bluuebunny/crossref_metadata_2025 huggingface dataset:
Buprenorphine-Precipitated Withdrawal Among Hospitalized Patients Using Fentanyl
Authors: Thakrar Ashish P. , Christine Paul J. , Siaw-Asamoah Andrew , Spadaro Anthony , Faude Sophia , Snider Christopher K. , Delgado M. Kit , Lowenstein Margaret , Kampman Kyle , Perrone Jeanmarie , Nelson Lewis S. , Kilaru Austin S.
Published: September 2024

Importance

Buprenorphine treatment of opioid use disorder (OUD) is safe and effective, but opioid withdrawal during treatment initiation is associated with poor retention in care. As fentanyl has replaced heroin in the drug supply, case reports and surveys have indicated increased concern for buprenorphine-precipitated withdrawal (PW); however, some observational studies have found a low incidence of PW.

Objective

To estimate buprenorphine PW incidence and assess factors associated with PW among emergency department (ED) or hospitalized patients.

Design, Setting, and Participants

This retrospective cohort study at 3 academic hospitals in Philadelphia, Pennsylvania, included adults with OUD who underwent traditional or high-dose buprenorphine initiation between January 1, 2020, and December 31, 2021. Exclusion criteria included low-dose buprenorphine initiation and missing documentation of opioid withdrawal severity within 4 hours of receiving buprenorphine.

Exposure

Buprenorphine initiation with an initial dose of at least 2 mg of sublingual buprenorphine after a Clinical Opiate Withdrawal Scale (COWS) score of 8 or higher. Additional exposures included 4 predefined factors potentially associated with PW: severity of opioid withdrawal before buprenorphine (COWS score of 8-12 vs ≥13), initial buprenorphine dose (2 vs 4 or ≥8 mg), body mass index (BMI) (<25 vs 25 to <30 or ≥30; calculated as weight in kilograms divided by height in meters squared), and urine fentanyl concentration (0 to <20 vs 20 to <200 or ≥200 ng/mL).

Main Outcome and Measures

The main outcome was PW incidence, defined as a 5-point or greater increase in COWS score from immediately before to within 4 hours after buprenorphine initiation. Logistic regression was used to estimate the odds of PW associated with the 4 aforementioned predefined factors.

Results

The cohort included 226 patients (150 [66.4%] male; mean [SD] age, 38.6 [10.8] years). Overall, 26 patients (11.5%) met criteria for PW. Among patients with PW, median change in COWS score was 9 points (IQR, 6-13 points). Of 123 patients with confirmed fentanyl use, 20 (16.3%) had PW. In unadjusted and adjusted models, BMI of 30 or greater compared with less than 25 (adjusted odds ratio [AOR], 5.12; 95% CI, 1.31-19.92) and urine fentanyl concentration of 200 ng/mL or greater compared with less than 20 ng/mL (AOR, 8.37; 95% CI, 1.60-43.89) were associated with PW.

Conclusions and Relevance

In this retrospective cohort study, 11.5% of patients developed PW after buprenorphine initiation in ED or hospital settings. Future studies should confirm the rate of PW and assess whether bioaccumulated fentanyl is a risk factor for PW.
Prehospital Intervention Among Black Patients With Traumatic Injury in Los Angeles County
Authors: Loss Lindsey , Schreiber Martin , Matsushima Kazuhide , Tinoco-Garcia Luis , Ding Li , Inaba Kenji , Henry Reynold
Published: September 2024

This cohort study examined the differences in prehospital treatment received by patients with traumatic injury belonging to different racial and ethnic groups between 2013 and 2020 in Los Angeles County.
Pilot study: Evaluating the feasibility of real‐time kinematic GNSS as a tool for tracking movable chairs in outdoor urban public spaces
Authors: Chheang Kim , Ohmura Ren , Karashima Kazuki , Hatayama Yosuke , Matsuo Kajiro , Mizutani Akihiro , Ono Haruka
Published: September 2024

As urban public spaces evolve to accommodate human activities, there arises a pressing need for effective methodologies to understand public life within these environments. This pilot study assesses the accuracy of the Real‐Time Kinematic Global Navigation Satellite System (RTK GNSS) in the Toyohashi South Side Station Square, aiming to validate its utility as a privacy‐sensitive tool for studying public life, particularly in tracking movable chairs in urban settings. The findings indicate that RTK GNSS exhibits sufficient accuracy in recording the positions of movable chairs, thus facilitating public life studies. Given the variability of GNSS accuracy across environments, we propose the Silhouette Index as a metric for evaluating GNSS suitability across different scales. A Silhouette Index exceeding 0.9 signifies highly accurate data, suitable for comprehending the spatial arrangement and utilization of movable chairs in compact urban spaces. Conversely, an index below 0.8 indicates insufficient accuracy for this purpose. Nevertheless, RTK GNSS, akin to GPS, offers diverse applications in urban research. It can aid in analyzing pedestrian flows in city centers or expansive parks, as well as elucidating spatial behavioral patterns among distinct demographic groups in large‐scale urban public spaces.
Use of Monte Carlo Simulation in XRF Analysis
Authors: Brunetti Antonio
Published: September 2024

X‐ray fluorescence (XRF) is a well‐established nondestructive analytical technique that allows for the characterization of the chemical contents of the specimen examined. Furthermore, it can be made portable and therefore usable for samples that cannot be brought to the laboratory. Despite its great versatility, characterizing samples from the standpoint of elemental content becomes challenging when dealing with complex and irregular structures. In such cases, analytical quantification algorithms struggle, sometimes yielding unreliable results. An alternative to these algorithms is provided by Monte Carlo algorithms, which enable simulation with a level of detail surpassing that achievable with analytical algorithms. They encompass the entire experiment, including the sample's structure and composition. However, the time required to obtain accurate quantification, typically much longer than the measurement time, may pose an insurmountable limit to their practical use. This work will describe and discuss the use of Monte Carlo algorithms for XRF analysis, their performance, and their limitations.
Multi‐Functional Gelatin‐Dithiolane Hydrogels for Tissue Engineering
Authors: Asim Saad , Tuftee Cody , Qureshi Asma Talib , Callaghan Rachel , Geary Moira L. , Santra Mithun , Pal Vaibhav , Namli Ilayda , Yam Gary Hin‐Fai , Ozbolat Ibrahim T. , Rizwan Muhammad
Published: September 2024

Biomaterials that integrate multiple functionalities, mimic the extracellular matrix (ECM) microenvironment to support cellular growth, and adhere robustly to damaged tissues are highly needed to advance tissue engineering. Protein‐based biomaterials are promising due to their inherent biocompatibility, biomimicry, biodegradation, and cell‐supportive properties. Herein, by leveraging the unique ability of dithiolanes to generate on‐demand in situ thiols, a new class of dithiolane‐modified, protein‐based biomaterial that combines unique, seemingly opposing functions for tissue engineering is developed. Dithiolane‐modified gelatin, a model protein used herein, enabled photoinitiator‐free photo‐crosslinking to form multi‐functional gelatin‐dithiolane (GelDT) hydrogels, which displayed exceptional long‐term stability in cell culture media (>28 days) to support the growth of both surface‐seeded and encapsulated cells. GelDT hydrogels allowed pre‐gelation tuning of biomechanical properties and biodegradation via introducing physical crosslinks, and post‐gelation tuning of matrix stress‐relaxation rate, via responding to exogenous thiols, independently of other parameters. Furthermore, GelDT enabled covalent immobilization of bio‐active molecules, glutathione‐responsive drug release, supported efficient 3D bioprinting due to its shear‐thinning ability, and demonstrated robust tissue adhesion in various contexts (bare skin, ex‐vivo, in‐vivo) due to covalent disulfide coupling with endogenous tissue thiols. Together, this study presents a novel multi‐responsive and multi‐functional protein‐based biomaterial, anticipated to advance tissue engineering and regeneration.
Epitaxial Growth of PdH@Ru Hollow Nanobamboos for Efficient Hydrogen Evolution in Anion Exchange Membrane Electrolyzer
Authors: Jiang Xian , Wang Yufei , Ding Jiaqian , Wang Caikang , Tang Yawen , Cao Yingnan , Wang Wenchao , Fu Gengtao
Published: September 2024

In‐depth comprehension and improvement of the sluggish hydrogen evolution kinetics in alkaline media is highly important to enhance the activity and durability of anion exchange membrane water electrolysis (AEMWE) for green hydrogen production. Herein, a hydrogen atom‐terminated core–shell PdH@Ru nanobamboos (NBs) is developed by the synergetic strategy of epitaxial growth and in situ DMF hydrogenation. The synthesized PdH@Ru NBs demonstrate exceptional activity for hydrogen evolution reaction (HER) in alkaline media, requiring only a 14 mV overpotential at the 10 mA cm−2, surpassing those of commercial Pt/C (35 mV) and H‐free Pd@Ru NBs (37 mV). Furthermore, an AEMWE device using PdH@Ru NBs as the cathode also achieves the current density of 1000 mA cm−2 at ≈1.80 V in 1.0 m KOH at 60 °C, with continuous operation for 50 h. The operando spectroscopic analysis and density functional theory calculations suggest that hydrogen insertion into the Pd@Ru NBs induces tensile strain on the Ru surface layer, altering the Pd/Ru electronic structure and weakening H adsorption, thereby enhancing the HER efficiency. The bamboo‐like hollow structure features numerous active sites, which contribute to the optimization of electron/mass diffusion in the alkaline electrolyte. This work provides a potential high‐efficiency cathodic electrocatalyst for industrial hydrogen production.
Elastocaloric Heat Pump by Twist Induced Periodical Non‐Linear Stress for Low Hysteresis and High Carnot Efficiency
Authors: Xiao Yicheng , Mei Guangkai , Feng Danyang , Zhao Wubin , Guo Wenjin , Leng Xueqi , Qian Dong , Zhao Weiqiang , Bai Jie , Wang Zongqian , Zhu Meifang , Zhou Xiang , Liu Zunfeng
Published: September 2024

Elastocaloric cooling is one of the most promising solid‐state cooling approaches to address the issues of energy shortage and global warming. However, the cooling efficiency and cycle life of this technology need to be improved, and the required driving force shall be reduced. Here, a novel elastocaloric heat pump by periodic non‐linear stress is developed by employing fiber twisting and separated cooling and heating media. The non‐linear stress generated by fiber twisting yields a hierarchical, rigid‐yet‐flexible architecture and a periodic entropy spatial distribution, which result in a low mechanical hysteresis work and a high cooling efficiency (a maximum material coefficient of performance (COP) of 30.8 and a maximum Carnot efficiency of 82%). The torsional non‐linear stress inhibits crack propagation and results in a highly extended cycle life (14752 cycles, more than ten times of fiber stretching). The heat pump exhibits a maximum average temperature span of 25.6 K, a maximum specific cooling power of 1850 W Kg−1, a maximum device COP of 19.5, and a maximum device power of 5.0 W, under each optimal condition.
Controlling the Relaxation Dynamics of Polymer Networks by Combining Associative and Dissociative Dynamic Covalent Bonds
Authors: Cornellà Aleix Costa , Furia Francesca , Van Assche Guy , Brancart Joost
Published: September 2024

Dynamic polymer networks offer a promising solution to key challenges in polymers such as recyclability, processability, and damage repair. However, the trade‐off between combining facile processability, fast self‐healing, and high creep resistance remains a major obstacle to implementation. To overcome this, two very distinct dynamic covalent chemistries, Diels–Alder and transesterification, is combined in a single network. The resulting dual dynamic networks offer an unprecedented set of properties and control over the relaxation times. The system decouples the relaxation dynamics of the network from the spatial motifs, and the tuning of the ratio between chemistries enables to control of the relaxation dynamics over six orders of magnitude. Taking advantage of this control, the composition and rheological behavior is optimized to drastically improve the resolution for extrusion‐based additive manufacturing of dynamic covalent networks. Additionally, two well‐defined and separated stress relaxation peaks are observed at compositions close to 50% of each dynamic chemistry, accentuating the double character of the system's relaxation dynamics. This atypical situation, enables to preparation of self‐healing materials with negligible creep, and with shape‐memory properties solely leveraging the two distinct relaxation dynamics, instead of the glass transition temperature or the melting point.
Ultrafast Intramolecular Singlet Fission in Homoconjugated Oligomers of Azapentacene with Rigid Connecting Unit
Authors: Kong Wei , Chen Hong , Li Jiaxin , Zhao Yilun , Deng Junpeng , Chen Wangqiao , Ma Lin
Published: September 2024

A novel series of homoconjugated oligomers of azapentacene, linked via the rigid connecting unit bicyclo[2.2.2]octane bridge is presented. The investigation delves into intramolecular singlet fission (iSF) within these dimeric and trimeric frameworks, employing various time‐resolved spectroscopies and quantum chemical calculations. Combining the merits of both through‐space and through‐bond couplings between the constituent chromophores within these rigid homoconjugated structures, iSF proceeds within a few picoseconds, exhibiting a 2–3 orders of magnitude acceleration compared to traditional covalently linked oligomers and achieving an iSF efficiency approaching unity. In the homoconjugated trimer, the larger interplanar angle between neighboring chromophores leads to a relatively slower iSF rate compared to that of the homoconjugated dimer. Furthermore, the active involvement of the charge transfer state is demonstrated to accelerate the iSF process in the trimer, while exerting no influence on the iSF process in the dimer. The study provides novel avenues for investigating the influence of molecular geometry on singlet fission and reveals the crucial role of the interplay between spatial and covalent coupling in facilitating intramolecular singlet fission.
A Wireless‐Driven Electric Responsive Long‐Lived Room Temperature Phosphorescent Switching Device
Authors: Yan Yan , Wang Yuyang , Wei Jinbei , Zhu Jinbao , Shen Ruipeng , Feng Yuliang , Zhang Weiran , Liu Xuesong , Wang Pengfei , Wang Hualiang , Zhang Yu‐Mo , Zhang Sean Xiao‐An , Lin Tingting
Published: September 2024

Long‐lived room temperature phosphorescent (RTP) materials have prospective applications, but endowing long‐lived RTP materials with on‐off regulation property is challenging. Here, the first electric responsive long‐lived RTP switching device under photoexcitation with a wireless power transmission (WPT) system is demonstrated. It exhibits long persistent phosphorescence (180.1 ms for the film and 180.8 ms for the device) and excellent reversibility (>1000 cycles). Due to the effective dual‐state Förster resonance energy transfer (FRET) process from the triplet and singlet states of the chromophore donor to the singlet state of the dye acceptor, the devices exhibit switching characteristics. The appearance of the dye's absorption can be modulated by electro‐acid based on proton‐coupled electron transfer (PCET) mechanism, resulting in the device being electrically controlled. In addition, by integrating WPT coils outside the device, it can be driven wirelessly, thereby overcoming the reliance on electrical stimulation methods on the power supply. Finally, due to the multiple switching characteristics (color, fluorescence, phosphorescence) of this device, it is successfully applied in anti‐counterfeiting and information encryption.
Metal Centers Drive Selectivity of Electrocatalytic Oxygen Reduction Reaction Promoted by Tetrapyrazinoporphyrazine Complexes
Authors: Sordello Fabrizio , Azzi Emanuele , Pellegrino Francesco , Deagostino Annamaria , Renzi Polyssena
Published: September 2024

Fuel cells represent a promising technology for the future decarbonization of the mobility sector. However, the efficient use of H2 and O2 to produce electricity still requires noble metal catalysts such as platinum and ruthenium. In particular, the Oxygen Reduction Reaction (ORR) is complex and limiting due to its mechanism, which involves the transfer of four electrons and four protons to produce water. The search for alternative catalysts exhibiting high selectivity is progressing at a rapid pace. In this context, this group previously unveiled a homogeneous catalyst based on titanium‐centered tetrapyrazinoporphyrazines (TPyzPz) for the ORR, noting a certain modularity in the selectivity toward either a two‐ or four‐electron reduction reaction. In this study, the influence of different metal centers (magnesium (Mg), cobalt (Co), copper (Cu), and zinc (Zn)) and various substituents is investigated on the tetrapyrazinoporphyrazine ring. The findings indicate a strong dependence of activity and selectivity on these modifications. Notably, cobalt and copper catalysts exhibit a selectivity greater than 90% toward H2O production in the ORR. However, alterations to the macrocycle structure significantly affected the reactivity of these catalysts. These new insights highlighted the importance of careful structural design in the development of the next generation of ORR catalysts.
Exploiting Spatial Ionic Dynamics in Solid‐State Organic Electrochemical Transistors for Multi‐Tactile Sensing and Processing
Authors: Hou Kunqi , Chen Shuai , John Rohit Abraham , He Qiang , Zhou Zhongliang , Mathews Nripan , Lew Wen Siang , Leong Wei Lin
Published: September 2024

The human nervous system inspires the next generation of sensory and communication systems for robotics, human‐machine interfaces (HMIs), biomedical applications, and artificial intelligence. Neuromorphic approaches address processing challenges; however, the vast number of sensors and their large‐scale distribution complicate analog data manipulation. Conventional digital multiplexers are limited by complex circuit architecture and high supply voltage. Large sensory arrays further complicate wiring. An ʻin‐electrolyte computingʼ platform is presented by integrating organic electrochemical transistors (OECTs) with a solid‐state polymer electrolyte. These devices use synapse‐like signal transport and spatially dependent bulk ionic doping, achieving over 400 times modulation in channel conductance, allowing discrimination of locally random‐access events without peripheral circuitry or address assignment. It demonstrates information processing from 12 tactile sensors with a single OECT output, showing clear advantages in circuit simplicity over existing all‐electronic, all‐digital implementations. This self‐multiplexer platform offers exciting prospects for circuit‐free integration with sensory arrays for high‐quality, large‐volume analog signal processing.
Tumor Microenvironment Activated Cu Crosslinked Near‐Infrared Sonosensitizers for Visualized Cuproptosis‐Enhanced Sonodynamic Cancer Immunotherapy
Authors: Hu Jinyan , Yan Lang , Cao Zhi , Geng Bijiang , Cao Xiqian , Liu Bing , Guo Jiaming , Zhu Jiangbo
Published: September 2024

Reactive oxygen species (ROS)‐mediated sonodynamic therapy (SDT) holds increasing potential in treating deep‐seated tumor owing to the high tissue‐penetration depth. However, the inevitable accumulation of sonosensitizers in normal tissues not only make it difficult to realize the in situ SDT, but also induces sonodynamic effects in normal tissues. Herein, this work reports the passivation and selective activation strategies for the sonodynamic and near‐infrared (NIR) imaging performances of an intelligent antitumor theranostic platform termed Cu‐IR783 nanoparticles (NPs). Owing to the ruptured coordination bond between IR783 with Cu ions by responding to tumor microenvironment (TME), the selective activation of IR783 only occurred in tumor tissues to achieve the visualized in‐situ SDT. The tumor‐specific released Cu ions not only realized the cascade amplification of ROS generation through Cu+‐mediated Fenton‐like reaction, but also triggered cuproptosis through Cu+‐induced DLAT oligomerization and mitochondrial dysfunction. More importantly, the immunosuppressive TME can be reversed by the greatly enhanced ROS levels and high‐efficiency cuproptosis, ultimately inducing immunogenic cell death that promotes robust systemic immune responses for the eradication of primary tumors and suppression of distant tumors. This work provides a distinct paradigm of the integration of SDT, CDT, and cuproptosis in a controlled manner to achieve visualized in‐situ antitumor therapy.
Foams with 3D Spatially Programmed Mechanics Enabled by Autonomous Active Learning on Viscous Thread Printing
Authors: Emery Brett , Snapp Kelsey L. , Revier Daniel , Sarkar Vivek , Nakura Masa , Brown Keith A. , Lipton Jeffrey Ian
Published: September 2024

Foams are versatile by nature and ubiquitous in a wide range of applications, including padding, insulation, and acoustic dampening. Previous work established that foams 3D printed via Viscous Thread Printing (VTP) can in principle combine the flexibility of 3D printing with the mechanical properties of conventional foams. However, the generality of prior work is limited due to the lack of predictable process‐property relationships. In this work, a self‐driving lab is utilized that combines automated experimentation with machine learning to identify a processing subspace in which dimensionally consistent materials are produced using VTP with spatially programmable mechanical properties. In carrying out this process, an underlying self‐stabilizing characteristic of VTP layer thickness is discovered as an important feature for its extension to new materials and systems. Several complex exemplars are constructed to illustrate the newly enabled capabilities of foams produced via VTP, including 1D gradient rectangular slabs, 2D localized stiffness zones on an insole orthotic and living hinges, and programmed 3D deformation via a cable‐driven humanoid hand. Predictive mapping models are developed and validated for both thermoplastic polyurethane (TPU) and polylactic acid (PLA) filaments, suggesting the ability to train a model for any material suitable for material extrusion (ME) 3D printing.
Wild introgression as an effective tool for aiding the expansion and adaptation of cultivated safflower
Authors: Majidi Mohammad Mahdi , Pirnajmedin Fatemeh , Espanani Soheila
Published: September 2024

Safflower is a multipurpose crop grown in different regions, mainly for its high oil quality. Crop wild relatives serve as a valuable reservoir of genes that have been depleted due to evolutionary bottlenecks, which are poorly applied in safflower. During the last decade, we developed three populations from hybridization of safflower with its wild relatives and selected the superior lines to develop new varieties. From each of three different interspecific populations (TP: Carthamus tinctorius × Carthamus palaestinus, PO: C. palaestinus × Carthamus oxyacantha, and TO: C. tinctorius × C. oxyacantha), 10 genotypes were selected (a total of 30 lines) in the “F8” generation and were evaluated along with their parents (T, P, and O) and one control cultivar (Golsfid) at the field during 2019–2022 to assess genetic variation, estimate genetic parameters, and evaluate the stability. Considerable genetic variability for oil, seed yield, and other agronomic traits between and within the interspecific populations suggests the high potential of these new recombinant lines for introducing beneficial alleles. Our results indicated that recombinant inbred lines derived from the hybridization of TP were superior in terms of seed yield, oil content, and stability parameters. The use of stability indices of Wricke, Lin and Binns, Eberhart and Russell, and HMRPGVi, along with the biplot analysis, allowed the identification of preferable and stable safflower genotypes. Moderately high values of heritability were found for yield‐related traits. New recombinant lines can be introduced to the safflower gene pool to improve the genetic base of this valuable oil seed crop.
Violating Lorentz Invariance Minimally by the Emergence of Nonmetricity? A Perspective
Authors: Obukhov Yuri N. , Hehl Friedrich W.
Published: September 2024

Lorentz invariance belongs to the fundamental symmetries of nature. It is basic for the successful Standard Model of Particle Physics. Nevertheless, within the last decades, Lorentz invariance has been repeatedly questioned. In fact, there exist different research programs addressing this problem. It is argued that a most adequate understanding of a possible violation of Lorentz invariance is achieved in the framework of the gauge‐theoretic approach to gravity: a non‐vanishing nonmetricity of a metric‐affine geometry of spacetime heralds the violation of the Lorentz symmetry.
Interfacial Thermoconvection and Atomic Relay Catalysis Enable Equilibrium Shifting and Rapid Glucose‐to‐Fructose Isomerization
Authors: Huang Jinshu , Li Hu , Saravanamurugan Shunmugavel , Su Yaqiong , Yang Song , Riisager Anders
Published: September 2024

The aqueous glucose‐to‐fructose isomerization is controlled by thermodynamics to an equilibrium limit of ~50 % fructose yield. However, here we report an in situ fructose removal strategy enabled by an interfacial local photothermal effect in combination with relay catalysis of geminal and isolated potassium single atoms (K SAs) on graphene‐type carbon (Ksg/GT) to effectively bypass the equilibrium limit and markedly speed up glucose‐to‐fructose isomerization. At 25 °C, an unprecedented fructose yield of 68.2 % was obtained over Ksg/GT in an aqueous solution without any additives under 30‐min solar‐like irradiation. Mechanistic studies expounded that the interfacial thermoconvection caused by the local photothermal effect of the graphene‐type carbon and preferable glucose adsorption on single‐atom K could facilitate the release of in situ formed fructose. The geminal K SAs were prone to form a stable metal‐glucose complex via bidentate coordination, and could significantly reduce the C−H bond electron density by light‐driven electron transfer toward K. This facilitated the hydride shift rate‐determining step and expedited glucose isomerization. In addition, isolated K SAs favored the subsequent protonation and ring‐closure process to furnish fructose. The integration of the interfacial thermoconvection‐enhanced in situ removal protocol and tailored atomic catalysis opens a prospective avenue for boosting equilibrium‐limited reactions under mild conditions.
Switching Sides: Regiochemistry and Functionalization Dictate the Photoswitching Properties of Imines
Authors: Wu Jiarong , Kreimendahl Lasse , Greenfield Jake L.
Published: September 2024

Photoswitchable imines demonstrate light‐dependent dynamic covalent chemistry and can function as molecular ratchets. However, the design of aryliminopyrazoles (AIPs) has been limited to N‐pyrazole derivatives with ortho‐pyrrolidine motifs. The impact of other functionalization patterns on the photoswitching properties remains unknown. Here, we present a systematic structure‐property analysis and study how the photoswitching properties can be tuned through ortho‐ and para‐functionalization of the phenyl ring in N‐pyrazole and N‐phenyl AIPs. This study establishes the first set of design rules for these AIP photoswitches and reports the most stable Z‐isomer of an AIP to date, enabling its crystallization and resulting in the first reported crystal structure of a metastable Z‐aldimine. Finally, we demonstrate that the AIPs are promising candidates for photoswitching in the condensed phase.
One‐Pot Transition‐Metal‐Free Synthesis of Alkynyl Amides
Authors: Wu Yu , Sátiro Bárbara G. , Mao Jianyou , Walsh Patrick J.
Published: September 2024

Alkynyl amides play crucial roles in organic synthesis in the production of bioactive compounds and valuable heterocycles. Despite numerous studies on their synthesis, challenges persist due to the necessity of harsh or hazardous conditions and the use of costly or unstable reagents. Herein, we present a one‐pot method for the synthesis of all three bonds of the alkyne under transition‐metal‐free conditions. An important feature of this chemistry is the use of readily available feedstock chemicals, such as methyl esters and acetamides. This approach offers efficient access to a wide range of aryl and alkyl alkynyl amides and demonstrates excellent tolerance towards various functional groups in a sustainable and cost‐effective manner.
Organic Materials with Ultrabright Phosphorescence at Room Temperature under Physiological Conditions for Bioimaging
Authors: Gu Juqing , Yuan Wentao , Chang Kai , Zhong Cheng , Yuan Yufeng , Li Jinghua , Zhang Yufeng , Deng Tian , Fan Yuanyuan , Yuan Likai , Liu Siwei , Xu Yongzhen , Ling Sisi , Li Chunyan , Zhao Zheng , Li Qianqian , Li Zhen , Tang Ben Zhong
Published: September 2024

In contrast to the high efficiency of room temperature phosphorescence in crystal states, the generally utilized nanoparticles of organic materials in bioimaging demonstrated sharply decreased performance by orders of magnitude under physiological conditions, badly limiting the realization of their unique advantages. This case, especially for organic red/near‐infrared (NIR) phosphorescence materials, is not only the challenge present in reality but more importantly, for the theoretical problem of deeply understanding and avoiding the quenching effect by oxygen and water toward excited triplet states. Herein, thanks to the intelligent molecular design by the introduction of abundant hydrophobic chains and highly‐branched structures, bright and persistent red/NIR phosphorescence under physiological conditions has been realized, which demonstrated the shielding effect towards oxygen, and the strengthened intermolecular interactions to suppress the non‐radiative transitions. Accordingly, the record phosphorescence intensity of nanoparticles in bioimage, up to 8.21±0.36×108 p s−1 cm−2 sr−1, was achieved, to realize the clear phosphorescence imaging of liver and tumors in living mice, even lymph nodes in rabbit models with high SBRs. This work afforded an efficient way to achieve the bright red/NIR phosphorescence nanoparticles, guiding their further applications in biology and medicine.
Fe−N Co‐Doped BiVO4 Photoanode with Record Photocurrent for Water Oxidation
Authors: Yang Jie , Deng Chaoyuan , Lei Yu , Duan Mengyu , Yang Yisen , Chen Xiaoran , Yang Sipeng , Li Jikun , Sheng Hua , Shi Weiqun , Chen Chuncheng , Zhao Jincai
Published: September 2024

Bismuth vanadate (BVO) ranks among the most promising photoanodes for photoelectrochemical (PEC) water splitting. Nonetheless, slow charge separation and transport, besides the sluggish water oxidation kinetics, are key barriers to its photoefficiency. Here, we present a co‐doping strategy that significantly improves the charge separation performance of BVO photoanodes. We found that, under standard one sun illumination, the Fe−N co‐doped BVO photoanode (Fe−N−BVO) by N‐coordinated Fe precursor reaches a record photocurrent density of 7.01 mA cm−2 at 1.23 V vs RHE after modified a surface co‐catalyst (FeNiOOH), and exhibits an outstanding stability. By contrast, much lower photocurrent density is obtained for the N‐doped, Fe‐doped and Fe/N‐doped BVO photoanode with separated N and Fe precursors. The detailed experimental characterizations show that the high activity of the Fe−N co‐doped BVO photoanode is attributed to the enhanced photo‐induced bulk charge separation, as well as the accelerated surface water oxidation kinetics. XPS, EXAFS and DFT calculations clearly show that, instead of formation of deep trapping state in the individually doped BVO, the co‐doping of Fe−N into BVO generates Fe‐based electronic states just below the bottom of conduction band and N‐derived states just above the top of valence band. Such modulations in electronic structure enable the efficient trap of the electrons and holes to enhance the separation of photo‐induced carriers, but hinder the charge recombination originated from the deep trapping sites.
Anticancer, Antihaemolytic and Anticoagulant Studies of Coumarin‐Substituted Sterically Tuned N‐Heterocyclic Carbene Silver(I) Complexes
Authors: Vickraman Ilavarasan , Shashidhara Vaishnavi , R. Thrilokraj , Małecki Jan Grzegorz , Alwarsamy Madhavarani , Ganapathy Kavina , Keri Rangappa S. , Budagumpi Srinivasa
Published: September 2024

A series of sterically varied silver‐based N‐heterocyclic carbene (NHC) complexes (14–17) were synthesized by embroidering biomedically active coumarin and 1,2,4‐triazole core as NHC precursors (10–13). The structure of all the synthesized salts (10–13) and complexes (14–17) were elucidated by FT‐IR and NMR (proton and carbon) spectroscopic techniques. Complex 15 was characterized by single‐crystal x‐ray diffraction. The data obtained from this characterization of the small molecule 15 confirmed the three‐dimensional arrangement of the complex. This also indicated agostic‐type interactions between the Ag atom and the CH modules of one of the NHC ligands. Further, the synthesized complexes (14–17) were studied for the antihaemolytic, anticoagulant and anticancer activities. The complexes 15 and 17 exhibited anticoagulant properties comparable to that of the standard anticoagulant EDTA. Notably, all the complexes evidenced anticancer activity on leukaemic cell lines (K562) with the IC50 values below 100 μM, the concentration at which antihaemolytic property was evidenced. Complex 15 exhibited the lowest IC50 value of 18.44 ± 0.76 μM, which could be attributed by the appropriate steric bulk around the metal atom. The cumulative data of the three analyses validate potential of the complexes 15 and 17 to exhibit antihaemolytic, anticancer and anticoagulant properties.
The Role of Lactic Fermentation in Ensuring the Safety and Extending the Shelf Life of African Indigenous Vegetables and Its Economic Potential
Authors: Lys Irakoze Marie
Published: September 2024

Lactic fermentation is a traditional preservation method that has been pivotal in enhancing the safety and extending the shelf life of various food products particularly where other technologies are not affordable. The present review paper explores the role of lactic fermentation in African Indigenous vegetables, emphasizing its impact on food safety and shelf life extension. The paper systematically examines the biochemical mechanisms of lactic acid bacteria in suppressing pathogenic microorganisms and spoilage organisms, thereby improving the safety and shelf life of these vegetables. Additionally, it briefly addresses how lactic fermentation contributes to the nutritional and sensory qualities of Indigenous vegetables, which are crucial for their marketability. The review further delves into the economic implications of integrating lactic fermentation of African Indigenous vegetables practices into local agricultural and food systems, considering aspects such as cost‐effectiveness, market potential, and value addition of African Indigenous vegetables. By synthesizing the current research and practices, the paper highlights the dual benefits of lactic fermentation of African Indigenous vegetables in enhancing food security and creating economic opportunities in Africa. The findings suggest that leveraging traditional fermentation techniques could significantly bolster the shelf life, safety, and economic viability of African Indigenous vegetables, offering a sustainable approach to food preservation and economic development.
Post‐Estimation Shrinkage in Full and Selected Linear Regression Models in Low‐Dimensional Data Revisited
Authors: Kipruto Edwin , Sauerbrei Willi
Published: September 2024

The fit of a regression model to new data is often worse due to overfitting. Analysts use variable selection techniques to develop parsimonious regression models, which may introduce bias into regression estimates. Shrinkage methods have been proposed to mitigate overfitting and reduce bias in estimates. Post‐estimation shrinkage is an alternative to penalized methods. This study evaluates effectiveness of post‐estimation shrinkage in improving prediction performance of full and selected models. Through a simulation study, results were compared with ordinary least squares (OLS) and ridge in full models, and best subset selection (BSS) and lasso in selected models. We focused on prediction errors and the number of selected variables. Additionally, we proposed a modified version of the parameter‐wise shrinkage (PWS) approach named non‐negative PWS (NPWS) to address weaknesses of PWS. Results showed that no method was superior in all scenarios. In full models, NPWS outperformed global shrinkage, whereas PWS was inferior to OLS. In low correlation with moderate‐to‐high signal‐to‐noise ratio (SNR), NPWS outperformed ridge, but ridge performed best in small sample sizes, high correlation, and low SNR. In selected models, all post‐estimation shrinkage performed similarly, with global shrinkage slightly inferior. Lasso outperformed BSS and post‐estimation shrinkage in small sample sizes, low SNR, and high correlation but was inferior when the opposite was true. Our study suggests that, with sufficient information, NPWS is more effective than global shrinkage in improving prediction accuracy of models. However, in high correlation, small sample sizes, and low SNR, penalized methods generally outperform post‐estimation shrinkage methods.
“Hey you!”: An extension of the speaker immersion protocol to recruit the attention of a listener
Authors: Verdun Victoria R. , Naresh Aparna , Kazee Amanda , Yosick Rachel
Published: September 2024

The speaker immersion protocol (SIP) is an intervention that attempts to increase the frequency and spontaneity of a child's spoken communication. SIP has demonstrated effectiveness with increasing mands and other verbal operants (Ross et al., 2006); however, prior investigations have not examined SIP in the context of needing to recruit the social attention of a communicative partner in the presence of an establishing operation. The current study sought to extend the literature on SIP by adding a recruitment for social attention component to the intervention with two children with Autism spectrum disorder and limited spontaneous language. Prior to intervention, both participants engaged in low levels of target‐requesting behavior even when a communication partner was readily available close by. After receiving an intervention designed to increase vocal requests, both participants demonstrated a significant increase in the number of vocal requests they emitted; however, that did not generalize to making appropriate bids for attention until recruitment for attention was embedded within SIP. Future studies should continue to examine the most effective and efficient ways to improve both the quantity and the quality of autistic children's social communication.
OSBPL10‐CNBP axis mediates hypoxia‐induced pancreatic cancer development
Authors: Huang Yishu , Zhang Ronghao , Fan Shuyang , Shi Minmin , Tang Xiaomei , Wang Xinjing , Deng Xiaxing
Published: September 2024

Pancreatic ductal adenocarcinoma (PDAC) is one of malignancies with worst outcomes among digestive system tumors. Identification of novel biomarkers is of great significance for treatment researches and prognosis prediction of pancreatic cancer patients. Due to OSBPL10 known involvement in oncogenic activity in other tumors, we elucidated the mechanism underlying its contribution to pancreatic cancer progression. We employed data from the Gene Expression Omnibus database to detect the expression of OSBPL10 in normal and pancreatic cancer tissues. A series of assays were conducted to assess the impact of OSBPL10 on the proliferation and metastatic capacities of pancreatic cancer cells and the influence of OSBPL10 on macrophages were evaluated by Flow cytometry. In addition, Co‐immunoprecipitation, mass spectrometry, and western blot assays were utilized to investigate the potential mechanisms of OSBPL10 activity. From our study, OSBPL10 is revealed to be upregulated in pancreatic cancer, with poor prognosis. The overexpression promotes malignant behaviors of pancreatic cancer cells and has an impact on tumor immune microenvironment by stimulating the transformation M1 macrophages into M2 macrophages. Mechanistically, hypoxia induces the expression of OSBPL10 through interaction between hypoxia‐inducible factor 1‐α and the promoter region of OSBPL10. Additionally, OSBPL10 directly bound to CNBP, mediating CNBP expression and ultimately regulating the proliferation and metastasis capacity of pancreatic cancer cells, as well as influencing macrophage polarization. The research emphasized the oncogenic role of OSBPL10 in pancreatic cancer, uncovering key mechanisms involving hypoxia, HIF‐1α, and CNBP. The finding suggests that OSBPL10 is a novel biomarker in pancreatic cancer, making it a potential therapeutic target for intervention in this malignancy.
Stability‐indicating RP‐HPLC method development and validation for the quantification of amlodipine besylate and valsartan tablets in solid oral dosage form
Authors: Kamireddy Teja , Sambu Pranitha , Lankalapalli Prasanna Kumar , Myneni Rama Krishna , Divadari Hareesh
Published: September 2024

The present study discusses the development of simple, rapid, specific, precision, accuracy, stability indicating the HPLC method for the analysis of amlodipine besylate and valsartan tablet dosage form. The chromatographic separation was achieved using phosphate buffer with 1% triethyl amine (pH 3.0) as mobile phase‐A and mixed Methanol and buffer in the ratio of (65:35)(v/v) as mobile phase‐B. The detection of components was made at 237 nm for amlodipine besylate and valsartan. Analytical techniques should enrich sensitivity and specificity for the estimation of pharmaceutical drug products. Evaluated stress studies under different types of ICH conditions. The optimized HPLC method was validated as per the current ICH guidelines. The validated HPLC method was obtained highly specific with linearity ranging between 25 and 200 μgmL−1 of amlodipine besylate and 40–320 μgmL−1 of valsartan and both components correlation coefficient was > 0.999. The method showed high accuracy more than 97%. In stress studies, amlodipine besylate and valsartan were found to be sensitive to acid stress conditions and oxidation stress conditions. The method was found to be suitable for the quality control of amlodipine besylate and valsartan in the tablet as well as in stability‐indicating studies. The method was applied to the analysis of stability samples.
Synthesis of Novel 3,4‐Dihydropyrimidine Derivatives, Cytotoxic Activity Evaluation, Apoptosis, Molecular Docking Studies, and MD Simulations
Authors: Faeze Mortazavi Seyyede , Ebadi Ahmad , Navid Mohammadian Mohammad , Mojaddami Ayyub , Toolabi Mahsa
Published: September 2024

In this study, twelve 3,4‐dihydropyrimidines derivatives were synthesized through Biginelli multi‐component reaction. The efficacy of these compounds against MCF‐7, A549, and HeLa cells was evaluated using the MTT method. The results showed that designed derivatives were more effective against A549 cancer cells than MCF‐7 and HeLa cells. Compound 5l (bearing 4‐Cl‐phenyl at C4 of 3, 4‐dihydropyrimidin‐2(1H)‐one ring) was the most potent analogue (A549: 18.65±1.87 μM, HeLa: 26.59±2.71 μM, MCF‐7: 31.82±2.64 μM). The presence of an electron‐withdrawing group with optimum lipophilicity at the C4 position of the phenyl ring increased the cytotoxic effect. The flow cytometry findings indicated that compound 5l induced apoptosis in A549 cancer cells in a dose‐dependent manner. Eg5 and AKT1 were selected as molecular modeling target by applying pharmacology network analyses. The molecular docking results indicated that both enantiomers of compound 5l had significant interactions with key residues in both Eg5 (Gly117 and Glu116) and AKT1 (Ala123 and Glu121) active sites. However, MD simulation revealed that the R enantiomer had a more stable complex and a higher binding affinity to the Eg5 enzyme active site than the S‐enantiomer. The affinity of 5l (R enantiomer) to Eg5 was predicted more than AKT1.
The Role of Pyruvate Kinase M2 Posttranslational Modification in the Occurrence and Development of Hepatocellular Carcinoma
Authors: Chunlian Zhao , Qi Wan , Rui Zhao
Published: September 2024

Hepatocellular carcinoma (HCC) is one of the deadly malignant tumors that directly leads to the death of nearly one million people worldwide every year, causing a serious burden on society. In the presence of sufficient oxygen, HCC cells rapidly generate energy through aerobic glycolysis, which promotes tumor cell proliferation, immune evasion, metastasis, angiogenesis, and drug resistance. Pyruvate kinase M2 (PKM2) is a key rate‐limiting enzyme in glycolysis. In recent years, studies have found that PKM2 not only exerts pyruvate kinase activity in the process of glucose metabolism, but also exerts protein kinase activity in non‐metabolic pathways to affect tumor cell processes, and its activity is flexibly regulated by various posttranslational modifications such as acetylation, phosphorylation, lactylation, ubiquitination, SUMOylation, and so forth. This review summarizes the role of posttranslational modifications of PKM2‐related sites in the development of HCC.
Chiral Pd(II) Nanofiber Promoting Electron Transfer of g‐C3N4 for Efficient Photocatalytic Hydrogen Production
Authors: Zhou Xiaoqin , Miao Wangen , Xu Limei , Luo Jin , Fan Xuliang , Ning Xiaomei , Zhou Xunfu , Zhou Xiaosong
Published: September 2024

The rapid transfer and separation of photogenerated electrons is very important for the improvement of photocatalytic efficiency. Here, chiral induced spin selectivity effect (CISS effect) was developed to accelerate electron transfer for efficient photocatalytic hydrogen production. A chiral and achiral racemic supramolecular Pd(II) complex nanofiber was fabricated via supramolecular self‐assembly of chiral L−Py or its racemes with Pd(II) and used to modify carbon nitride (g‐C3N4). The obtained chiral photocatalyst L−Py−Pd/g‐C3N4‐4 and achiral photocatalyst Rac‐Pd/g‐C3N4‐4, show enhanced photocatalytic activities with hydrogen evolution rates of 2476 and 1339 μmol g−1 h−1, respectively, while that of pure g‐C3N4 is 30.5 μmol g−1 h−1. Chiral photocatalyst has 85 % higher activity than achiral one and is 82.5‐fold of pure g‐C3N4, due to better suppression of the recombination of photogenerated electron‐hole pairs in the interface of g‐C3N4 contact with chiral molecule. Spectral tests and photoelectrochemical tests proved that the chiral supramolecular Pd(II) complex can act both as an electron spin filter and hydrogen reduction catalytic center to enhance photocatalytic efficiency. This work offers a new route to facilitate electron transfer by the CISS effect for photocatalytic hydrogen evolution.