bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tunable Resonant‐Photopyroelectric Detector Using Chalcogenide−Metal−Fluoropolymer Nanograting
Authors: Wei Le , Monshat Hosein , Qian Jingjing , Dong Liang , Lu Meng 
Published: September 2021

AbstractPyroelectric detectors are often broadband and require external filters for wavelength‐specific applications. This paper reports a tunable, narrowband, and lightweight pyroelectric infrared detector built upon a flexible membrane of As2S3−Ag−P(VDF‐TrFE) with subwavelength grating, which is capable of both on‐chip filtering and photopyroelectric energy conversion. The top surface of this hybrid membrane is a corrugated As2S3−Ag film contributing to narrowband light absorption in the near‐infrared (NIR) regime, and the bottom part is a polyvinylidene fluoride‐trifluoroethylene (PVDF‐TrFE) membrane for the conversion of the absorbed light to an electrical signal. Uniquely, applying a bias voltage to the PVDF‐TrFE membrane enables the tuning of the device's absorption and pyroelectric characteristics owing to the piezoelectrically induced mechanical bending. The resonator exhibited a resonant absorption coefficient of 80% and a full‐width‐half‐maximum of 15 nm within the NIR, a responsivity of 1.4 mV mW−1, and an equivalent noise power of 13 µW Hz−1/2 at 1560 nm. By applying a 15‐V bias to the PVDF‐TrFE membrane, the absorption coefficient decreased to 18% due to the change in the grating period and incident angle. The narrowband and tunable features of the As2S3−Ag−P(VDF‐TrFE) pyroelectric detector will benefit a variety of potential applications in sensors, optical spectroscopy, and imaging.
Oxoammonium Salt‐Mediated Vicinal Oxyazidation of Alkenes with NaN3: Access to β‐Aminooxy Azides
Authors: Chen Fei , Tang Yu‐Ting , Li Xin‐Ru , Duan Yan‐Yan , Chen Chao‐Xing , Zheng Yang 
Published: September 2021

AbstractAn approach to the vicinal oxyazidation of alkenes has been achieved under mild and transition metal‐free conditions. This method utilizes NaN3 as the azidation agent and 2,2,6,6‐tetramethylpiperidine‐1‐oxoammonium tetrafluoroborate (TEMPO+BF4−) as the single‐electron oxidant as well as the oxygen source. By using this protocol, various β‐aminooxy azides were synthesized and several complex bioactive molecules were functionalized.magnified image
Metal‐Free Multi‐Component Sulfur Dioxide Insertion Reaction Leading to Quinoxalin‐2‐One‐Containing Vinyl Sulfones under Visible‐Light Photoredox Catalysis
Authors: Lv Yufen , Luo Jinyun , Lin Muze , He Lin , Yue Huilan , Liu Ruisheng , Wei Wei 
Published: September 2021

AbstractA metal‐free multi‐component sulfur dioxide insertion reaction of alkynes, sodium metabisulfite, aryldiazonium, and quinoxalin‐2‐ones has been developed under visible‐light photoredox‐catalysis. This photocatalytic tandem reaction would be conducted at room temperature by using of Rhodamine 6G as organic photocatalyst and sodium metabisulfite as the SO2 surrogate. This protocol provides a synthetic strategy for the construction of various quinoxalin‐2‐one‐containing vinyl sulfones with favourable functional group tolerance, in which one C−C bond and two C−S bonds were constructed in one pot procedure.magnified image
NOCICEPTRA: Gene and microRNA Signatures and Their Trajectories Characterizing Human iPSC‐Derived Nociceptor Maturation
Authors: Zeidler Maximilian , Kummer Kai K. , Schöpf Clemens L. , Kalpachidou Theodora , Kern Georg , Cader M. Zameel , Kress Michaela 
Published: September 2021

AbstractNociceptors are primary afferent neurons serving the reception of acute pain but also the transit into maladaptive pain disorders. Since native human nociceptors are hardly available for mechanistic functional research, and rodent models do not necessarily mirror human pathologies in all aspects, human induced pluripotent stem cell‐derived nociceptors (iDN) offer superior advantages as a human model system. Unbiased mRNA::microRNA co‐sequencing, immunofluorescence staining, and qPCR validations, reveal expression trajectories as well as miRNA target spaces throughout the transition of pluripotent cells into iDNs. mRNA and miRNA candidates emerge as regulatory hubs for neurite outgrowth, synapse development, and ion channel expression. The exploratory data analysis tool NOCICEPTRA is provided as a containerized platform to retrieve experimentally determined expression trajectories, and to query custom gene sets for pathway and disease enrichments. Querying NOCICEPTRA for marker genes of cortical neurogenesis reveals distinct similarities and differences for cortical and peripheral neurons. The platform provides a public domain neuroresource to exploit the entire data sets and explore miRNA and mRNA as hubs regulating human nociceptor differentiation and function.
Engineering a Smart Agent for Enhanced Immunotherapy Effect by Simultaneously Blocking PD‐L1 and CTLA‐4
Authors: Jiang Chunjuan , Zhang Le , Xu Xiaoping , Qi Ming , Zhang Jianping , He Simin , Tian Qiwei , Song Shaoli 
Published: September 2021

AbstractCombinations of immune checkpoint therapies show encouraging results in the treatment of many human cancers. However, the higher costs and greater side effects of such combinations compared with single‐agent immunotherapies limit their further applications. In this work, a novel smart agent, KN046@19F‐ZIF‐8, is developed to overcome these limitations. KN046 is a novel recombinant humanized PD‐L1/CTLA‐4 bispecific single‐domain antibody‐Fc fusion protein, which can bind to both PD‐L1 and CTLA‐4 effectively. ZIF‐8 is a smart delivery system, which can safely and effectively deliver KN406 to a tumor. In vitro and in vivo results demonstrate that the smart agent KN046@19F‐ZIF‐8 not only improves the immune response rate of the antibody drug in treatment of tumors but also reduces its toxic side effects, thereby achieving excellent antitumor efficacy. This study provides an engineering strategy for clinical applications of a more effective immunotherapy.
A Bioinspired Stress‐Response Strategy for High‐Speed Soft Grippers
Authors: Lin Yangqiao , Zhang Chao , Tang Wei , Jiao Zhongdong , Wang Jinrong , Wang Wei , Zhong Yiding , Zhu Pingan , Hu Yu , Yang Huayong , Zou Jun 
Published: September 2021

AbstractThe stress‐response strategy is one of the nature's greatest developments, enabling animals and plants to respond quickly to environmental stimuli. One example is the stress‐response strategy of the Venus flytrap, which enables such a delicate plant to perceive and prey on insects at an imperceptible speed by their soft terminal lobes. Here, inspired by this unique stress‐response strategy, a soft gripper that aims at the challenges of high‐speed dynamic grasping tasks is presented. The gripper, called high‐speed soft gripper (HSG), is based on two basic design concepts. One is a snap‐through instability that enables the HSG to sense the mechanical stimuli and actuating instantly. The other one is the spider‐inspired pneumatic‐powered control system that makes the trigger process repeatable and controllable. Utilizing the stress‐response strategy, the HSG can accomplish high‐speed sensing and grasping and handle a dynamic grasping task like catching a thrown baseball. Whereas soft machines typically exhibit slow locomotion speed and low manipulation strength for the intrinsic limitations of soft materials, the exploration of the stress‐response strategy in this study can help pave the way for designing a new generation of practical high‐speed soft robots.
Boosting Nitrogen Reduction to Ammonia on FeN4 Sites by Atomic Spin Regulation
Authors: Wang Yajin , Cheng Wenzheng , Yuan Pengfei , Yang Gege , Mu Shichun , Liang Jialin , Xia Huicong , Guo Kai , Liu Mengli , Zhao Shuyan , Qu Gan , Lu Bang‐An , Hu Yongfeng , Hu Jinsong , Zhang Jia‐Nan 
Published: September 2021

AbstractUnderstanding the relationship between the electronic state of active sites and N2 reduction reaction (NRR) performance is essential to explore efficient electrocatalysts. Herein, atomically dispersed Fe and Mo sites are designed and achieved in the form of well‐defined FeN4 and MoN4 coordination in polyphthalocyanine (PPc) organic framework to investigate the influence of the spin state of FeN4 on NRR behavior. The neighboring MoN4 can regulate the spin state of Fe center in FeN4 from high‐spin (dxy2dyz1dxz111) to medium‐spin (dxy2dyz2dxz11), where the empty d orbitals and separate d electron favor the overlap of Fe 3d with the N 2p orbitals, more effectively activating N≡N triple bond. Theoretical modeling suggests that the NRR preferably takes place on FeN4 instead of MoN4, and the transition of Fe spin state significantly lowers the energy barrier of the potential determining step, which is conducive to the first hydrogenation of N2. As a result, FeMoPPc with medium‐spin FeN4 exhibits 2.0 and 9.0 times higher Faradaic efficiency and 2.0 and 17.2 times higher NH3 yields for NRR than FePPc with high‐spin FeN4 and MoPPc with MoN4, respectively. These new insights may open up opportunities for exploiting efficient NRR electrocatalysts by atomically regulating the spin state of metal centers.
Graphene and MXene Based Free‐Standing Carbon Memristors for Flexible 2D Memory Applications
Authors: Fatima Sabeen , Bin Xu , Mohammad Mohammad Ali , Akinwande Deji , Rizwan Syed 
Published: September 2021

Abstract2D carbon materials are examined extensively by virtue of having functional‐groups richness and adaptable interlayer spacing with exquisite electrochemical characteristics and flexibility. The phenomenal character of these materials enables them to be resilient in building memristive flexible electronics. The present work reports on a facile, inexpensive fabrication scheme of free‐standing memory devices based on graphene and MXene, exhibiting complementary and capacitive resistive switching (RS) mechanisms for a retention time of 104 s with higher durability for >2400 cycles. The complementary RS in the single trilayer reduced graphene oxide/graphene oxide/reduced graphene oxide (rGO/GO/rGO) carbon cell helps in reducing fabrication complexity with its direct integration in crossbar arrays. While the observed capacitive switching enables MXene paper/graphene oxide paper/MXene paper (M/GO/M) memory device ensemble to retain combine capacitive as well as switching properties for designing self‐generating memory frameworks, sustaining a continuous current even when the external applied bias is removed. The present work will pave pathways for carbon memristors as considerably competent candidates toward designing high performance flexible non‐volatile memory architectures.
Genetic Manipulation of M13 Bacteriophage for Enhancing the Efficiency of Virus‐Inoculated Perovskite Solar Cells with a Certified Efficiency of 22.3%
Authors: Han Jiye , Kim Kyusun , Nam Jeong‐Seok , Hong Sung Jun , Choi Eun Jung , Kim Dawoon , Chung In , Lin Hao‐Sheng , Kim Tae‐Dong , Strano Michael S. , Han Byungchan , Oh Jin‐Woo , Kim Hyung Do , Jeon Il 
Published: September 2021

AbstractPerovskite solar cells (PSCs) are considered to be one of the most promising solar energy harvesters owing to their high power conversion efficiency (PCE). To increase their PCE even further, additives are used; however, some of these additives pose certain disadvantages, which limit their applications to PSCs. Therefore, in this study, the nature‐inspired ecofriendly M13 bacteriophage is genetically engineered to maximize its performance as a perovskite crystal growth template and as a passivator for PSCs. The genetic manipulation of the M13 bacteriophage enhances the Lewis coordination between the perovskite materials and single‐stranded virus by amplifying a designated amino acid group. Among the 20 types of amino acids, lysine (Lys or K), arginine (Arg or R), and methionine (Aug or M) exhibit the strongest interaction with the perovskite materials. Results suggest that the K‐amplified genetically engineered M13 bacteriophage is the most effective. The K‐type M13 virus‐inoculated PSCs yield a PCE of 23.6% in the laboratory. This device, when taken to a national laboratory for verification, exhibits a certified forward and reverse bias‐combined efficiency (22.3%), which, to the best of the authors’ knowledge, is one of the highest efficiencies reported among the biomaterial‐based PSCs.
Congenital heart defects and copy number variants associated with neurodevelopmental impairment
Authors: Findley Tina O. , Crain Alyssa K. , Mahajan Smridhi , Deniwar Ahmed , Davis Jessica , Solis Zavala Ana S. , Corno Antonio F. , Rodriguez‐Buritica David 
Published: September 2021

AbstractA genetic etiology is identifiable in 20%–30% of patients with congenital heart defects (CHD). Chromosomal microarray analysis (CMA) can detect copy number variants (CNV) associated with CHD. In previous studies, the diagnostic yield of postnatal CMA testing ranged from 4% to 28% in CHD patients. However, incidental pathogenic CNV and variants of unknown significance are often discovered without any known association with CHD. The study objective was to describe the rate of pathogenic CNV associated with neurodevelopmental impairment (NDI) and compare clinical findings in CHD neonates with genetic results. A single‐center retrospective review was performed on all consecutive newborns with CHD admitted to a tertiary neonatal intensive care unit from January 2013 to March 2019 (n = 525). CHD phenotypes were classified as per the National Birth Defect Prevention Study. CMA detected pathogenic CNV in 21.3% (61/287) of neonates, and karyotype or fluorescence in situ hybridization detected aneuploidies in an additional 11% of the overall cohort (58/525). Atrioventricular septal defects and conotruncal defects showed the highest diagnostic yield by CMA (28.6% and 27.2%, respectively). Among neonates with pathogenic CNV on CMA, 78.7% (48/61) were associated with NDI. Neonates with pathogenic CNV were smaller in length at birth compared to those with benign CNV or variants of unknown significance (p = 0.005) and were more likely to be discharged with an enteral feeding tube (p = 0.027). CMA can discover genetic variants associated with NDI and are common in neonates with CHD. Genetic testing in the neonatal period can heighten awareness of genetic risk for NDI.
Esophageal atresia/tracheoesophageal fistula and proximal symphalangism in a patient with a NOG nonsense mutation
Authors: Chooey Jonathan , Trexler Connor , Becker Amy M. , Hogue Jacob S. 
Published: September 2021

AbstractEsophageal atresia and tracheoesophageal fistula (EA/TEF) are relatively common malformations of the human foregut. The etiology remains incompletely understood with genetic causes identified in a small minority of affected patients. We present the case of a newborn with type C EA/TEF along with proximal symphalangism found to have a de novo NOG nonsense mutation. Patients with chromosome 17q deletions including the NOG gene have previously been reported to have EA/TEF but mutations in the gene have not been identified in patients with this malformation. This case provides evidence that haploinsufficiency for NOG may be the cause for EA/TEF in the 17q deletion syndrome and suggests that the clinical spectrum of NOG‐related symphalangism spectrum disorders may include EA/TEF.
Ambimodal Transition States in Diels–Alder Cycloadditions of Tropolone and Tropolonate with N‐Methylmaleimide**
Authors: Zhang Hong , Thøgersen Mathias Kirk , Jamieson Cooper S. , Xue Xiao‐Song , Jørgensen Karl Anker , Houk Kendall N. 
Published: September 2021

AbstractThe Diels–Alder reactions of tropolone and its conjugate base with N‐methylmaleimide have been explored computationally and experimentally. Previous studies of the [4+2] cycloaddition under basic conditions show that both endo‐ and exo‐products are obtained in similar, but variable amounts. Density functional theory (ωB97X‐D) explorations of potential energy surfaces, and molecular dynamics trajectories show that the reaction involves an ambimodal transition state for the reaction of the ammonium tropolonate with N‐methylmaleimide, and that similar amounts of endo‐ and exo‐products are obtained. The thermal reaction, studied experimentally in detail here for the first time, is predicted to form the endo‐adduct through an ambimodal transition state. The exo‐adduct can be formed from the same transition state, but requires a hydrogen shift, that hinders this reaction dynamically. Longer reaction times give a small excess of the exo‐product, which is thermodynamically more stable.
Enantiopure C5 Pentaindenocorannulenes: Chiral Graphenoid Materials
Authors: Guo Tianjian , Li Ansu , Xu Jun , Baldridge Kim K. , Siegel Jay 
Published: September 2021

AbstractChiral carbon nanomaterials offer numerous prospects for material science. As a fundamental building block for non‐planar graphenoid materials, pentaindenocorannulene (PIC) with its C5v symmetrical structure presents a platform for creation of supramolecular chiral carbon materials. Specifically, when uniformly penta‐substituted on its periphery, PIC generates C5 symmetrical chiral buckybowls capable of columnar stacking. The synthesis and resolution of such PICs are achieved, assignment of absolute configuration is established by comparison of ECD and VCD spectra with theory, and material characterization is reported. Evidence for columnar stacking in solution and in the crystal is presented.
The Complex Crystal Structure and Abundant Local Defects of Zeolite EMM‐17 Unraveled by Combined Electron Crystallography and Microscopy
Authors: Liu Xiaona , Liu Lingmei , Pan Tingting , Yan Nana , Dong Xinglong , Li Yuanhao , Chen Lu , Tian Peng , Han Yu , Guo Peng , Liu Zhongmin 
Published: September 2021

AbstractIn this study, we successfully solve polymorphs A and B of zeolite EMM‐17, which can only crystallize in sub‐micrometer‐sized crystals while containing complex stacking disorders, from the three‐dimensional (3D) electron diffraction (ED) data. This is the first time that the atomic structure of this polymorph has been ab initio solved, and the result reveals a unique 10(12)×10(12)×11‐ring channel system. Moreover, we acquire the first atomic‐resolution images of EMM‐17 using integrated differential phase‐contrast scanning transmission electron microscopy. The images allow us to directly observe polymorphs B and C and discover a large number of local structural defects. Based on structural features unraveled from the reciprocal‐space 3D ED data and real‐space images, we propose a series of energetically feasible local structures in EMM‐17. We also demonstrate that the unique porous structure of EMM‐17 enables efficient kinetic separation of C6 alkane isomers.
Photocatalytic Arylation of P4 and PH3: Reaction Development Through Mechanistic Insight
Authors: Rothfelder Robin , Streitferdt Verena , Lennert Ulrich , Cammarata Jose , Scott Daniel J. , Zeitler Kirsten , Gschwind Ruth M. , Wolf Robert 
Published: September 2021

AbstractDetailed 31P{1H} NMR spectroscopic investigations provide deeper insight into the complex, multi‐step mechanisms involved in the recently reported photocatalytic arylation of white phosphorus (P4). Specifically, these studies have identified a number of previously unrecognized side products, which arise from an unexpected non‐innocent behavior of the commonly employed terminal reductant Et3N. The different rate of formation of these products explains discrepancies in the performance of the two most effective catalysts, [Ir(dtbbpy)(ppy)2][PF6] (dtbbpy=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine) and 3DPAFIPN. Inspired by the observation of PH3 as a minor intermediate, we have developed the first catalytic procedure for the arylation of this key industrial compound. Similar to P4 arylation, this method affords valuable triarylphosphines or tetraarylphosphonium salts depending on the steric profile of the aryl substituents.
Impact of the Difluoromethylene Group in the Organocatalyzed Acylative Kinetic Resolution of α,α‐Difluorohydrins
Authors: Desrues Titouan , Merad Jérémy , Andrei Daniela , Pons Jean‐Marc , Parrain Jean‐Luc , Médebielle Maurice , Quintard Adrien , Bressy Cyril 
Published: September 2021

AbstractDue to the omnipresence of chiral organofluorine compounds in pharmaceutical, agrochemical, and material chemistry, the development of enantioselective methods for their preparation is highly desirable. In the present study, the enantioselective organocatalyzed acylation of α,α‐difluorohydrins using a commercially available chiral isothiourea is reported through a kinetic resolution (KR) process. It reveals that the difluoromethylene moiety (C(sp3)F2) can serve as a directing group through electrostatic fluorine–cation interactions, greatly improving the enantioselectivity of the KR. In this context, a broad range of fluorinated alcohols such as valuable 4,4‐difluoro‐1,3‐diols could be synthesized with exquisite enantiocontrol (typically >99:1 er). Turning to 2,2‐difluoro‐1,3‐diols, we also demonstrated that aromatic and fluorinated groups were mutually compatible to provide the expected enantioenriched adducts with >99:1 er.
Green synthesis of poly(o‐phenylenediamine) polymer film on stainless steel as a corrosion protection layer
Authors: Zhang Jia‐Wei , Li Ying 
Published: September 2021

AbstractThe concept of green chemistry is promoted by more fields. Therefore, it is necessary for the preparation of organic film under the gentle polymerization condition. In this article, the traditional strong acid polymerization electrolyte is replaced by a citric acid‐disodium hydrogen phosphate buffer system (pH 5.6). On the one hand, it reduces the negative effects of strong acid, and on the other hand, it avoids the damage of the metal substrate during the polymerization process. In addition, with o‐phenylenediamine (oPD) as the monomer, poly(oPD) (PoPD) films were successfully prepared by cyclic voltammetry under this system. The effects of concentration, temperature, and immersion time were investigated in 3.5% NaCl solution. It is found that temperature has a negative effect on the corrosion resistance of the coating. But when the temperature rises to 333 K, the resistance of the PoPD film is still five times higher than that of bare steel. The immersion test showed that when the film was immersed for 21.5 h, the impedance of the PoPD film was an order of magnitude larger than that of the bare steel that was impregnated at the same time. This research can provide new ideas for organic film in daily industrial production.
Thermally improved crystalline phase and intercalated PEO/OMMT nanocomposites for high to ultrahigh radio frequency range low‐permittivity nanodielectrics
Authors: Sengwa Ram Jeewan , Dhatarwal Priyanka 
Published: September 2021

AbstractPoly(ethylene oxide) (PEO)/organomodified‐montmorillonite (OMMT) nanoclay based nanocomposites having 1, 3, 5, 10, and 20 wt% OMMT nanofiller were prepared by homogeneous mixing and the melt‐compounding method. These hybrid materials were characterized by employing X‐ray diffractometer, differential scanning calorimeter, and radio frequency impedance analyzer. The experimental results confirmed the formation of OMMT intercalated structures with reduced crystallinity and increased melting temperature of PEO crystallites which are predominantly ruled by the nanofiller amounts in the PEO/OMMT nanocomposites. Dielectric permittivity of these nanocomposites measured at 20°C exhibited a gradual decrease with increasing frequencies of the applied harmonic electric field of high to ultrahigh range (i.e., 1 MHz–1 GHz), but it changed anomalously in the range of 2.6–3.6 with the increase of OMMT amounts in the PEO matrix. The dielectric losses in these composites were found low and their loss spectra exhibited a hydrogen bond dipolar reorientation relaxation process around 1 GHz. The alternating current electrical conductivity of these nanocomposites increased with frequency and also changed with the OMMT concentrations. These PEO/OMMT nanocomposites are classified as low permittivity nanodielectrics which could be potential candidates for advances in flexible and biodegradable radio‐electronic devices.