bluuebunny/crossref_metadata_2025_split huggingface dataset:
Anxiety Symptoms Among Patients With Systemic Lupus Erythematosus Persist Over Time and Are Independent of SLE Disease Activity
Authors: Lew Daphne , Huang Xinliang , Kellahan Sara R. , Xian Hong , Eisen Seth , Kim Alfred H. J. 
Published: February 2022

ObjectiveThe objectives of this study are to identify patterns of anxiety symptomology over time among patients with systemic lupus erythematosus (SLE) and to assess the longitudinal relationship between SLE disease activity and anxiety symptomology.MethodsLongitudinal data from 139 patients with American College of Rheumatology or Systemic Lupus International Collborating Clinic (SLICC)‐classified SLE were analyzed. Anxiety symptomology was assessed using the Patient‐Reported Outcomes Measurement Information System (PROMIS) Emotional Distress: Anxiety Short Form 8a. SLE disease activity was measured using the Systemic Lupus Erythematosus Disease Activity Index (SLEDAI)‐2000 (S2K) and S2K Responder Index 50 (S2K RI‐50). Group‐based trajectory modeling (GBTM) identified longitudinal trajectories of anxiety symptomology. The relationship between disease activity and anxiety over time was assessed using multilevel linear regressions.ResultsThe mean patient age was 40.2 years (standard deviation [SD], 12.7); 90.6% were female, and 56.1% were of Black race. All patients had at least three PROMIS anxiety scores over an average of 30.9 months (SD, 13.0). GBTM identified four trajectories of anxiety symptomology, labeled as the following: low (LA), average (AA), moderate (MA), and high anxiety (HA). Black patients were 2.47 (95% confidence interval: 1.19‐5.12) times as likely as White patients to be classified into the MA or HA groups compared with the LA or AA groups. On multivariable analysis, active SLE disease was not significantly associated with anxiety over time (P = 0.19).ConclusionAnxiety trajectories remained stable over time, and racial differences in anxiety severity were observed. SLE disease activity was not longitudinally associated with anxiety after controlling for depression and other factors. Further understanding of the factors that contribute to the persistence of anxiety among individuals with SLE is necessary.
Cation‐Vacancy‐Enriched Nickel Phosphide for Efficient Electrosynthesis of Hydrogen Peroxides
Authors: Zhou Zheng , Kong Yuan , Tan Hao , Huang Qianwei , Wang Cheng , Pei Zengxia , Wang Haozhu , Liu Yangyang , Wang Yihan , Li Sai , Liao Xiaozhou , Yan Wensheng , Zhao Shenlong 
Published: February 2022

AbstractElectrocatalytic hydrogen peroxide (H2O2) synthesis via the two‐electron oxygen reduction reaction (2e ORR) pathway is becoming increasingly important due to the green production process. Here, cationic vacancies on nickel phosphide, as a proof‐of‐concept to regulate the catalyst's physicochemical properties, are introduced for efficient H2O2 electrosynthesis. The as‐fabricated Ni cationic vacancies (VNi)‐enriched Ni2−xP‐VNi electrocatalyst exhibits remarkable 2e ORR performance with H2O2 molar fraction of >95% and Faradaic efficiencies of >90% in all pH conditions under a wide range of applied potentials. Impressively, the as‐created VNi possesses superb long‐term durability for over 50 h, suppassing all the recently reported catalysts for H2O2 electrosynthesis. Operando X‐ray absorption near‐edge spectroscopy (XANES) and synchrotron Fourier transform infrared (SR‐FTIR) combining theoretical calculations reveal that the excellent catalytic performance originates from the VNi‐induced geometric and electronic structural optimization, thus promoting oxygen adsorption to the 2e ORR favored “end‐on” configuration. It is believed that the demonstrated cation vacancy engineering is an effective strategy toward creating active heterogeneous catalysts with atomic precision.
Photothermal Optimization of Quantum Dot Converters for High‐Power Solid‐State Light Sources
Authors: Li Jiexin , Li Zongtao , Qiu Jiayong , Li Jiasheng 
Published: February 2022

AbstractQuantum dots (QDs) exhibit remarkable photoelectric performance. However, the conversion efficiency and thermal performance of QD converters so far is not satisfactory for high‐power solid‐state light (SSL) applications owing to the serious reabsorption loss of QDs and the poor thermal diffusion of polymer materials. Here, an efficient QD converter based on an anodic aluminum membrane (AAM), with high light enhancement and thermal diffusion, is introduced for high‐power SSL applications. Nanoporous AAMs are utilized as templates for confining the QD deposition into the nanowire (NW) shape by incorporating inkjet printing and vacuum‐deposition methods, forming vertical QD NW arrays. Compared with conventional converters, QD‐AAM yields nearly twofold photoluminescence intensity. Three‐dimensional finite‐difference (FDTD) simulations attribute the fluorescence‐enhancement mechanism to the enhancement of QD conversions and boosting of the waveguide effect in QD‐AAM. Furthermore, QD‐AAM exhibits excellent thermal diffusion performance under high‐power excitation, owing to the inner heat conduction path in the AAM framework. This study provides a practical and efficient strategy to comprehensively enhance the optical and thermal performance of QD converters for high‐power SSL applications.
Widely Tunable GRIN Lenses Using Negative Dielectrophoretic Manipulation of Phosphate Nanosheets Colloid
Authors: Priyadharshana P. A. N. S. , Shen Tian‐Zi , Hong Seung‐Ho , Song Jang‐Kun 
Published: February 2022

AbstractTunable gradient refractive index (GRIN) lens has attracted increasing attention from researchers due to its promising applicability in various optical and electronic applications. However, the polarization‐insensitive, large sized, and focal‐length‐controllable GRIN lens is highly difficult to implement due to the lack of available functional materials with the property of tunable refractive index. Herein, a two dimensional (2D) α‐ZrP nanocolloid is introduced to fabricate a GRIN lens in which the 2D nanosheet density distribution is precisely controlled by negative dielectrophoresis. Interestingly, the geometrical 2D shape of nanosheets plays an essential role in reducing optical light scattering in colloids and enhancing the dielectrophoretic controllability of nanosheet distribution. Moreover, despite the nematic assembly of 2D nanosheets in colloids, the birefringence effect is negligible, and polarization‐independent properties are obtained. Using a simple nanocolloidal cell with designed electrodes and various thicknesses, not only tunable lenses with either positive or negative focal lengths but also wide tunable lenses across positive and negative focal lengths are successfully demonstrated. Thus, the results reveal new possibilities for 2D nanocolloids in tunable GRIN optical applications.
Engineering Robust Ag‐Decorated Polydopamine Nano‐Photothermal Platforms to Combat Bacterial Infection and Prompt Wound Healing
Authors: Qi Xiaoliang , Huang Yijing , You Shengye , Xiang Yajing , Cai Erya , Mao Ruiting , Pan Wenhao , Tong Xianqin , Dong Wei , Ye Fangfu , Shen Jianliang 
Published: February 2022

AbstractPolydopamine (PDA) nanoparticles have emerged as an attractive biomimetic photothermal agent in photothermal antibacterial therapy due to their ease of synthesis, good biodegradability, long‐term safety, and excellent photostability. However, the therapeutic effects of PDA nanoparticles are generally limited by the low photothermal conversion efficiency (PCE). Herein, PDA@Ag nanoparticles are synthesized via growing Ag on the surface of PDA nanoparticles and then encapsulated into a cationic guar gum (CG) hydrogel network. The optimized CG/PDA@Ag platform exhibits a high PCE (38.2%), which is more than two times higher than that of pure PDA (16.6%). More importantly, the formulated CG/PDA@Ag hydrogel with many active groups can capture and kill bacteria through effective interactions between hydrogel and bacteria, thereby benefiting the antibacterial effect. As anticipated, the designed CG/PDA@Ag system combined the advantages of PDA@Ag nanoparticles (high PCE) and hydrogel (preventing aggregation of PDA@Ag nanoparticles and possessing inherent antibacterial ability) is demonstrated to have superior antibacterial efficacy both in vitro and in vivo. This study develops a facile approach to boost the PCE of PDA for photothermal antibacterial therapy, providing a significant step forward in advancing the application of PDA nano‐photothermal agents.
Nanographene with Multiple Embedded Heptagons: Cascade Radical Photocyclization
Authors: Qiu Zhen‐Lin , Chen Xuan‐Wen , Huang Yu‐Dong , Wei Rong‐Jing , Chu Ke‐Shan , Zhao Xin‐Jing , Tan Yuan‐Zhi 
Published: February 2022

AbstractAlthough heptagons are widely found in graphenic materials, the precise synthesis of nanocarbons containing heptagons remains a challenge, especially for the nanocarbons containing multiple‐heptagons. Herein, we show that photo‐induced radical cyclization (PIRC) can be used to synthesize multi‐heptagon‐embedded nanocarbons. Notably, a nanographene containing six heptagons (1) was obtained via a six‐fold cascade PIRC reaction. The structure of 1 was clearly validated and showed a Monkey‐saddle‐shaped conformation. Experimental bond analysis and theoretical calculations indicated that the heptagons in 1 were non‐aromatic, whereas the peripheral rings were highly aromatic. Compared to planar nanographene with the same number of π electrons, 1 had a similar optical gap due to a compromise between the decreased conjugation in the wrapped structure and enhanced electronic delocalization at the rim. Electrochemical studies showed that 1 had low‐lying oxidation potentials, which was attributed to the nitrogen‐doping.
Increasing the Number of Aluminum Atoms in T3 Sites of a Mordenite Zeolite by Low‐Pressure SiCl4 Treatment to Catalyze Dimethyl Ether Carbonylation
Authors: Liu Rongsheng , Fan Benhan , Zhang Wenna , Wang Linying , Qi Liang , Wang Yingli , Xu Shutao , Yu Zhengxi , Wei Yingxu , Liu Zhongmin 
Published: February 2022

AbstractControlling the location of aluminum atoms in a zeolite framework is critical for understanding structure–performance relationships of catalytic reaction systems and tailoring catalyst design. Herein, we report a strategy to preferentially relocate mordenite (MOR) framework Al atoms into the desired T3 sites by low‐pressure SiCl4 treatment (LPST). High‐field 27Al NMR was used to identify the exact location of framework Al for the MOR samples. The results indicate that 73 % of the framework Al atoms were at the T3 sites after LPST under optimal conditions, which leads to controllably generating and intensifying active sites in MOR zeolite for the dimethyl ether (DME) carbonylation reaction with higher methyl acetate (MA) selectivity and much longer lifetime (25 times). Further research reveals that the Al relocation mechanism involves simultaneous extraction, migration, and reinsertion of Al atoms from and into the parent MOR framework. This unique method is potentially applicable to other zeolites to control Al location.
Near‐Infrared Light‐Activatable Spherical Nucleic Acids for Conditional Control of Protein Activity
Authors: Zhang Jingfang , Zhao Peng , Li Wenzhe , Ye Ling , Li Lele , Li Zhengping , Li Mengyuan 
Published: February 2022

AbstractOptical control of protein activity represents a promising strategy for precise modulation of biological processes. We report rationally designed, aptamer‐based spherical nucleic acids (SNAs) capable of noninvasive and programmable regulation of target protein activity by deep‐tissue‐penetrable near‐infrared (NIR) light. The photoresponsive SNAs are constructed by integrating activatable aptamer modules onto the surface of upconversion nanoparticles. The SNAs remain inert but can be remotely reverted by NIR light irradiation to capture the target protein and thus function as an enzyme inhibitor, while introduction of antidote DNA could further reverse their inhibition functions. Furthermore, we demonstrate the potential of the SNAs as controllable anticoagulants for the NIR light‐triggered regulation of thrombin function. Ultimately, the availability of diverse aptamers would allow the design to regulate the activities of various proteins in a programmable manner.
Cove‐Edged Hexa‐peri‐hexabenzo‐bis‐peri‐octacene: Molecular Conformations and Amplified Spontaneous Emission
Authors: Gu Yanwei , Vega‐Mayoral Victor , Garcia‐Orrit Saül , Schollmeyer Dieter , Narita Akimitsu , Cabanillas‐González Juan , Qiu Zijie , Müllen Klaus 
Published: February 2022

AbstractThe bottom‐up synthesis of an unprecedentedly large cove‐edged nanographene, hexa‐peri‐hexabenzo‐bis‐peri‐octacene (HBPO), is reported in this work. Chiral high‐performance liquid chromatography and density functional theory (DFT) calculations revealed multiple conformations in solution. Two different molecular conformations, “waggling” and “butterfly”, were found in crystals by X‐ray crystallography, and the selectivity of conformations could be tuned by solvents. The optoelectronic properties of HBPO were investigated by UV/Vis absorption and fluorescence spectroscopies, cyclic voltammetry, and DFT calculations. The contorted geometry and branched alkyl groups suppress the aggregation of HBPO in solution, leading to a high fluorescence quantum yield of 79 %. The optical‐gain properties were explored through transient absorption and amplified spontaneous emission spectroscopies, which enrich the choices of edge structures for potential applications in laser cavities.
The SARS‐CoV‐2 Spike Glycoprotein Directly Binds Exogeneous Sialic Acids: A NMR View
Authors: Unione Luca , Moure María J. , Lenza Maria Pia , Oyenarte Iker , Ereño‐Orbea June , Ardá Ana , Jiménez‐Barbero Jesús 
Published: February 2022

AbstractThe interaction of the SARS CoV2 spike glycoprotein with two sialic acid‐containing trisaccharides (α2,3 and α2,6 sialyl N‐acetyllactosamine) has been demonstrated by NMR. The NMR‐based distinction between the signals of those sialic acids in the glycans covalently attached to the spike protein and those belonging to the exogenous α2,3 and α2,6 sialyl N‐acetyllactosamine ligands has been achieved by synthesizing uniformly 13C‐labelled trisaccharides at the sialic acid and galactose moieties. STD‐1H,13C‐HSQC NMR experiments elegantly demonstrate the direct interaction of the sialic acid residues of both trisaccharides with additional participation of the galactose moieties, especially for the α2,3‐linked analogue. Additional experiments with the spike protein in the presence of a specific antibody for the N‐terminal domain and with the isolated receptor binding and N‐terminal domains of the spike protein unambiguously show that the sialic acid binding site is located at the N‐terminal domain.
Dynamic Full‐Color Tuning of Organic Chromophore in a Multi‐Stimuli‐Responsive 2D Flexible MOF
Authors: Yao Zhao‐Quan , Wang Kai , Liu Rui , Yuan Yi‐Jia , Pang Jing‐Jing , Li Quan Wen , Shao Tian Yin , Li Zhi Gang , Feng Rui , Zou Bo , Li Wei , Xu Jian , Bu Xian‐He 
Published: February 2022

AbstractDeveloping universal stimuli‐responsive materials capable of emitting a broad spectrum of colors is highly desirable. Herein, we deliberately grafted a conformation‐adaptable organic chromophore into the established coordination space of a flexible metal–organic framework (MOF). In terms of the coupled structural transformations and the space confinement, the chromophore in the MOF matrix underwent well‐regulated conformational changes under physical and chemical stimuli, simultaneously displaying thermo‐, piezo‐, and solvato‐fluoro‐chromism with color tunability over the visible range. Owing to the resilient nature and the reduced dimensionality of the selected coordination space, all three color modulations behaved in a sensitive and self‐reversible manner, each following a linear correlation of the emission maximum with stimulus. Single‐crystal X‐ray diffraction of the variable‐temperature structures and solvent‐inclusion crystals elucidated the intricate color varying mechanisms.
Real‐Time Fluorescent Monitoring of Kinetically Controlled Supramolecular Self‐Assembly of Atom‐Precise Cu8 Nanocluster
Authors: Sun Pan‐Pan , Han Bao‐Liang , Li Hong‐Guang , Zhang Cheng‐Kai , Xin Xia , Dou Jian‐Min , Gao Zhi‐Yong , Sun Di 
Published: February 2022

AbstractKinetically stable and long‐lived intermediates are crucial in monitoring the progress and understanding of supramolecular self‐assembly of diverse aggregated structures with collective functions. Herein, the complex dynamics of an atomically precise CuI nanocluster [Cu8(tBuC6H4S)8(PPh3)4] (Cu8a) is systematically investigated. Remarkably, by monitoring the aggregation‐induced emission (AIE) and electron microscopy of the kinetically stable intermediates in real time, the directed self‐assembly (DSA) process of Cu8a is deduced. The polymorphism and different emission properties of Cu NCs aggregates were successfully captured, allowing the structure–optical property relationship to be established. More importantly, the utilization of a mathematical “permutation and combination” ideology by introducing a heterogeneous luminescent agent of a carbon dot (CD) to Cu8a aggregates enriches the “visualization” fluorescence window, which offers great potential in real time application for optical sensing of materials.
Proton‐Assisted Aqueous Manganese‐Ion Battery Chemistry
Authors: Bi Songshan , Zhang Yan , Deng Shenzhen , Tie Zhiwei , Niu Zhiqiang 
Published: February 2022

AbstractAqueous manganese‐ion batteries (MIBs) are promising energy storage systems because of the distinctive merits of Mn metal, in terms of high abundance, low cost, nontoxicity, high theoretical capacity and low redox potential. Conventional MIBs are based on the Mn2+ ion storage mechanism, whereas the capacity in cathode materials is generally limited due to the high charge density and large solvated ionic radius of Mn2+ ions in aqueous electrolytes. Herein, proton intercalation chemistry is introduced in aqueous MIBs, in which the layered Al0.1V2O5⋅1.5 H2O (AlVO) cathode exhibits a consequent Mn2+ and H+ ion intercalation/extraction process. Such an energy storage mechanism contributes to enhanced electrochemical performance, including high capacity, fast reaction kinetics and stable cycling behavior. Benefiting from this proton intercalation chemistry, the aqueous Mn||AlVO cells could deliver high specific energy and power simultaneously. This work provides a route for the design of high‐performance aqueous MIBs.
Divergent Total Synthesis of Four Kopsane Alkaloids: N‐Carbomethoxy‐10,22‐dioxokopsane, Epikopsanol‐10‐lactam, 10,22‐Dioxokopsane, and N‐Methylkopsanone
Authors: Qin Bo , Lu Zhepei , Jia Yanxing 
Published: February 2022

AbstractWe have achieved the divergent total synthesis of four kopsane alkaloids which share a complex heptacyclic caged ring system. Key transformations include an asymmetric Diels–Alder reaction to assemble the central bicyclo[2.2.2]octane moiety and the quaternary stereocenter at C20, a SmI2‐mediated cascade reduction/aldol reaction to construct the five‐membered ring and the quaternary stereocenter at C7, and a late‐stage cascade reductive amination/cyclization to establish the highly strained caged ring system.
Self‐assembly of Gold Nanoparticles into an Adjustable Plasmonic 3D Lattice using Janus‐type Forked Mesogenic Ligands
Authors: Zhao Yang‐yang , Cao Yu , Siligardi Giuliano , Mehl Georg H. , Liu Feng , Ungar Goran 
Published: February 2022

AbstractWe report the formation of a 3D body‐centred self‐assembled superlattice of gold nanoparticles whose interparticle gap, and hence its plasmonic properties, are adjustable exclusively in the xy‐plane. Thus, even though the particles are spherical, their anisotropic packing generates tailorable plasmonic dichroism. The gold nanoparticles are coated with forked ligands containing two mesogens: either two cholesterols (“twin”), one cholesterol and one azobenzene (“Janus”), or a mixture of the two. Beside the body‐centered arrangement of gold nanoparticles, the structure also contains unusual two‐dimensionally x‐y dual undulated (eggbox‐like) smectic‐like layers of mesogens. Moreover, the presence of azobenzene mesogens allows the superlattice to be melted through UV‐induced photo‐isomerization; the process is reversible displaying low fatigue on repeated cycling.
A Rhodol‐based Fluorescent Probe with a Pair of Hydrophilic and Rotatable Wings for Sensitively Monitoring Intracellular Polarity
Authors: Wasim Afzal Muhammad , Duan Kaixuan , Zhang Yanhui , Gao Ying , Qin Bo , Wang Guangwei , Lei Lin , Tang Haoyang , Guo Yuan 
Published: February 2022

AbstractCell polarity, as a vital intracellular microenvironment characteristic, has immense effects on numerous pathological and biological processes. Therefore, the tracking of polarity variations is highly essential to explore the role and mechanism of the polarity in pathophysiological processes. Herein, we designed and synthesized a novel rhodol‐based fluorescent probe (RDS) sensitive to polarity by introducing a bis(2‐hydroxyethylthio)methyl group, like a pair of hydrophilic and rotatable wings, into the rhodol skeleton. This unique design makes RDS adopt the colorless and non‐fluorescent spirocyclic form in a low‐polarity medium while the colored and fluorescent ring‐open form is present in a high‐polarity system, resulting in a positive‐correlation response of fluorescence intension to polarity. Importantly, RDS was successfully applied to monitor the polarity changes in living cells including cancer cells, healthy cells and senescent healthy cells, visualizing that the polarity of cancer cells is lower than that of healthy cells in which the more senescent ones have higher polarity.
Detection of cellular metabolites by redox enzymatic cascades
Authors: Tinikul Ruchanok , Trisrivirat Duangthip , Chinantuya Wachirawit , Wongnate Thanyaporn , Watthaisong Pratchaya , Phonbuppha Jittima , Chaiyen Pimchai 
Published: February 2022

AbstractDetection of cellular metabolites that are disease biomarkers is important for human healthcare monitoring and assessing prognosis and therapeutic response. Accurate and rapid detection of microbial metabolites and pathway intermediates is also crucial for the process optimization required for development of bioconversion methods using metabolically engineered cells. Various redox enzymes can generate electrons that can be employed in enzyme‐based biosensors and in the detection of cellular metabolites. These reactions can directly transform target compounds into various readout signals. By incorporating engineered enzymes into enzymatic cascades, the readout signals can be improved in terms of accuracy and sensitivity. This review critically discusses selected redox enzymatic and chemoenzymatic cascades currently employed for detection of human‐ and microbe‐related cellular metabolites including, amino acids, d‐glucose, inorganic ions (pyrophosphate, phosphate, and sulfate), nitro‐ and halogenated phenols, NAD(P)H, fatty acids, fatty aldehyde, alkane, short chain acids, and cellular metabolites.