bluuebunny/crossref_metadata_2025 huggingface dataset:
Electrocatalytic Reduction of Dioxygen to Water by a Carbon Electrode Coated with (μ-Oxo)bis[(meso-tetraphenylporphyrinato)iron(III)]: a Convenient Template for Cofacially Oriented Iron(II) Porphyrins
Authors: Haryono Agus , Oyaizu Kenichi , Yamamoto Kimihisa , Natori Junichiro , Tsuchida Eishun
Published: March 2003

Electroreduction of an oxo-bridged iron(III) porphyrin dimer adsorbed on an electrode surface produced solid state, cofacially fixed two iron(II) porphyrin molecules when immersed in aqueous acid, allowing an efficient catalysis of the four-electron reduction of O2 to H2O.
The First Spectroscopic Observation of an Equilibrium between a Digermene and Germylenes and Experimental Determination of a Bond Dissociation Energy of a Ge-Ge Double Bond
Authors: Kishikawa Kuniyuki , Tokitoh Norihiro , Okazaki Renji
Published: March 2003

An extremely hindered digermene (E)-Tbt(Mes)Ge=Ge(Mes)Tbt (2; Tbt=2, 4, 6-tris[bis(trimethylsilyl)methyl]phenyl; Mes=mesityl) was synthesized. The temperature dependent change of UV-vis absorptions of 2 in solution indicated the quantitative interconversion between 2 and the corresponding germylene 3. The thermodynamic parameters (ΔH=14.7 ± 0.2 kcal mol−1 and ΔS=42.4 ± 0.8 cal mol−1 K−1) (1cal=4.184 J) for the dissociation of digermene 2 to germylene 3 were obtained from temperature dependence of the absorptions of 2.
Oxidative and Random Cleavage of DNA by the Novel Iron(II) Complex Capable of Yielding an Iron(III) Hydroperoxide Intermediate
Authors: Ishikawa Yoshinobu , Morishita Yuko , Yamamoto Teruo , Kurosaki Hiromasa , Goto Masafumi , Matsuo Hiroaki , Sugiyama Masanori
Published: March 2003

A novel Fe(II) complex and H2O2 system causes sequence non-specific double-strand breaks of duplex DNAs at micromolar concentrations and the DNA cleavage is independent of the presence of hydroxyl radical scavengers. The same system can also oxidize hydrocarbons and the active species in the system is likely to be a Fe(III) hydroperoxide complex supported by characteristic purple absorption and EPR signals.
The New Possibility of Vinylideneruthenium(II) Complexes Derived from Terminal Alkynes: Ring-Opening Metathesis Polymerization of Norbornene Derivatives
Authors: Katayama Hiroyuki , Ozawa Fumiyuki
Published: March 2003

Vinylideneruthenium(II) complexes RuCl2[=C=CH(t-Bu)](PR3)2 (R=Ph, i-Pr, Cy) serve as good catalyst precursors for the ring-opening metathesis polymerization of norbornene derivatives.
Barotropic Phase Transitions and Pressure-induced Interdigitation on Bilayer Membrane of Dimyristoylphosphatidylcholine
Authors: Ichimori Hayato , Matsuki Hitoshi , Kaneshina Shoji
Published: March 2003

The thermotropic and barotropic phase transitions of dimyristoylphosphatidylcholine (DMPC) multilamellar vesicle have been studied. Both temperatures of the main transition and pretransition were elevated by pressure. A pressure-induced interdigitation of DMPC bilayer membrane was observed at high pressures above 300 MPa.
Novel Spiroacetal Synthesis via Hydroboration of Alkynediols
Authors: Fugami Keigo , Hagiwara Nobuhito , Okeda Takeaki , Kosugi Masanori
Published: March 2003

Alkynediols were transformed to the corresponding spiroacetals by the sequence of hydroboration with disiamylborane, oxidation of the resulting alkenylboron intermediate with alkaline hydrogen peroxide, and catalytic treatment with p-TsOH. By this transformation, 6-(2-hydroxymethyl)phenyl-3-methyl-5-hexyn-1-ol was converted to spiro[3,4-dihydro-1H-2-benzopyran-3,2′-[4′]methyl[3′,4′,5′,6′]tetrahydro-2′H-pyran] as a single diastereomer.
Synthesis and Unusual Spectral Properties of (Alkoxycarbonyl)methyl-Substituted Polysilanes
Authors: Hatanaka Yasuo , Okada Shingo , Onozawa Shun-ya , Suzuki Yohichi , Tanaka Masato
Published: March 2003

UV–vis spectra of partially branched polysilanes having (alkoxycarbonyl)methyl substituents exhibit unusual spectral properties such as absorption of very long wavelength and temperature- and solvent-dependent change of the spectra. These observations suggest that polar substituents effectively promote the σ-conjugation of the silicon backbones.
Synthesis of 4-Hydroxy-3-quinolinecarboxylic Acid Derivatives by a Condensation/Cyclization Sequence between o-Isocyanobenzoates and Magnesium Enolates
Authors: Kobayashi Kazuhiro , Nakashima Toshio , Mano Masaaki , Morikawa Osamu , Konishi Hisatoshi
Published: March 2003

Addition of magnesium ester and amide enolates, generated using an excess amount of a magnesium amide (from diisopropylamine and ethylmagnesium bromide), to o-isocyanobenzoates affords 4-hydroxy-3-quinolinecarboxylic esters and amides by a tandem Claisen-type condensation/cyclization sequence.
Molecular Design of Low Molecular-weight Aqueous Gels Bearing an Azo-hydrazone Tautomeric Group Useful as a Solvent Polarity Probe
Authors: Amaike Masato , Kobayashi Hideki , Shinkai Seiji
Published: March 2003

Novel low molecular-weight gelators for aqueous gels were exploited by systematically search varying sugars and adjusting hydrophilic/lipophilic balance. The azonaphthol group was used as a lipophilic group, which was also useful as a measure of the microscopic solvent polarity. From the azo-hydrazone tautomerism the polarity in the gelator aggregates was estimated to be much less polar than that in the gelation media.
Molecular Wrapping of a Fluorescent Dye with TiO2-Gel and Capping Reagents
Authors: Ichinose Izumi , Kunitake Toyoki
Published: March 2003

A fluorescent molecule, fluorescein, was covered with an ultrathin TiO2-gel layer and the resulting nano-particles were stabilized by additional capping. Electron microscopy suggested aggregation and subsequent capping of wrapped fluorescein. The molecular wrapping was effective for suppressing fluorescence quenching by iodine.
A Novel Method for the Synthesis of Thiols from the Corresponding Olefins by Using Thiocarbonates and Ti(IV) Halides
Authors: Mukaiyama Teruaki , Saitoh Terunobu , Jona Hideki
Published: March 2003

A convenient method for the preparation of secondary or tertiary thiols from the corresponding olefins was established by using thiocarbonate, titanium(IV) chloride or fluoride and copper(II) oxide. Various thiols were obtained regioselectively in good to excellent yields according to the Markovnikov rule.
Aromatization of Highly Alkyl-substituted Dihydroanthracenes Using n-BuLi/TMEDA/MeI
Authors: Kitamura Masanori , Shen Baojian , Liu Yanjun , Zheng Hegen , Takahashi Tamotsu
Published: March 2003

Aromatization of highly alkyl-substituted dihydroanthracene was performed with the n-BuLi/TMEDA/MeI. Treatment of 1,2,3,4,5,6,7,8-octapropyl-9,10-dihydroanthracene with 2.2 equiv of n-BuLi, TMEDA at 50 °C in hexane for 3 h, followed by 1.1 equiv of MeI at room temperature for 1 h gave the corresponding anthracene in 98% yield.
Effect of Mn Doping on the Electronic Structure of ZnGa2O4 with Spinel-Type Structure
Authors: Nonaka Moriyasu , Tanizaki Takumi , Matsushima Shigenori , Mizuno Masataka , Xu Chao-Nan
Published: March 2003

The electronic structures of ZnGa2O4 and ZnGa2O4:Mn are calculated by the discrete variational Xα method on model clusters. For ZnGa2O4, it is found that Zn–O and Ga–O bondings are not perfectly ionic but partially covalent. When a central Zn atom of the cluster is replaced with a Mn atom, the new energy states originating from Mn 3d orbitals appear in the energy gap. The energy levels of t2 up-spin states and e down-spin states seem to relate to the green emission.
Simultaneous Electroanalysis of Ascorbic Acid, Dihydroxyphenylacetic Acid, Homovanillic Acid and Uric Acid Using Gold Electrode Modified with Cationic Self-Assembled Monolayers
Authors: Raj Chellappan Retna , Ohsaka Takeo
Published: March 2003

Cationic self-assembled monolayers (SAMs) of cystamine (CYST) and dithiobishexaneamine (DTH) are utilized for the simultaneous electroanalysis of four different anions, ascorbic acid (AA), dihydroxyphenylacetic acid (DOPAC), homovanillic acid (HVA) and uric acid (UA).
Fluorescence Studies on Binary Aromatic Compounds by Utilizing the Intermolecular Quadruple Hydrogen Bonding
Authors: Ikegami Masashi , Arai Tatsuo
Published: March 2003

Quadruple intermolecular hydrogen bonding of ureidopyrimidinone derivatives can be utilized to construct novel fluorescent excimer or exciplex system.
Synthesis of Fluorescent Amorphous Diarylethenes
Authors: Kim Myeong-Suk , Kawai Tsuyoshi , Irie Masahiro
Published: March 2003

1,2-Bis(2-methyl-1-benzothiophen-3-yl)perfluorocyclopentene derivatives having 2,4-diphenylphenyl substituents at 6 and 6′ positions of the benzothiophene rings were synthesized. Both mono- and di-substituted derivatives, compounds 1a and 2a, formed amorphous states at room temperature and their glass transition temperatures were observed at 88 °C and 127 °C, respectively. Remarkable spectral shift of the fluorescence from 650 nm to 450 nm was observed for the amorphous film of closed-ring isomer 2b upon visible (λ > 450 nm) light irradiation.
Oxidative Deamination of Various Primary Amines to the Corresponding Carbonyl Compounds by Using N-tert-Butylphenylsulfinimidoyl Chloride
Authors: Matsuo Jun-ichi , Kawana Asahi , Fukuda Yoshio , Mukaiyama Teruaki
Published: March 2003

Various linear and non-linear primary amines were oxidatively deaminated to afford the corresponding carbonyl compounds in good to excellent yields by the following procedure: (i) initial formation of their N-cyclohexylated or N-mesylated derivatives, (ii) subsequent oxidation of these derivatives by using N-tert-butylphenylsulfinimidoyl chloride (1) and DBU, (iii) one-pot acid-hydrolysis of thus formed imines to carbonyl compounds.
High Performance CO2 Gas Sensing with Combination of Multivalent Ion Conducting Solid Electrolytes with Water-Insoluble Auxiliary Electrode
Authors: Imanaka Nobuhito , Ogura Akio , Kamikawa Masayuki , Adachi Gin-ya
Published: March 2003

A carbon dioxide gas sensor was fabricated by combination of multivalent cation and anion conducting solid electrolytes with a water-insoluble Li and Ba codoped Nd2O2CO3 solid solution as an auxiliary electrode. The present sensor shows such a high durability not only in the atmosphere of gas phase water vapor coexistence but also after the exposure to the liquid phase water dew, in addition to persisting the rapid, reproducible response with a high stability from the operation.
Spectroscopic Evidence for Cooperative Binding of a Host in Molecular Hinge
Authors: Kitamura Noboru , Suzuki Yusuke , Chiba Masahiro , Sakata Norio , Kim Haeng-Boo
Published: March 2003

Recognition of a thymine derivative by a molecular-hinge type compound was investigated on the basis of absorption and fluorescence spectroscopies. Spectroscopic evidence for hydrogen-bonding and charge-transfer interactions in molecular recognition was demonstrated.
Use of 1-Methoxy-1-trimethylsilylallene Oxide and Titanium Tetraiodide as a Dianion Synthon of Methoxyacetone
Authors: Hayakawa Ryuuichirou , Makino Hiroaki , Shimizu Makoto
Published: March 2003

A dianion equivalent of methoxyacetone was successfully generated using 1-methoxy-1-trimethylsilylallene oxide and titanium tetraiodide and subsequent reaction with acetals or aldehydes gave α-methoxy-α,β-unsaturated ketones in good yields.
Hydrothermal Synthesis and Characterization of Single-Molecular-Layer MoS2 and MoSe2
Authors: Peng Yiya , Meng Zhaoyu , Zhong Chang , Lu Jun , Yu Weichao , Jia YunBo , Qian Yitai
Published: March 2003

Single-molecular-layer (SML) MoS2 and MoSe2 were synthesized by a hydrothermal method at 150–180 °C. XPS, XRD, ICP, and TEM were used to characterize the samples, and BET study indicated that the SML MoS2 has very large surface area. And it was found that the SML MoS2 has strong ability to catalytically decompose hydrazine monohydrate, just like platinum black.
Spectroscopy and Photocurrent Generation in Nanostructured Thin Films of Porphyrin–Fullerene Dyad Clusters
Authors: Imahori Hiroshi , Hasobe Taku , Yamada Hiroko , Kamat Prashant V , Barazzouk Said , Fujitsuka Mamoru , Ito Osamu , Fukuzumi Shunichi
Published: March 2003

Porphyrin–fullerene dyad cluster films, when cast on nanostructured SnO2 films, are photoelectrochemically active and generate anodic photocurrent under visible light excitation (maximal IPCE value = ∼ 0.4%).
Photo- and Proton-Coupled Isomerization of Novel Azo-Conjugated Platinadithiolene Complex
Authors: Nihei Masayuki , Kurihara Masato , Mizutani Jun , Nishihara Hiroshi
Published: March 2003

A platinum tolylazophenylenedithiolato complex was synthesized. This new azo-conjugated complex shows reversible trans-to-cis photoisomerization, protochromism, and novel proton-coupled cis-to-trans isomerization.
Reductive Dechlorination of α,ω-Dichloroalkanes Adsorbed on Molecular Sieve 13X
Authors: Yamamoto Yukio , Tagawa Seiichi
Published: March 2003

Reductive dechlorination of chlorinated alkanes adsorbed on molecular sieve 13X occurs at room temperature. The dechlorination yields for α,ω-dichloroalkanes, such as 1,4-dichlorobutane, 1,5-dichloropentane, and 1,6-dichlorohexane, did not exceed 50%, suggesting that only one of the chlorine atoms is activated for the reductive dechlorination in the cage of the molecular sieve. Effects of an irradiation with γ-rays on the dechlorination are described.
Formal Total Synthesis of Testudinariol A, a Triterpene with C2 Symmetry
Authors: Hioki Hideaki , Hamano Masayo , Kubo Miwa , Uno Tomoko , Kodama Mitsuaki
Published: March 2003

The alcohol corresponding to half of the molecule of testudinariol A, a triterpene with a symmetric C2 structure isolated from Pleurobrancus testudinarius, was enantioselectively synthesized. The alcohol has been converted to testudinariol A by Mori et al.
Structure and Properties of Diastereoisomers of a Ruthenium(II) Complex Having a Pyridylpyrazoline Derivative as a Ligand
Authors: Wang Pengfei , Onozawa-Komatsuzaki Nobuko , Katoh Ryuzi , Himeda Yuichiro , Sugihara Hideki , Arakawa Hironori , Kasuga Kazuyuki
Published: March 2003

Diastereoisomers of a heteroleptic ruthenium complex, [Ru(bpy)2L]2+ (bpy = 2,2′-bipyridine, L = 5-(4-nitrophenyl)-1-phenyl-3-(2-pyridyl)-2-pyrazoline) have been isolated. Two isomers have quite similar redox potentials and show MLCT absorptions in the region of 400 to 500 nm with similar absorption maxima at room temperature. By contrast, quite different emission maxima and lifetimes are observed at 77 K.
Synthesis and Optical Resolution of an anti-O,O′-Dialkylated Calix[4]arene
Authors: Narumi Fumitaka , Yamabuki Waka , Hattori Tetsutaro , Kameyama Hiroshi , Miyano Sotaro
Published: March 2003

Proximally O,O′-disiloxane-bridged calix[4]arene (1) was treated with benzyl bromide in the presence of Cs2CO3 to afford, after desilylation, anti-O,O′-dibenzylcalix[4]arene (4a) in 90% yield. Chromatographic separation of its diastereomeric (S)-2-methoxy-2-(1-naphthyl)propionic esters allowed the first optical resolution of this kind of dialkylated calix[4]arenes.
Spin Crossover Complex Film, [FeII(H-trz)3]-Nafion, with a Spin Transition around Room Temperature
Authors: Nakamoto Akio , Ono Yuuki , Kojima Norimichi , Matsumura Daiju , Yokoyama Toshihiko
Published: March 2003

We have synthesized [FeII(H-trz)3]n complex film by using ion-exchange resin(Nafion) as counter anion, and have found the spin crossover phenomenon about at 260 K. Moreover, we have proved the existence of straight one-dimensional Fe chain structure of [FeII(H-trz)3]n on Nafion by means of EXAFS.
New VUV Phosphor, NaLnGeO4:Eu3+ (Ln = Rare Earth)
Authors: Toda Kenji , Imanari Yu-ichiro , Nonogawa Takashi , Uematsu Kazuyoshi , Sato Mineo
Published: March 2003

The synthesis and luminescence properties of Eu3+-doped ordered olivine-type NaLnGeO4 (Ln = rare earth) phosphors are reported. Under vacuum-UV (VUV) excitation, this phosphor showed intense red emission due to the 5D0-7F2 transition. The Na(Y0.3Gd0.65Eu0.05)GeO4 phosphor with optimum composition and synthetic condition under 147 nm excitation were higher than those of (Y0.95Eu0.05)2O3.
Long-Term Microvascular Changes in Multisystem Inflammatory Syndrome in Children
Authors: Boever Julie , Nussbaum Claudia , Arnold Leonie , Haas Nikolaus A. , Dold Simone K. , Oberhoffer Felix S. , Jakob André
Published: January 2024

This case-control study investigates changes in microcirculation and endothelial function in the acute phase of multisystem inflammatory syndrome in children and 3 to 6 months after onset.
Systemic Racism as a Determinant of Health Inequities for People With Substance Use Disorder
Authors: Jegede Oluwole , Bellamy Chyrell , Jordan Ayana
Published: January 2024

This Viewpoint describes how systemic racism is a determinant of inequities in treatment for people with substance use disorder and suggests an antiracism framework in addiction practice.
Adjuvant Radiotherapy for Surgically Resected Stage III Merkel Cell Carcinoma
Authors: Pairawan Seyed Saeed , Dominguez Chloe E. , Solomon Naveenraj , Caba-Molina David , O’Leary Michael , Reeves Mark E. , Namm Jukes P.
Published: January 2024

This case-control study evaluates whether adjuvant radiotherapy is associated with overall survival among patients with surgically resected stage III Merkel cell carcinoma.
Dual targeting of the androgen receptor and PI3K/AKT/mTOR pathways in prostate cancer models improves antitumor efficacy and promotes cell apoptosis
Authors: Sugawara Tatsuo , Nevedomskaya Ekaterina , Heller Simon , Böhme Annika , Lesche Ralf , von Ahsen Oliver , Grünewald Sylvia , Nguyen Holly M. , Corey Eva , Baumgart Simon J. , Georgi Victoria , Pütter Vera , Fernández‐Montalván Amaury , Vasta James D. , Robers Matthew B. , Politz Oliver , Mumberg Dominik , Haendler Bernard
Published: January 2024

Prostate cancer is a frequent malignancy in older men and has a very high 5‐year survival rate if diagnosed early. The prognosis is much less promising if the tumor has already spread outside the prostate gland. Targeted treatments mainly aim at blocking androgen receptor (AR) signaling and initially show good efficacy. However, tumor progression due to AR‐dependent and AR‐independent mechanisms is often observed after some time, and novel treatment strategies are urgently needed. Dysregulation of the PI3K/AKT/mTOR pathway in advanced prostate cancer and its implication in treatment resistance has been reported. We compared the impact of PI3K/AKT/mTOR pathway inhibitors with different selectivity profiles on in vitro cell proliferation and on caspase 3/7 activation as a marker for apoptosis induction, and observed the strongest effects in the androgen‐sensitive prostate cancer cell lines VCaP and LNCaP. Combination treatment with the AR inhibitor darolutamide led to enhanced apoptosis in these cell lines, the effects being most pronounced upon cotreatment with the pan‐PI3K inhibitor copanlisib. A subsequent transcriptomic analysis performed in VCaP cells revealed that combining darolutamide with copanlisib impacted gene expression much more than individual treatment. A comprehensive reversal of the androgen response and the mTORC1 transcriptional programs as well as a marked induction of DNA damage was observed. Next, an in vivo efficacy study was performed using the androgen‐sensitive patient‐derived prostate cancer (PDX) model LuCaP 35 and a superior efficacy was observed after the combined treatment with copanlisib and darolutamide. Importantly, immunohistochemistry analysis of these treated tumors showed increased apoptosis, as revealed by elevated levels of cleaved caspase 3 and Bcl‐2‐binding component 3 (BBC3). In conclusion, these data demonstrate that concurrent blockade of the PI3K/AKT/mTOR and AR pathways has superior antitumor efficacy and induces apoptosis in androgen‐sensitive prostate cancer cell lines and PDX models.
Estrogen‐induced glial IL‐1β mediates extrinsic retinal ganglion cell vulnerability in murine Nf1 optic glioma
Authors: Tang Yunshuo , Chatterjee Jit , Wagoner Ngan , Bozeman Stephanie , Gutmann David H.
Published: January 2024

Optic pathway gliomas (OPGs) arising in children with neurofibromatosis type 1 (NF1) can cause retinal ganglion cell (RGC) dysfunction and vision loss, which occurs more frequently in girls. While our previous studies demonstrated that estrogen was partly responsible for this sexually dimorphic visual impairment, herein we elucidate the underlying mechanism. In contrast to their male counterparts, female Nf1OPG mice have increased expression of glial interleukin‐1β (IL‐1β), which is neurotoxic to RGCs in vitro. Importantly, both IL‐1β neutralization and leuprolide‐mediated estrogen suppression decrease IL‐1β expression and ameliorate RGC dysfunction, providing preclinical proof‐of‐concept evidence supporting novel neuroprotective strategies for NF1‐OPG‐induced vision loss.
Distributed finite‐time adaptive fault‐tolerant consensus control of second‐order multi‐agent systems under deception attacks
Authors: Liu Chun , Wang Wanyi , Yu Ziquan , Patton Ron J.
Published: January 2024

This study addresses the issue of distributed fault‐tolerant consensus control for second‐order multi‐agent systems subject to simultaneous actuator bias faults in the physical layer and deception attacks in the cyber layer. Cyber‐physical threats (malicious state‐coupled nonlinear attacks and physical deflection faults), unknown control gains, external disturbances and uncertainties force the failure of the existing graph theory‐based consensus control schemes, leading to disruptions in the cooperation and coordination of multi‐agent systems. Then, the power integrator‐based virtual control is incorporated in the distributed fault‐tolerant consensus to achieve unknown parameter estimations with the adaptive technique. The consensus‐based robustness to lumped uncertainties, resilience to attacks, compensation to faults, and novel finite‐time convergence of the neighborhood errors and velocity errors are also realized within a prescribed finite‐time settling bound. The simulation is conducted to verify the effectiveness of the distributed finite‐time adaptive fault‐tolerant consensus algorithm.
Electronic Reconstruction via Low‐Degree Fluorination for High‐Performance Zinc‐Ion Battery
Authors: Zhang Yu , Wang Yixun , Liu Xiaoqi , Wang Liying , Sun Hongman , Pan Yuan , Hu Han , Zhao Lianming , Xing Wei , Yan Zifeng
Published: January 2024

The development of transition metal oxide cathodes with high capacity and ultralong lifespan is one of the keys to promoting the performance of aqueous zinc–ion batteries, but it remains a crucial challenge. Herein, cobalt oxide is applied as an example to demonstrate that low‐degree fluorination is a novel approach to synergistically boost charge storage kinetics and stability. Specifically, partial substitution of O2− with F− intensifies electron delocalization of Co 3d orbitals, which reduces bulk charge transfer impedance and endows surface active sites with higher reactivity, thus achieving boosted redox kinetics and energy density. Moreover, the modification of coordination structure with the highest‐electronegativity F− can effectively inhibit irreversible phase transition and structural deformation, which assures significantly optimized cycling stability. As a result, the fluorinated Co3O4 demonstrates a distinctly improved specific capacity of 406 mAh g−1 at 1 A g−1, approximately a threefold increase compared to one of pristine Co3O4 (131 mAh g−1). The assembled fluorinated Co3O4//Zn battery delivers an ultrahigh energy density of 658 Wh kg−1 at 3.5 kW kg−1 and 95.7% capacity retention after 10 000 cycles. This work offers a new understanding of the electronic engineering of metal oxides toward high‐performance energy storage applications.
Oxygen Release Suppression and Electronic Conductivity Enhancement for High Performance Li‐ and Mn‐Rich Layered Oxides Cathodes by Chalcogenide Redox Couple and Oxygen Vacancy Generations
Authors: Yan Chenhui , Shao Qinong , Yang Yaxiong , Gao Mingxia , Lin Yue , Gao Mingxi , Chen Zichong , Wei Yiqi , Liu Yongfeng , Sun Wenping , Jiang Yinzhu , Zhang Xin , Chen Jian , Wu Zhijun , Pan Hongge
Published: January 2024

Li‐ and Mn‐rich layered oxides (LMROs) are promising cathode materials for next‐generation lithium‐ion batteries (LIBs) due to their high capacity and high energy density. However, they suffer from severe capacity and voltage fading during cycling, where the irreversible oxygen release during cycle is deemed to a severe factor. Herein, this put forward a general oxygen release suppression strategy by introducing small amounts of sodium chalcogenides during cathode slurry preparation. The formed unstable surface peroxide ions O22− of LMRO during charging is reduced to stable O2− by chalcogen ion and couples the formation of sodium chalcogenic oxides, which is reduced to sodium chalcogenides and O2− during discharging. As a result, the oxygen release is significantly suppressed and the structural stability of LMRO is greatly enhanced. Meanwhile, abundant surface oxygen vacancies are generated coupling with evidently increased carrier concentration and mobility, thus enhancing electronic conductivity significantly. The Li1.2Ni0.13Co0.13Mn0.54O2 cathode with 3 wt% Na2Se shows a capacity retention as high as 96.2% and a capacity of 225 mAh g−1 after 500 cycles at 1 C, coupling with a high capacity of 135 mAh g−1 at 10 C. The relevant mechanism for the improved electrochemical properties is revealed, which is hopefully helpful for novel strategy design to high‐performance LMRO cathodes.
Chemical‐Stabilized Aldehyde‐Tuned Hydrogen‐Bonded Organic Frameworks for Long‐Cycle and High‐Rate Sodium‐Ion Organic Batteries
Authors: Guo Chaofei , Gao Yun , Li Shang‐Qi , Wang Yuxuan , Yang Xue‐Juan , Zhi Chuanwei , Zhang Hang , Zhu Yan‐Fang , Chen Shuangqiang , Chou Shu‐Lei , Dou Shi‐Xue , Xiao Yao , Luo Xiping
Published: January 2024

Hydrogen‐bonded organic frameworks (HOFs) are considered as potential choice for future energy storage systems due to their adjustable chemistry, environment friendliness, and cost‐effectiveness. In this study, structurally stabilized and aldehyde‐tuned hydrogen‐bonded organic frameworks (HOFs‐8) are designed and prepared to contain arrayed electronegative sites for sodium‐ion storage. Benefitting from the flexible hydrogen bond and unique structural symmetry, HOFs‐8 can achieve efficient utilization of the active sites and fast transport of sodium ions and electrons. The HOFs‐8 electrode exhibits an impressive lifespan of 5000 cycles at 3.66 A g−1 (20 C). In situ Fourier Transform infrared spectroscopy (in situ FT‐IR) and ex situ X‐ray Photoelectron Spectroscopy (ex situ XPS) analyses are performed to illustrate the mechanism of sodium‐ion storage involving aldehyde‐tuned C═O. Additionally, flexible hydrogen bonds in HOFs materials with unique structural symmetries are investigated to elucidate the mechanism of hydrogen bonding for improving their electrochemical properties. Density functional theory (DFT) simulations verified that HOFs‐8 has excellent Na+ diffusion kinetics, enabling it to demonstrate outstanding rate capability. This work offers insight into the design of new electrodes and improved HOFs, which are expected to have tremendous potential in energy storage systems.
Bioinspired Gradient Covalent Organic Framework Membranes for Ultrafast and Asymmetric Solvent Transport
Authors: Zuo Hongyu , Lyu Baokang , Yao Jiaao , Long Wenhua , Shi Yu , Li Xinghao , Hu Huawei , Thomas Arne , Yuan Jiayin , Hou Bo , Zhang Weiyi , Liao Yaozu
Published: January 2024

Gradients play a pivotal role in membrane technologies, e.g., osmotic energy conversion, desalination, biomimetic actuation, selective separation, and more. In these applications, the compositional gradients are of great relevance for successful function implementation, ranging from solvent separation to smart devices; However, the construction of functional gradient in membranes is still challenging both in scale and directions. Inspired by the specific function‐related, graded porous structures in glomerular filtration membranes, a general approach for constructing gradient covalent organic framework membranes (GCOMx) applying poly (ionic liquid)s (PILs) as template is reported here. With graded distribution of highly porous covalent organic framework (COF) crystals along the membrane, GCOMx exhibts an unprecedented asymmetric solvent transport when applying different membrane sides as the solvent feed surface during filtration, leading to a much‐enhanced flux (10–18 times) of the “large‐to‐small” pore flow comparing to the reverse direction, verified by hydromechanical theoretical calculations. Upon systematic experiments, GCOMx achieves superior permeance in nonpolar (hexane ≈260.45 LMH bar−1) and polar (methanol ≈175.93 LMH bar−1) solvents, together with narrow molecular weight cut‐off (MWCO, 472 g mol−1) and molecular weight retention onset (MWRO, <182 g mol−1). Interestingly, GCOMx shows significant filtration performance in simulated kidney dialysis, revealing great potential of GCOMx in bionic applications.
Ultrasensitive Ionic Conductors with Tunable Resistance Switching Temperature Enabled by Phase Transformation of Polymer Cocrystals
Authors: Zhou Yichen , Yu Chengtao , Zhang Xing , Zheng Ying , Wang Bao , Bao Yongzhong , Shan Guorong , Wang Hangxiang , Pan Pengju
Published: January 2024

Phase‐transformable ionic conductors (PTICs) show significant prospects for functional applications due to their reversible resistance switching property. However, the representative design principle of PTICs is utilizing the melt‐crystallization transition of ionic liquids, and the resistance switching temperatures of such PTICs cannot be tuned as desired. Herein, a new strategy is proposed to design PTICs with on‐demand resistance switching temperatures by using the melt‐crystallization transition of polymer cocrystal phase, whose melting temperature shows a linear relationship with the polymer compositions. Owing to the melt of polymer cocrystal domains and the tunable migration of ions in the resistance switching region, the obtained PTICs display ultrahigh temperature sensitivity with a superior temperature coefficient of resistance of −8.50% °C−1 around human body temperature, as compared to various ionic conductors previously reported. Therefore, the PTICs can detect tiny temperature variation, allowing for the intelligent applications for overheating warning and heat dissipation. It is believed that this work may inspire future researches on the development of advanced soft electrical devices.
A Photolithographable Electrolyte for Deeply Rechargeable Zn Microbatteries in On‐Chip Devices
Authors: Qu Zhe , Ma Jiachen , Huang Yang , Li Tianming , Tang Hongmei , Wang Xiaoyu , Liu Siyuan , Zhang Kai , Lu Jing , Karnaushenko Dmitriy D. , Karnaushenko Daniil , Zhu Minshen , Schmidt Oliver G.
Published: January 2024

Zn batteries show promise for microscale applications due to their compatibility with air fabrication but face challenges like dendrite growth and chemical corrosion, especially at the microscale. Despite previous attempts in electrolyte engineering, achieving successful patterning of electrolyte microscale devices has remained challenging. Here, successful patterning using photolithography is enabled by incorporating caffeine into a UV‐crosslinked polyacrylamide hydrogel electrolyte. Caffeine passivates the Zn anode, preventing chemical corrosion, while its coordination with Zn2+ ions forms a Zn2+‐conducting complex that transforms into ZnCO3 and 2ZnCO3·3Zn(OH)2 over cycling. The resulting Zn‐rich interphase product significantly enhances Zn reversibility. In on‐chip microbatteries, the resulting solid‐electrolyte interphase allows the Zn||MnO2 full cell to cycle for over 700 cycles with an 80% depth of discharge. Integrating the photolithographable electrolyte into multilayer microfabrication creates a microbattery with a 3D Swiss‐roll structure that occupies a footprint of 0.136 mm2. This tiny microbattery retains 75% of its capacity (350 µAh cm−2) for 200 cycles at a remarkable 90% depth of discharge. The findings offer a promising solution for enhancing the performance of Zn microbatteries, particularly for on‐chip microscale devices, and have significant implications for the advancement of autonomous microscale devices.
Recyclable Solid–Solid Phase Change Materials with Superior Latent Heat via Reversible Anhydride‐Alcohol Crosslinking for Efficient Thermal Storage
Authors: Wu Yahe , Chen Mingsen , Zhao Guangzhi , Qi Debang , Zhang Xuanhao , Li Yiran , Huang Yanbin , Yang Wantai
Published: January 2024

Solid–solid phase change materials (SSPCMs) with crosslinked polymer structures have received sustained interest due to their remarkable shape stability, enabling their application independently without the need for encapsulation or supporting materials. However, the crosslinking structure also compromises their latent heat and poses challenges to their recyclability. Herein, a novel strategy harnessing the internal‐catalyzed reversible anhydride‐alcohol crosslinking reaction to fabricate SSPCMs with superior latent heat and exceptional dual recyclability is presented. Easily accessible anhydride copolymers (e.g., propylene‐maleic anhydride alternating copolymers), provide abundant reactive anhydride sites within the polymer matrix; polyethylene glycol serves as both the grafted phase change component and the crosslinker. The resulting SSPCMs attain a peak latent heat value of 156.8 J g−1 which surpasses all other reported recyclable crosslinked SSPCMs. The materials also exhibit certain flexibility and a tunable tensile strength ranging from 6.6 to 11.0 MPa. Beyond that, leveraging the reversible anhydride‐alcohol crosslinks, the SSPCMs demonstrate dual recyclability through bond‐exchange remolding and reversible‐dissociation‐enabled dissolving‐recrosslinking without any reactive chemicals. Furthermore, by integrating solar‐thermal conversion fillers like polydopamine nanoparticles, the potential of the system in efficient conversion, storage, and release of solar energy is highlighted.
High Luminescence in Layered Double Perovskite via Formation of Terbium Intercalation Complex
Authors: Yadav Priyesh , Khurana Swati , Lamba Raman Singh , Singh Sahil , Jha Varsha , Kumar Shubham , Sapra Sameer
Published: January 2024

As the field of perovskite emerges, doping presents an optimistic way to upgrade the functionalities of these materials and improve the photoluminescence quantum yield (PLQY). While doping is well‐explored in perovskites, it has received less attention in layered double perovskites (LDPs). Doping with lanthanides is particularly interesting for these wide bandgap materials because of their narrow and intense luminescence spectra. Here, the doping of (PEA)4NaInCl8 LDP (PEA = Phenylethylammonium) with Tb3+ and complex of Tb3+ with hexafluoroacetylacetonate (hfa) is studied, i.e., tetrakis β‐diketonate complex. In both cases, energy transfer from host to dopant leading to photoluminescence (PL) emission due to Tb3+ f‐f transitions is observed. However, in the case of Tb3+ doping, sensitization is not very efficient due to the nonideal alignment of energy levels of the host and resonance acceptor energy levels of Tb3+. Whereas, doping of (PEA)4NaInCl8 with Tb3+ in the form of hfa complex, provides a more ideal energetic environment for the efficient energy transfer from host to Tb3+ in the LDP matrix, resulting in a 20‐fold enhancement in the luminescence efficiency. The doping of Tb3+ and Tb3+ complex in LDP sets the foundation for a new approach for the synthesis of LDPs‐lanthanide host‐guest systems for high PLQY.
Nanoscale Metal–Organic Frameworks‐Mediated Degradation of Mutant p53 Proteins and Activation of cGAS‐STING Pathway for Enhanced Cancer Immunotherapy
Authors: Sun Li , Gao Hongbo , Wang Han , Zhou Jingwei , Ji Xiuru , Jiao Yuxin , Qin Xiaojia , Ni Dalong , Zheng Xiangpeng
Published: January 2024

Activating cGAS‐STING pathway has great potential to achieve effective antitumor immunotherapy. However, mutant p53 (mutp53), a commonly observed genetic alteration in over 50% of human cancer, will impede the therapeutic performance of the cGAS‐STING pathway. Herein, multifunctional ZIF‐8@MnO2 nanoparticles are constructed to degrade mutp53 and facilitate the cGAS‐STING pathway. The synthesized ZIF‐8@MnO2 can release Zn2+ and Mn2+ in cancer cells to induce oxidative stress and cytoplasmic leakage of fragmented mitochondrial double‐stranded DNAs (dsDNAs). Importantly, the released Zn2+ induces variable degradation of multifarious p53 mutants through proteasome ubiquitination, which can alleviate the inhibitory effects of mutp53 on the cGAS‐STING pathway. In addition, the released Mn2+ further increases the sensitivity of cGAS to dsDNAs as immunostimulatory signals. Both in vitro and in vivo results demonstrate that ZIF‐8@MnO2 effectively promotes the cGAS‐STING pathway and synergizes with PD‐L1 checkpoint blockades, leading to remarkable regression of local tumors as well as distant metastases of breast cancer. This study proposes an inorganic metal ion‐based nanoplatform to enhance the cGAS‐STING‐mediated antitumor immunotherapy, especially to those tumors with mutp53 expression.
High‐Resolution Large‐Area Image Analysis Deciphers the Distribution of Salmonella Cells and ECM Components in Biofilms Formed on Charged PEDOT:PSS Surfaces
Authors: Ray Sanhita , Löffler Susanne , Richter‐Dahlfors Agneta
Published: January 2024

Biofilms, comprised of cells embedded in extracellular matrix (ECM), enable bacterial surface colonization and contribute to pathogenesis and biofouling. Yet, antibacterial surfaces are mainly evaluated for their effect on bacterial cells rather than the ECM. Here, a method is presented to separately quantify amounts and distribution of cells and ECM in Salmonella biofilms grown on electroactive poly(3,4‐ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS). Within a custom‐designed biofilm reactor, biofilm forms on PEDOT:PSS surfaces electrically addressed with a bias potential and simultaneous recording of the resulting current. The amount and distribution of cells and ECM in biofilms are analyzed using a fluorescence‐based spectroscopic mapping technique and fluorescence confocal microscopy combined with advanced image processing. The study shows that surface charge leads to upregulated ECM production, leaving the cell counts largely unaffected. An altered texture is also observed, with biofilms forming small foci or more continuous structures. Supported by mutants lacking ECM production, ECM is identified as an important target when developing antibacterial strategies. Also, a central role for biofilm distribution is highlighted that likely influences antimicrobial susceptibility in biofilms. This work provides yet a link between conductive polymer materials and bacterial metabolism and reveals for the first time a specific effect of electrochemical addressing on bacterial ECM formation.
Bioinspired Confined Assembly of Cellulosic Cholesteric Liquid Crystal Bubbles
Authors: Wang Qiao , Zhang Zhuohao , Wang Chong , Yang Xinyuan , Fang Zhonglin , Shang Luoran
Published: January 2024

Construction of biomimetic models for structural color evolution not only gives new photonic phenomena but also provide cues for biological morphogenesis. Here, a novel confined self‐assembly method is proposed for the generation of hydroxypropyl cellulose (HPC)‐based cholesteric liquid crystals (CLCs) microbubbles. The assembly process relies on the combination of droplet microfluidics, solvent extraction, and a volume confined environment. The as‐prepared HPC structural color microbubbles have a transparent shell, an orderly arranged cholesteric liquid crystal (CLC) middle layer, and an innermost bubble core. The size of the microbubble, shell thickness, and the color of the CLC layer can be adjusted by altering the microfluidic parameters. Intriguingly, benefited from the compartmentalization effect provided by droplet microfluidics, microbubbles with multiple cores of different color combinations are generated under precise control. The self‐assembled CLCs microbubbles have bright structural color, suspending ability, and good temperature‐sensitive characteristics, making them ideal underwater sensors. The present confined assembly approach will shed light on creating novel photonic structures and the HPC microbubble will find widespread applications in multifunctional sensing, optical display, and other related fields are believed.
Enabling Broadband Solar‐Blind UV Photodetection by a Rare‐Earth Doped Oxyfluoride Transparent Glass‐Ceramic
Authors: Jia Hong , Zhang Rui , Niu Xuying , Zhang Xian , Zhou Hui , Liu Xiaofeng , Fang Zaijin , Chang Fei , Guan Bai‐Ou , Qiu Jianrong
Published: January 2024

Oxyfluoride transparent glass‐ceramics (GC) are widely used as the matrix for rare‐earth (RE) ions due to their unique properties such as low phonon energy, high transmittance, and high solubility for RE ions. Tb3+ doped oxyfluoride glasses exhibit a large absorption cross section for ultraviolet (UV) excitation, high stability, high photoluminescence quantum efficiency, and sensitive spectral conversion characteristics, making them promising candidate materials for use as the spectral converter in UV photodetectors. Herein, a Tb3+ doped oxyfluoride GC is developed by using the melt‐quenching method, and the microstructure and optical properties of the GC sample are carefully investigated. By combining with a Si‐based photo‐resistor,a solar‐blind UV detector is fabricated, which exhibits a significant photoelectric response with a broad detection range from 188 to 400 nm. The results indicate that the designed UV photodetector is of great significance for the development of solar‐blind UV detectors.
Anaesthetic management of a parturient with an unrepaired coronary arteriovenous fistula for caesarean section
Authors: King E. , Al‐Nahdi S. , Ludwig N.
Published: January 2024

Coronary arteriovenous fistulas are an abnormal conduit between a coronary artery and another cardiovascular lumen, without an intervening capillary bed. The reported prevalence is 0.002–0.3%. Physiologic consequences such as congestive heart failure, coronary steal phenomenon and fistula aneurysm formation and rupture are possible. There are limited reports of symptomatic coronary arteriovenous fistulas in association with pregnancy. We describe a 19‐year‐old woman with symptomatic left circumflex artery to coronary sinus fistula, terminating into a large exophytic varix in the right atrium, presenting for an elective caesarean section at 37 weeks gestational age. Our anaesthetic management strategy aimed to optimise myocardial perfusion, maintain euvolemia, avoid right ventricular obstruction from exophytic varix and avoid sympathetic stimulation or sudden increases in pulmonary vascular resistance. A slowly titrated epidural was used as the primary anaesthetic. Our patient tolerated the procedure well and was discharged home on postoperative day two. Understanding of the potential physiologic consequence of coronary arteriovenous fistulas, and interaction with the physiologic changes of pregnancy and delivery, are essential for the management of these cases.
Enhancing formation and retention of hollow structural integrity through intermediate and outermost layer design in seeded emulsion polymerization of hollow latex particles
Authors: Sun Guanqing , Guan Zepeng , Shen Zekai , Liu Ren
Published: January 2024

The synthesis of hollow latex particles through seeded emulsion polymerization involves a series of intricate steps, including the formation of distinct polymer layers with specific properties. Despite extensive research, preserving the desired hollow structure remains challenging due to the unclear role of the encapsulating polymer layers. This study systematically adjusts the glass transition temperature (Tg) of the intermediate layer by varying the butyl acrylate (BA) ratio in the monomer feed mixture. By controlling the reaction temperature during alkali swelling, we explore the critical influence of Tg on hollow latex particle formation from carboxylated core latex particles. To ensure long‐term hollow structure retention after drying, a rigid outer layer is polymerized onto the intermediate layer. Surprisingly, higher divinylbenzene (DVB) mass ratios (5.0 and 10.0 wt%) do not result in a highly crosslinked hollow shell due to DVB self‐nucleation. This paper emphasizes the importance of precise design parameters for both intermediate and outermost layers in achieving and maintaining hollow latex particle structures. Understanding each layer's role and optimizing their compositions contribute to advancing hollow latex particle synthesis through seeded emulsion polymerization.
Conservation implications of isotopic variation in nails and blood with wetland quality in three species of Australian freshwater turtle
Authors: Francis Roxane J. , Brandis Kate J. , Chessman Bruce C. , Slavich Eve , Kingsford Richard T.
Published: January 2024

Australian freshwater turtles are declining, reflecting global turtle trends. Understanding variation in turtle diets and habitat requirements can guide protection and restoration of ecosystems. Diet and niche overlap were investigated in three co‐existing species of turtle—the broad‐shelled turtle Chelodina expansa, the eastern long‐necked turtle C. longicollis and the Macquarie turtle Emydura macquarii, in three rivers in the Murray–Darling Basin, Australia, in relation to environmental variables.

Dietary variation in relation to water quality (salinity) and macrophyte cover was investigated using stable isotope analyses (δ15N and δ13C) of turtle tissues (plasma, red blood cell, whole blood and nail) representing food assimilation over different antecedent periods. These stable isotope results were consistent with current dietary understanding based on stomach flushing, indicating that isotope analyses are a non‐invasive method for obtaining dietary information.

There were temporal dietary differences, with strong shifts between spring and summer sampling periods, particularly in the blood plasma. Intraspecific variation in diets reflected in δ15N and δ13C related to body size. There was evidence of high dietary overlap among the three species, potentially creating competition, particularly when they co‐occur or resources might be limited.

Continued degradation of turtle habitats and water quality affects turtle diet and reduces habitat availability, forcing the three species of turtle to co‐exist in diminishing refugia, increasing interspecific competition for food. Protecting and restoring freshwater ecosystems, including maintaining freshwater refugia, is essential to conserve already declining populations of the three Australian freshwater turtle species.
Synthesis of 2‐(pyridylvinyl)chromen‐4‐ones and their N‐oxide analogs for assessment of their biological activities as anticancer agents
Authors: Ding Yu Chun , Chu Yi‐Cheng , Chang Chuan‐Hsin , Liang Jia‐Hua , Chen Jih‐Jung , Shih Tzenge‐Lien
Published: January 2024

2‐Styrylchromones have been shown to possess a broad spectrum of biological activities. Replacing the carbon atom in 2‐styrylchromones with a nitrogen atom in the benzene rings forms 2‐(pyridylvinyl)chromen‐4‐ones (aza‐2‐styrylchromones). We have synthesized a series of novel 2‐(pyridylvinyl)chromen‐4‐ones and their pyridine N‐oxides to evaluate them as potential anticancer agents against human non‐small‐cell lung cancer cells (A549). Among the 18 synthesized molecules, compounds 18 and 8a exhibited comparable inhibitory effects to 5‐fluorouracil and showed no toxicity against normal cells.