bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractFlexible 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

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

AbstractWithin 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

AbstractOxygen 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

AbstractA 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

AbstractDynamic 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

AbstractEsters 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

AbstractEnantioselective 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

AbstractInsufficient 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

AbstractThis 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

AbstractThe 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

AbstractNa 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

AbstractPhotocatalytic 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

AbstractBackgroundCongenital 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).MethodsWe 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.ResultsTotal 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.ConclusionsThis 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

AbstractBuilding 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

AbstractThe 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

AbstractThe 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.