published: February 2023

Background

Congenital anomalies represent an important global health issue. Data on the prevalence and pattern of congenital anomalies in the Caribbean region are scarce and lacking altogether in Aruba, Bonaire and Curaçao (ABC islands).

Methods

We performed a population‐based surveillance study to determine the prevalence of structural congenital anomalies in the ABC islands, including all live births and stillbirths between January 1, 2008 and December 31, 2017 with major congenital anomalies according to EUROCAT guide 1.5. Terminations of pregnancy for fetal anomaly were included as well. Cases were identified by active case ascertainment, using multiple sources including pediatric patient files and discharge letters, delivery records, and clinical genetic patient files. Total and subgroup prevalence rates were compared between the three islands and to the French West Indies and Northern Netherlands.

Results

Total prevalence of congenital anomalies on the ABC islands was 242.97 per 10,000 births. Total prevalence of congenital anomalies in Bonaire (325.15 per 10,000 births) was higher compared to Aruba (233.29 per 10,000 births) and Curaçao (238.58 per 10,000 births), which was mainly attributable to a higher prevalence of limb anomalies, in particular polydactyly, in Bonaire. Total prevalence of congenital anomalies on the ABC islands was comparable to the French West Indies (248.69 per 10,000 births) but significantly lower compared to the Northern Netherlands (298.98 per 10,000 births). In the subgroup prevalence analysis, the prevalence of polydactyly and atrial septal defect on the ABC islands was significantly higher compared with the French West Indies and the Northern Netherlands, while the prevalence of congenital anomalies of the kidney and urinary tract and genetic disorders was significantly lower.

Conclusions

This is the first study to establish the prevalence and pattern of congenital anomalies on the ABC islands, which is important to inform healthcare managers and policymakers and to provide a basis for continuous surveillance of congenital anomalies.
Competitive programming in computational thinking and problem solving education
Authors: Yuen Kevin K. F. , Liu Dennis Y. W. , Leong Hong Va
Published: February 2023

Building practical programming competency requires a long‐lasting journey of discovery, trial and error, learning and improvement. This article presents essential findings of a case study of a Python programming contest with an automatic judgement system for Competitive Programming training extending the learning experiences for students in an introductory course, computational thinking and problem‐solving. The benefits and challenges are discussed. Due to the coronavirus disease 2019 (COVID‐19) epidemic, a hybrid model of the contest was adopted, that is, some students participated in the contest on‐site, while others participated remotely. To alleviate human effort in judging the submissions, the DOMjudge platform, a web‐based automatic judgement system, has been deployed as an online automatic judgement system and contest management in competitive programming. The implementation roadmap and framework were provided. The contest problems and contestants' performances were discussed. Not many junior contestants could solve at least one problem(s), and competitive computing training should be offered if the students are keen on open competitions. An empirical study was conducted to evaluate the student feedback after the contest. Preliminary results revealed that the contest offering the chance to stimulate student learning interests could enhance their independent learning, innovative thinking and problem‐solving skills, and could thus lead to the overall benefits of the learning experiences, which further encourage them to participate in future contests to improve their learning and therefore enhance their employability. Employers often treasure student experiences in competitive programming events, like association for computing machinery programming contests, Google Code Jam or Microsoft Imagine Cup. Sharp vision requiring skills to tackle unseen problems within a short period is also instrumental to students planning for graduate school.
MATLAB applications for teaching Applied Thermodynamics: Thermodynamic cycles
Authors: Domínguez Juan Carlos , Lorenzo David , García Julián , Hopson Cynthia , Rigual Victoria , Alonso M. Virginia , Oliet Mercedes
Published: February 2023

The main objective of this study is to describe the teaching experience in an applied thermodynamics course, using MATLAB applications developed with MATLAB® App Designer. This course is compulsory for students in their sophomore year of the BSc in Chemical Engineering. MATLAB applications are developed to serve as tools for the teaching of thermodynamic cycles: steam and gas power, and vapor‐compression refrigeration cycles. The computer applications are case‐based problem generators, that is, based on chosen groups of initial variables, which values are randomly selected each time the MATLAB applications are run. Solutions of the cycle problems, which include thermodynamic cycles plotted in p–h, T–s, and p–v diagrams, and thermodynamic properties of each state of the cycle, are shown when students want to check their calculations. Moreover, the applications allow exporting initial data and solutions to an MS Excel file. The usability and learning experience of the applications were evaluated through anonymous surveys to students and the feedback of the academic staff involved in the course. The main problem, that the students referred, to was the utilization of the MATLAB applications that they considered it was not straightforward. The students believed that the utilization of these computer applications represented a significant improvement in teaching (70%) and expressed their interest in having similar materials in other degree courses (75%). After implementing the computer applications, the academic results showed an increase of ca. 16% in the pass rate.
ROS‐Triggered Gel‐Sol Transition and Kinetics‐Controlled Cargo Release by Methionine‐Containing Peptides
Authors: Hara Yoshika , Yaguchi Atsuya , Hiramatsu Hirotsugu , Muraoka Takahiro
Published: February 2023

The gel‐sol transition of self‐assembling peptides is a useful switch for environment‐dependent drug release. For their applications, kinetics control of the responses is important for matching the velocity of release to the target biological events. Here we demonstrate the chemical control of redox‐triggered gel‐sol transition kinetics of self‐assembling peptides by altering the amino acid sequence. Amphiphilic peptides were developed in which a methionine residue was located in the middle (JigSAP‐IMI) or near the N terminus (JigSAP‐MII). Both peptides formed hydrogels under physiological conditions—forming β‐sheet‐based supramolecular nanofibers. In contrast, the oxidized forms remained in the solution state under identical conditions—adopting α‐helix‐rich secondary structures. Upon oxidation with H2O2, a reactive oxygen species, JigSAP‐MII showed a faster gel‐to‐sol transition and cargo‐releasing than JigSAP‐IMI, thus indicating that the phase‐transition and releasing kinetics of self‐assembling peptides can be rationally controlled by the position of the reactive amino acid residue.
Potentially fatal atrium perforation due to right jugular vein catheterization recognized by venography: A case report
Authors: Jahanshahi Fatemeh , Parsaei Amirhossein , Naderi Delaram , Zeraatian Nejad Davani Sam , Khaleghian Mohsen
Published: February 2023

Central venous catheters are the prevalent path for dialysis. Our case was a 54‐years‐old male with a new case of end‐stage renal disease with a complaint of right jugular hemodialysis catheter dysfunction. In our case, the early dysfunctional catheter should be evaluated with contrast studies to achieve accurate information.
Post‐COVID‐19 vaccine acute encephalitis in an adult patient: A case report and literature review
Authors: Pakfetrat Maryam , Malekmakan Leila , Najafi Bijan , Zamani Taraneh , Mashayekh Mina
Published: February 2023

Several vaccines were approved after COVID‐19 pandemic, which have been fast‐tracked for emergency use. The short‐ and long‐term safety profile has been an area of concern. We presented a patient with encephalitis followed by hyponatremia who developed hallucination and seizure 1 day after receiving the second dose of Sinopharm vaccine.
A case of chronic ossified hematoma presented as a skull lesion: A literature review on two rare conditions, cephalhematoma, and intradiploic hematoma
Authors: Iranmehr Arad , Sarpoolaki Mohammad Kazem , Zeinalizadeh Mehdi
Published: February 2023

Cephalhematoma is a frequent condition in newborn infants due to birth‐related trauma, but ossified cephalhematoma (OCH) is a rare condition, especially when it presents as a skull lesion in the older pediatric population. Chronic intradiploic hematoma (CIH) is another rare condition caused by an organized hematoma between the inner and outer tables of the skull. Differentiating CIH from OCH could be difficult for young neurosurgeons. We present an 18‐month‐old girl with an OCH presented as a skull lesion, which was managed with craniectomy and en‐bloc excision of the organized hematoma. This manuscript discusses the differences between OCH and CIH in diagnosis and management.
Clinical manifestations of Apert syndrome
Authors: Khan Qaisar Ali , Farkouh Christopher , Uzair Muhammad , Ghosh Bikona
Published: February 2023

Apert syndrome presents similarly to the one we presented in this image, and a genetic study is used for confirmation. This image shows the typical findings of physical examination, so that if this appears in the outpatient department, the diagnosis of Apert syndrome should be assumed.
Metastatic sigmoid adenocarcinoma to the larynx: A case report and updated literature review
Authors: Aljariri Adham A. , Nashwan Abdulqadir J. , Hammoud Rani , Wazwaz Bara , Al Hyassat Samir , Haidar Hassan
Published: February 2023

Metastatic laryngeal cancer is a rare entity, usually indicating an advanced disease once discovered. In this report, we are describing a case of a 60‐year‐old male patient with stage IV colorectal cancer (CRC), who presented to our clinic with dysphonia; further workups showed metastatic CRC.
Polypyridine Iridium(III) and Ruthenium(II) Complexes for Homogeneous and Graphene‐Supported Photoredox Catalysis
Authors: Jacques Alexandre , Devaux Alexandre , Rubay Christophe , Pennetreau Florence , Desmecht Antonin , Robeyns Koen , Hermans Sophie , Elias Benjamin
Published: February 2023

Iridium(III) and ruthenium(II) polypyridyl based photocatalysts have been prepared and their structure determined using 1H NMR, HR‐MS and single crystal XRD. Their spectroscopic and electrochemical properties have been studied by UV‐vis absorption, emission spectroscopy and cyclic voltammetry. These complexes have been used as photoredox homogeneous catalysts in an intramolecular cyclization model reaction in which they show high activity. They have been covalently anchored on graphene oxide (GO) via an esterification reaction and non‐covalently fixed on reduced graphene oxide (rGO) via pyrene moieties. Heterogenized complexes exhibit good photocatalytic activities and, interestingly, the use of a pyrene‐derivatized Ir(III) terpyridine‐based complex highlights an unexpected “on/off” effect of the photocatalytic activity triggered by the presence or absence of rGO.
Biohybrid Microswimmers for Antibiotic Drug Delivery Based on a Thiol‐Sensitive Release Platform
Authors: Studer Tetiana , Morina Daria , Shchelik Inga S. , Gademann Karl
Published: February 2023

This study reports on the design and engineering of biohybrid microswimmers exploiting a thiol‐mediated self‐immolative antibiotic release strategy. The design features a covalent attachment of a vancomycin conjugate via a disulfide‐based linker to the surface of the microalgae Chlamydomonas reinhardtii. The antibiotic release from the surface of these biohybrids was triggered by the addition of a thiol‐based reducing agent, and, subsequently, the inhibition of bacterial growth was observed for Bacillus subtilis and Staphylococcus aureus. These engineered microbots represent the first example of a microalgae‐based drug delivery system with a thiol‐mediated, reductive release of an antibiotic drug.
Computational Evidence of the Incipient Oxocarbenium Ion as a “Hidden Intermediate” During the Cyclization of Hydroxyenol Ether into Spiroketal Under Mild Acidic Condition
Authors: Jindani Sana , Ganguly Bishwajit
Published: February 2023

The synthesis of spiroketals has gained attention because of their importance in chemical and biological reactions. Yet, the mechanistic investigation of mild acid‐catalyzed spiroketalization remains elusive and less explored in the literature and speculated that such transformations may proceed through the oxocarbenium ion intermediate; however, the existence of such species in mild acid‐catalyzed spiroketalization is not documented. The computational study has been performed at M06‐2X/6‐31+G(d) level to examine the kinetically controlled product formation for such reactions and the intrinsic reaction coordinates of 1 d suggest that the reaction proceeds via a “one‐step, two‐stage” mechanism with the formation of transient oxocarbenium as a “hidden intermediate” in the reaction. This study reveals that stereoelectronic interactions devoid the formation of stable oxocarbenium ion intermediate after the proton transfer transition state in the mild acid catalyzed spiroketalization process.