bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dual‐Cascade Responsive Nanoparticles Enhance Pancreatic Cancer Therapy by Eliminating Tumor‐Resident Intracellular Bacteria
Authors: Kang Xiaoxu , Bu Fanqiang , Feng Wenli , Liu Fang , Yang Xuankun , Li Haofei , Yu Yingjie , Li Guofeng , Xiao Haihua , Wang Xing 
Published: September 2022

AbstractThe limited drug penetration and robust bacteria‐mediated drug inactivation in pancreatic cancer result in the failure of chemotherapy. To fight against these issues, a dual‐cascade responsive nanoparticle (sNP@G/IR) that can sequentially trigger deep penetration, killing of intratumor bacteria, and controlled release of chemo‐drug, is reported. sNP@G/IR consists of a hyaluronic acid (HA) shell and glutathione (GSH)‐responsive polymer‐core (NP@G/IR), that encapsulates gemcitabine (Gem) and photothermal agent (IR1048). The polymer core, as an antibiotic alternative, is tailored to exert optimal antibacterial activity and selectivity. sNP@G/IR actively homes in on the tumor due to the CD44 targeting of the HA shell, which is subsequently degraded by the hyaluronidase in the extracellular matrix. The resultant NP@G/IR in decreased size and reversed charge facilitates deep tumor penetration. After cellular endocytosis, the exposed guanidine on NP@G/IR kills intracellular bacteria through disrupting cell membranes. Intracellular GSH further triggers the controlled release of the cargo. Thus, the protected Gem eventually induces cell apoptosis. Under laser irradiation, the hyperthermia of IR1048 helps further elimination of tumors and bacteria. Moreover, sNP@G/IR activates immune response, thereby reinforcing anticancer capacity. Therefore, this dual‐cascade responsive sNP@G/IR eliminates tumor‐resident intracellular bacteria and augments drug delivery efficacy, providing a new avenue for improving cancer therapy.
Engineering of Covalent Organic Framework‐Based Advanced Platforms for Enzyme Immobilization: Strategies, Research Progress, and Prospects
Authors: Wang Shizhao , Xia Xiaocong , Chen Fen‐Er 
Published: September 2022

AbstractDriven by green and sustainable methodologies for chemical manufacturing, enzymes are forecast to have much to prospect in the coming years due to their high activity and selectivity. However, the fragile active spatial‐conformation of an enzyme is predominantly maintained by weak intermolecular interactions, showing quite sensitive to thermal, pH, and chemical chemoreception. Thus, the low activity and recyclability result from structural instability can hardly meet the prototype of green chemistry in commercial process. Covalent organic frameworks (COFs) are stable extended porous network materials assembled by organic linkers in a moderate way. Due to their pre‐designable structures, an enzyme possesses the access to be immobilized to the interior or surface of COF skeletons via covalent or noncovalent processes, which can afford protection to enzymes in harsh conditions. Moreover, with the improved stability and cyclicity, the formed COF/enzyme biocomposites can facilitate broader horizon. Herein, this review mainly canvasses the advances in the emerging field of COF/enzyme biocomposites, sketching the factors that are critical in building COF/enzyme systems and the applications of registered enzyme host platforms reported in recent years.
Bacteriophobic Zwitterionic/Dopamine Coatings for Medical Elastomers
Authors: Texidó Robert , Cabanach Pol , Kaplan Richard , García‐Bonillo Cristina , Pérez Darío , Zhang Shuo , Borrós Salvador , Pena‐Francesch Abdon 
Published: September 2022

AbstractDespite modern advancements in sterilization and medical practices, bacterial infections remain a significant concern in the implantation of medical devices. There is currently an urgent need for long‐lasting and high‐stable strategies to avoid the adhesion of bacteria to the wide range of materials present in medical devices. Here, a versatile methodology to create anti‐biofouling coatings that prevent the adhesion of bacteria to silicone‐based materials used in healthcare is reported. These coatings consist of bifunctional ethylene glycol dimethacrylate as an anchor between a zwitterionic polymer (SBMA), which provides antifouling properties, and a polydopamine layer that operates as an interfacial binder, providing mechanical strength and strong adhesion to elastomeric substrates. The coatings exhibit superhydrophilic and anti‐biofouling properties, creating a strong “bacteriophobic effect” that leads to a >99% reduction in bacterial adhesion. This bacteriophobic coating is successfully implemented and validated in a commercial urinary catheter, reducing bacterial adhesion by 1–2 orders of magnitude and avoiding bacterial colonization to prevent catheter‐associated urinary tract infections. The results presented here demonstrate the versatility, durability, and scalability of the coating methodology for preventing bacterial adhesion in silicone elastomers, which can be easily applied to other elastomeric materials used in medical devices beyond urinary tract infection prevention.
Dual Patterning of Self‐Assembling Spider Silk Protein Nanofibrillar Networks
Authors: Lamberger Zan , Kocourková Karolína , Minařík Antonín , Humenik Martin 
Published: September 2022

AbstractSelf‐assembly of a recombinant spider silk protein into nanofibrillar networks in combination with photolithography is used to produce diversely functionalized micropattern. Amino‐modified substrates coated with a positive tone photoresist are processed into 1 µm deep arbitrarily shaped microwells, at the bottom of which spider silk proteins are covalently coupled to the deprotected aminated surface. The protein layer serves to seed the self‐assembly of nanofibrils from the same protein in the microwells, forming immobilized few nanometers thin networks after the stripping of the photoresist. The nanofibrous micropattern can be functionalized by employing fluorescently modified spider silk variants during the self‐assembly or by later covalent modification with nucleic acids. By repeating the photolithography and fibril assembly procedures, two functionally different and spatially defined pattern are created.
2+δ‐Dimensional Materials via Atomistic Z‐Welding
Authors: Sahu Tumesh Kumar , Motlag Maithilee , Bandyopadhyay Arkamita , Kumar Nishant , Cheng Gary J. , Kumar Prashant 
Published: September 2022

AbstractPivotal to functional van der Waals stacked flexible electronic/excitonic/spintronic/thermoelectric chips is the synergy amongst constituent layers. However; the current techniques viz. sequential chemical vapor deposition, micromechanical/wet‐chemical transfer are mostly limited due to diffused interfaces, and metallic remnants/bubbles at the interface. Inter‐layer‐coupled 2+δ‐dimensional materials, as a new class of materials can be significantly suitable for out‐of‐plane carrier transport and hence prompt response in prospective devices. Here, the discovery of the use of exotic electric field ≈106 V cm−1 (at microwave hot‐spot) and 2 thermomechanical conditions i.e. pressure ≈1 MPa, T ≈ 200 °C (during solvothermal reaction) to realize 2+δ‐dimensional materials is reported. It is found that PzPz chemical bonds form between the component layers, e.g., CB and CN in G‐BN, MoN and MoB in MoS2‐BN hybrid systems as revealed by X‐ray photoelectron spectroscopy. New vibrational peaks in Raman spectra (BC ≈1320 cm–1 for the G‐BN system and MoB ≈365 cm–1 for the MoS2‐BN system) are recorded. Tunable mid‐gap formation, along with diodic behavior (knee voltage ≈0.7 V, breakdown voltage ≈1.8 V) in the reduced graphene oxide‐reduced BN oxide (RGO‐RBNO) hybrid system is also observed. Band‐gap tuning in MoS2‐BN system is observed. Simulations reveal stacking‐dependent interfacial charge/potential drops, hinting at the feasibility of next‐generation functional devices/sensors.
Revealing the Electrophilic‐Attack Doping Mechanism for Efficient and Universal p‐Doping of Organic Semiconductors
Authors: Guo Jing , Liu Ying , Chen Ping‐An , Wang Xinhao , Wang Yanpei , Guo Jing , Qiu Xincan , Zeng Zebing , Jiang Lang , Yi Yuanping , Watanabe Shun , Liao Lei , Bai Yugang , Nguyen Thuc‐Quyen , Hu Yuanyuan 
Published: September 2022

AbstractDoping is of great importance to tailor the electrical properties of semiconductors. However, the present doping methodologies for organic semiconductors (OSCs) are either inefficient or can only apply to some OSCs conditionally, seriously limiting their general applications. Herein, a novel p‐doping mechanism is revealed by investigating the interactions between the dopant trityl tetrakis(pentafluorophenyl) borate (TrTPFB) and poly(3‐hexylthiophene) (P3HT). It is found that electrophilic attack of the trityl cations on thiophenes results in the formation of tritylated thiophenium ions, which subsequently induce electron transfer from neighboring P3HT chains to realize p‐doping. This unique p‐doping mechanism enables TrTPFB to p‐dope various OSCs including those with high ionization energy (IE ≈ 5.8 eV). Moreover, this doping mechanism endows TrTPFB with strong doping capability, leading to doping efficiency of over 80% in P3HT. The discovery and elucidation of this novel doping mechanism not only points out that strong electrophiles are a class of efficient p‐dopants for OSCs, but also provides new opportunities toward highly efficient doping of various OSCs.
Quantitative and Real‐Time Evaluation of Human Respiration Signals with a Shape‐Conformal Wireless Sensing System
Authors: Chen Sicheng , Qian Guocheng , Ghanem Bernard , Wang Yongqing , Shu Zhou , Zhao Xuefeng , Yang Lei , Liao Xinqin , Zheng Yuanjin 
Published: September 2022

AbstractRespiration signals reflect many underlying health conditions, including cardiopulmonary functions, autonomic disorders and respiratory distress, therefore continuous measurement of respiration is needed in various cases. Unfortunately, there is still a lack of effective portable electronic devices that meet the demands for medical and daily respiration monitoring. This work showcases a soft, wireless, and non‐invasive device for quantitative and real‐time evaluation of human respiration. This device simultaneously captures respiration and temperature signatures using customized capacitive and resistive sensors, encapsulated by a breathable layer, and does not limit the user's daily life. Further a machine learning‐based respiration classification algorithm with a set of carefully studied features as inputs is proposed and it is deployed into mobile clients. The body status of users, such as being quiet, active and coughing, can be accurately recognized by the algorithm and displayed on clients. Moreover, multiple devices can be linked to a server network to monitor a group of users and provide each user with the statistical duration of physiological activities, coughing alerts, and body health advice. With these devices, individual and group respiratory health status can be quantitatively collected, analyzed, and stored for daily physiological signal detections as well as medical assistance.
Toward Excellence in Photocathode Engineering for Photoelectrochemical CO2 Reduction: Design Rationales and Current Progress
Authors: Putri Lutfi Kurnianditia , Ng Boon‐Junn , Ong Wee‐Jun , Chai Siang‐Piao , Mohamed Abdul Rahman 
Published: September 2022

AbstractPhotoelectrochemical CO2 reduction reaction (PEC CO2RR) is a promising technology which offers the possibility of a carbon‐neutral solar fuel production via artificial photosynthesis. The challenging proton‐coupled multielectron transfers with high energy barriers in CO2RR however pose as a huge hindrance to the technology, which demands strict specifications in the design of photocathode materials so as to improve PEC performances. This review underscores effective design strategies and current material progress for the judicious assembly of photocathode materials for CO2RR. The review begins with elucidating the fundamental principles of CO2 reduction process and photocathode electrochemistry. Based on these, the design criteria and trade‐offs in the design of PEC CO2RR photocathodes are highlighted. The various promotive strategies for photocathodes and their underlying rationales such as doping, defect engineering, nanostructuring, cocatalyst loading, passivation, heterojunction formation, and innovative multijunction configurations are further outlined and design propositions in the area are provided. Following that, various photocathode semiconductor materials categorized into photovoltaic (PV) grade (silicon, III–V semiconductors, chalcogenides) and non‐PV grade (metal oxides) materials are summarized and extensively discussed, along with their recent advances. Finally, perspectives on the design of photocathodes for CO2RR and new paradigms in the field are put forward.
Missing data in bioarchaeology II: A test of ordinal and continuous data imputation
Authors: Wissler Amanda , Blevins Kelly E. , Buikstra Jane E. 
Published: September 2022

AbstractObjectivesPrevious research has shown that while missing data are common in bioarchaeological studies, they are seldom handled using statistically rigorous methods. The primary objective of this article is to evaluate the ability of imputation to manage missing data and encourage the use of advanced statistical methods in bioarchaeology and paleopathology. An overview of missing data management in biological anthropology is provided, followed by a test of imputation and deletion methods for handling missing data.Materials and MethodsMissing data were simulated on complete datasets of ordinal (n = 287) and continuous (n = 369) bioarchaeological data. Missing values were imputed using five imputation methods (mean, predictive mean matching, random forest, expectation maximization, and stochastic regression) and the success of each at obtaining the parameters of the original dataset compared with pairwise and listwise deletion.ResultsIn all instances, listwise deletion was least successful at approximating the original parameters. Imputation of continuous data was more effective than ordinal data. Overall, no one method performed best and the amount of missing data proved a stronger predictor of imputation success.DiscussionThese findings support the use of imputation methods over deletion for handling missing bioarchaeological and paleopathology data, especially when the data are continuous. Whereas deletion methods reduce sample size, imputation maintains sample size, improving statistical power and preventing bias from being introduced into the dataset.
Impaired B Cell Expression of the Inhibitory Fcγ Receptor IIB in Myasthenia Gravis
Authors: Keller Christian W. , Chuquisana Omar , Derdelinckx Judith , Gross Catharina C. , Berger Klaus , Robinson James , Nimmerjahn Falk , Wiendl Heinz , Willcox Nick , Lünemann Jan D. 
Published: September 2022

Myasthenia gravis (MG) is an autoimmune disease in which pathogenic immunoglobulin G antibodies bind to acetylcholine receptors (or to functionally related molecules at the neuromuscular junction). B cell expression of the inhibitory immunoglobulin G receptor, Fc‐gamma receptor (FcγR) IIB, maintains peripheral immune tolerance, and its absence renders B cells hyperresponsive to autoantigen. Here, we report that FcγRIIB expression levels are substantially reduced in B lineage cells derived from immunotherapy‐naïve patients with acetylcholine receptor antibody‐positive early‐onset MG. In contrast, genetic variants associated with impaired FcγRIIB expression are not enriched in MG, indicating post‐transcriptional dysregulation. FcγR‐targeted therapies could have therapeutic benefits in MG. ANN NEUROL 2022;92:1046–1051
sp2 to sp3 Hybridization Transformation in Ionic Crystals under Unprecedentedly Low Pressure
Authors: Jiang Xingxing , Molokeev Maxim S. , Wang Naizheng , Wang Yonggang , Wen Ting , Dong Zhichao , Liu Youquan , Li Wei , Lin Zheshuai 
Published: September 2022

AbstractUnder cold pressure sp1/sp2‐to‐sp3 hybridization transformation has been exclusively observed in covalent or molecular crystals overwhelmingly above ≈10 GPa, and the approaches to lower the transition pressure are limited on external heat‐treatment and/or catalyzers. Herein we demonstrate that, by internal‐lattice stress‐transfer from ionic to covalent groups, the transformation can be significantly prompted, as shown in a crystal of LiBO2 under 2.85 GPa for the first case in ionic crystals. This unprecedentedly low transformation pressure is ascribed to the enhanced localized stress on covalent B−O frames transferred from ionic Li−O bonds in LiBO2, and accordingly the corresponding structural feature is summarized. This work provides an internal structural regulation strategy for pressure‐reduction of the s‐p orbital hybridization transformation and extends the sp1/sp2‐to‐sp3 transformation landscape from molecular and covalent compounds to ionic systems.
3D Blockage Mapping for Identifying Familial Point Mutations in Single Amyloid‐β Peptides with a Nanopore
Authors: Xin Kai‐Li , Hu Zheng‐Li , Liu Shao‐Chuang , Li Xin‐Yi , Li Jun‐Ge , Niu Hongyan , Ying Yi‐Lun , Long Yi‐Tao 
Published: September 2022

AbstractAccurate discrimination of amyloid‐β (Aβ) peptides containing familial point mutations would advance the knowledge of their roles in early‐onset Alzheimer's disease. Herein, we simultaneously identified the mutant A21G, E22G, E22Q, and the wild‐type (WT) Aβ18–26 peptides with aerolysin nanopore using a 3D blockage mapping strategy. The standard deviation of current blockade fluctuations (σb) was proposed as a new supplement to current blockage (Ib/I0) and duration time (tD) to profile the blockage characteristics of single molecules. Although the WT and A21G Aβ18‐26 are indistinguishable in a traditional Ib/I0‐tD 2D description, ∼87 % of the blockade events can be accurately classified with half reduction of false identification using a combination of Ib/I0, tD, and σb. This work offers an easy and reliable strategy to promote nanopore sensitivity of peptide mutants, leading to a more precise analysis of pathogenic mutations for developing effective diagnosis and treatment.
Targeted Singlet Oxygen Delivery: A Bioorthogonal Metabolic Shunt Linking Hypoxia to Fast Singlet Oxygen Release
Authors: Wu Hao , Wang Lei , Wang Yang , Shao Yujie , Li Guangzhe , Shao Kun , Akkaya Engin U. 
Published: September 2022

AbstractSinglet oxygen can be generated by thermal cycloreversion of aromatic endoperoxides. However, for any practical potential of chemically generated singlet oxygen within a therapeutic context, the time and place of the release of this cytotoxic species must be tightly regulated. We now show that using a bimodular design with a hypoxia responsive unit and fluoride‐triggered endoperoxide unit, a bioorthogonal metabolic shunt can be established, where an enzymatically generated submicromolar fluoride signal plays a crucial role. Thus, cellular nitroreductase is repurposed in a bioorthogonal enzymatic activity, where it releases fluoride ions upon the reduction of a targeted compound. The fluoride ions released in the initial reaction remove the silyl stopper, yielding a highly accelerated release of singlet oxygen. The result is a remarkable difference in cytotoxicity between hypoxic and normoxic conditions as evidenced by microscopy, viability assays and the use of control compounds.
Temperature‐Controlled Mechanochemistry for the Nickel‐Catalyzed Suzuki–Miyaura‐Type Coupling of Aryl Sulfamates via Ball Milling and Twin‐Screw Extrusion.**
Authors: Bolt Robert R. A. , Raby‐Buck Sarah E. , Ingram Katharine , Leitch Jamie A. , Browne Duncan L. 
Published: September 2022

AbstractThe use of temperature‐controlled mechanochemistry to enable the mechanochemical nickel‐catalyzed Suzuki–Miyaura coupling is herein described. Transitioning from a capricious room‐temperature protocol, through to a heated, PID‐controlled programmable jar heater manifold was required to deliver an efficient method for the coupling of aryl sulfamates (derived from ubiquitous phenols) and aryl boronic acid species. Furthermore, this process is conducted using a base‐metal nickel catalyst, in the absence of bulk solvent, and in the absence of air/moisture sensitive reaction set‐ups. This methodology is showcased through translation to large‐scale twin‐screw extrusion methodology enabling 200‐fold scale increase, producing decagram quantities of C−C coupled material.
Ti‐doped CeO2 Stabilized Single‐Atom Rhodium Catalyst for Selective and Stable CO2 Hydrogenation to Ethanol
Authors: Zheng Ke , Li Yufeng , Liu Bing , Jiang Feng , Xu Yuebing , Liu Xiaohao 
Published: September 2022

AbstractDevelopment of effective and stable catalysts for CO2 hydrogenation into ethanol remains a challenge. Herein, we report that Rh1/CeTiOx single‐atom catalyst constructed by embedding monoatomic Rh onto Ti‐doped CeO2 support has shown a super high ethanol selectivity (≈99.1 %), record‐breaking turnover frequency (493.1 h−1), and outstanding stability. Synergistic effects of Ti‐doption and monoatomic Rh contribute to this excellent catalytic performance by firstly facilitating oxygen vacancies formation to generate oxygen‐vacancy‐Rh Lewis‐acid‐base pairs, which favor CO2 adsorption and activation, cleavage of C−O bonds in CHxOH* and COOH* into CHx* and CO* species, subsequent C−C coupling and hydrogenation into ethanol, and secondly generating strong Rh−O bond by Ti‐doping‐induced crystal reconstruction, which contributes to striking stability. This work highlights the importance of support elaborating regulation for single‐atom catalyst design to substantially improve the catalytic performance.
Regioselective Access to Vicinal Diamines by Metal‐Free Photosensitized Amidylimination of Alkenes with Oxime Esters
Authors: Zheng Yu , Wang Zhu‐Jun , Ye Zhi‐Peng , Tang Kai , Xie Zhen‐Zhen , Xiao Jun‐An , Xiang Hao‐Yue , Chen Kai , Chen Xiao‐Qing , Yang Hua 
Published: September 2022

AbstractA metal‐free photosensitized protocol for regioselective diamination of alkene feedstocks over a single step was developed based on the rationally designed bifunctional diamination reagent, thus affording a range of differentially protected 1,2‐diamines in moderate to high yields. Mechanistic studies reveal that the reaction is initiated with a triplet‐triplet energy transfer between thioxanthone catalyst and diamination reagent, followed by fragmentation to simultaneously generate long‐lived iminyl radical and transient amidyl radical. The excellent regioselectivity presumably stems from the large reactivity difference between two different N‐centered radical species. This protocol is characterized by excellent regioselectivity, broad functional group tolerance, and mild reaction conditions, which would enrich the diversity and versatility of facilitate the diversity‐oriented synthesis of 1,2‐diamine‐containing complex molecule scaffolds.
Conferring BiVO4 Nanorods with Oxygen Vacancies to Realize Enhanced Sonodynamic Cancer Therapy
Authors: Yang Zhuang , Yuan Meng , Liu Bin , Zhang Wenying , Maleki Aziz , Guo Baolin , Ma Ping'an , Cheng Ziyong , Lin Jun 
Published: September 2022

AbstractOwing to the high depth of tissue penetration, non‐invasiveness, and controllability, ultrasound (US)‐mediated sonodynamic therapy (SDT) has shown broad application prospects for tumor treatment. However, the electron‐hole separation inefficiency of sonosensitizers and the tumor hypoxia remain two major challenges limiting the effect of SDT. Here, ultrafine photoetched bismuth vanadate (BiVO4) nanorods modified with DSPE‐PEG2000 (PEBVO@PEG NRs) were fabricated to achieve in situ self‐supply of oxygen (O2) and reactive oxygen species (ROS) for hypoxic tumor therapy. The photoetching approach could enhance the charge separation by inducing enriched oxygen vacancies on the surface of BiVO4, thereby improving the generation efficiency of ROS and O2. The PEBVO@PEG overcome the main obstacles of traditional sonosensitizers in the SDT process and show promising sonodynamic therapeutic effects, thus providing new strategies for improving the performance of sonosensitizer and hypoxic tumor elimination.