bluuebunny/crossref_metadata_2025 huggingface dataset:
Optically Mediated Nonvolatile Resistive Memory Device Based on Metal–Organic Frameworks
Authors: Yang Xue , Huang Jian , Li Jingjun , Zhao Yanqi , Li Hongfang , Yu Zhiyang , Gao Shuiying , Cao Rong
Published: July 2024

Metal–organic frameworks (MOFs), characterized by tunable porosity, high surface area, and diverse chemical compositions, offer unique prospects for applications in optoelectronic devices. However, the prevailing research on thin‐film devices utilizing MOFs has predominantly focused on aspects such as information storage and photosensitivity, often neglecting the integration of the advantages inherent in both photonics and electronics to enhance optical memory. This work demonstrates a light‐mediated resistive memory device based on a highly oriented porphyrin‐based MOFs film, in which the resistance state of the memristor is modulated by light, realizing the integration of the perception and storage of optical information. The memristor shows excellent performance with a wide light range of 405–785 nm and a persistent photoconductivity phenomenon up to 8.3 × 103 s. Further mechanistic studies have revealed that the resistive switching effect in the memristor is primarily associated with the reversible formation and annihilation of Ag conductive filaments.
A General Approach to Activate Second‐Scale Room Temperature Photoluminescence in Organic Small Molecules
Authors: Ivancevic Marko R. , Wisch Jesse A. , Burlingame Quinn C. , Rand Barry P. , Loo Yueh‐Lin
Published: July 2024

Organic small molecules that exhibit second‐scale phosphorescence at room temperature are of interest for potential applications in sensing, anticounterfeiting, and bioimaging. However, such materials systems are uncommon—requiring millisecond to second‐scale triplet lifetimes, efficient intersystem crossing, and slow rates of nonradiative recombination. Here, a simple and scalable approach is demonstrated to activate long‐lived phosphorescence in a wide variety of molecules by suspending them in rigid polymer hosts and annealing them above the polymer's glass transition temperature. This process produces submicron aggregates of the chromophore, which suppresses intramolecular motion that leads to nonradiative recombination and minimizes triplet–triplet annihilation that quenches phosphorescence in larger aggregates. In some cases, evidence of excimer‐mediated intersystem crossing that enhances triplet generation in aggregated chromophores is found. In short, this approach circumvents the current design rules for long‐lived phosphors, which will streamline their discovery and development.
Protein Interfacial Gelation toward Shuttle‐Free and Dendrite‐Free Zn–Iodine Batteries
Authors: Zhang Shao‐Jian , Hao Junnan , Wu Han , Chen Qianru , Ye Chao , Qiao Shi‐Zhang
Published: July 2024

Aqueous zinc–iodine (Zn–I2) batteries hold potential for large‐scale energy storage but struggle with shuttle effects of I2 cathodes and poor reversibility of Zn anodes. Here, an interfacial gelation strategy is proposed to suppress the shuttle effects and improve the Zn reversibility simultaneously by introducing silk protein (SP) additive. The SP can migrate bidirectionally toward cathode and anode interfaces driven by the periodically switched electric field direction during charging/discharging. For I2 cathodes, the interaction between SP and polyiodides forms gelatinous precipitate to avoid the polyiodide dissolution, evidenced by excellent electrochemical performance, including high specific capacity and Coulombic efficiency (CE) (215 mAh g−1 and 99.5% at 1 C), excellent rate performance (≈170 mAh g−1 at 50 C), and extended durability (6000 cycles at 10 C). For Zn anodes, gelatinous SP serves as protective layer to boost the Zn reversibility (99.7% average CE at 2 mA cm−2) and suppress dendrites. Consequently, a 500 mAh Zn–I2 pouch cell with high‐loading cathode (37.5 mgiodine cm−2) and high‐utilization Zn anode (20%) achieves remarkable energy density (80 Wh kg−1) and long‐term durability (>1000 cycles). These findings underscore the simultaneous modulation of both cathode and anode and demonstrate the potential for practical applications of Zn–I2 batteries.
Polymorphic Localized Heterostructure Design for High‐Performance Amorphous/Nanocrystalline Composite Film
Authors: Huang Rui , Wang Jian , Wang Hongye , Tao Cheng , Hao Hua , Yao Zhonghua , Liu Hanxing , Shen Zhonghui , Cao Minghe
Published: July 2024

Analogous to linear dielectric, amorphous perovskite dielectrics characterized of high breakdown strength and low remanent polarization possess in‐depth application in the sea, land, and air fields. Amorphous engineering is a common approach to balance the inverse relationship between polarization and breakdown strength in dielectric ceramic capacitor, however, the low polarization is the major barrier limiting the improvement of energy storage density. To address this concern, the polymorphic localized heterostructure confirmed by high‐resolution transmission electron microscope (HR‐TEM) and HADDF images is constructed in BaTiO3‐Bi(Ni0.5Zr0.5)O3 amorphous/nanocrystalline composite film with SiO2 addition (BT‐BNZ‐xS, x = 3, 5, 7, 10 mol%). The stability of nanocrystalline region achieved by Si‐rich transition region and the enhancive ultra‐short‐range ordering in the amorphous region synergistically result in large breakdown strength and nonhysteretic polarized response. This polymorphic localized heterostructure optimizes the thermal stability in a wide temperature range and contributes ultrahigh energy storage density of 149.9 J cm−3 with markedly enhanced efficiency of 79.0%. This study provides a universal strategy to design the polarization behavior in other amorphous perovskite‐based dielectrics.
Breaking Down the Arsenal: Recent Progress in the Nanotherapeutic Strategies for Hepatocellular Carcinoma Treatment
Authors: Roy Sumit , Harish Vancha , Mohd Sharfuddin , Singh Sachin Kumar
Published: July 2024

Hepatocellular carcinoma (HCC) is a progressed form of advanced liver cancer and is one of the major causes of global cancer burden. The primary causes for high HCC mortality is the delayed diagnosis of the diseaseas early stage HCC is typically asymptomatic and patients frequently overlook the warning signs. Currently, the most efficacious single‐drug therapy approved by the food and drug administration (FDA) for HCC is Sorafenib and Nivolumab  as a second‐line therapy for late stage HCC. Nowadays nanotechnology is used to deliver either a diagnostic tool for biomolecular imaging ortherapeutic agent. Gene therapy based on clustered regularly interspaced short palindromic repeats (CRISPR)‐CRISPR associated protein 9 (CRISPR‐Cas9) are currently studied to find a potential curative option for HCC. Natural products from plants are being extensively extracted and isolated as they may offer a promising alternative in order to control and treat HCC. They exhibit anti‐HCC effects by stimulating the immune system and by hindering various growth pathways involved in cancer development and progression. In this review article, an overview is provided on the current global incidence, ongoing systemic treatment strategies, and recent advances in nanomedicine for the management of HCC and also ongoing efforts to overcome these challenges.
Stretchable and Self‐Powered Mechanoluminescent Triboelectric Nanogenerator Fibers toward Wearable Amphibious Electro‐Optical Sensor Textiles
Authors: Wu Jiajun , Zhou Xuhui , Luo Jie , Zhou Jianxian , Lu Zecheng , Bai Zhiqing , Fan Yuan , Chen Xuedan , Zheng Bin , Wang Zhanyong , Wei Lei , Zhang Qichong
Published: July 2024

Flexible electro‐optical dual‐mode sensor fibers with capability of the perceiving and converting mechanical stimuli into digital‐visual signals show good prospects in smart human‐machine interaction interfaces. However, heavy mass, low stretchability, and lack of non‐contact sensing function seriously impede their practical application in wearable electronics. To address these challenges, a stretchable and self‐powered mechanoluminescent triboelectric nanogenerator fiber (MLTENGF) based on lightweight carbon nanotube fiber is successfully constructed. Taking advantage of their mechanoluminescent‐triboelectric synergistic effect, the well‐designed MLTENGF delivers an excellent enhancement electrical signal of 200% and an evident optical signal whether on land or underwater. More encouragingly, the MLTENGF device possesses outstanding stability with almost unchanged sensitivity after stretching for 200%. Furthermore, an extraordinary non‐contact sensing capability with a detection distance of up to 35 cm is achieved for the MLTENGF. As application demonstrations, MLTENGFs can be used for home security monitoring, intelligent zither, traffic vehicle collision avoidance, and underwater communication. Thus, this work accelerates the development of wearable electro‐optical textile electronics for smart human‐machine interaction interfaces.
Design and Development of Metasurface Materials for Enhancing Photodetector Properties
Authors: Guan Renquan , Xu Hao , Lou Zheng , Zhao Zhao , Wang Lili
Published: July 2024

Recently, metasurface‐based photodetectors (metaphotodetectors) have been developed and applied in various fields. Metasurfaces are artificial materials with unique properties that have emerged over the past decade, and photodetectors are powerful tools used to quantify incident electromagnetic wave information by measuring changes in the conductivity of irradiated materials. Through an efficient microstructural design, metasurfaces can effectively regulate numerous characteristics of electromagnetic waves and have demonstrated unique advantages in various fields, including holographic projection, stealth, biological image enhancement, biological sensing, and energy absorption applications. Photodetectors play a crucial role in military and civilian applications; therefore, efficient photodetectors are essential for optical communications, imaging technology, and spectral analysis. Metaphotodetectors have considerably improved sensitivity and noise‐equivalent power and miniaturization over conventional photodetectors. This review summarizes the advantages of metaphotodetectors based on five aspects. Furthermore, the applications of metaphotodetectors in various fields including military and civil applications, are systematically discussed. It highlights the potential future applications and developmental trends of metasurfaces in metaphotodetectors, provides systematic guidance for their development, and establishes metasurfaces as a promising technology.
Control of Hybrid Exciton Lifetime in MoSe2/WS2 Moiré Heterostructures
Authors: Xu Haowen , Wang Jiangcai , Liu Huan , Chen Shihong , Sun Zejun , Wang Chong , Han Rui , Wang Yong , Wang Yutang , Wang Zihao , Huang Shuchun , Ma Lingwei , Liu Dameng
Published: July 2024

Hybrid excitons, characterized by their strong oscillation strength and long lifetimes, hold great potential as information carriers in semiconductors. They offer promising applications in exciton‐based devices and circuits. MoSe2/WS2 heterostructures represent an ideal platform for studying hybrid excitons, but how to regulate the exciton lifetime has not yet been explored. In this study, layer hybridization is modulated by applying electric fields parallel or antiparallel to the dipole moment, enabling us to regulate the exciton lifetime from 1.36 to 4.60 ns. Furthermore, the time‐resolved photoluminescence decay traces are measured at different excitation power. A hybrid exciton annihilation rate of 8.9 × 10−4 cm2 s−1 is obtained by fitting. This work reveals the effects of electric fields and excitation power on the lifetime of hybrid excitons in MoSe2/WS2 1.5° moiré heterostructures, which play important roles in high photoluminescence quantum yield optoelectronic devices based on transition‐metal dichalcogenides heterostructures.
A Novel Thiazole‐Core Spacer Based Dion–Jacobson Perovskite with Type II Quantum Well Structure for Efficient Photovoltaics
Authors: Zhang Lin , Zhang Yiqing , Wu Haotian , Wang Fei , Yan Kangrong , Zhou Ying , Xu Xiaoyi , Fu Weifei , Hu Hanlin , Wu Gang , Du Miao , Chen Hongzheng
Published: July 2024

2D Dion–Jacobson (DJ) perovskites show structural stability and tunability and are regarded as promising photovoltaic materials. The spacer cations play an important impact on exciton separation and charge transport of 2D perovskites. Herein, a novel spacer with thiazole as core, 2‐thiazolemethanammonium (AMT), owning characters of small molecular size, delocalized π‐electrons, and strong electron‐withdrawing ability, is introduced to construct 2D DJ perovskites. Owing to the strong orbital coupling between AMT spacer and inorganic layers, the AMT‐based perovskite exhibits type II quantum well structure, which is favorable for exciton separation. On contrary, such interaction does not appear in the DJ perovskite when aliphatic propyldiammonium (PDA), with a similar length, is used as spacer. The AMT spacer can also induce better crystallinity, resulting in reduced defect density and improved charge transport ability. The optimized device based on (AMT)MA3Pb4I13 exhibits a power conversion efficiency (PCE) of 19.69%, which is a record for 2D DJ perovskite solar cells (PSCs) (n ≤ 4). This work provides deep understanding of the impact of aromatic spacer on the electronic structure of 2D DJ perovskites and the corresponding photovoltaic performance and provides a new opportunity toward highly efficient and stable PSCs.
Interface Charge Regulation Enhancing Output and Durability of Triboelectric Nanogenerator for Efficient Wastewater Treatment
Authors: Liu Dongyang , Zhou Linglin , Gao Yikui , Liu Di , Qiao Wenyan , Shi Jianxun , Liu Xiaoru , Zhao Zhihao , Wang Zhong Lin , Wang Jie
Published: July 2024

Harvesting mechanical energy through triboelectric nanogenerators (TENGs) for effectively purifying water, self‐powered wastewater treatment system presents a promising solution to address both energy and environmental crises. However, issues such as side‐discharge and wear, resulting from interfacial charge transfer, seriously hinder the output and durability of TENGs, and then reduce the efficiency of self‐powered wastewater treatment. Here, an interface charge regulation technique is introduced that simultaneously boosts both output performance and durability of TENG, enabling a greater efficiency in self‐powered wastewater treatment. The interface charge regulation method, suppressing side‐discharge around electrodes with an innovative insulator design as well as boosting charge density through secondary collection, fully utilizes surface charges for power output and results in minimum wear by reducing the interface electrostatic force. Surface charge density of 0.8 mC m−2 between the Ethyl tetrafluoro ethylene and copper (µ = 0.35), with a threefold enhancement under ambient conditions, and durability of 500 000 cycles (a 12.5‐fold enhancement) are achieved. Furthermore, the removal efficiency for proposed self‐powered sewage filter system is improved onefold, indicating the potential for sustainable and practical applications.
Longitudinal plasma phosphorylated‐tau217 and other related biomarkers in a non‐demented Alzheimer's risk‐enhanced sample
Authors: Du Lianlian , Langhough Rebecca E. , Wilson Rachael E. , Reyes Ramiro Eduardo Rea , Hermann Bruce P. , Jonaitis Erin M. , Betthauser Tobey J. , Chin Nathaniel A. , Christian Bradley , Chaby Lauren , Jeromin Andreas , Molfetta Guglielmo Di , Brum Wagner S. , Arslan Burak , Ashton Nicholas , Blennow Kaj , Zetterberg Henrik , Johnson Sterling C.
Published: July 2024

INTRODUCTION

Understanding longitudinal change in key plasma biomarkers will aid in detecting presymptomatic Alzheimer's disease (AD).

METHODS

Serial plasma samples from 424 Wisconsin Registry for Alzheimer's Prevention participants were analyzed for phosphorylated‐tau217 (p‐tau217; ALZpath) and other AD biomarkers, to study longitudinal trajectories in relation to disease, health factors, and cognitive decline. Of the participants, 18.6% with known amyloid status were amyloid positive (A+); 97.2% were cognitively unimpaired (CU).

RESULTS

In the CU, amyloid‐negative (A–) subset, plasma p‐tau217 levels increased modestly with age but were unaffected by body mass index and kidney function. In the whole sample, average p‐tau217 change rates were higher in those who were A+ (e.g., simple slopes(se) for A+ and A– at age 60 were 0.232(0.028) and 0.038(0.013))). High baseline p‐tau217 levels predicted faster preclinical cognitive decline.

DISCUSSION

p‐tau217 stands out among markers for its strong association with disease and cognitive decline, indicating its potential for early AD detection and monitoring progression.

Highlights

Phosphorylated‐tau217 (p‐tau217) trajectories were significantly different in people who were known to be amyloid positive.

Subtle age‐related trajectories were seen for all the plasma markers in amyloid‐negative cognitively unimpaired.

Kidney function and body mass index were not associated with plasma p‐tau217 trajectories.

Higher plasma p‐tau217 was associated with faster preclinical cognitive decline.
CSF proteomic profiles of neurodegeneration biomarkers in Alzheimer's disease
Authors: Delvenne Aurore , Gobom Johan , Schindler Suzanne E. , Kate Mara ten , Reus Lianne M. , Dobricic Valerija , Tijms Betty M. , Benzinger Tammie L. S. , Cruchaga Carlos , Teunissen Charlotte E. , Ramakers Inez , Martinez‐Lage Pablo , Tainta Mikel , Vandenberghe Rik , Schaeverbeke Jolien , Engelborghs Sebastiaan , Roeck Ellen De , Popp Julius , Peyratout Gwendoline , Tsolaki Magda , Freund‐Levi Yvonne , Lovestone Simon , Streffer Johannes , Barkhof Frederik , Bertram Lars , Blennow Kaj , Zetterberg Henrik , Visser Pieter Jelle , Vos Stephanie J. B.
Published: July 2024

INTRODUCTION

We aimed to unravel the underlying pathophysiology of the neurodegeneration (N) markers neurogranin (Ng), neurofilament light (NfL), and hippocampal volume (HCV), in Alzheimer's disease (AD) using cerebrospinal fluid (CSF) proteomics.

METHODS

Individuals without dementia were classified as A+ (CSF amyloid beta [Aβ]42), T+ (CSF phosphorylated tau181), and N+ or N− based on Ng, NfL, or HCV separately. CSF proteomics were generated and compared between groups using analysis of covariance.

RESULTS

Only a few individuals were A+T+Ng−. A+T+Ng+ and A+T+NfL+ showed different proteomic profiles compared to A+T+Ng− and A+T+NfL−, respectively. Both Ng+ and NfL+ were associated with neuroplasticity, though in opposite directions. Compared to A+T+HCV−, A+T+HCV+ showed few proteomic changes, associated with oxidative stress.

DISCUSSION

Different N markers are associated with distinct neurodegenerative processes and should not be equated. N markers may differentially complement disease staging beyond amyloid and tau. Our findings suggest that Ng may not be an optimal N marker, given its low incongruency with tau pathophysiology.

Highlights

In Alzheimer's disease, neurogranin (Ng)+, neurofilament light (NfL)+, and hippocampal volume (HCV)+ showed differential protein expression in cerebrospinal fluid.

Ng+ and NfL+ were associated with neuroplasticity, although in opposite directions.

HCV+ showed few proteomic changes, related to oxidative stress.

Neurodegeneration (N) markers may differentially refine disease staging beyond amyloid and tau.

Ng might not be an optimal N marker, as it relates more closely to tau.
Variable Spatial Dynamics of Optical Vortices Produced by a Double Fork‐Shaped Grating
Authors: Darmaev Erdeny C. , Ikonnikov Denis A. , Myslivets Sergey A. , Arkhipkin Vasily G. , Vyunishev Andrey M.
Published: July 2024

Light diffraction is studied numerically and experimentally on a double fork‐shaped grating representing a periodic grating containing two spaced dislocations. The spatial dynamics of the phase singularities (optical vortices) has been investigated as a function of dislocation parameters. Produced optical vortices affect each other while propagating in a free space. For dislocations of the same topological charge, the propagation trajectories and their transverse displacement coordinates depend on the dislocation spacing, and the larger the dislocation spacing, the smaller the relative displacement of the optical vortices and the smaller their trajectory curvatures. For oppositely charged dislocations, three types of spatial behavior of optical vortices are found. The numerical results agree well with the experimental data.
Cone Angles Quantify and Predict the Affinity and Reactivity of Anion Complexes between Trifluoroborates and Rigid Macrocycles
Authors: Zhang Zhao , Sheetz Edward G. , Pink Maren , Yamamoto Nobuyuki , Flood Amar H.
Published: July 2024

Steric manipulation is a known concept in molecular recognition but there is currently no linear free energy relationship correlating sterics to the stability of receptor‐anion complexes nor to the reactivity of the bound anion. By analogy to Tolman cone angles in cation coordination chemistry, we explore how to define and correlate cone angles of organo‐trifluoroborates (R−BF3−) to the affinities observed for cyanostar‐anion binding. We extend the analogy to a rare investigation of the anion's reactivity and how it changes upon binding. The substituent on the anion is used to define the cone angle, θ. A series of 10 anions were studied including versions with ethynyl, ethylene, and ethyl substituents to tune steric bulk across the sp, sp2 and sp3 hybridized α‐carbons bearing 0, 1 and 2 hydrogen atoms. A linear relationship between affinity and cone angle is observed for anions bearing substituents larger than the −BF3− headgroup. This correlation predicted affinities of two new anions to within ±5 %. We explored how complexation affects the reactivity of fluoride exchange. The yield of fluoride transfer from R−BF3− to Lewis acid triphenylborane is correlated with cone angle. We predict that other rigid macrocycles, like commercially available bambusuril, could follow these trends.
Regional Functionalization Molecular Design Strategy: A Key to Enhancing the Efficiency of Multi‐Resonance OLEDs
Authors: Wu Lin , Mu Xilin , Liu Denghui , Li Wei , Li Deli , Zhang Jiashen , Liu Chunyu , Feng Tingting , Wu Yujie , Li Jiuyan , Su Shi‐Jian , Ge Ziyi
Published: July 2024

Herein, we propose a regional functionalization molecular design strategy that enables independent control of distinct pivotal parameters through different molecule segments. Three novel multiple resonances thermally activated delayed fluorescence (MR‐TADF) emitters A‐BN, DA‐BN, and A‐DBN, have been successfully synthesized by integrating highly rigid and three‐dimensional adamantane‐containing spirofluorene units into the MR framework. These molecules form two distinctive functional parts: part 1 comprises a boron‐nitrogen (BN)‐MR framework with adjacent benzene and fluorene units forming a central luminescent core characterized by an exceptionally rigid planar geometry, allowing for narrow FWHM values; part 2 includes peripheral mesitylene, benzene, and adamantyl groups, creating a unique three‐dimensional “umbrella‐like” conformation to mitigate intermolecular interactions and suppress exciton annihilation. The resulting A‐BN, DA‐BN, and A‐DBN exhibit remarkably narrow FWHM values ranging from 18 to 14 nm and near‐unity photoluminescence quantum yields. Particularly, OLEDs based on DA‐BN and A‐DBN demonstrate outstanding efficiencies of 35.0 % and 34.3 %, with FWHM values as low as 22 nm and 25 nm, respectively, effectively accomplishing the integration of high color purity and high device performance.
A novel binuclear Zn2+ and Cd2+ complexes of carbothiohydrazide chelating agent for the corrosion protection of carbon steel alloy in 15% HCl solution
Authors: El‐Sawaf Ayman K. , Madkour Metwally , Nassar Amal A. , Shalabi Kamal , Nazeer Ahmed Abdel , Shaaban Saad , El‐Samanody El‐Sayed A.
Published: July 2024

Equimolar reactions of Zn2+ and Cd2+acetates with the carbothiohydrazide, [2‐HO‐C6H4‐C(H) = N‐N(H)‐C(=S)‐N(C2H4)2O] chelating agent (H2L) have produced the binuclear [M(L)]2 metal chelates. The isolated compounds have been evaluated by elemental analyses, XRD, molar conductivities, 1H and 13C‐NMR, FTIR, FAB‐MS, UV–Vis, and thermal analyses. The crystal structure of the chelating agent has been resolved and indicates the presence of the chelating agent exclusively in its E conformer regarding the C(H) = N bond. Elemental analyses and molar conductance data indicated that the investigated metal chelates are nonelectrolytes and were formed with 2 M:2 L stoichiometry. FT‐IR along 1H‐NMR spectral data gave evidence for a di‐anionic chelating agent that bonded with central metal ions via azomethine N, deprotonated phenolic O, and thiolate S atoms. The anti‐corrosion performance of the chelating agent and its metal chelates have been evaluated for protecting carbon steel (CS) in 15% HCl aqueous solution using electrochemical examination (EIS and PDP), surface examination (SEM and XPS) and theoretical approach (DFT calculations and MC simulation). The results revealed that [Zn(L)]2 complexes remarkably performed with an inhibition efficiency of about 94.7%, which was better than those for [Cd(L)]2 complex (93.0%) and H2L (88.2%), respectively. The EIS results revealed the gradual rise of charge transfer resistance (Rct) with concentration, while the PDP proved the mixed‐type inhibition performance with cathodic advantage consistent with the Langmuir adsorption model. It was verified that the Zn (II) complex could adsorb on the metallic surface, forming a protective layer responsible for mitigating the corrosion reaction and ions diffusion. This study provided novel inhibitors with structures designed and developed for inhibiting the corrosion process with marked performance. The results derived from various methodologies contribute to a substantiated interpretation of the mechanism of inhibition.
Oxorhenium(V) complexes with pyridinedicarboxylic ligands: Synthesis, density functional theory calculations, and drug combination study
Authors: Petrović Tamara , Gligorijević Nevenka , Medaković Vesna , Veljković Dušan , Aranđelović Sandra , Grgurić‐Šipka Sanja , Poljarević Jelena
Published: July 2024

Three oxorhenium(V) complexes [ReOLCl2(PPh3)] (C1–C3) were synthesized in the reaction of 2,3‐pyridinedicarboxylic acid (HL1), 2,5‐pyridinedicarboxylic acid (HL2), and 2,6‐pyridinedicarboxylic acid (HL3) with [ReOCl3(PPh3)2]. Chemical structures of synthesized compounds were confirmed using standard analytical techniques. The most stable geometry of complexes was proposed using density functional theory calculations. The antiproliferative activity of the synthesized complexes was evaluated in a panel of human tumor cell lines (A549, PANC‐1, OVCAR‐3, and MDA‐MB‐231) and in one nontumor cell line (MRC‐5), in comparison with the activity of cisplatin as a reference drug. The complex C3 exhibited the highest antiproliferative potential in PANC‐1 cells, with IC50 48.73 ± 0.31 μM. Our previous research of oxorhenium(V) complexes suggested the involvement of drug‐efflux transporter P‐glycoprotein (Pgp) in the detoxification of rhenium complexes in pancreatic adenocarcinoma cells. In the present study, the effect of verapamil hydrochloride, the specific pharmacological blocker of Pgp, was tested in combination with novel rhenium complexes C1–C3 or cisplatin (CDDP), in PANC‐1 cells. The verapamil enhanced the antiproliferative activity of complex C3, indicating again the role of Pgp in detoxification of oxorhenium(V) complexes in highly invasive and resistant PANC‐1 cells.
Flame‐retardant rigid polyurethane foam composites with the incorporation of steel slag and DMMP: A novel strategy for utilizing metallurgical solid waste
Authors: Shen Haifeng , Jiang Shudong , Gao Shun , Xu Zichen , Chen Qiuyu , Hou Yanbei , Zhang Shihua , Liu Jiayang , Liu Xiuyu , Tang Gang
Published: July 2024

Steel slag (SS) as solid waste, has low resource utilization efficiency and seriously endangers environmental safety and human health. To explore the potential utilization value of SS and address the flammability challenge of rigid polyurethane foam (RPUF), with a novel flame‐retardant system composed by SS and dimethyl methyl phosphonate (DMMP) was explored. The DMMP/SS system effectively improved the high temperature stability of the RPUF composites. When the mass ratio of SS and DMMP was 1:1, the limiting oxygen index of RPUF/DMMP/SS reached 23.1 vol% and UL‐94 vertical combustion tests passed V‐2 level. Upon incorporation of 15 wt% DMMP, the initial decomposition temperature (T−5 wt%) reduced to 165.3°C, a decrease of 32.2%, while the Tmax2 and residue yield at 700°C exhibited negligible alteration. The peak heat release rate of RPUF/DMMP/SS composite (118.20 W g−1) was 11.02% lower than that of pure RPUF, indicating the significant enhancement of fire safety of the composites. Results confirmed that a synergistic flame‐retardant mechanism was existed between DMMP and SS in enhancing the fire safety of RPUF composite. Introducing a 20 wt% SS content reduces the ID/IG ratio to 1.85, thereby markedly enhancing its heat resistance. This work provides a new application field of SS and paves a novel approach to enhance fire safety of polymers.
Construction of polyimide films with highly linear structures using a structural reorganization approach
Authors: Li Tao , Ke Zhao , Xu Ke , Li Dongpeng , Qian Guangtao , Deng Zhiqing , Li Dandan , Chen Chunhai
Published: July 2024

To improve the thermodynamic and mechanical properties of asymmetric polyimide (PI), a method to enhance the linearity of PI by using a structural reorganization approach was designed. First, two novel diamines containing benzimidazole and benzoxazole groups, namely PADBZ and PDBOA, were constructed and synthesized. Thereafter, two new kinds of PI films (PADBZ‐PMDA and PDBOA‐PMDA) were prepared and polymerized with 1,2,4,5‐benzenetetracarboxylic anhydride (PMDA). Based on structural reorganization, PADBZ‐PMDA and PDBOA‐PMDA had repeating units of the same chemical composition and different linearity with PABZ‐BPDA and BOA‐BPDA, respectively. Comparing PADBZ‐PMDA and PABZ‐BPDA, due to the transfer in the position of benzene, PADBZ‐PMDA with high linearity showed the improved heat resistance (Tg up to 448°C), dimensional stability (CTE down to 2.3 ppm/K) and mechanical properties. PDBOA‐PMDA and BOA‐BPDA had the same situation. This study provided a unique solution to enhance the performances of PI by increasing the linearity using a structural reorganization approach.
Effects of branched chains on plasticization properties of trioctyl citrate: Experiments and molecular dynamic simulations
Authors: Gao Li , Yuan Rui , Tu Chang , Tan Rui , Xu Shiai
Published: July 2024

To replace traditional phthalate plasticizers, our previous research revealed that trioctyl citrate (CA) with an alkyl chain containing 8 carbon atoms (C8) exhibited excellent plasticizing properties. In order to delve deeper into the plasticization effects of CA isomers, CA with different side‐chain structures (C8‐Line, C8‐Branch, and C8‐Star) were synthesized by esterification reactions, and various CA/polyvinyl chloride (PVC) composite films with different CA contents were prepared using a solution casting method. The plasticization mechanisms of these isomers were systematically explored through experimental and molecular dynamics simulations. The results indicate that C8‐Branch demonstrates the optimal plasticizing effect, followed by C8‐Line, while C8‐Star exhibits poorer performance. The C8‐Branch/PVC composite system displays the best plasticizing effect, attributed to the strong interaction forces between the Cl atoms of PVC and the COO groups of CA. On the contrary, the formation of stable dipole pairs between C8‐Star and PVC is impeded by steric hindrance effects. The interaction between the two is predominantly dependent on the intertwining of the alkyl chains in C8‐Star with the PVC chains, also elucidating the observed higher migration rate in the C8‐Star/PVC system. This study provides technical guidance and theoretical basis for the optimized design of high‐performance CA/PVC composites.
Preparing novel polylactic acid based bone scaffold composites with enhanced calcium phosphate deposition behavior and bioactivity via simple one‐step melt extrusion
Authors: Fang Yong‐Gan , Lin Jian‐Yun , Zhou Yong‐Jun , Li Ze‐Hao , Liang Yong‐Tong , Zeng Yu , Wang Zhao‐Yang
Published: July 2024

Polylactic acid (PLA) is regarded as the most representative biomedical polymer materials. However, some problems, that is, its big brittleness, high hydrophobicity, and poor bioactivity, limit its application. Here, using poly(butylene adipate‐co‐terephthalate) (PBAT) as toughening agent, and incorporating ethylene diamine tetra(methylene phosphonic acid) (EDTMPA) for the first time with nano‐hydroxyapatite (nHA) as reinforcement filler, series of PLA/PBAT/nHA/EDTMPA as novel bone scaffold composites are successfully prepared via simple one‐step melt extrusion. The chemical composition, microstructures, thermodynamic properties, mechanical properties, hydrophilicity, and bioactivities of PLA/PBAT/nHA/EDTMPA were characterized. The test results show that these developed PLA‐based composites from safe biosources are greatly potential raw materials for bone scaffold because the existence of EDTMPA can chelate with calcium ions to promote calcium phosphate (CaP) deposition on the surface of bone scaffold composites. Especially, when the content of EDTMPA is 6 wt%, the comprehensive performance of the bone scaffold composite is the best. The research results indicate that these developed PLA‐based materials are greatly potential raw materials for bone scaffold composites.
Polyethersulfone mixed matrix membrane with abundant sponge pores for high‐separation performance with high flux retention and cycling stability
Authors: Zhang Mingyu , Hadi Mohammed Kamal , Guo Dongli , Yao Tao , Ran Fen
Published: July 2024

In recent years, a series of high‐performance ultrafiltration membranes have been developed, but maintaining high flux and high pollutant retention rate without sacrificing service life remains a long‐standing challenge. In this study, a porous polyethersulfone ultrafiltration membrane enriched with ZIF‐8 and TiO2 additives is prepared based on a non‐solvent induced phase separation method. During the phase transition process, the addition of organic nanocrystals ZIF‐8 and inorganic nanocrystals TiO2 delayed the phase transition rate, resulting in the transformation of the polyethersulfone modified membrane from a finger‐like pore structure to a sponge‐like pore structure. Compared to other structures, the sponge‐like modified membrane has a uniform and narrow pore size distribution, fewer surface defects, stable retention performance, and can simultaneously improve membrane permeability and mechanical strength. Therefore, the polyethersulfone modified membrane with a sponge‐like pore structure prepared in this research exhibits high flux for small molecules and good retention rate for large molecules. Long‐term cycling stability tests of the modified membrane shows high retention rate (over 98%), high flux, long service life, and good cycling stability for solute molecules. The study indicates that the prepared polyethersulfone modified membrane has high potential for application in relevant environmental separation processes.
Synthesis and photodynamic activity of new 5‐[(E)‐2‐(3‐alkoxy‐1‐phenyl‐1H‐pyrazol‐4‐yl)ethenyl]‐2‐phenyl‐3H‐indoles
Authors: Varvuolytė Gabrielė , Řezníčková Eva , Bieliauskas Aurimas , Kleizienė Neringa , Vojáčková Veronika , Opichalová Alena , Žukauskaitė Asta , Kryštof Vladimír , Šačkus Algirdas
Published: July 2024

A series of new indole‐pyrazole hybrids 8a–m were synthesized through the palladium‐catalyzed ligandless Heck coupling reaction from easily accessible unsubstituted, methoxy‐ or fluoro‐substituted 4‐ethenyl‐1H‐pyrazoles and 5‐bromo‐3H‐indoles. These compounds exerted cytotoxicity to melanoma G361 cells when irradiated with blue light (414 nm) and no cytotoxicity in the dark at concentrations up to 10 µM, prompting us to explore their photodynamic effects. The photodynamic properties of the example compound 8d were further investigated in breast cancer MCF‐7 cells. Evaluation revealed comparable anticancer activities of 8d in both breast and melanoma cancer cell lines within the submicromolar range. The treatment induced a massive generation of reactive oxygen species, leading to different types of cell death depending on the compound concentration and the irradiation intensity.
Feasibility of using phytoremediation biomass for sustainable biofuel production via thermochemical conversion
Authors: Kick Christopher , Kidikas Žygimantas , Kasiulienė Alfreda , Maletić Snežana , Zeremski Tijana , Rubežius Mantas , Eschen Marcus , Ortner Markus
Published: July 2024

This study explores a novel approach that combines soil recovery with biofuel production, presenting a strategy that addresses the increasing demand for biofuels while sidestepping the food–fuel debate. It also introduces an innovative method for recovering heavy metals from soils through their translocation into the solid product of the conversion process. Phytoremediation trials were conducted under real field conditions, and the thermochemical conversion of the harvested biomass was carried out at lab scale. Field trials took place in 2021–2023 in Lithuania and Serbia. In Serbia, the contamination primarily involved heavy metals, whereas the Lithuanian site was predominantly contaminated with hydrocarbons from petroleum products. The harvested biomass underwent pretreatment and was then used as feedstock for conversion into high‐energy carriers. The conversion products were evaluated for their potential to substitute fossil fuels. Finally, the value chain, encompassing key stakeholders and factors impacting the profitability of this approach, was established, and initial estimates were made regarding the size of individual cost components.
Neuartige 3D‐Bewehrungen für den Betonbau
Authors: Schumann Alexander , Schütze Elisabeth , May Maximilian , Baumgärtel Enrico , Curbach Manfred , Ehlig Daniel , Fischer Oliver , Hummel Danny
Published: July 2024

Angesichts der Herausforderungen in der Bauindustrie, insbesondere des Strebens nach Nachhaltigkeit und Materialeffizienz, untersucht dieser Beitrag die Entwicklung und das Potenzial einer innovativen dreidimensionalen (3D) und vollautomatisiert hergestellten Bewehrungsstruktur aus Carbonfasern, bekannt als „Mesh“. Diese fortschrittliche Bewehrungsmethode bietet eine vielseitige und ressourceneffiziente Alternative zur herkömmlichen Stahlbewehrung und eine Erweiterung zu derzeit verwendeten Carbongittern/‐bewehrungselementen. Das Mesh zeichnet sich durch Anpassungsfähigkeit an verschiedene Formen und Belastungspfade aus, wodurch der Beton‐ und Bewehrungsbedarf reduziert wird, welches die ökologische Bilanz von Bauprojekten verbessert. Die Entwicklung der neuartigen Bewehrungsstruktur, von den anfänglichen Tastversuchen bis zum aktuellen Stand, sowie ihrer Anwendungsmöglichkeiten, einschließlich der möglichen zukünftigen Eignung als Querkraft‐, Oberflächen‐, Spaltzug‐ oder Wendelbewehrung, insbesondere in vorgespannten Bauteilen, werden erörtert. Dieser Beitrag beleuchtet den Beitrag des Mesh zur Weiterentwicklung der Bewehrungstechnologie im Betonbau und ist der erste Teil einer mehrteiligen Veröffentlichungsserie.
Modulating metabolism through synthetic biology: Opportunities for two‐stage fermentation
Authors: Rong Yixin , Jensen Sheila Ingemann , Woodley John M. , Nielsen Alex Toftgaard
Published: July 2024

Bio‐based production of fuels, chemicals and materials is needed to replace current fossil fuel based production. However, bio‐based production processes are very costly, so the process needs to be as efficient as possible. Developments in synthetic biology tools has made it possible to dynamically modulate cellular metabolism during a fermentation. This can be used towards two‐stage fermentations, where the process is separated into a growth and a production phase, leading to more efficient feedstock utilization and thus potentially lower costs. This article reviews the current status and some recent results in application of synthetic biology tools towards two‐stage fermentations, and compares this approach to pre‐existing ones, such as nutrient limitation and addition of toxins/inhibitors.
Exploring the cognitive assessment potential of MRI‐based volumetric hippocampal segmentation in Parkinson's disease
Authors: Tarhan Merve , Atalay Başak , Buz Yaşar Ayşenur , Özdilek Fatma Betül
Published: July 2024

Purpose

To investigate the potential of magnetic resonance imaging (MRI)‐based total and segmental hippocampus volume analysis in the assessment of cognitive status in Parkinson's disease (PD).

Methods

We divided participants into three groups Group A‐Parkinson patients (Pp) with normal cognitive status (n = 25), Group B‐Pp with dementia (n = 17), and Group C‐healthy controls (n = 37). Three‐dimensional T1W Fast Spoiled Gradient Recalled Echo images were used for Volbrain hippocampus subfield segmentation. We used the “Winterburn” protocol, which divides the hippocampus into five segments, Cornu Ammonis (CA),CA2/CA3, CA4/dentate gyrus, stratum radiatum, lacunosum, and moleculare, and subiculum.

Results

A total of 79 participants were included in the study, consisting of 42 individuals with PD (64.2% male) and 37 healthy controls (54.1% male). The mean age of PD was 60.9 ± 10.7 years and the mean age of control group was 59.27 ± 12.3 years. Significant differences were found in total hippocampal volumes between Group A and B (p = .047. Statistically significant group differences were found in total, right, and left CA1 volumes (analysis of variance [ANOVA]: F(2,76) = 8.098, p = .001; F(2,76) = 7.628, p = .001; F(2,76) = 5.084, p = .008, respectively), as well as in total subiculum volumes (ANOVA: F(2,76) = 4.368, p = .016). Post hoc tests showed that total subiculum volume was significantly lower in individuals with normal cognitive status (0.474 ± 0.116 cm3) compared to healthy controls (0.578 ± 0.151 cm3, p = .013).

Conclusion

Volumetric hippocampal MRI can be used to assess the cognitive status of Pp. Longitudinal studies that evaluate Pp who progress from normal cognition to dementia are required to establish a causal relationship.
Unveiling the role of dorsal root ganglia in spasticity reduction: Insights from contralateral seventh cervical nerve cross transfer surgery
Authors: Zhao Xuanyu , Ma Xingyi , Zhao Huali , Li Tie , Qiu Yanqun , Shen Yundong , Feng Juntao , Xu Wendong
Published: July 2024

Background

Central nervous system (CNS) disorders, such as stroke, often lead to spasticity, which result in limb deformities and significant reduction in quality of life. Spasticity arises from disruptions in the normal functioning of cortical and descending inhibitory pathways in the brainstem, leading to abnormal muscle contractions. Contralateral seventh cervical nerve cross transfer (CC7) surgery has been proven to effectively reduce spasticity, but the specific mechanism for its effectiveness is unclear.

Methods

This study aimed to investigate the changes in the dorsal root ganglia (DRG) following CC7 surgery. A comprehensive anatomical analysis was conducted through cadaveric study and magnetic resonance imaging (MRI) study, to accurately measure the regional anatomy of the C7 DRG. DRG perfusion changes were quantitatively assessed by comparing pre‐ and postoperative dynamic contrast‐enhanced (DCE) MRI.

Results

In CC7 surgery, the C7 nerve root on the affected side is cut close to the DRG (3.6 ± 1.0 mm), while the C7 nerve root on the healthy side is cut further away from the DRG (65.0 ± 10.0 mm). MRI studies revealed that after C7 proximal neurotomy on the affected side, there was an increase in DRG volume, vascular permeability, and perfusion; after C7 distal neurotomy on the healthy side, there was a decrease in DRG volume, with no significant changes in vascular permeability and perfusion.

Conclusion

This study provides preliminary insights into the mechanisms of spasticity reduction following CC7 surgery, indicating that changes in the DRG, such as increased vascular permeability and perfusion, could disrupt abnormal spinal γ‐circuits. The resulting high‐perfusion state of DRG, possibly due to heightened neuronal activity and metabolic demands, necessitating further research to verify this hypothesis.
Evaluating age‐and gender‐related changes in brain volumes in normal adult using synthetic magnetic resonance imaging
Authors: Zheng Zuofeng , Liu Yawen , Wang Zhenchang , Yin Hongxia , Zhang Dongpo , Yang Jiafei
Published: July 2024

Objective

Normal aging is associated with brain volume change, and brain segmentation can be performed within an acceptable scan time using synthetic magnetic resonance imaging (MRI). This study aimed to investigate the brain volume changes in healthy adult according to age and gender, and provide age‐ and gender‐specific reference values using synthetic MRI.

Methods

A total of 300 healthy adults (141 males, median age 48; 159 females, median age 50) were underwent synthetic MRI on 3.0 T. Brain parenchymal volume (BPV), gray matter volume (GMV), white matter volume (WMV), myelin volume (MYV), and cerebrospinal fluid volume (CSFV) were calculated using synthetic MRI software. These volumes were normalized by intracranial volume to normalized GMV (nGMV), normalized WMV (nWMV), normalized MYV (nMYV), normalized BPV (nBPV), and normalized CSFV (nCSFV). The normalized brain volumes were plotted against age in both males and females, and a curve fitting model that best explained the age dependence of brain volume was identified. The normalized brain volumes were compared between different age and gender groups.

Results

The approximate curves of nGMV, nWMV, nCSFV, nBPV, and nMYV were best fitted by quadratic curves. The nBPV decreased monotonously through all ages in both males and females, while the changes of nCSFV showed the opposite trend. The nWMV and nMYV in both males and females increased gradually and then decrease with age. In early adulthood (20s), nWMV and nMYV in males were lower and peaked later than that in females (p < .005). The nGMV in both males and females decreased in the early adulthood until the 30s and then remains stable. A significant decline in nWMV, nBPV, and nMYV was noted in the 60s (Turkey test, p < .05).

Conclusions

Our study provides age‐ and gender‐specific reference values of brain volumes using synthetic MRI, which could be objective tools for discriminating brain disorders from healthy brains