bluuebunny/crossref_metadata_2025_split huggingface dataset:
Utilizing Hairy Hollow Conjugated Microporous Polymers and Native Enzymes for Precise Aerobic Photocatalysis Under Near‐Infrared Wavelengths
Authors: Xiang Qian , Huang Yuan , Jiang Sheng Hong , Cheng Si‐Xue , Li Xue , Cai Tao 
Published: February 2024

AbstractUtilizing photoregenerated cofactors in conjunction with enzymes in a sequential manner presents an effective approach for the synthesis of targeted compounds in gentle reaction conditions. Nevertheless, the integration of enzymes and photocatalysts has faced challenges due to the swift breakdown of biomaterials caused by high‐energy or blue lights and photoinduced reactive oxygen species, leading to the denaturation and deactivation of enzymatic materials. This study details the deliberate development and production of hairy hollow conjugated microporous polymers (S‐hPrTZ‐P HCMPs), achieved via Sonogashira–Hagihara coupling on SiO2 templates, followed by sulfonation, polymer grafting and ultimately eliminating the SiO2 cores. This technique leverages the distinctive characteristics of low‐energy near‐infrared light, such as its superior penetration ability, to effectively regenerate the enzymatic cofactor NAD+ from NADH. It can accomplish this feat even when faced with synthetic or biological barriers that are impermeable to visible light. Simultaneously, photogenerated reactive oxygen species are captured and neutralized by the hydrophilic polymer brushes, safeguarding the integrity of the enzymatic material. The adaptability of S‐hPrTZ‐P with photocatalytic properties is showcased alongside glucose 1‐dehydrogenase and glycerol dehydrogenase. This structure and morphology‐controlled strategy offers a promising pathway for various enzymatic photobiocatalysis employing stable, efficient, and reusable hairy HCMPs.
A Gradient Stiffness‐Programmed Circuit Board by Spatially Controlled Phase‐Transition of Supercooled Hydrogel for Stretchable Electronics Integration
Authors: Kim Minwoo , Hong Sangwoo , Park Jung Jae , Jung Yeongju , Choi Seok Hwan , Cho Chulmin , Ha Inho , Won Phillip , Majidi Carmel , Ko Seung Hwan 
Published: February 2024

AbstractDue to emerging demands in soft electronics, there is an increasing need for material architectures that support robust interfacing between soft substrates, stretchable electrical interconnects, and embedded rigid microelectronics chips. Though researchers have adopted rigid‐island structures to solve the issue, this approach merely shifts stress concentrations from chip‐conductor interfaces to rigid‐island‐soft region interfaces in the substrate. Here, a gradient stiffness‐programmed circuit board (GS‐PCB) that possesses high stretchability and stability with surface mounted chips is introduced. The board comprises a stiffness‐programmed hydrogel substrate and a laser‐patterned liquid metal conductor. The hydrogel simultaneously obtains a large stiffness disparity and robust interfaces between rigid‐islands and soft regions. These seemingly contradictory conditions are accomplished by adopting a gradient stiffness structure at the interfaces, enabled by combining polymers with different interaction energies and a supercooled sodium acetate solution. By integrating the gel with laser‐patterned liquid metal with exceptional properties, GS‐PCB exhibits higher electromechanical stability than other rigid‐island research. To highlight the practicality of this approach, a finger‐sensor device that successfully distinguishes objects by direct physical contact is fabricated, demonstrating its stability under various mechanical disturbances.
Light‐Responsive Materials in Droplet Manipulation for Biochemical Applications
Authors: Cheng Guangyao , Kuan Chit Yau , Lou Kuan Wen , Ho Yi‐Ping 
Published: February 2024

AbstractMiniaturized droplets, characterized by well‐controlled microenvironments and capability for parallel processing, have significantly advanced the studies on enzymatic evolution, molecular diagnostics, and single‐cell analysis. However, manipulation of small‐sized droplets, including moving, merging, and trapping of the targeted droplets for complex biochemical assays and subsequent analysis, is not trivial and remains technically demanding. Among various techniques, light‐driven methods stand out as a promising candidate for droplet manipulation in a facile and flexible manner, given the features of contactless interaction, high spatiotemporal resolution, and biocompatibility. This review therefore compiles an in‐depth discussion of the governing mechanisms underpinning light‐driven droplet manipulation. Besides, light‐responsive materials, representing the core of light–matter interaction and the key character converting light into different forms of energy, are particularly assessed in this review. Recent advancements in light‐responsive materials and the most notable applications are comprehensively archived and evaluated. Continuous innovations and rational engineering of light‐responsive materials are expected to propel the development of light‐driven droplet manipulation, equip droplets with enhanced functionality, and broaden the applications of droplets for biochemical studies and routine biochemical investigations.
Self‐Charging Aqueous Zn//COF Battery with UltraHigh Self‐Charging Efficiency and Rate
Authors: Zhong Leheng , Wang Chunfang , He Jun , lin Zhiqing , Yang Xiaodong , Li Ran , Zhan Shuai , Zhao Linwei , Wu Dan , Chen Hui , Tang Zijie , ZHi Chunyi , Lv (Lyu) Haiming 
Published: February 2024

AbstractSelf‐charging zinc batteries that combine energy harvesting technology with batteries are candidates for reliable self‐charging power systems. However, the lack of rational materials design results in unsatisfactory self‐charging performance. Here, a covalent organic framework containing pyrene‐4,5,9,10‐tetraone groups (COF‐PTO) is reported as a cathode material for aqueous self‐charging zinc batteries. The ordered channel structure of the COF‐PTO provides excellent capacity retention of 98% after 18 000 cycles at 10 A g−1 and ultra‐fast ion transfer. To visually assess the self‐charging performance, two parameters, namely self‐charging efficiency (self‐charging discharge capacity/galvanostatic discharge capacity, η) and average self‐charging rate (total discharge capacity after cyclic self‐charging/total cyclic self‐charging time, ν), are proposed for performance evaluation. COF‐PTO achieves an impressive η of 96.9% and an ν of 30 mAh g−1 self‐charge capacity per hour in 100 self‐charging cycles, surpassing the previous reports. Mechanism studies reveal the co‐insertion of Zn2+ and H+ double ions in COF‐PTO of self‐charging zinc batteries. In addition, the C═N and C═O (on the benzene) in COF‐PTO are ortho structures to each other, which can easily form metal heterocycles with Zn ions, thereby driving the forward progress of the self‐charging reaction and enhancing the self‐charging performance.
Mechanically Interlocked Interphase with Energy Dissipation and Fast Li‐Ion Transport for High‐Capacity Lithium Metal Batteries
Authors: Shi Zhangqin , Wang Yongming , Yue Xinyang , Zhao Jun , Fang Mingming , Liu Jijiang , Chen Yuanmao , Dong Yongteng , Yan Xuzhou , Liang Zheng 
Published: February 2024

AbstractConstructing an artificial solid electrolyte interphase (ASEI) on Li metal anodes (LMAs) is a potential strategy for addressing the dendrite issues. However, the mechanical fatigue of the ASEI caused by stress accumulation under the repeated deformation from the Li plating/stripping is not taken seriously. Herein, this work introduces a mechanically interlocked [an]daisy chain network (DCMIN) into the ASEI to stabilize the Li metal/ASEI interface by combining the functions of energy dissipation and fast Li‐ion transport. The DCMIN featured by large‐range molecular motions is cross‐linked via efficient thiol‐ene click chemistry; thus, the DCMIN has flexibility and excellent mechanical properties. As an ASEI, the crown ether units in DCMIN not only interact with the dialkylammonium of a flexible chain, forming the energy dissipation behavior but also coordinate with Li ion to support the fast Li‐ion transport in DCMIN. Therefore, a stable 2800 h‐symmetrical cycling (1 mA cm−2) and an excellent 5 C‐rate (full cell with LiFePO4) performance are achieved by DCMIN‐based ASEI. Furthermore, the 1‐Ah pouch cell (LiNi0.88Co0.09Mn0.03O2 cathode) with DCMIN‐coated LMA exhibits improved capacity retention (88%) relative to the Control. The molecular design of DCMIN provides new insights into the optimization of an ASEI for high‐energy LMAs.
Sustainable Super‐Insulating Packaging Composite from Recycled Wood
Authors: Liu I‐Tseng , You Jhu‐Lin , Tung Shih‐Huang , Liao Ying‐Chih 
Published: February 2024

AbstractThermal insulation materials (TIMs) have been widely used over the past century. In this landscape, expandable polystyrene (EPS) is the dominant choice; however, the waste management of EPS is hampered by recycling challenges and lack of economic incentives. Concurrently, the order delivery and pharmaceutical distribution have experienced significant growth due to lifestyle shifts after the pandemic. For instance, the utilization of drones for transportation is illustrated (see abstract figure) as a prospective alternative transportation protocol. In this work, a synthetic method is developed to prepare bio‐degradable thermal insulator material from recycled wood and silica aerogel. The silica aerogel wood composite (SAWc) has the following properties: 1) low carbon emission (4.932 kg CO2e kg−1); 2) low thermal conductivity (0.032 W mK−1) with an anisotropy of 1.5; 3) high compressive strength (yield stress = 8.60 Mpa); 4) excellent resistance to organic solvents; 5) high biodegradability (49.4% weight loss after 28 days); 6) excellent flame retardancy, both of which are above EPS. The scalable, super‐insulating, and robust thermal insulator, as demonstrated in this work, holds high potential as an alternative packaging material poised to shape the next era in thermal insulation solutions.
Chromatin Remodeling in Patient‐Derived Colorectal Cancer Models
Authors: Xiang Kun , Wang Ergang , Mantyh John , Rupprecht Gabrielle , Negrete Marcos , Sanati Golshid , Hsu Carolyn , Randon Peggy , Dohlman Anders , Kretzschmar Kai , Bose Shree , Giroux Nicholas , Ding Shengli , Wang Lihua , Balcazar Jorge Prado , Huang Qiang , Sundaramoorthy Pasupathi , Xi Rui , McCall Shannon Jones , Wang Zhaohui , Jiang Chongming , Kang Yubin , Kopetz Scott , Crawford Gregory E. , Lipkin Steven M. , Wang Xiao‐Fan , Clevers Hans , Hsu David , Shen Xiling 
Published: February 2024

AbstractPatient‐Derived Organoids (PDO) and Xenografts (PDX) are the current gold standards for patient‐derived models of cancer (PDMC). Nevertheless, how patient tumor cells evolve in these models and the impact on drug response remains unclear. Herein, the transcriptomic and chromatin accessibility landscapes of matched colorectal cancer (CRC) PDO, PDX, PDO‐derived PDX (PDOX), and original patient tumors (PT) are compared. Two major remodeling axes are discovered. The first axis delineates PDMC from PT, and the second axis distinguishes PDX and PDO. PDOX are more similar to PDX than PDO, indicating the growth environment is a driving force for chromatin adaptation. Transcription factors (TF) that differentially bind to open chromatins between matched PDO and PDOX are identified. Among them, KLF14 and EGR2 footprints are enriched in PDOX relative to matched PDO, and silencing of KLF14 or EGR2 promoted tumor growth. Furthermore, EPHA4, a shared downstream target gene of KLF14 and EGR2, altered tumor sensitivity to MEK inhibitor treatment. Altogether, patient‐derived CRC cells undergo both common and distinct chromatin remodeling in PDO and PDX/PDOX, driven largely by their respective microenvironments, which results in differences in growth and drug sensitivity and needs to be taken into consideration when interpreting their ability to predict clinical outcome.
From Basic Science to Clinical Practice: A Review of Current Periodontal/Mucogingival Regenerative Biomaterials
Authors: De Lauretis Angela , Øvrebø Øystein , Romandini Mario , Lyngstadaas Ståle Petter , Rossi Filippo , Haugen Håvard Jostein 
Published: February 2024

AbstractPeriodontitis is a dysbiosis‐driven inflammatory disease affecting the tooth‐supporting tissues, characterized by their progressive resorption, which can ultimately lead to tooth loss. A step‐wise therapeutic approach is employed for periodontitis. After an initial behavioral and non‐surgical phase, intra‐bony or furcation defects may be amenable to regenerative procedures. This review discusses the regenerative technologies employed for periodontal regeneration, highlighting the current limitations and future research areas. The search, performed on the MEDLINE database, has identified the available biomaterials, including biologicals (autologous platelet concentrates, hydrogels), bone grafts (pure or putty), and membranes. Biologicals and bone grafts have been critically analyzed in terms of composition, mechanism of action, and clinical applications. Although a certain degree of periodontal regeneration is predictable in intra‐bony and class II furcation defects, complete defect closure is hardly achieved. Moreover, treating class III furcation defects remains challenging. The key properties required for functional regeneration are discussed, and none of the commercially available biomaterials possess all the ideal characteristics. Therefore, research is needed to promote the advancement of more effective and targeted regenerative therapies for periodontitis. Lastly, improving the design and reporting of clinical studies is suggested by strictly adhering to the Consolidated Standards of Reporting Trials (CONSORT) 2010 statement.
Identifying and Amplifying the Spontaneously Formed Photo‐Charge Contribution in Opaque and Semitransparent Organic Photovoltaics
Authors: Tang Yabing , Cui Yu , Zhang Rui , Xue Wenyue , Ma Wei , Yan Han 
Published: February 2024

AbstractSpontaneous photo‐charge (SP) generation within the non‐fullerene (NFA) bulk helps avoid exciton (EX) related loss as compared to the traditional heterojunction route in organic solar cells (OSCs). Unfortunately, the promising SP utilization attracts little attention at this time due to the lack of knowledge on its specific contribution to the photovoltaic performance and rational optimization in high‐efficiency devices. To fill the gap, the NFAs’ SP characteristics are related with their photocurrent loss and power conversion efficiency (PCE) in state‐of‐the‐art materials. Though higher SP population is good for efficient EX utilization, it simultaneously acts as an additional photo‐charge recombination channel. The former can be further enhanced by increasing the NFAs’ crystallinity with preferred lamellar growth, and the latter can be suppressed via electric doping. With the aid of the two‐step optimization strategy, the total photocurrent loss is reduced from 14.4% to 4.8%, accompanying with PCE increment from 16.9% to 18.5%. The SP utilization strategy is finally applied in the semitransparent OSCs (ST‐OSCs), due to its less heterojunction area sensitive photo‐charge generation characteristic. A light utilization efficiency (LUE) is then increased from 3.21% to 3.77%. The findings highlight the pursue of efficient SP utilization as a new design philosophy in future OSCs’ progresses.
Ligand Mediated Assembly of CdS Colloids in 3D Porous Metal–Organic Framework Derived Scaffold with Multi‐Sites Heterojunctions for Efficient CO2 Photoreduction
Authors: Zhang Tianxi , Li Tongtao , Gao Minmin , Lu Wanheng , Chen Zongwei , Ong Wei Li , Wong Andrew See Weng , Yang Liming , Kawi Sibudjing , Ho Ghim Wei 
Published: February 2024

AbstractThe inclusion of colloidal particles into 3D porous constructs to realize heterostructure ensembles enhances surface interactions and energy transfer that can transform the catalytic properties of conventional catalysts. However, assembling hydrophobic colloidal nanoparticles within hydrophilic 3D porous matrices to create tailored heterostructures and catalytic properties is particularly challenging. Here, a modified ligand grafting method is presented to spontaneously assemble CdS inorganic colloidal quantum dots within a metal‐organic framework (MOF) derived porous framework for efficient photocatalytic CO2 reduction. The grafted long chain molecular ligands effectively suppress phase separation and endow a molecular‐recognition effect to form ordered assembly microstructures. The proof‐of‐concept assembly of CdS and Prussian blue analogues (PBA) derived Co3O4 facilitates a high density of heterojunctions formation, improving charge transfer and extended lifetimes of photo‐induced electrons. Consequently, CdS/Co3O4 assembly exhibits exceptionally active and stable photocatalytic CO2 reduction activity, with a CO production rate of 73.9 µmol g−1 h−1 and CO selectivity of 98.9%. Importantly, the ligand grafting method can be generalized to achieve spontaneous assembly of quantum dots within various metal organic framework derived porous scaffolds. This work provides a rational strategy for precise self‐assembly of colloidal nanoparticles within porous microstructures, allowing tailored heterointerfaces for functional materials and applications.
Second‐ and third‐year medical students’ clinical encounters in the emergency department
Authors: Hoxha Ines , Hekman Daniel J. , Schnapp Benjamin 
Published: February 2024

AbstractBackgroundExperiential learning theory suggests that direct clinical experiences facilitate learning. Previous literature has focused primarily on the experiences of fourth‐year medical students. As more students gain early clinical exposure, it is important to understand the types of patients seen by junior students.ObjectivesThis study aims to categorize the clinical experiences of early (M2 and M3) students in the emergency department (ED).MethodsA retrospective review of the electronic health record of patients seen by M2s and M3s on a 2‐week emergency medicine rotation at a single urban academic ED in the Midwest was performed. Data elements extracted included total number of patients seen, Emergency Severity Index (ESI), disposition, and chief complaint. Students were not mandated to see any particular patients.ResultsMedical students (248) saw 2994 total patients from 2018 to 2022. The median number of patients seen by each student was 12.0 (range 1–32). Pediatric patients made up 6.5% (n = 194) of total patients. Encounters were primarily ESI 2 or 3, which accounted for 89.4% of all patients (n = 2676). The most encountered complaints were abdominal pain, chest pain, and dyspnea, making up 15.6% (n = 467), 8.7% (n = 260), and 5.5% (n = 165), respectively, of total cases. Obstetrics/gynecology, hematologic, and environmental disorders were the least frequently encountered domains. No students saw all Clerkship Directors in Emergency Medicine (CDEM)–recommended complaints.ConclusionsThere is significant variability in the ED encounters of M2s and M3s, with wide ranges of patient volume and presentations. This study provides some evidence that early students may not be meeting CDEM recommendations.
Crystalline porous materials for catalytic conversion of lignin‐related substances
Authors: Huang Qing , Wu Pengfei , Li Xiu‐Fen , Wang Yi‐Rong , Tian Dan , Lan Ya‐Qian 
Published: February 2024

AbstractThe conversion of the biomass into eco‐friendly fuels and chemicals has been extensively recognized as the essential pathway to achieve the sustainable economy and carbon neutral society. Lignin, as a kind of promising biomass energy, has been certified to produce the high‐valued chemicals and fuels. Numerous efforts have been made to develop various catalysts for lignin catalytic conversion. Both metal‐organic frameworks (MOFs) and covalent organic frameworks (COFs) belong to very important heterogeneous porous catalysts due to their regular porous structures, high specific surface area, and precisely tailored diversities. In the review, the first part focused on the catalytic conversion of lignin, lignin model compounds, and lignin derivatives using the pristine MOFs, functional MOF composites, and MOF‐derived materials. The second part summarized the catalytic conversion of lignin model compounds using pristine COFs and functional COF composites. The review here mainly concentrated on the design of the materials, screening of catalytic conditions, and explorations of the corresponded mechanisms. Specifically, (1) we summarized the MOF‐ and COF‐based materials for the effects on the catalytic transformation of lignin‐related substances; (2) we emphasized the catalytic mechanism of C–C and C–O bonds cleavage together with the structure–activity relationships; (3) we in‐depth realized the relationship between the chemical/electronic/structural properties of the MOF‐ and COF‐based catalysts and their catalytic performance for lignin‐related substances. Finally, the challenges and future perspectives were also discussed on the catalytic conversion of lignin‐related substances by MOF‐ and COF‐based catalysts.
Reaction Paradigms that Leverage Cycloaddition and Ring Strain to Construction Bicyclic Aryl Bioisosteres from Bicyclo[1.1.0]butanes
Authors: Sujansky Stephen J. , Ma Xiaoshen 
Published: February 2024

AbstractWithin a medicinal chemist's toolbox, one of the most effective strategies to improve the overall properties of a biologically active compound is bioisosteric replacement. Ever since the first example of replacing benzene with a bicyclo[1.1.1]pentane (BCP) group was published in the late 1990s,[1] the medicinal chemistry community has continually been expanding the scope of such phenyl bioisosteric replacements. Recent interest from academia has focused on novel synthetic strategies to access C(sp3)‐rich bicyclic hydrocarbons with expanded ring sizes. Herein, we summarize some of these transformations and reveal that most rely on strain releasing cycloadditions with bicyclo[1.1.0]butane (BCB) and bicyclo[2.1.0]pentane (housane). We have organized this review based on the mechanism of such strain release strategies, namely, carbene cycloadditions, energy transfer photocatalyzed cycloadditions, electron transfer catalyzed cycloadditions, and polar cycloadditions.
Using craniofacial fluctuating asymmetry to examine the effects of sex, socioeconomic status, and early life experiences on adult age at death in industrial England
Authors: Yaussy Samantha L. 
Published: February 2024

AbstractObjectivesHistorical evidence from 18th‐ and 19th‐century England suggests that industrialization's impacts on health were largely negative, especially among marginalized groups. However, available documentary evidence is often biased toward adult men and rarely sheds light on the experiences of other members of the population, such as women and children. Craniofacial fluctuating asymmetry (FA) can serve as a proxy measurement of developmental instability and stress during development. This study examines the associations among age, sex, socioeconomic status (SES), and FA in skeletal samples from industrial‐era England.Materials and MethodsThe sample for this study comes from four industrial‐era cemeteries from England (A.D. 1711–1857). Geometric morphometric analyses of three‐dimensional landmark coordinate data were used to generate a measure of FA for each individual (Mahalanobis distance). A three‐way ANOVA was used to evaluate the impacts of sex, SES, and FA scores on adult age at death (n = 168).ResultsSignificant associations existed between age at death and SES (p = 0.004) and FA scores (p = 0.094). Comparisons of the estimated means indicated that age at death was consistently higher among high SES individuals and individuals with FA scores less than one standard deviation from the mean.ConclusionsThis study supports findings from previous studies that have suggested that the differences in resource access and environmental buffering generated by socioeconomic inequality can impact longevity and patterns of mortality among socioeconomic status groups. Likewise, stress in early life—evinced by craniofacial fluctuating asymmetry—can influence observed patterns of longevity in adults decades later.