bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Alkoxide-Bridged Dinuclear Zinc(II) Hexaazacryptate: A Novel Phosphate Capture Molecule in Aqueous Solution
Authors: Kinoshita Eiji , Ishikawa Kouhei , Kinoshita-Kikuta Emiko , Ohtani Kazuhiro , Shiro Motoo , Koike Tohru 
Published: January 2005

Abstract
A novel dinuclear zinc(II) hexaazacryptate (Zn2L3+) has been synthesized as a phosphate capture molecule in aqueous solution (L = an alkoxide form of 4,16-(2-hydroxypropano)-1,4,7,13,16,19-hexaazacyclotetracosane). Potentiometric pH titration study disclosed a 1:1 phenyl phosphate complexation with Zn2L3+. The dissociation constant, Kd ( = [Zn2L3+][PhOPO32−]/[Zn2L3+–PhOPO32−]) is a small value of 6 × 10 − 7 M at 35 °C with I = 0.10 (NaNO3). The X-ray crystal analysis of the p-nitrophenyl phosphate complex with Zn2L3+ showed that the phosphate dianion binds as a bridging ligand to the two zinc(II) ions. The analogous 1:1 CH3COO−-bound Zn2L3+ complex was isolated and characterized by X-ray analysis.
Selective Nitration of Thiacalix[4]arene and an Investigation of Its Acid–Base Properties with a Chemometric Method
Authors: Hu Xiaojun , Shi Huijie , Shi Xianfa , Zhu Zhongliang , Sun Qiuhong , Li Yong , Yang Haijun 
Published: January 2005

Abstract
The selective dinitro-substituted derivative of thiacalix[4]arene was synthesized by a three-step route and characterized. Its acid–base properties in a water solution were studied by UV–vis spectroscopy. Its four pKa values were determined by Target Testing Factor Analysis (TTFA).
Synthesis and Structural Analysis of Oligo(naphthalene-2,3-diyl)s
Authors: Motomura Takahisa , Nakamura Hideko , Suginome Michinori , Murakami Masahiro , Ito Yoshihiko 
Published: January 2005

Abstract
Oligo(naphthalene-2,3-diyl)s are synthesized by the palladium-catalyzed cross-coupling reactions of 2-naphthylzinc compounds with 2-bromonaphthalene derivatives. An NMR analysis together with an X-ray diffraction study supports the conjecture that the helical secondary structure is a common feature of the assemblies in which naphthalene-like aromatic units are linked together between the β-positions in series.
Aqueous Ammonia as a New Activator for Sonogashira Coupling
Authors: Mohamed Ahmed Mohamed S , Sekiguchi Akitoshi , Masui Kentaro , Mori Atsunori 
Published: January 2005

Abstract
Sonogashira coupling, which is a coupling reaction of terminal alkynes with organic halides, takes place with dilute aqueous ammonia as an activator. The reaction of several terminal alkynes and aryl iodides in the presence of small excess of aqueous ammonia at room temperature furnishes the cross-coupling product in good-to-excellent yields. A water-soluble amine with a high boiling point is alternatively employed for reactions at higher temperatures. A related coupling reaction in the presence of carbon monoxide also proceeded at room temperature and under ambient pressure to afford α,β-alkynyl ketones efficiently.
Formation of Active Sites for the NO + CO Reaction over Palladium Catalysts Supported on Mesoporous Silica
Authors: Yamaguchi Aritomo , Hayashi Takamitsu , Oyaizu Kenichi , Yuasa Makoto 
Published: January 2005

Abstract
The catalytic activities and structural changes of Pd containing mesoporous silica (Pd/MCM-41) catalysts for the NO + CO reaction were investigated. Pd/MCM-41 after calcination in air showed a very high catalytic activity for the NO + CO reaction because Pd metal particles with an appropriate size for the reaction were formed by the reaction gases.
Synthesis, Structures, and Reactions of Coordinatively Unsaturated Trinuclear Ruthenium Polyhydrido Complexes, [{Ru(C5Me5)}3(μ-H)6](Y) (Y = BF4, CF3SO3, 1/2(SO4), C6H5CO2, CH3CO2, B(C6H5)4, PF6) and [{Ru(C5Me5)}3(μ-H)3(μ3-H)2]
Authors: Suzuki Hiroharu , Kakigano Takeaki , Tada Ken-ichi , Igarashi Minoru , Matsubara Kouki , Inagaki Akiko , Oshima Masato , Takao Toshiro 
Published: January 2005

Abstract
Cationic triruthenium hexahydrido complexes, [{Ru(C5Me5)}3(μ-H)6](Y) (Y = BF4, CF3SO3, 1/2(SO4), C6H5CO2, CH3CO2), have been synthesized by the reaction of diruthenium tetrahydride [{Ru(C5Me5)}2(μ-H)4] with the corresponding acid, HBF4, CF3CO2H, H2SO4, C6H5CO2H, and CH3CO2H. The trimeric structure of these complexes has been confirmed by a crystallographic study of [{Ru(C5Me5)}3(μ-H)6](PF6). The treatment of [{Ru(C5Me5)}3(μ-H)6](Y) with CH3ONa in methanol selectively afforded a neutral trinuclear pentahydrido complex, [{Ru(C5Me5)}3(μ-H)3(μ3-H)2], which underwent an intermolecular H/D exchange reaction with benzene-d6, toluene-d8, or o-xylene-d10 to give [{Ru(C5Me5)}3(μ-D)3(μ3-D)2] as the result of arene C–H bond activation via an η2-arene intermediate complex. A cationic hydrido complex, [{Ru(C5Me5)}3(μ-H)6](Y), having a carboxylate as a counter anion was equilibrated with [{Ru(C5Me5)}3(μ-H)3(μ3-H)2] in solution, and the equilibrium constant depended on the counter anion. An X-ray diffraction study showed that [{Ru(C5Me5)}3(μ-H)3(μ3-H)2] has a triangular reaction field surrounded by three C5Me5 ligands. The reaction of [{Ru(C5Me5)}3(μ-H)3(μ3-H)2] with 1 equiv of O2 proceeded with the retention of the Ru3 framework to yield an 80/20 mixture of a mono-μ3-oxo complex [{Ru(C5Me5)}3(μ-H)3(μ3-O)] and a di-μ3-oxo complex [{Ru(C5Me5)}3(μ-H)3(μ3-O)2]. A novel trinuclear μ3-iodo-tetra-μ-hydrido complex, [{Ru(C5Me5)}3(μ3-H)(μ-H)3(μ3-I)] was formed upon the treatment of [{Ru(C5Me5)}3(μ-H)3(μ3-H)2] with 1 equiv of CH3I in tetrahydrofuran. The treatment of [{Ru(C5Me5)}3(μ-H)3(μ3-H)2] with carbon monoxide generated a paramagnetic trinuclear tetracarbonyl complex, [{Ru(C5Me5)}3(μ-CO)3(μ3-CO)].
Effective scCO2-ionic Liquid Reaction System Based on Symmetric Aliphatic Ammonium Salts for the Rapid CO2 Fixation with Aziridine to 2-Oxazolidinone
Authors: Kawanami Hajime , Matsumoto Hajime , Ikushima Yutaka 
Published: January 2005

Abstract
The hybrid reaction system composed of supercritical carbon dioxide and room temperature ionic liquid based on symmetric tetraalkyl ammonium salts can effectively promote the carbon dioxide fixation from aziridine to 2-oxazolidinone in the presence of iodine in high yield of 98% within 5 min. The TOF value under this condition is 254 times larger than that using conventional organic solvent.
Thiocyanate-selective PVC Membrane Electrode Based on Tricoordinate Schiff Base Copper(II) Complex
Authors: Dai Jian-Yuan , Chai Ya-Qin , Yuan Ruo , Zhang Yi-Sen , Liu Yan , Zhong Xia , Tang Dian-Ping 
Published: January 2005

Abstract
A new thiocyanate selective PVC membrane electrode was prepared by using a tricoordinate dimethylaminobenzaldehyde Schiff base copper(II) complex as neutral carrier, which demonstrates highly selectivity response to thiocyanate with substantially improved performance such as long lifetime, wide potentiometric response range, and low detection limit.
Temperature Dependence on the Activation Energy of Dechlorination in Thermal Degradation of Polyvinylchloride
Authors: Yoshioka Toshiaki , Saitoh Nobuo , Okuwaki Akitsugu 
Published: January 2005

Abstract
The dechlorination of polyvinylchloride (PVC) powder initially progressed on an apparent zero order reaction, and proceeded in higher dechlorination range by an apparent first order reaction. The apparent activation energies indicate that the rate of the dehydrochlorination is controlled by the chemical reaction at low temperature, but that from 300 to 400 °C is controlled by heat transfer rate.
A Novel Patterning Method of Low-resistivity Metals
Authors: Noh Chang-Ho , Son Hae-Jung , Kim Jin-Young , Hwang Ok-Chae , Song Ki-Yong , Byk T V , Sokolov V G , Kim Jin-Baek 
Published: January 2005

Abstract
Photocatalytic layers of amorphous TiO2 and polyvinyl alcohol were used for the patterning of low-resistivity metals such as copper and silver without using high cost materials and equipment.
Denosumab and the Risk of Diabetes in Patients Treated for Osteoporosis
Authors: Huang Huei-Kai , Chuang Albert Tzu-Ming , Liao Tzu-Chi , Shao Shih-Chieh , Liu Peter Pin-Sung , Tu Yu-Kang , Lai Edward Chia-Cheng 
Published: February 2024

ImportanceDenosumab, a humanized monoclonal antibody against receptor activator of nuclear factor κB ligand (RANKL), is a widely used antiresorptive medication for osteoporosis treatment. Recent preclinical studies indicate that inhibition of RANKL signaling improves insulin sensitivity, glucose tolerance, and β-cell proliferation, suggesting that denosumab may improve glucose homeostasis; however, whether denosumab reduces the risk of incident diabetes remains unclear.ObjectiveTo evaluate whether denosumab use is associated with a lower risk of developing diabetes in patients with osteoporosis.Design, Setting, and ParticipantsThis nationwide, propensity score–matched cohort study used administrative data from Taiwan’s National Health Insurance Research Database. Adult patients who received denosumab for osteoporosis therapy in Taiwan between 2012 and 2019 were included. To eliminate the inherent bias from confounding by indication, the patients were categorized into a treatment group (34 255 patients who initiated denosumab treatment and adhered to it) and a comparison group (34 255 patients who initiated denosumab treatment but discontinued it after the initial dose) according to the administration status of the second dose of denosumab. Propensity score matching was performed to balance patient characteristics and to control for confounders.ExposureTreatment with denosumab.Main Outcomes and MeasuresThe primary outcome was incident diabetes requiring treatment with antidiabetic drugs. A Cox proportional hazards model was used to estimate the hazard ratio (HR) for incident diabetes. Data were analyzed from January 1 to November 30, 2023.ResultsAfter propensity score matching, 68 510 patients were included (mean [SD] age, 77.7 [9.8] years; 57 762 [84.3%] female). During a mean (SD) follow-up of 1.9 (1.6) years, 2016 patients developed diabetes in the treatment group and 3220 developed diabetes in the comparison group (incidence rate, 35.9 vs 43.6 per 1000 person-years). Compared with the comparison group, denosumab treatment was associated with a lower risk of incident diabetes (HR, 0.84; 95% CI, 0.78-0.90). Several sensitivity analyses also demonstrated similar results of lower diabetes risk associated with denosumab treatment.Conclusions and relevanceThe results from this cohort study indicating that denosumab treatment was associated with lower risk of incident diabetes may help physicians choose an appropriate antiosteoporosis medication for patients with osteoporosis while also considering the risk of diabetes.
Merging MOF Chemistry & Biocatalysis: A Perspective for Achieving Efficient Organic Synthetic Processes and Applications in the Chemical Industry?
Authors: Gröger Harald , Allahverdiyev Adil , Yang Jianing , Stiehm Johannes 
Published: February 2024

AbstractBiocatalysis has emerged in recent decades toward a widely applied catalysis technology in the chemical industry. In particular the fine chemicals and pharmaceuticals industries benefit from the advantages of biocatalysis, which made its way to a dominating industrial core technology for manufacturing chiral molecules. However, often biocatalysis is still to a certain extent away from having solved all challenges being needed for a “perfect industrial process technology”. Among existing challenges are, e.g., stability under process conditions and easy separation of the catalyst from the reaction mixture with the additional option of recyclability. Here metal‐organic framework (MOF) structures offer unique advantages, which can be beneficial for biocatalysis. A particular valuable option is integration of enzymes into MOF‐subunits, thus having a potential positive impact on stability (by reducing the tendency of unfolding) and enabling compartmentalization as a beneficial strategy in, e.g., chemoenzymatic synthesis. In this “Perspective”‐article, first the state of the art in biocatalysis is briefly summarized together with current challenges. Then, a short overview about current research achievements in “merging” MOF chemistry and biocatalysis is given as well as an outlook written from a biocatalysis practitioner's view, how MOF‐enzyme hybrid systems can play a major role in future process development to overcome existing hurdles of enzymatic catalysis.
Tempospatially Confined Catalytic Membranes for Advanced Water Remediation
Authors: Lu Na , Liu Fu 
Published: February 2024

AbstractThe application of homogeneous catalysts in water remediation is limited by their excessive chemical and energy input, weak regenerability, and potential leaching. Heterogeneous catalytic membranes (CMs) offer a new approach to facilitate efficient, selective, and continuous pollutant degradation. Thus, integrating membranes and continuous filtration with heterogeneous advanced oxidation processes (AOPs) can promote thermodynamic and kinetic mass transfers in spatially confined intrapores and facilitate diffusion‐reaction processes. Despite the remarkable advantages of heterogeneous CMs, their engineering application is practically restricted due to the fuzzy design criteria for specific applications. Herein, the recent advances in CMs for advanced water remediation are critically reviewed and the design flow for tempospatially confined CMs is proposed. Further, state‐of‐the‐art CM materials and their catalytic mechanisms are reviewed, after which the tempospatial confinement mechanisms comprising the nanoconfinement effect, interface effect, and kinetic mass transfer are emphasized, thus clarifying their roles in the construction and performance optimization of CMs. Additionally, the fabrication methods for CMs based on their catalysts and pore sizes are summarized and an overview of their application and performance evaluations is presented. Finally, future directions for CMs in materials research and water treatment, are presented.
Dilute Nanocomposites: Tuning Polymer Chain Local Nanostructures to Enhance Dielectric Responses
Authors: Rui Guanchun , Bernholc Jerzy (Jerry) , Zhang Shihai , Zhang Qiming 
Published: February 2024

AbstractDielectric polymers possessing high energy and low losses are of great interest for electronic and electric devices and systems. Nanocomposites in which high dielectric constant (high‐K) nanofillers at high loading (>10 vol%) are admixed with polymer matrix have been investigated for decades, aiming at enhancing the dielectric performance, but with limited success. In 2017, it is discovered that reducing nanofiller loading to less than 0.5 vol% in polymer matrix can lead to marked enhancement in dielectric performance. Here, we reviewed the discoveries and advances of this unconventional approach to enhance dielectric performance of polymers. Experimental studies uncover that nanofillers lead to interfaces changes over distances larger than 100 nm. Experimental and modeling results show that introducing free volume in polymers reduces the constraints of glass matrix on dipoles in polymers, leading to enhanced K without affecting breakdown. Moreover, low‐K nanofillers at low‐volume loading serve as deep traps for charges, lowering conduction losses and increasing breakdown strength. The dilute nanocomposites provide new avenues for designing dielectric polymers with high K, minimal losses, and robust breakdown fields, thus achieving high energy and power density and low loss for operation over a broad temperature regime.
Emerging Strategies for the Synthesis of Correlated Single Atom Catalysts
Authors: Huang Yucong , Xiong Jingjing , Zou Zhigang , Chen Zhongxin 
Published: February 2024

AbstractPeople have been looking for an energy‐efficient and sustainable method to produce future chemicals for decades. Heterogeneous single‐atom catalysts (SACs) with atomic dispersion of robust, well‐characterized active centers are highly desirable. In particular, correlated SACs with cooperative interaction between adjacent single atoms allow the switching of the single‐site pathway to the dual or multisite pathway, thus promoting bimolecular or more complex reactions for the synthesis of fine chemicals. Herein, the structural uniqueness of correlated SACs, including the intermetal distance and electronic interaction in homo/heteronuclear metal sites is featured. Recent advances in the production methods of correlated SACs, showcasing the research status and challenges in traditional methods (such as pyrolysis, wet impregnation, and confined synthesis) for building a comprehensive multimetallic SAC library, are summarized. Emerging strategies such as process automation and continuous‐flow synthesis are highlighted, minimizing the inconsistency in laboratory batch production and allowing high throughput screening and upscaling toward the next‐stage chemical production by correlated SACs.
Emerging Co‐Assembled and Sustained Released Natural Medicinal Nanoparticles for Multitarget Therapy of Choroidal Neovascularization
Authors: Shen Jingjing , Chen Linfu , Lv Xinying , Liu Nanhui , Miao Yu , Zhang Qiang , Xiao Zhisheng , Li Maoyi , Yang Yang , Liu Zhuang , Chen Qian 
Published: February 2024

AbstractAge‐related macular degeneration (AMD) disease has become a worldwide senile disease, and frequent intravitreal injection of anti‐vascular endothelial growth factor (anti‐VEGF) is the mainstream treatment in the clinic, which is associated with sight‐threatening complications. Herein, nintedanib, an inhibitor of angiogenesis, and lutein, a potent antioxidant, can co‐assemble into nanoparticles through multiple noncovalent interactions. Interestingly, the co‐assembled lutein/nintedanib nanoparticles (L/N NPs) exhibit significantly improved stability and achieve long‐term sustained release of two drugs for at least two months in mice. Interestingly, in rabbit eyeball with a more complete barrier system, the L/N NPs still successfully distribute in the retina and choroid for a month. In the laser‐induced mouse choroidal neovascularization model, the L/N NPs after a minimally invasive subconjunctival administration can successfully inhibit angiogenesis and achieve comparable and even better therapeutic results to that of standard intravitreal injection of anti‐VEGF. Therefore, the subconjunctival injection of L/N NPs with long‐term sustained drug release behavior represents a promising and innovative strategy for AMD treatment. Such minimally invasive administration together with the ability to effectively inhibit angiogenesis reduce inflammation and counteract oxidative stress and holds great potential for improving patient outcomes and quality of life in those suffering from this debilitating eye condition.
Lattice Strain Enhanced Phase Transformation of NaYbF4: 2% Er3+ Upconverting Nanoparticles by Tuning the Molar Ratio of Na+/Yb3+
Authors: Xiao Weitong , Chen Jingyang , Wang Feiran , Luan Weiling , Wu Yiting , Turyanska Lyudmila 
Published: February 2024

AbstractNaYbF4 upconverting nanoparticles (UCNPs) have enhanced optical properties compared to the NaYF4 UCNPs. However, synthesis of monodisperse NaYbF4 with controllable size and optical properties poses challenges, and the mechanism of phase transformation remains to be understood. Here, they report on the effect of Na+/Yb3+ molar ratio on the morphological and optical properties of upconverting NaYbF4: 2% Er3+ nanoparticles. Controllable transformation of cubic phase nanoparticles produced with [Na+]/[Yb3+] = 1 to hexagonal phase is achieved by increasing Na+ content. The hexagonal UCNPs produced with [Na+]/[Yb3+] = 4 have significantly enhanced intensity of optical emission of ≈600 times compared with the pure cubic phase crystal. The work reveals that the increasing dislocation of sodium and ytterbium distribution cause the accumulation of the lattice strain with increasing Na+ content, and triggers the lattice strain‐mediated phase transformation in cubic cell, as confirmed by the Density Function Theory simulations. These results provide new insights into the growth of UCNPs and pave the way for developing controlled synthesis of UCNPs for applications as bio‐probes and for energy harvesting.
ZrO2 Holographic Metasurfaces for Efficient Optical Trapping in The Visible Range
Authors: Biabanifard Mohammad , Plaskocinski Tomasz , Xiao Jianling , Di Falco Andrea 
Published: February 2024

AbstractHolographic Metasurfaces (HMs) in the visible range enable advanced imaging applications in compact, planarized systems. The ability to control and structure light with high accuracy and a high degree of freedom is particularly relevant in lab‐on‐chip biophotonic applications. Pushing the operation wavelength into the blue region and below is an open challenge. Here, it is demonstrated that Zirconium dioxide (ZrO2) metasurfaces (MSs) are particularly well‐suited to satisfy these requirements. Specifically, MSs are designed for optical trapping applications with a high numerical aperture (NA = 1.2) at a wavelength as low as 488 nm, with trap stiffness >200 pN (µmW)−1.
Facile Construction of Chestnut‐Like Structural Fireproof PDMS/Mxene@BN for Advanced Thermal Management and Electromagnetic Shielding Applications
Authors: Bian Fuping , Huang Rui , Li Xiaobin , Hu Jiwen , Lin Shudong 
Published: February 2024

AbstractComposite polymer materials featured superior thermal conductivity, flame retardancy, and electromagnetic shielding performance are increasingly in demand due to the rapid development of highly miniaturized, portable, and flexible electronic devices. Herein, a facile and green ball milling shear method is utilized for generating MXene@Boron nitride (MXene@BN). The multi‐functional fillers (MXene@BN) are constructed and incorporated into polydimethylsiloxane (PDMS) to prepare a multifunctional composite (PDMS/MXene@BN) for achieving improved electromagnetic interference (EMI) shielding performance and thermal conductivity as well as flame retardancy simultaneously. When the PDMS/MXene@BN composite has a MXene@BN loading of 2.4 wt.%, it exhibits a high thermal conductivity of 0.59 W m−1K−1, which is 210% higher than that of the pure PDMS matrix. This is attributed to its unique chestnut‐like double‐layer structure. With a smoke production rate (SPR) of 0.04 m2 s−1 and total smoke production (TSP) of 3.51 m2, PDMS/MXene@BN 2.4 composite exhibits superb smoke suppression properties. These SPR and TSP values are 63.20% and 63.50% lower than the corresponding values of pure PDMS. Moreover, the EMI SE of the PDMS/MXene@BN 2.4 can reach 26.3 dB at 8.5 GHz. The work reported herein provides valuable insight into developing composites with multiple functions, which show strong potential for application in advanced packaging materials.