bluuebunny/crossref_metadata_2025 huggingface dataset:
OligoHydrogelArray (OHA) for Parallelized Solid‐Phase Extraction of Oligonucleotides
Authors: Iwohn Michelle J. , Seifermann Maximilian , Reiser Patrick , Höpfner Julius , El Khaled El Faraj Razan , Heißler Stefan , Popova Anna A. , Levkin Pavel A.
Published: June 2023

Immobilization of oligonucleotides on solid surfaces is an important step in many experimental workflows in biology, such as gene expression analysis, genotyping, and drug discoveries. Capturing oligonucleotides in a highly efficient miniaturized format is still challenging. In this work, preparation of functionalized miniaturized acrylamide hydrogels on a droplet microarray (DMA) chip is reported. By further modification of these hydrogels through the Cu‐catalyzed alkyne‐azide cycloaddition, oligonucleotides are attached covalently, creating the OligoHydrogelArray (OHA). OHA enables the hybridization of oligonucleotides with defined sequences in a parallelized, miniaturized, and high‐throughput manner with an overall loading capacity and extraction efficiency suitable for most biological and chemical applications. This system enables the parallelized solid‐phase extraction of target oligonucleotides out of a mixture for purification and enrichment of DNA/RNA/PNA for application in fields such as transcriptomics. In the current study, are establish the chemical procedure for reproducible preparation of OHA and determine key characteristics, such as height, diameter, and shape of miniaturized gel pads as well as the loading capacity of oligonucleotides within the material. Finally, the ability to extract complementary oligonucleotide strands out of solution through hybridization is demonstrated to set the course for future applications.
Spectroscopic Analysis for the Identification of Loss Mechanisms in Back‐Contact Perovskite Solar Cells
Authors: Sun Hongyu , Gillespie Sarah , Rigter Susan A. , van der Burgt Julia S. , Datta Kunal , Garnett Erik C.
Published: June 2023

Back‐contact perovskite solar cells offer a significant potential to reach high efficiency due to reduced parasitic absorption from the top surface. However, the currently reported efficiencies are considerably lower (<10%) than planar perovskite solar cells (>20%). Herein, back‐contact perovskite solar cells are fabricated to study loss mechanisms that cause low device efficiency. This work spatially resolves the short‐circuit current, open‐circuit voltage, photoluminescence quantum yield, carrier lifetime, and external quantum efficiency of the devices. The results indicate that the front surface recombination, increased nonradiative recombination at hole contact layer/perovskite interface, and the extraction barriers are three main mechanisms limiting devices from achieving high efficiencies.
Full‐Color High‐Capacity Dynamic Information Encryption Based on Femtosecond Laser‐Induced Forward Transfer
Authors: Liang Shu‐Yu , Liu Yue‐Feng , Ji Zhi‐Kun , Xia Hong , Sun Hong‐Bo
Published: June 2023

The development of dynamic 3D codes is widely studied, especially for smart information protection and advanced dynamic information encryption. However, it is challenging to fabricate information carriers with full color, dynamic properties under external stimuli, and high capacity, which restricts their applications. Here, microsized dynamic full color fluorescent 3D codes are successfully fabricated using the multilayer‐independent femtosecond laser‐induced forward transfer (FsLIFT) technology, which achieves simultaneous high‐resolution transferring and patterning. The combination and excitation of multilayered quantum dots film with different colors and patterns ensure dynamic information transformation of the 3D codes. Due to the high spatial resolution of the FsLIFT, the minimum line width of the patterns can reach 1.78 µm, which ensures a high capacity for encoding. In addition, the decoding process of the microsized dynamic fluorescent 3D codes only requires smartphones, microscope patches, and portable light sources. Finally, the facile fabrication and decoding process as well as the customizable patterning abilities demonstrate the practical application potential for the advanced dynamic coding.
Redox‐Modulated Circularly Polarized Luminescence in Chiral Photonic Films Derived from Cellulose Nanocrystals and Polyoxometalate
Authors: Zhang Jing , Niu Chengyan , Yang Xuekang , Liu Jiaqi , Wu Qiulan , Tan Jingjing , Wei Xuehong , Tang Zhiyong
Published: June 2023

Achieving smart circularly polarized luminescence (CPL) materials with large luminescence dissymmetry factor (glum) is in high demand for potential technological applications in the chiroptical fields. Herein, a series of chiral photonic crystals (CPCs) derived from cellulose nanocrystals (CNCs) and photosensitive inorganic polyoxometalates (POMs) through an evaporation‐induced self‐assembly strategy are reported. The photonic bandgaps (PBGs) of CPC films are well regulated by controlling the amount of doped POMs, yielding the tunable right‐handed CPL emission with tailored glum. By locating the maximum emission peak of POMs at the center of the PBG of CPC films, the composite shows remarkable CPL performance with a |glum| value up to 0.53. Furthermore, the CPL can be reversibly switched on/off through a fluorescence resonance energy transfer (FRET) process controlled by alternate UV irradiation reduction and air oxidation. The CPC films hold the great promise as next‐generation chiroptical memory devices.
Highly Efficient Doping‐Free Thermally Activated Delayed Fluorescent Organic Light‐Emitting Diodes with an Ultrathin Quasi‐Host‐Guest Emission Layer
Authors: Peng Xiaomei , Gao Kuo , Qiu Weidong , Xu Zhida , Li Mengke , Xie Wentao , Yang Jiaji , Li Deli , Liu Kunkun , Su Shi‐Jian
Published: June 2023

Doping‐free organic light‐emitting diodes (OLEDs) are beneficial to reduce manufacturing costs for mass production, which, however, are limited by the ubiquitous aggregation‐caused quenching (ACQ) effect, especially for thermally activated delayed fluorescence (TADF) emitters with relatively long exciton lifetimes. Herein, two typical TADF emitters pACRS and pACRSO with different sulfur atom valence states are developed, where pACRS with a thioether unit exhibits suppressed intermolecular interaction, alleviated ACQ effect, and higher efficiency in a conventional doping‐free device, in contract to pACRSO with a sulfone unit. It is of interest that comparable efficiencies are achieved for both emitters in doping‐free OLEDs with an ultrathin emission layer (UEML), in which the emitter molecules are deposited onto the surface of the underlying organic layer of host material to form an ultrathin quasi‐host‐guest system with alleviated ACQ effect. Besides, the suppressed trap effect is the key to guarantee the efficiency of UEML‐OLEDs, while different intermolecular interactions of emitters that determine the optimized UEML thickness will affect the efficiency roll‐off. Furthermore, benefiting from the UEML structure, highly efficient doping‐free OLEDs are also successfully achieved for red TADF emitters with stronger intermolecular interactions. Such an UEML strategy meeting efficiency and cost demands holds great promise for doping‐free OLEDs.
Modulating the Room Temperature Phosphorescence by Tweaking SOC and P = X Interactions (X = O, S, and Se) in Phosphoramides: Magnetic Circularly Polarized Luminescence from Achiral Phosphoramides
Authors: Jena Satyam , Behera Santosh Kumar , Eyyathiyil Jusaina , Kitahara Maho , Imai Yoshitane , Thilagar Pakkirisamy
Published: June 2023

Herein, the synthesis, structure, room temperature phosphorescence, and magnetic chiroptical properties of phosphoramides 1‐6 with donor–acceptor architecture are reported.5). The electronic interactions between donor phenothiazine (PTZ) and acceptor (C6H5)n‐P = X (n = 1, 2; X = O, S, and Se)moieties in 1–6 are modulated by varying the number of donor units. The Lewis acidity of the phosphorus center is controlled by the nature of heteroatoms and the number of phenyl moieties attached to it. All compounds exhibit phosphorescence in the solid state under ambient conditions with a photoluminescence lifetime in the millisecond range (≈8–40 ms). The energy of the phosphorescence bands and their excited state lifetimes are governed by the P=X units. The phosphorescence features observed for 1–6 are in complete contrast to the observations noted for (PTZ)3P = X (X = O, S, and Se), where the phosphorescence process is completely controlled by the PTZ moiety, and there is a negligible contribution from the P = X moiety. Thus, the present and earlier studies together reveal that the steric crowding and the number of C6H5 moieties around the P = X unit play a crucial role in controlling the electronic coupling between the donor and acceptor moieties in phosphoramides containing non‐planar donor moieties. Furthermore, for the first time, the magnetic chiroptical properties of achiral phosphoramides 1–6, exhibiting a luminescence dissymmetry factor (gMCPL) in the order of 10−3 (≈4.0 × 10−3–7.4 × 10−3) are demonstrated.
Self‐Organized Stick Insect‐Like Locomotion under Decentralized Adaptive Neural Control: From Biological Investigation to Robot Simulation
Authors: Larsen Alexander Dupond , Büscher Thies H. , Chuthong Thirawat , Pairam Thipawan , Bethge Hendrik , Gorb Stanislav N. , Manoonpong Poramate
Published: June 2023

Living animals and legged robots share similar challenges for movement control. In particular, the investigation of neural control mechanisms for the self‐organized locomotion of insects and hexapod robots can be informative for other fields. The Annam stick insectMedauroidea extradentatais used as a template to develop a biorobotic model to infer walking self‐organization with strongly heterogeneous leg lengths. Body dimensions and data on the walking dynamics of the actual stick insect are used for the development of a neural control mechanism, generating self‐organized gait patterns that correspond to the real insect observations. The combination of both investigations not only proposes solutions for distributed neural locomotion control but also enables insights into the neural equipment of the biological template. Decentralized neural central pattern generation is utilized with phase modulation based on foot contact feedback to generate adaptive periodic base patterns and a radial basis function premotor network in each leg based on the target trajectories of actual stick insect legs during walking for complex intralimb coordination and self‐organized interlimb coordination control. Furthermore, based on both study objects, a robot with heterogeneous leg lengths is constructed to preliminary validate the findings from the simulations and real insect observations.
Engineering 2D Multienzyme‐Mimicking Pyroptosis Inducers for Ultrasound‐Augmented Catalytic Tumor Nanotherapy
Authors: Song Xinran , Huang Hui , Xia Lili , Jia Wencong , Yang Shaoling , Wang Chenglong , Chen Yu
Published: June 2023

Overcoming apoptosis resistance is necessary to ensure an effective cancer treatment; however, it is currently very difficult to achieve. A desirable alternative for cancer treatment is the targeted activation of pyroptosis, a unique type of programmed cell death. However, the pyroptosis inducers that are efficient for cancer therapy are limited. This work reports the engineering of 2D NiCoOx nanosheets as inducers of the production of harmful reactive oxygen species (ROS), which promote intense cell pyroptosis, and that can be applied to ultrasound (US)‐augmented catalytic tumor nanotherapy. The main therapeutic task is carried out by the 2D NiCoOx nanosheets, which have four multienzyme‐mimicking activities: peroxidase‐ (POD), oxidase‐ (OXD), glutathione peroxidase‐ (GPx), and catalase‐ (CAT) mimicking activities. These activities induce the reversal of the hypoxic microenvironment, endogenous glutathione depletion, and a continuous ROS output. The ROS‐induced pyroptosis process is carried out via the ROS‐NLRP3‐GSDMD pathway, and the exogenous US activation boosts the multienzyme‐mimicking activities and favors the incremental ROS generation, thus inducing mitochondrial dysfunction. The anti‐cancer experimental results support the dominance of NiCoOx nanosheet‐induced pyroptosis. This work expands on the biomedical applications of engineering 2D materials for US‐augmented catalytic breast cancer nanotherapy and deepens the understanding of the multienzyme activities of nanomaterials.
Tough Gelatin Hydrogel for Tissue Engineering
Authors: Yuan Ximin , Zhu Zhou , Xia Pengcheng , Wang Zhenjia , Zhao Xiao , Jiang Xiao , Wang Tianming , Gao Qing , Xu Jie , Shan Debin , Guo Bin , Yao Qingqiang , He Yong
Published: June 2023

Tough hydrogel has attracted considerable interest in various fields, however, due to poor biocompatibility, nondegradation, and pronounced compositional differences from natural tissues, it is difficult to be used for tissue regeneration. Here, a gelatin‐based tough hydrogel (GBTH) is proposed to fill this gap. Inspired by human exercise to improve muscle strength, the synergistic effect is utilized to generate highly functional crystalline domains for resisting crack propagation. The GBTH exhibits excellent tensile strength of 6.67 MPa (145‐fold that after untreated gelation). Furthermore, it is directly sutured to a ruptured tendon of adult rabbits due to its pronounced toughness and biocompatibility, self‐degradability in vivo, and similarity to natural tissue components. Ruptured tendons can compensate for mechanotransduction by GBTH and stimulate tendon differentiation to quickly return to the initial state, that is, within eight weeks. This strategy provides a new avenue for preparation of highly biocompatible tough hydrogel for tissue regeneration.
Modulating Water Splitting Kinetics via Charge Transfer and Interfacial Hydrogen Spillover Effect for Robust Hydrogen Evolution Catalysis in Alkaline Media
Authors: Jiang Yiming , Leng Juncai , Zhang Shiqi , Zhou Tingyi , Liu Mingxuan , Liu Shuoming , Gao Yahui , Zhao Jianwei , Yang Lei , Li Li , Zhao Wei
Published: June 2023

Designing and synthesizing advanced electrocatalysts with superior intrinsic activity toward hydrogen evolution reaction (HER) in alkaline media is critical for the hydrogen economy. Herein, a novel Ir@Rhene heterojunction electrocatalyst is synthesized via epitaxially confining ultrasmall and low‐coordinate Ir nanoclusters on the ultrathin Rh metallene accompanying the formation of Ir/IrO2 Janus nanoparticles. The as‐prepared heterojunctions display outstanding alkaline HER activity, with an overpotential of only 17 mV at 10 mA cm−2 and an ultralow Tafel slope of 14.7 mV dec−1. Both structural characterizations and theoretical calculations demonstrate that the Ir@Rhene heterointerfaces induce charge density redistribution, resulting in the increment of the electron density around the O atoms in the IrO2 site and thus delivering much lower water dissociation energy. In addition, the dual‐site synergetic effects between IrO2 and Ir/Rh interface trigger and improve the interfacial hydrogen spillover, thereby subtly avoiding the steric blocking of the active site and eventually accelerating the alkaline HER kinetics.
3‐Masks‐Processed Sub‐100 nm Amorphous InGaZnO Thin‐Film Transistors for Monolithic 3D Capacitor‐Less Dynamic Random Access Memories
Authors: Zhang Yuqing , Li Jiye , Li Jinxiong , Huang Tengyan , Guan Yuhang , Zhang Yuhan , Yang Huan , Chan Mansun , Wang Xinwei , Lu Lei , Zhang Shengdong
Published: June 2023

The capacitor–less embedded dynamic random access memory (eDRAM) based on oxide semiconductor (OS) transistors exhibits a promising future and thus has lead to a growing demand for nanoscale OS thin–film transistors (TFTs). In this work, a self–aligned top–gate (SATG) amorphous InGaZnO (a‐IGZO) TFT is demonstrated by using the simplest 3‐masks (3M) process, and the downscaling‐related issues are carefully addressed to strengthen its back–end–of–line (BEOL) compatibility and mass producibility. The gate insulator (GI) and associated interface defects of the TFTs are jointly optimized with 4–nm atomic‐layer‐deposited (ALD) AlOx on the pre‐oxidized a‐IGZO. The defects in a‐IGZO channel are further manipulated with a rapid thermal anneal (RTA) in oxygen. By virtue of the strengthened gate controllability and modified channel properties, the fabricated TFT with 97‐nm gate length (Lg) exhibits decent performance, such as a maximum on–state current (ION) of 32.4 µA µm−1, as well as clear linear and saturation characteristics. Based on such 3M SATG a‐IGZO TFTs with high device performance and inherently minimal parasitic capacitances, the developed capacitor‐less eDRAM bit cell achieves a wide sensing margin and a long retention time of over 500 s. A highly manufacturable oxide TFT technology for high–performance and high–density monolithic–3D (M3D) integration is thus well established.
Increased blood reactive oxygen species and hepcidin in obstructive sleep apnea precludes expected erythrocytosis
Authors: Song Jihyun , Sundar Krishna M. , Horvathova Monika , Gangaraju Radhika , Indrak Karel , Christensen Robert D. , Genzor Samuel , Lundby Carsten , Divoky Vladimir , Ganz Tomas , Prchal Josef T.
Published: June 2023

Obstructive sleep apnea (OSA) causes intermittent hypoxia during sleep. Hypoxia predictably initiates an increase in the blood hemoglobin concentration (Hb); yet in our analysis of 527 patients with OSA, >98% did not have an elevated Hb. To understand why patients with OSA do not develop secondary erythrocytosis due to intermittent hypoxia, we first hypothesized that erythrocytosis occurs in these patients, but is masked by a concomitant increase in plasma volume. However, we excluded that explanation by finding that the red cell mass was normal (measured by radionuclide labeling of erythrocytes and carbon monoxide inhalation). We next studied 45 patients with OSA before and after applying continuous positive airway pressure (CPAP). We found accelerated erythropoiesis in these patients (increased erythropoietin and reticulocytosis), but it was offset by neocytolysis (lysis of erythrocytes newly generated in hypoxia upon return to normoxia). Parameters of neocytolysis included increased reactive oxygen species from expanded reticulocytes' mitochondria. The antioxidant catalase was also downregulated in these cells from hypoxia‐stimulated microRNA‐21. In addition, inflammation‐induced hepcidin limited iron availability for erythropoiesis. After CPAP, some of these intermediaries diminished but Hb did not change. We conclude that in OSA, the absence of significant increase in red cell mass is integral to the pathogenesis, and results from hemolysis via neocytolysis combined with inflammation‐mediated suppression of erythropoiesis.
Heterozygous variants in TBCK cause a mild neurologic syndrome in humans and mice
Authors: Nair Divya , Diaz‐Rosado Abdias , Varella‐Branco Elisa , Ramos Igor , Black Aaron , Angireddy Rajesh , Park Joseph , Murali Svathi , Yoon Andrew , Ciesielski Brianna , O'Brien W. Timothy , Passos‐Bueno Maria Rita , Bhoj Elizabeth
Published: June 2023

TBCK‐related encephalopathy is a rare pediatric neurodegenerative disorder caused by biallelic loss‐of‐function variants in the TBCK gene. After receiving anecdotal reports of neurologic phenotypes in both human and mouse TBCK heterozygotes, we quantified if TBCK haploinsufficiency causes a phenotype in mice and humans. Using the tbck+/− mouse model, we performed a battery of behavioral assays and mTOR pathway analysis to investigate potential alterations in neurophysiology. We conducted as well a phenome‐wide association study (PheWAS) analysis in a large adult biobank to determine the presence of potential phenotypes associated to this variant. The tbck+/− mouse model demonstrates a reduction of exploratory behavior in animals with significant sex and genotype interactions. The concurrent PheWAS analysis of 10,900 unrelated individuals showed that patients with one copy of a TBCK loss‐of‐function allele had a significantly higher rate of acquired toe and foot deformities, likely indicative of a mild peripheral neuropathy phenotype. This study presents an example of what may be the underappreciated occurrence of mild neurogenic symptoms in heterozygote individuals of recessive neurogenetic syndromes.
Five siblings expand the spectrum of GPC6‐related skeletal dysplasia
Authors: Crenshaw Molly M. , Meyers Mariana L. , Brown Kathleen , Slegesky Valerie , Duis Jessica , Elias Ellen R. , Saenz Margarita , Shi Wen , Filmus Jorge , Meeks Naomi J. L.
Published: June 2023

Skeletal dysplasias broadly include disorders of cartilage or bone. Omodysplasia‐1 is a type of skeletal dysplasia caused by biallelic loss of function variants in the GPC6 gene. GPC6 codes for the protein glypican 6 (GPC6) (OMIM *604404), which stimulates bone growth. We report a family in which five out of nine children were presented with a skeletal dysplasia characterized phenotypically by mild short stature and rhizomelia. All affected individuals were found to have homozygous missense variants in GPC6: c.511 C>T (p.Arg171Trp). Radiograph findings included rhizomelic foreshortening of all four extremities, coxa breva, and ulna minus deformity. Using a Hedgehog (Hh) reporter assay, we demonstrate that the variant found in this family results in significantly reduced stimulation of Hh activity when compared to the wild‐type GPC6 protein, however protein function is still present. Thus, the milder phenotype seen in the family presented is hypothesized due to decreased GPC6 protein activity versus complete loss of function as seen in omodysplasia‐1. Given the unique phenotype and molecular mechanism, we propose that this family's findings widen the phenotypic spectrum of GPC6‐related skeletal dysplasias.
Recent Advances in Carbonyl‐Photoredox/Transition Metal Dual Catalysis
Authors: Zhu Da‐Liang , Li Jie , Young David James , Wang Yanqing , Li Hong‐Xi
Published: June 2023

Organic transformations using carbonyl‐photoredox/metal dual catalysis have attracted much attention in recent years. Abundant and inexpensive carbonyl photosensitizers effectively serve as single electron, energy or hydrogen atom transfer agents to induce metal‐catalyzed cross‐coupling and dicarbofunctionalization of olefins. This review covers literature reports of metal‐catalyzed photocatalytic coupling reactions from 2020 to mid‐2023, with a focus on C−C (C(sp3)−C(sp3), C(sp3)−C(sp2), C(sp2)−C(sp2), C(sp2)−C(sp)) and C‐heteroatom (C(sp3)−S, C(sp3)−N, C(sp2)−O, C(sp2)−S, C(sp2)−P, C(sp2)−B) bond forming reactions.
There is an obstetrical dilemma: Misconceptions about the evolution of human childbirth and pelvic form
Authors: Grunstra N. D. S. , Betti L. , Fischer B. , Haeusler M. , Pavlicev M. , Stansfield E. , Trevathan W. , Webb N. M. , Wells J. C. K. , Rosenberg K. R. , Mitteroecker P.
Published: June 2023

Compared to other primates, modern humans face high rates of maternal and neonatal morbidity and mortality during childbirth. Since the early 20th century, this “difficulty” of human parturition has prompted numerous evolutionary explanations, typically assuming antagonistic selective forces acting on maternal and fetal traits, which has been termed the “obstetrical dilemma.” Recently, there has been a growing tendency among some anthropologists to question the difficulty of human childbirth and its evolutionary origin in an antagonistic selective regime. Partly, this stems from the motivation to combat increasing pathologization and overmedicalization of childbirth in industrialized countries. Some authors have argued that there is no obstetrical dilemma at all, and that the difficulty of childbirth mainly results from modern lifestyles and inappropriate and patriarchal obstetric practices. The failure of some studies to identify biomechanical and metabolic constraints on pelvic dimensions is sometimes interpreted as empirical support for discarding an obstetrical dilemma. Here we explain why these points are important but do not invalidate evolutionary explanations of human childbirth. We present robust empirical evidence and solid evolutionary theory supporting an obstetrical dilemma, yet one that is much more complex than originally conceived in the 20th century. We argue that evolutionary research does not hinder appropriate midwifery and obstetric care, nor does it promote negative views of female bodies. Understanding the evolutionary entanglement of biological and sociocultural factors underlying human childbirth can help us to understand individual variation in the risk factors of obstructed labor, and thus can contribute to more individualized maternal care.
Use of the patient portal among older adults with diagnosed dementia and their care partners
Authors: Gleason Kelly T. , Wu Mingche M. J. , Wec Aleksandra , Powell Danielle S. , Zhang Talan , Gamper Mary Jo , Green Ariel R. , Nothelle Stephanie , Amjad Halima , Wolff Jennifer L.
Published: June 2023

INTRODUCTION

Care partners are at the forefront of dementia care, yet little is known about patient portal use in the context of dementia diagnosis.

METHODS

We conducted an observational cohort study of date/time‐stamped patient portal use for a 5‐year period (October 3, 2017–October 2, 2022) at an academic health system. The cohort consisted of 3170 patients ages 65+ with diagnosed dementia with 2+ visits within 24 months. Message authorship was determined by manual review of 970 threads involving 3065 messages for 279 patients.

RESULTS

Most (71.20%) older adults with diagnosed dementia were registered portal users but far fewer (10.41%) had a registered care partner with shared access. Care partners authored most (612/970, 63.09%) message threads, overwhelmingly using patient identity credentials (271/279, 97.13%).

DISCUSSION

The patient portal is used by persons with dementia and their care partners. Organizational efforts that facilitate shared access may benefit the support of persons with dementia and their care partners.

Highlights

Patient portal registration and use has been increasing among persons with diagnosed dementia.

Two thirds of secure messages from portal accounts of patients with diagnosed dementia were identified as being authored by care partners, primarily using patient login credentials.

Care partners who accessed the patient portal using their own identity credentials through shared access demonstrate similar levels of activity to patients without dementia.

Organizational initiatives should recognize and support the needs of persons with dementia and their care partners by encouraging awareness, registration, and use of proper identity credentials, including shared, or proxy, portal access.
Sustainable and High‐Rate Electrosynthesis of Nitrogen Fertilizer
Authors: Zhao Qinglan , Lu Xinxin , Wang Yinuo , Zhu Shangqian , Liu Yushen , Xiao Fei , Dou Shi Xue , Lai Wei‐Hong , Shao Minhua
Published: June 2023

The conventional industrial production of nitrogen‐containing fertilizers, such as urea and ammonia, relies heavily on energy‐intensive processes, accounting for approximately 3 % of global annual CO2 emissions. Herein, we report a sustainable electrocatalytic approach that realizes direct and selective synthesis of urea and ammonia from co‐reduction of CO2 and nitrates under ambient conditions. With the assistance of a copper (Cu)‐based salphen organic catalyst, outstanding urea (3.64 mg h−1 mgcat−1) and ammonia (9.73 mg h−1 mgcat−1) yield rates are achieved, in addition to a remarkable Faradaic efficiency of 57.9±3 % for the former. This work proposes an appealing sustainable route to converting greenhouse gas and waste nitrates by renewable energies into value‐added fertilizers.
Steering the Selectivity of Electrocatalytic Glucose Oxidation by the Pt Oxidation State
Authors: van der Ham Matthijs P. J. M. , van Keulen Ellis , Koper Marc T. M. , Tashvigh Akbar Asadi , Bitter Johannes H.
Published: June 2023

Electrocatalytic glucose oxidation can produce high value chemicals, but selectivity needs to be improved. Here we elucidate the role of the Pt oxidation state on the activity and selectivity of electrocatalytic oxidation of glucose with a new analytical approach, using high‐pressure liquid chromatography and high‐pressure anion exchange chromatography. It was found that the type of oxidation, i.e. dehydrogenation of primary and secondary alcohol groups or oxygen transfer to aldehyde groups, strongly depends on the Pt oxidation state. Pt0 has a 7‐fold higher activity for dehydrogenation reactions than for oxidation reactions, while PtOx is equally active for both reactions. Thus, Pt0 promotes glucose dialdehyde formation, while PtOx favors gluconate formation. The successive dehydrogenation of gluconate is achieved selectively at the primary alcohol group by Pt0, while PtOx also promotes the dehydrogenation of secondary alcohol groups, resulting in more complex reaction mixtures.
Regio‐ and Z‐Selective Alkyne Hydroamination and Hydrophenoxylation using Tetrafluoro‐λ6‐Sulfanyl Alkynes under Superbasic, Naked Anion Conditions
Authors: Aggarwal Trapti , Hada Kenshiro , Murata Yusuke , Sumii Yuji , Tanagawa Kazuhiro , Niina Kiyoteru , Mori Soichiro , Escorihuela Jorge , Shibata Norio
Published: June 2023

Alkyne hydroamination is an effective approach for the production of enamines and enamine‐containing N‐heterocycles. However, stereoselectivity control is a considerable challenge in this reaction because of the electronic repulsion between an incoming nitrogen lone pair and the alkyne π‐system. Herein, we propose a methodology involving β‐regio‐ and Z‐selective alkyne hydroamination by using tetrafluoro‐λ6‐sulfanyl (SF4) alkynes under superbasic, naked anion conditions. The reaction is compatible with a wide variety of N‐heterocycles, including indoles, carbazoles, pyrazoles, and imidazoles, and selectively furnishes SF4‐linked Z‐vinyl enamines with β‐regioselectively. Moreover, the method can be extended to the β‐ and Z‐controlled, base‐mediated alkyne hydrophenoxylation with phenols to provide SF4‐linked Z‐vinyl ethers in high yields. As the SF4 unit has attracted attention as a bioisostere for alkynes, p‐benzenes, bicyclo[1.1.1]pentyl (BCP) groups, and cubanes in medicinal chemistry, this chemistry represents an effective approach to creating novel drug candidates incorporating SF4‐containing molecules.
Achieving anti‐moisture absorption and high thermal properties in bio‐based polyamide 56/F‐based heat‐resistant agent composites through crystal regulation
Authors: He Lulu , An Taofang , He Min , Fan Qiao , Yang Jifei , Liu Yufei , Qin Shuhao , Yu Jie
Published: June 2023

The anti‐moisture absorption and thermal properties of bio‐based polyamide 56 (PA56) were improved by adding heat‐resistant agents to expand its application in the automotive field. Two macromolecular heat‐resistant agents, p(N‐(4‐F‐phenylmaleimide)‐alt‐styrene) (PFS) and p(N‐(4‐F‐phenylmaleimide)‐alt‐triallyl isocyanurate) (PFT), were synthesized via precipitation polymerization, and their effects on the thermal properties, mechanical properties, and anti‐moisture absorption of PA56 were studied. Compared with PA56, the heat deflection temperature of PA56/PFS and PA56/PFT composites was improved by 11.9% and 21.2%, with their anti‐moisture absorption increasing by 14.6% and 15.5%, respectively. This is due to the crystallization of PA56 has been promoted and its more complete crystal structure has been obtained.
Research on the thermal oxygen aging mechanism of the composite curing system epoxy asphalt with different curing agent proportions on the molecular scale
Authors: Li Mingyue , Min Zhaohui , Shi Zhiyong , Wang Qichang , Huang Wei , Shao Kaimo
Published: June 2023

To study the influence of the cross‐linking network on the thermal oxygen aging performance of the epoxy asphalt, the laser copolymerization microscopy, Fourier transform infrared spectroscopy and element analysis tests were used to characterize the changes in chemical components of epoxy asphalt with composite curing system during thermal oxygen aging. According to the changes in chemical components, the epoxy asphalt molecular models were constructed. The diffusion behavior of oxygen atoms was analyzed, the aging degree was determined. Moreover, the Tg and radial distribution function were calculated to determine the effect of aging on the low‐temperature performance and component distribution of epoxy asphalt. The results show that a proper proportion of curing agent helped to uniform distribution of the asphalt phase. The rise in anhydride curing agent content increased the density of crosslinking network, limited the diffusion of oxygen atoms, and contributed to the resistance of epoxy asphalt chemical components to thermal oxygen aging. However, the high proportion of anhydride aggravated the oxidation reaction of the asphalt phase due to the uneven coating of the asphalt phase. After thermal oxygen aging, the distribution of asphaltene and epoxy resin phase showed a concomitant phenomenon due to polarity adsorption.
Effects of using superheroes in an undergraduate human anatomy curriculum
Authors: Grachan Jeremy J. , Marek Mason , Cray James , Quinn Melissa M.
Published: June 2023

Students often find human anatomy courses to be difficult due to the large amount of content covered at a fast pace, which can result in students failing to retain pertinent information. Superheroes are at the forefront of today's popular culture, with many students identifying with specific characters. Utilizing aspects of students' lives, or their agency, that they can resonate with in the classroom, such as their interests in superheroes or personal connections to fictional characters, may help drive students' motivation to learn course content. This study investigated if the use of superheroes in an anatomy curriculum helped undergraduate students learn, apply, and improve their anatomical knowledge. Two courses at The Ohio State University—Columbus Campus, one with a superhero‐based curriculum and one with a traditional anatomy curriculum were compared over three semesters using quizzes and survey data. Results from this project found that the use of superheroes/pop culture in anatomy education is an effective way to teach content. The study also showed that most students found the use of superheroes increased their motivation to learn, helped them gain a deeper understanding of the material, and helped them find the content more approachable and enjoyable. In summary, anatomy curricula can still be taught and explained through these creative and “marvel”‐ous examples as it can help students connect the material to their own agency and drive motivation to learn.
Differences in self‐other control as cognitive mechanism to characterize theory of mind reasoning in autistic and non‐autistic adults
Authors: Schuwerk Tobias , Sodian Beate
Published: June 2023

In cognitive science, altered Theory of Mind is a central pillar of etiological models of autism. Yet, recent evidence, showing comparable Theory of Mind abilities in autistic and non‐autistic people, draws a more complex picture and renders previous descriptions of Theory of Mind abilities in autism and their role in autistic symptomatology insufficient. Here, we addressed self‐other control as a potential candidate cognitive mechanism to explain subtle Theory of Mind reasoning differences between autistic and non‐autistic adults. We investigated flexible shifting between another's and one's own congruent or incongruent points of view, an ability that is important for reciprocal social interaction. Measuring response accuracy and reaction time in a multiple‐trial unexpected location false belief task, we found evidence for altered self‐other control in Theory of Mind reasoning in autistic adults, with a relative difficulty in flexibly considering the other's perspective and less interference of the other's incongruent viewpoint when their own perspective is considered. Our results add to previous findings that social cognitive differences are there but subtle and constitute one step further in characterizing Theory of Mind reasoning in autism and explaining communication and interaction difficulties with non‐autistic people in everyday life.
Biodiesel production from cagaite seeds (Eugenia dysentericaDC) oil: An alternative for biofuel production
Authors: Rial Rafael Cardoso , de Freitas Osmar Nunes , da Silva Fonseca Amanda Maria , Domingues João Manuel Hernandes Dorce , de Souza Maria Luiza Medeiros , de Almeida Silva Yasmin Alves , Santos Piter Hernanny Michalski , Melo Luiz Felipe Dias , Nazário Carlos Eduardo Domingues , Viana Luiz Henrique
Published: June 2023

In the present work, cagaite (Eugenia dysenterica DC.) seed oil was studied as a potential inedible raw material for biodiesel production. The oil was extracted using a Soxhlet extractor and the fatty acids acyl esters that make up biodiesel were obtained by alkaline transesterification using sodium hydroxide. The influence of reaction parameters was also evaluated: molar ratio, time, and amount of catalyst. The conversion of fatty acids into fatty acid methyl esters (FAME), which make up biodiesel, was calculated using Nuclear Magnetic Resonance Spectroscopy (1HNMR) spectra. In a 30 min reaction period, the molar ratio of oil to methanol was 1:4, resulting in a conversion of 63.57%. However, when the molar ratio was increased to 1:8, the conversion reached 81.74% during the same 30 min reaction period. After 60 min of reaction, additional increases in conversion were observed when molar ratios of 1:4, 1:6, and 1:8 were used. Under these conditions, the conversions achieved were 92.08%, 98.24%, and 98.78%, respectively. The physico‐chemical properties were evaluated and the results showed that cagaite seed oil biodiesel was similar to soybean biodiesel, which is the most commonly produced biodiesel in Brazil. It was thus an important substitute for soybean biodiesel.
Students at a crossroad: A cross‐sectional survey gauging the impact of COVID‐19 on medical and biomedical graduates in the United States and Sweden
Authors: Lange Stephan , Soták Matúš , Hagberg Carolina E. , Bagunu Grace , Vigmo Sylvi , Börgeson Emma
Published: June 2023

Graduate programs in medicine and biomedical sciences have been severely impacted by the SARS‐CoV‐2/COVID‐19 pandemic over the last 2 years. Following 2 years since beginning of the pandemic, data on student support, educational and academic performance as well as sentiment on changes to educational programs are starting to emerge. We performed and compared results of two cross‐sectional surveys of Swedish and U.S.‐based medical and biomedical graduate students on how the pandemic has affected their studies, research productivity and career trajectory. Students were also asked to assess support provided by the university and supervisors. The surveys also captured student demographics and a range of other factors, such as pressures brought on by caretaking and financial responsibilities. We analyzed answers from 264 and 106 students attending graduate programs in universities in Sweden and the United States, respectively. U.S.‐based students faced more severe restrictions on their research program compared to students in Sweden, reporting more delays in productivity, scientific output and graduation, and increased worries about their career trajectory. Swedish students had more caretaking responsibilities, although these did not cause any delays in graduation. While support by universities and supervisors was comparable between the countries, financial worries and mental health concerns were particularly prominent in the U.S. cohort. Student performance and outlook was hugely dependent on the breadth of the restrictions and the available support. Besides the governmental and university‐led approach to counter the pandemic, societal differences also played a role in how well students were handling effects of the pandemic.
Simultaneous quantitation of urine aldosterone and tetrahydroaldosterone in healthy Chinese subjects using a validated LC–MS/MS method
Authors: Cheng Jenny Yeuk Ki , Lo Clara Wai Shan , Chan Alan Shek Lun , Luk Yue Kin , Tsui Teresa Kam Chi , Ho Chung Shun
Published: June 2023

Aldosterone (ALD) is excreted in urine mainly as glucuronide conjugates of ALD and tetrahydroaldosterone. Measuring these urinary metabolites might be an alternative screening test to plasma ALD for primary aldosteronism. We report a validated LC–MS/MS method to measure both analytes simultaneously. Urine samples underwent enzymatic hydrolysis to release the analytes from their glucuronide conjugates followed by organic solvent extraction and LC–MS/MS. The analytical performance of this method was evaluated. The within‐batch and between‐batch coefficients of variation for urine ALD and urine THA were all ≤5.2 and ≤3.7%. The lower limit of quantification was 0.5 nmol/L, and the linearity was up to at least 2770 nmol/L for both analytes. No significant matrix interference and carryover were observed. Both analytes in urine were stable for at least 48 h at 10°C and at least 18 months at −80°C. Local reference intervals were established from 126 healthy normotensive Chinese subjects (53% women, age: 20–65 years). Reference intervals for urine ALD and tetrahydroaldosterone were 2–38 and 9–139 nmol/day, respectively. This validated method can be applied to screening and diagnosing primary aldosteronism.
Secure reversal of immune evasion from refractory NSCLC and highly contagious CoV‐2 mutants by using 3D‐engineered multifunctional biologics
Authors: Zhang Yanna , Li Qian , Liu Nanxi , Hu Jianchuan , Lin Xiaojuan , Huang Meijuan , Wei Yuquan , Qi Xiaorong , Chen Xiancheng
Published: June 2023

There is an imperative choice to develop a secure feasible strategy to address evasion dynamics of refractory tumors and SARS‐CoV‐2‐variants, while stem cell‐based protocol may be more reliable as its unique ability for resetting multifunctional immunity to address progressive tumor and the constantly‐evolving virus. In this study, spheroid‐embryonoid stem cells from mature somatic cells were engineered as multifunctional biologics (3D‐E/BSC) and inoculated in senile rhesus to identify secure potential against immune‐evasion from viral‐variants. Meanwhile, a cohort of eligible patients with stage IV NSCLC were approved for phase I clinical trials. Subsequently, long‐lasting security and efficacy were validated by primate and clinical trials (p < 0.01) in that it could not only stimulate serological immunity, but also reset core immunity for hosts to address variant evasion after 3D‐E/BSC withdrawal. Particularly, illustrated by single‐cell evolving trajectory, 3D‐E/BSC had securely reset senile thymus of aging hosts to remodel core immunity by rearranging naive rhythm to evolve TRGC2+/JCHAIN+NKT clusters to abolish tumoral and viral evasion dynamics with path‐feedbacks of NSCLC and COVID‐19 simultaneously activated, leading to continuous blockade of breakthrough infection of viral‐mutants and long‐term survival in one‐third of terminal patients without adjuvant required. Our study may pioneer a practical multifunctional strategy to eliminate evasion of SARS‐CoV‐2 variants and refractory NSCLC so as for victims to restart a new life‐equation.
Roles and implications of mRNA N6‐methyladenosine in cancer
Authors: Zeng Lingxing , Huang Xudong , Zhang Jialiang , Lin Dongxin , Zheng Jian
Published: June 2023

RNA N6‐methyladenosine modification is the most prevalent internal modification of eukaryotic RNAs and has emerged as a novel field of RNA epigenetics, garnering increased attention. To date, m6A modification has been shown to impact multiple RNA metabolic processes and play a vital role in numerous biological processes. Recent evidence suggests that aberrant m6A modification is a hallmark of cancer, and it plays a critical role in cancer development and progression through multiple mechanisms. Here, we review the biological functions of mRNA m6A modification in various types of cancers, with a particular focus on metabolic reprogramming, programmed cell death and tumor metastasis. Furthermore, we discuss the potential of targeting m6A modification or its regulatory proteins as a novel approach of cancer therapy and the progress of research on m6A modification in tumor immunity and immunotherapy. Finally, we summarize the development of different m6A detection methods and their advantages and disadvantages.
Development of a metabolite calculator for diagnosis of pancreatic cancer
Authors: Choi Munseok , Park Minsu , Lee Sung Hwan , Lee Min Jung , Paik Young‐Ki , Jang Sung Il , Lee Dong Ki , Lee Sang‐Guk , Kang Chang Moo
Published: June 2023

Background

Carbohydrate antigen (CA) 19–9 is a known pancreatic cancer (PC) biomarker, but is not commonly used for general screening due to its low sensitivity and specificity. This study aimed to develop a serum metabolites‐based diagnostic calculator for detecting PC with high accuracy.

Methods

A targeted quantitative approach of direct flow injection‐tandem mass spectrometry combined with liquid chromatography–tandem mass spectrometry was employed for metabolomic analysis of serum samples using an Absolute IDQ™ p180 kit. Integrated metabolomic analysis was performed on 241 pooled or individual serum samples collected from healthy donors and patients from nine disease groups, including chronic pancreatitis, PC, other cancers, and benign diseases. Orthogonal partial least squares discriminant analysis (OPLS‐DA) based on characteristics of 116 serum metabolites distinguished patients with PC from those with other diseases. Sparse partial least squares discriminant analysis (SPLS‐DA) was also performed, incorporating simultaneous dimension reduction and variable selection. Predictive performance between discrimination models was compared using a 2‐by‐2 contingency table of predicted probabilities obtained from the models and actual diagnoses.

Results

Predictive values obtained through OPLS‐DA for accuracy, sensitivity, specificity, balanced accuracy, and area under the receiver operating characteristic curve (AUC) were 0.9825, 0.9916, 0.9870, 0.9866, and 0.9870, respectively. The number of metabolite candidates was narrowed to 76 for SPLS‐DA. The SPLS‐DA‐obtained predictive values for accuracy, sensitivity, specificity, balanced accuracy, and AUC were 0.9773, 0.9649, 0.9832, 0.9741, and 0.9741, respectively.

Conclusions

We successfully developed a 76 metabolome‐based diagnostic panel for detecting PC that demonstrated high diagnostic performance in differentiating PC from other diseases.
The combination of etoposide and platinum for the treatment of thymic neuroendocrine neoplasms: A retrospective analysis
Authors: Guan Yelan , Yao Qifeng , Hao Yue , Zeng Xiaohong , Wang Wenxian , Gu Xiadong , Xiang Jing , Sun Yan , Song Zhengbo
Published: June 2023

Background

To provide real‐world outcomes for the combination of etoposide and platinum as a first‐line treatment for advanced thymic neuroendocrine neoplasms (TNENs).

Methods

Retrospective analysis was performed on patients with advanced TNENs confirmed by pathology who received etoposide combined with platinum as a first‐line chemotherapy in our institution between 2010 and 2022.

Results

A total of 16 patients were included in this study. Twelve patients (75%) received etoposide combined with cisplatin, and four patients (25%) received etoposide combined with carboplatin. Efficacy was evaluated in all patients, with an objective response rate of 31.3%. One patient achieved a complete response, four achieved a partial response, and in eight patients the disease remained stable; the disease control rate was 81.3%. The median progression‐free survival (PFS) was 7.2 months with a 95% confidence interval (CI) of 2.1–12.3 months. The median overall survival (OS) was 50.4 months with a 95% CI of 32.1–68.8 months. No significant difference in efficacy was observed between the treatment groups with regards to PFS (p = 0.095) and OS (p = 0.061). Treatment‐related adverse events were observed in all 12 patients when evaluated for toxicity, manifesting as hematologic toxicity. Grade 3–4 bone marrow suppression occurred in six patients (50%). No treatment‐related deaths were recorded.

Conclusion

This retrospective analysis, conducted in a real‐life setting, suggests that the combination of etoposide and platinum has a promising anti‐tumor activity in advanced TNENs, with a clinically significant overall response rate.