bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enzyme‐Activatable Near‐Infrared Photosensitizer with High Enrichment in Tumor Cells Based on a Multi‐Effect Design
Authors: Li Yuyao , Zhang Chaoying , Wu Qingyi , Peng Yan , Ding Yiru , Zhang Zhengwei , Xu Xiaoyong , Xie Hexin 
Published: December 2023

AbstractEnzyme‐activatable near‐infrared (NIR) fluorescent probes and photosensitizers (PSs) have emerged as promising tools for molecular imaging and photodynamic therapy (PDT). However, in living organisms selective retention or even enrichment of these reagents after enzymatic activation at or near sites of interest remains a challenging task. Herein, we integrate non‐covalent and covalent retention approaches to introduce a novel “1‐to‐3” multi‐effect strategy—one enzymatic stimulus leads to three types of effects—for the design of an enzyme‐activatable NIR probe or PS. Using this strategy, we have constructed an alkaline phosphatase (ALP)‐activatable NIR fluorogenic probe and a NIR PS, which proved to be selectively activated by ALP to switch on NIR fluorescence or photosensitizing ability, respectively. Additionally, these reagents showed significant enrichment (over 2000‐fold) in ALP‐overexpressed tumor cells compared to the culture medium, accompanied by massive depletion of intracellular thiols, the major antioxidants in cells. The investigation of this ALP‐activatable NIR PS in an in vivo PDT model resulted in complete suppression of HeLa tumors and full recovery of all tested mice. Encouragingly, even a single administration of this NIR PS was sufficient to completely suppress tumors in mice, demonstrating the high potential of this strategy in biomedical applications.
Selective 1,2‐Hydroarylation(Alkenylation) of gem‐Difluoroalkenes to Access (−CF2H) Motifs
Authors: Lin Leroy Qi Hao , Rentería‐Gómez Ángel , Martin Robert T. , Zhang Ying‐Qi , Ong Kelvin Zhi Wei , Parris Adam B. , Gutierrez Osvaldo , Koh Ming Joo 
Published: December 2023

AbstractAn emerging class of C−C coupling transformations that furnish drug‐like building blocks involves catalytic hydrocarbonation of alkenes. However, despite notable advances in the field, hydrocarbon addition to gem‐difluoroalkenes without additional electronic activation remains largely unsuccessful. This owes partly to poor reactivity and the propensity of difluoroalkenes to undergo defluorinative side reactions. Here, we report a nickel catalytic system that promotes efficient 1,2‐selective hydroarylation and hydroalkenylation, suppressing defluorination and providing straightforward access to a diverse assortment of prized organofluorides bearing difluoromethyl‐substituted carbon centers. In contrast to radical‐based pathways and reactions triggered by hydrometallation via a nickel‐hydride complex, our experimental and computational studies support a mechanism in which a catalytically active nickel‐bromide species promotes selective carbonickelation with difluoroalkenes followed by alkoxide exchange and hydride transfer, effectively overcoming the difluoroalkene's intrinsic electronic bias.
Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence
Authors: Wu Tianhui , Jiang Xingxing , Duanmu Kaining , Wu Chao , Lin Zheshuai , Huang Zhipeng , Humphrey Mark G. , Zhang Chi 
Published: December 2023

AbstractConsiderable effort has been invested in the development of non‐centrosymmetric (NCS) inorganic solids for ferroelectricity‐, piezoelectricity‐ and, particularly, optical nonlinearity‐related applications. While great progress has been made, a persistent problem is the difficulty in constructing NCS materials, which probably stems from non‐directionality and unsaturation of the ionic bonds between metal counter‐cations and covalent anionic modules. We report herein a secondary‐bond‐driven approach that circumvents the cancellation of dipole moments between adjacent anionic modules that has plagued second‐harmonic generation (SHG) material design, and which thereby affords a polar structure with strong SHG properties. The resultant first NCS counter‐cation‐free iodate, VO2(H2O)(IO3) (VIO), a new class of iodate, crystallizes in a polar lattice with
VO2(H2O)(IO3)] zigzag chains connected by weak hydrogen bonds and intermolecular forces. VIO exhibits very large SHG responses (18 × KH2PO4 @ 1200 nm, 1.5 × KTiOPO4 @ 2100 nm) and sufficient birefringence (0.184 @ 546 nm). Calculations and crystal structure analysis attribute the large SHG responses to consistent polarization orientations of the
VO2(H2O)(IO3)] chains controlled by secondary bonds. This study highlights the advantages of manipulating the secondary bonds in inorganic solids to control NCS structure and optical nonlinearity, affording a new perspective in the development of high‐performance NLO materials.
Design eines Phosphor‐zentrierten Disbiradikals
Authors: Rosenboom Jan , Taube Florian , Teichmeier Leon , Villinger Alexander , Reinhard Maik , Demeshko Serhiy , Bennati Marina , Bresien Jonas , Corzilius Björn , Schulz Axel 
Published: December 2023

AbstractPhosphor‐zentrierte Disbiradikale, in denen die Radikalzentren als einzelne Spin‐Dubletts mit schwacher Spin‐Spin‐Wechselwirkung vorliegen, waren bisher nicht bekannt. Ausgehend von Monoradikalen des Typs [⋅P(μ‐NTer)2P−R] ist es uns nun gelungen, zwei monoradikalische Phosphorzentren durch geeignete Wahl eines Linkers zu verknüpfen. Zu diesem Zweck wurde das Biradikal [⋅P(μ‐NTer)2P⋅] (1) mit 1,6‐Dibromhexan umgesetzt, wodurch die bromierte Spezies {Br[P(μ‐NTer)]2}2C6H12 (3) entstand. Die anschließende Reduktion mit KC8 führte zur Bildung des Disbiradikals {⋅[P(μ‐NTer)]2}2C6H12 (4), das sich durch einen großen Abstand zwischen den radikalischen Phosphorzentren im Festkörper auszeichnet und mit annähernd 100 % den bisher höchsten Biradikalcharakter in einem P‐zentrierten Biradikal aufweist. Die EPR‐spektroskopische Untersuchung ergab ein Drei‐Linien‐Signal in Lösung mit einer erheblich größeren Austauschwechselwirkung als es aufgrund der Molekülstruktur im Einkristall zu erwarten wäre. Quantenchemische Berechnungen ergaben einen hochdynamischen Konformationsraum; demnach können sich die beiden Radikalstellen in Lösung mit einem viel geringeren Abstand einander nähern. Die weitere Reduktion von 4 führte zur Bildung eines Kaliumsalzes mit dem ersten strukturell charakterisierten P‐zentrierten distonischen Radikalanion (5−). Außerdem konnte 4 für die Aktivierung kleiner Moleküle eingesetzt werden.
Polyoxometalate‐Nanozyme‐Integrated Nanomotors (POMotors) for Self‐Propulsion‐Promoted Synergistic Photothermal‐Catalytic Tumor Therapy
Authors: Tang Minglu , Ni Jiatong , Yue Zhengya , Sun Tiedong , Chen Chunxia , Ma Xing , Wang Lei 
Published: December 2023

AbstractEnzyme‐powered nanomotors have demonstrated promising potential in biomedical applications, especially for catalytic tumor therapy, owing to their ability of self‐propulsion and bio‐catalysis. However, the fragility of natural enzymes limits their environmental adaptability and also therapeutic efficacy in catalysis‐enabled tumor therapy. Herein, polyoxometalate‐nanozyme‐based light‐driven nanomotors were designed and synthesized for targeted synergistic photothermal‐catalytic tumor therapy. In this construct, the peroxidase‐like activity of the P2W18Fe4 polyoxometalates‐based nanomotors can provide self‐propulsion and facilitate their production of reactive oxygen species thus killing tumor cells, even in the weakly acidic tumor microenvironment. Conjugated polydopamine endows the nanomotors with the capability of light‐driven self‐propulsion behavior. After 10 min of NIR (808 nm) irradiation, along with the help of epidermal growth factor receptor antibody, the targeted accumulation and penetration of nanomotors in the tumor enabled highly efficient synergistic photothermal‐catalytic therapy. This approach overcomes the disadvantages of the intrinsically fragile nature of enzyme‐powered nanomotors in physiological environments and, more importantly, provides a motility‐behavior promoted synergistic anti‐tumor strategy.
Palladium‐Catalyzed Regioselective Synthesis of 2‐SF5‐Indenols and Further Derivatizations
Authors: Popek Lucas , Cihan Murat , Blanchard Nicolas , Bizet Vincent 
Published: December 2023

AbstractA palladium‐catalyzed synthesis of 2‐SF5‐indenols has been developed by reacting commercially available boronic acid derivatives and readily accessible SF5‐alkynes. The present methodology is fully regioselective thanks to the intrinsic polarization of SF5‐alkynes. A selection of downstream functionalizations has been performed to highlight the versatility of 2‐SF5‐indenols and indenones as platforms for the design of more complex SF5‐containing molecules.
Discrimination of Disaccharide Isomers of Different Glycosidic Linkages Using a Modified MspA Nanopore
Authors: Zhang Shanyu , Cao Zhenyuan , Fan Pingping , Sun Wen , Xiao Yunqi , Zhang Panke , Wang Yuqin , Huang Shuo 
Published: December 2023

AbstractDisaccharides are composed of two monosaccharide subunits joined by a glycosidic linkage in an α or β configuration. Different combinations of isomeric monosaccharide subunits and different glycosidic linkages result in different isomeric disaccharide products. Thus, direct discrimination of these disaccharide isomers from a mixture is extremely difficult. In this paper, a hetero‐octameric Mycobacterium smegmatis porin A (MspA) nanopore conjugated with a phenylboronic acid (PBA) adapter was applied for disaccharide sensing, with which three most widely known disaccharides in nature, including sucrose, lactose and maltose, were clearly discriminated. Besides, all six isomeric α‐D‐glucopyranosyl‐D‐fructoses, differing only in their glycosidic linkages, were also well resolved. Assisted by a custom machine learning algorithm, a 0.99 discrimination accuracy is achieved. Nanopore discrimination of disaccharide isomers with different glycosidic linkages, which has never been previously demonstrated, is inspiring for nanopore saccharide sequencing. This sensing capacity was also applied in direct identification of isomaltulose additives in a commercial sucrose‐free yogurt, from which isomaltulose, lactose and L‐lactic acid were simultaneously detected.
Single Zn Atoms with Acetate‐Anion‐Enabled Asymmetric Coordination for Efficient H2O2 Photosynthesis
Authors: Li Yunxiang , Guo Yan , Fan Guilan , Luan Deyan , Gu Xiaojun , Lou Xiong Wen (David) 
Published: December 2023

AbstractExploring unique single‐atom sites capable of efficiently reducing O2 to H2O2 while being inert to H2O2 decomposition under light conditions is significant for H2O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single‐Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single‐Zn sites on CN, forming asymmetric Zn−N3O moiety on CN (denoted as CN/Zn−OAc), in contrast to the obtained Zn−N4 sites when sulfate (SO4) is adopted (CN/Zn−SO4). Both experimental and theoretical investigations demonstrate that the Zn−N3O moiety exhibits higher intrinsic activity for O2 reduction to H2O2 than the Zn−N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn−OAc catalyst exhibits significantly improved photocatalytic H2O2 production activity under visible light irradiation.
Rational Design of a Phosphorus‐Centered Disbiradical
Authors: Rosenboom Jan , Taube Florian , Teichmeier Leon , Villinger Alexander , Reinhard Maik , Demeshko Serhiy , Bennati Marina , Bresien Jonas , Corzilius Björn , Schulz Axel 
Published: December 2023

AbstractPhosphorus‐centered disbiradicals, in which the radical sites exist as individual spin doublets with weak spin‐spin interaction have not been known so far. Starting from monoradicals of the type [⋅P(μ‐NTer)2P−R], we have now succeeded in linking two such monoradical phosphorus centers by appropriate choice of a linker. To this end, biradical [⋅P(μ‐NTer)2P⋅] (1) was treated with 1,6‐dibromohexane, affording the brominated species {Br[P(μ‐NTer)]2}2C6H12 (3). Subsequent reduction with KC8 led to the formation of the disbiradical {⋅[P(μ‐NTer)]2}2C6H12 (4) featuring a large distance between the radical phosphorus sites in the solid state and formally the highest biradical character observed in a P‐centered biradical so far, approaching 100 %. EPR spectroscopy revealed a three‐line signal in solution with a considerably larger exchange interaction than would be expected from the molecular structure of the single crystal. Quantum chemical calculations revealed a highly dynamic conformational space; thus, the two radical sites can approach each other with a much smaller distance in solution. Further reduction of 4 resulted in the formation of a potassium salt featuring the first structurally characterized P‐centered distonic radical anion (5−). Moreover, 4 could be used in small molecule activation.
Cocrystallization‐driven Formation of fcc‐based Ag110 Nanocluster with Chinese Triple Luban Lock Shape
Authors: Qu Mei , Zhang Fu‐Qiang , Zhang Gai‐Li , Qiao Miao‐Miao , Zhao Li‐Xiang , Li Shi‐Li , Walter Michael , Zhang Xian‐Ming 
Published: December 2023

AbstractLuban locks with mortise and tenon structure have structural diversity and architectural stability, and it is extremely challenging to synthesize Luban lock‐like structures at the molecular level. In this work, we report the cocrystallization of two structurally related atom‐precise fcc silver nanoclusters Ag110(SPhF)48(PPh3)12 (Ag110) and Ag14(μ6‐S)(SPhF)12(PPh3)8 (Ag14). It is worth noting that the Ag110 cluster is the first compound to simulate the complex Luban lock structure at the molecular level. Meanwhile, Ag110 is the largest known fcc‐based silver nanocluster, so far, there is no precedent for fcc silver nanocluster with more than 100 silver atoms. DFT calculations show that Ag110 is a 58‐electron superatom with an electronically closed shell1S21P61D102S21F142P61G18. Ag110⋅Ag14 can rapidly catalyze the reduction of 4‐nitrophenol within 4 minutes. In addition, Ag110 presents clear structural evidence to reveal the critical size and mechanism of the transformation of metal core from fcc stacking to quasi‐spherical superatom. This research work provides an important structural model for studying the nucleation mechanism and structural assembly of silver nanoclusters.
Selective Synthesis and Functionalization of an Acyclic Methylene‐Bridged‐Arene Trimer in a Cage
Authors: Takezawa Hiroki , Iizuka Kenta , Fujita Makoto 
Published: December 2023

AbstractArene‐formaldehyde condensation is a versatile reaction for producing various oligomeric/polymeric materials. However, the precise control of oligomerization degree is still challenging because the starting materials and intermediates have similar reactivities. Here, we demonstrate the selective synthesis of a methylene‐bridged arene trimer using the confined cavity of a coordination cage. The limited space of the cavity prevents unregulated polymerization. The confinement effect for the kinetic protection is also demonstrated by the subsequent site‐selective iodination of the trimer product within the cage.
Unveiling the potential of Pd(II)‐covalent organic polyimide framework in Suzuki coupling reactions: A study on synthesis, characterization, and catalytic efficiency
Authors: Moeinpour Farid 
Published: December 2023

In this research, a highly effective heterogeneous Pd catalytic system was conceived by immobilizing Pd(II) onto a substrate composed of covalent organic polyimide frameworks (PI‐COF). The synthesized catalyst underwent comprehensive characterization using techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 adsorption analysis (Brunauer–Emmett–Teller [BET]), Fourier transform infrared (FT‐IR), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectroscopy (ICP‐AES). Subsequently, the catalytic activity of this immobilized Pd catalyst was explored in the context of the Suzuki reaction. The reactions at 70°C up to 1 h under a normal atmosphere in water result in biaryls at good to excellent yields (>90%). More importantly, the leaching of Pd(II) during the reaction process could be negligible (about 0.5 ppm), which is crucially important when preparing bioactive species. The loading of Pd(II) ions on the PI‐COF was 0.49 mmol/g. The catalyst exhibited exceptional performance, demonstrating remarkable efficacy in catalyzing a wide range of aryl halides (excluding aryl chlorides) when reacted with phenylboronic acid under environmentally friendly reaction conditions. Notably, the catalyst exhibited robust recyclability, retaining its catalytic activity throughout 5 reaction cycles without any significant decrease.
The psychometric properties and treatment outcomes associated with two measures of the adult therapeutic alliance using naturalistic data
Authors: Mahon Daryl , Minami Takuya , Brown (G. S.) Jeb 
Published: December 2023

AbstractPurposeThis is the first of two articles that examine the psychometric properties and treatment outcomes associated with measures of the therapeutic alliance collected in naturalistic settings rather than clinical trials. These articles break new ground in understanding the relationship between measures of alliance and treatment outcome by performing detailed item analyses in order to assess the psychometric properties of each individual item, its propensity to change from session to session and its utility in predicting change in the outcome measure.MethodsData were taken from the ACORN database for adults attending for psychotherapy treatment in naturalistic settings (N = 147,399). The sample, the largest to date, included only those completing both an alliance measure and an outcome measure at every session. Two sets of three different alliance items are used across three different treatment populations: general outpatient, substance use, and severe and persistent mental health difficulties. To investigate this possibility, the psychometric properties of each item were evaluated, including factor analysis, likelihood of change over time in treatment and correlations between changes in alliance and magnitude of client‐reported improvement in therapy. The predictive validity of each individual item is compared with the predictive validity of their respective three‐item measures. The problem of alliance scores being heavily skewed in a positive direction and the resulting lack of variability from session to session is addressed by categorising change in alliance as same, better or worse, regardless of the magnitude of change.ResultsFindings tended to differ from those in clinical trials, with the last alliance score being most predictive of outcome. In this data set, the alliance accounted for, at most, 2% of the variance in outcomes. Measures of the therapeutic alliance demonstrate ceiling effects, and the alliance–outcome correlation is far from linear. Change in alliance score, rather than a single assessment, is more predictive of outcome, regardless of the magnitude of change in the alliance measure, with effect sizes of up to 50% more for those who rated the alliance as worse than for those rating it as no change or better.ConclusionTherapists using therapeutic alliance questionnaires will benefit from being aware of how the psychometric properties of alliance measures impact outcomes. Even the smallest drop in alliance is predictive of significant clinically meaningful differences. Implications for practice, training and research are considered.
Membrane‐Based Preparation Process and Antioxidant and Anti‐AGEs Activities of a Novel Propolis Ultrafiltrate
Authors: Liang Xiao‐lu , Wu Yong‐lin , Chen Yu‐jia , Zhang Jia‐min , He Jian , Yuan Min , Pan Tian‐ling , Pineda Miguel A. , Li Kun‐ping 
Published: December 2023

AbstractPropolis is one functional supplement with hundreds of years of usage. However, it's rarely consumed directly for its resinous property. Herein, a pre‐treated process which can remove the impurity while preserve its bioactivities is needed to maximise its therapeutic opportunities. In the present study, a membrane‐based ultrafiltration process was developed on a KM1812‐NF experimental instrument. Using Brazilian green propolis as testing material, all experimental steps and parameters were sequentially optimized. In addition, a mathematical model was developed to fit the process. As a result, the optimum solvent was 60 % ethanol adjusted to pH 8–9, while the optimum MWCO (molecular weight cut‐off) value of membrane was 30 KDa. The membrane filtration dynamic model fitted with the function y=(ax+b)/(1+cx+dx2). The resulting propolis ultrafiltrate from Brazilian green propolis, termed P30K, contains the similar profile of flavonoids and phenolic acids as raw propolis. Meanwhile, the ORAC (oxygen radical absorbance capacity) value of P30K is 11429.45±1557.58 μM TE/g and the IC50 value of inhibition of fluorescent AGEs (advanced glycation end products) formation is 0.064 mg/mL. Our work provides an innovative alternative process for extraction of active compounds from propolis and reveals P30K as an efficient therapeutic antioxidant.
Four New Steroidal Saponins from the Roots of Dracaena cambodiana with NO Production Inhibition Activity in LPS Activated RAW 264.7 Cells
Authors: Yen Pham Hai , Tai Bui Huu , Hoang Nguyen Huy , Dung Duong Thi , Nhiem Nguyen Xuan , Yen Duong Thi Hai , Huong Phan Thi Thanh , Dung Nguyen Viet , Hang Dan Thi Thuy , Ha Nguyen Thi , Trang Do Thi , Thu Vu Kim , Kiem Phan Van 
Published: December 2023

AbstractSeven steroidal saponins including three new 16,23‐cyclocholestanes (1‐3) and one new pregane (4) were isolated from the roots of Dracaena cambodiana Pierre ex Gagnep. Their chemical structures were elucidated to be (23R,25R)‐26‐O‐β‐D‐glucopyranosyl‐16,23‐cyclocholesta‐5,17(20)‐dien‐22‐one‐3β,16α,26‐triol‐3‐O‐α‐L‐rhamnopyranosyl‐(1→2)‐[α‐L‐rhamnopyranosyl‐(1→3)]‐β‐D‐glucopyranoside (1), (23R,25R)‐26‐O‐β‐D‐glucopyranosyl‐16,23‐cyclocholesta‐5,17,20(22)‐trien‐3β,22,26‐triol‐3‐O‐α‐L‐rhamnopyranosyl‐(1→3)‐β‐D‐glucopyranoside (2), (23R,25R)‐16,23‐cyclocholesta‐5,16,20(22)‐trien‐3β,22,26‐triol‐3‐O‐α‐L‐rhamnopyranosyl‐(1→3)‐β‐D‐glucopyranoside (3), 3β‐[(O‐α‐L‐rhamnopyranosyl‐(1→3)‐[α‐L‐rhamnopyranosyl‐(1→2)]‐β‐D‐gluco‐pyranosyl)oxy]‐pregna‐5,17(20)‐diene‐16‐one‐20‐carboxylic acid 4′′′′‐O‐β‐D‐glucopyranosylisopentyl ester (4), cambodianoside A (5), diosbulbiside C (6), and diosbulbiside D (7), by IR, HR‐ESI‐MS, 1D and 2D NMR spectra. Compounds 1 and 4–7 inhibited nitric oxide (NO) production in lipopolysaccharide activated RAW 264.7 cells with IC50 values ranging from 19.03±1.84 to 67.92±3.81 μM, whereas compounds 2 and 3 were inactive with IC50 values over 100 μM.