bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bithiophene‐Functionalized Infrared Two‐Photon Absorption Metal Complexes as Single‐Molecule Platforms for Synergistic Photodynamic, Photothermal, and Chemotherapy
Authors: Li Xue‐Lian , Wang Meng‐Fan , Zeng Li‐Zhen , Li Guo‐Kui , Zhao Run‐Yu , Liu Fu‐Dan , Li Yun , Yan Yu‐Fei , Liu Qishuai , Li Zhao , Zhang Hongbin , Ren Xiaoxia , Gao Feng 
Published: April 2024

AbstractA planar conjugated ligand functionalized with bithiophene and its Ru(II), Os(II), and Ir(III) complexes have been constructed as single‐molecule platform for synergistic photodynamic, photothermal, and chemotherapy. The complexes have significant two‐photon absorption at 808 nm and remarkable singlet oxygen and superoxide anion production in aqueous solution and cells when exposed to 808 nm infrared irradiation. The most potent Ru(II) complex Ru7 enters tumor cells via the rare macropinocytosis, locates in both nuclei and mitochondria, and regulates DNA‐related chemotherapeutic mechanisms intranuclearly including DNA topoisomerase and RNA polymerase inhibition and their synergistic effects with photoactivated apoptosis, ferroptosis and DNA cleavage. Ru7 exhibits high efficacy in vivo for malignant melanoma and cisplatin‐resistant non‐small cell lung cancer tumors, with a 100 % survival rate of mice, low toxicity to normal cells and low residual rate. Such an infrared two‐photon activatable metal complex may contribute to a new generation of single‐molecule‐based integrated diagnosis and treatment platform to address drug resistance in clinical practice and phototherapy for large, deeply located solid tumors.
Hierarchical Self‐Assembly of Multidimensional Functional Materials from Sequence‐Defined Peptoids
Authors: Shao Li , Hu Dehong , Zheng Shao‐Liang , Trinh Thi Kim Hoang , Zhou Wenhao , Wang Haoyu , Zong Yanxu , Li Changning , Chen Chun‐Long 
Published: April 2024

AbstractHierarchical self‐assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular‐level understanding of the hierarchical assembly of sequence‐defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron‐based powder X‐ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence‐defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.
Living Self‐Assembly of Monodisperse Micron‐Sized Polymer Vesicles
Authors: Pan Hui , Zhang Changxu , Jiang Wenfeng , Zhou Yongfeng 
Published: April 2024

AbstractArtificial vesicles are recognized as powerful platforms for a large body of research across the disciplines of chemistry, physics and biology. Despite the great progress, control of the size distribution to make uniform vesicles remains fundamentally difficult due to the highly uncontrollable growth kinetics, especially for micron‐sized vesicles. Here we report a template‐free living self‐assembly method to prepare monodisperse vesicles around 1 μm from an alternating copolymer. The polymer forms nanodisks (ca. 9 nm) in N,N‐dimethylformamide (DMF), acting as seeds for subsequent growth. By adding water, the nanodisks gradually grow into larger circular bilayer nanosheets, which bend to crowns and continue to grow into uniform micron‐sized vesicles. The first‐order growth kinetics as well as the small size polydispersity index (<0.1) suggests the living self‐assembly characteristics. This work paves a new way in both living self‐assembly and monodisperse polymer vesicles.
Crystalline Porous Organic Frameworks Based on Multiple Dynamic Linkages
Authors: Liu Bo , Guo Panyue , Guan Xinyu , Tian Xuexue , Du Fei , Xie Weiqing , Jiang Hai‐Long 
Published: April 2024

AbstractA novel class of crystalline porous materials has been developed utilizing multilevel dynamic linkages, including covalent B−O, dative B←N and hydrogen bonds. Typically, boronic acids undergo in situ condensation to afford B3O3‐based units, which further extend to molecular complexes or chains via B←N bonds. The obtained superstructures are subsequently interconnected via hydrogen bonds and π–π interactions, producing crystalline porous organic frameworks (CPOFs). The CPOFs display excellent solution processability, allowing dissolution and subsequent crystallization to their original structures, independent of recrystallization conditions, possibly due to the diverse bond energies of the involved interactions. Significantly, the CPOFs can be synthesized on a gram‐scale using cost‐effective monomers. In addition, the numerous acidic sites endow the CPOFs with high NH3 capacity, surpassing most porous organic materials and commercial materials.
On the Dendrite‐Suppressing Effect of Laser‐Processed Polylactic Acid‐Derived Carbon Coated Zinc Anode in Aqueous Zinc Ion Batteries
Authors: Abouali Maryam , Adhami Sadaf , Haris Somayeh Asadi , Yuksel Recep 
Published: April 2024

AbstractA major bottleneck limiting the commercialization of aqueous zinc ion batteries (AZIBs) is dendrite formation on the zinc (Zn) anode during the plating/stripping process, which leads to rapid deterioration in performance and, consequently to the device failure. In this regard, researchers are trying to design more stable anodes toward suppressing dendrite formation. One possible solution to tackle this problem and to extend the cycling life of AZIBs is to modify the zinc anode surface by coating carbonaceous materials, enabling more controlled charge flux and uniform ion distribution. This work reports sustainable and bio‐derived polylactic acid (PLA) as a coating layer on the zinc anode. Carbonizing this polymer under ambient conditions using a high‐power nanosecond laser forms a carbon‐coated zinc foil, which was directly utilized as the anode in aqueous zinc ion batteries. The fabricated laser‐processed PLA‐derived carbon‐coated zinc anode demonstrated an extended cycling life of almost 1600 hours, significantly outperforming the bare zinc anode. A full aqueous zinc ion battery assembled from as‐modified anode and as‐prepared V2O5 nanofibers as cathode was able to deliver a specific capacity of 238 mAh g−1 at 1.0 A g−1 with a capacity retention of 70 % after 1000 cycles.
Including the Ensemble of Unstructured Conformations in the Analysis of Protein's Native State by High‐Pressure NMR Spectroscopy
Authors: Berner Frederic , Kovermann Michael 
Published: April 2024

AbstractThe analysis of pressure induced changes in the chemical shift of proteins allows statements on structural fluctuations proteins exhibit at ambient pressure. The inherent issue of separating general pressure effects from structural related effects on the pressure dependence of chemical shifts has so far been addressed by considering the characteristics of random coil peptides on increasing pressure. In this work, chemically and pressure denatured states of the cold shock protein B from Bacillus subtilis (BsCspB) have been assigned in 2D 1H‐15N HSQC NMR spectra and their dependence on increasing hydrostatic pressure has been evaluated. The pressure denatured polypeptide chain has been used to separate general from structural related effects on 1H and 15N chemical shifts of native BsCspB and the implications on the interpretation of pressure induced changes in the chemical shift regarding the structure of BsCspB are discussed. It has been found that the ensemble of unstructured conformations of BsCspB shows different responses to increasing pressure than random coil peptides do. Thus, the approach used for considering the general effects that arise when hydrostatic pressure increases changes the structural conclusions that are drawn from high pressure NMR spectroscopic experiments that rely on the analysis of chemical shifts.
Repurposing Visible‐Light‐Excited Ene‐Reductases for Diastereo‐ and Enantioselective Lactones Synthesis
Authors: Yu Jinhai , Zhang Qiaoyu , Zhao Beibei , Wang Tianhang , Zheng Yu , Wang Binju , Zhang Yan , Huang Xiaoqiang 
Published: April 2024

AbstractRepurposing enzymes to catalyze non‐natural asymmetric transformations that are difficult to achieve using traditional chemical methods is of significant importance. Although radical C−O bond formation has emerged as a powerful approach for constructing oxygen‐containing compounds, controlling the stereochemistry poses a great challenge. Here we present the development of a dual bio‐/photo‐catalytic system comprising an ene‐reductase and an organic dye for achieving stereoselective lactonizations. By integrating directed evolution and photoinduced single electron oxidation, we repurposed engineered ene‐reductases to steer non‐natural radical C−O formations (one C−O bond for hydrolactonizations and lactonization‐alkylations while two C−O bonds for lactonization‐oxygenations). This dual catalysis gave a new approach to a diverse array of enantioenhanced 5‐ and 6‐membered lactones with vicinal stereocenters, part of which bears a quaternary stereocenter (up to 99 % enantiomeric excess, up to 12.9 : 1 diastereomeric ratio). Detailed mechanistic studies, including computational simulations, uncovered the synergistic effect of the enzyme and the externally added organophotoredox catalyst Rh6G.
Synthesis of 18F‐labeled Aryl Trifluoromethyl Sulfones, ‐Sulfoxides, and ‐Sulfides for Positron Emission Tomography
Authors: Veth Lukas , Windhorst Albert D. , Vugts Danielle J. 
Published: April 2024

AbstractPositron emission tomography (PET) is becoming increasingly important in nuclear medicine and drug discovery. To date, the development of many potential PET tracers is hampered by the lack of suitable synthetic pathways for their preparation. This is particularly true for the highly desired radiolabeling of compounds bearing [18F]CF3‐groups. For instance, S(O)nCF3‐groups (n=0, 1, 2) serve as structural motif in a range of biologically active compounds, but their radiosynthesis remains largely unprecedented (for n=1, 2). Herein, we describe general methods for the radiosynthesis of 18F‐labeled aryl trifluoromethyl sulfones, ‐sulfoxides, and ‐sulfides. All three methods are operationally straightforward, start from widely available precursors, i.e., sulfonyl fluorides and thiophenols, and make use of the recently established [18F]Ruppert‐Prakash reagent. Further, the syntheses display good functional group tolerance as demonstrated by the 18F‐labeling of more than 40 compounds. The applicability of the new method is demonstrated by the radiolabeling of three bioactive molecules, optionally to be used as PET tracers. In a broader context, this work presents a substantial expansion of the chemical space of radiofluorinated structural motifs to be used for the development of new PET tracers.
Silylenes with a Small Chalcogenide Substituent: Tuning Frontier Orbital Energies from O to Te
Authors: Müller Maximilian P. , Hinz Alexander 
Published: April 2024

AbstractThe general synthesis of heteroleptic acyclic silylenes with a bulky carbazolyl substituent (dtbpCbz) is detailed and a series of compounds with a chalcogenide substituent of the type [(dtbpCbz)SiE16R] (E16R=OtBu, SEt, SePh, TePh) is reported. With the bulky carbazolyl substituent present, the chalcogenide moiety can be very small, as is shown by incorporating groups as small as ethyl, phenyl or tert‐butyl. For the first time, the electronic properties of the silylene can be tuned along a complete series of chalcogenide substituents. The effects are clearly visible in the NMR and UV/Vis spectra, and were rationalised by DFT computations. The reactivity of the heaviest chalcogenide‐substituted silylenes was probed by reactions with trimethylphosphine selenide and the terphenyl azide TerN3 (Ter=2,6‐dimesitylphenyl).
Efficient enzymatic synthesis of vitamin E succinate using an organic solvent‐stable immobilized lipase
Authors: Li Wenlin , Lin Sen , Lan Dongming , Wang Yonghua 
Published: April 2024

AbstractVitamin E succinate has gained substantial attention as a potential therapeutic agent for cancer treatment due to its biomedical activities. One of the prominent methods of synthesizing vitamin E succinate is through enzymatic processes, which, although advantageous, presents inherent challenges related to optimization, scalability, and particularly, the poor stability of lipases in organic solvents. Our study addresses these challenges by conducting a comprehensive comparative analysis between Lipase UM1 and three other immobilized commercial lipases, demonstrating Lipase UM1's enhanced resistance to organic solvents and its superior efficiency in vitamin E succinate production. Further optimization experiments with Lipase UM1 led to an unprecedented conversion of 99%. Additionally, we scaled the reaction to a proof‐of‐concept industrial level. The synthesized product was verified using Fourier transform infrared spectroscopy and nuclear magnetic resonance analysis, ensuring its quality and consistency. This study validates Lipase UM1 as an efficient catalyst for vitamin E succinate synthesis, offering a promising avenue for industrial production with potential applications in cancer therapy and beyond.
One‐pot synthesis of aluminum phosphate‐supported, chitosan‐linked expandable graphite as a novel flame retardant for textile
Authors: Dey Riya , Bhakare Madhuri A. , Some Surajit 
Published: April 2024

AbstractAlthough cotton is the most common polymer in daily life, its limited use is due to its propensity to catch fire. To solve this issue, we developed an innovative flame‐retardant aluminum phosphate‐supported, chitosan‐linked expandable graphite composite (CAlPEG). The CAlPEG was synthesized by the reaction of natural graphite, aluminum phosphate, and chitosan biopolymer in a one‐pot method. When CAlPEG was coated with cotton fabric and exposed to continuous flame, the fabric did not catch fire up to 760 s, whereas only expandable graphite (EG), aluminum phosphate (AIP), and CS, coated cotton fabric burned within 20 s. Flame‐retardant proficiency of CAlPEG‐coated cloth was confirmed by flame tests such as a limiting oxygen index (LOI) and vertical flammability test. The blank cotton has 17% LOI and is completely burnt out. On the other hand, the as‐prepared composite has a 43% LOI rating, which denotes a high level of flame retardancy. The VFT test result showed the formation of a 3 cm char, which confirms the flame‐retardant material possesses self‐extinguishing qualities. The article develops a new method for utilizing bioresources such as chitosan and offers fresh perspectives on the environmentally friendly synthesis of phosphorylated EG‐linked chitosan on the AlPO4 matrix.
Nano and micro co‐filled aluminum nitride/magnesium dihydrate—Silicone rubber composites for high voltage insulation
Authors: Ashitha Parambalath Narendran , Shanker Tangella Bhavani , Meena K. Parameswaran , Varughese Konnanilkunnathil Thomas 
Published: April 2024

AbstractCo‐filled composites of micro magnesium dihydrate (MDH) and hydrophobically treated nano aluminum nitride (nH‐AlN) fillers in high temperature vulcanizing silicone gum are studied for thermal and dielectric characteristics for use as an insulating material in high voltage applications. The study begins with description of the compounding protocol adopted, followed by spectroscopic and optical characterization. Fourier transform infrared spectroscopy (FTIR) and energy dispersive X‐ray spectroscopy (EDX) analysis are used to verify the presence of nH‐AlN and MDH in the composites. Thermal analysis through thermogravimetric analysis revealed a stark enhancement in the onset of polymer degradation temperature, with an improvement of 208 °C achieved at 30 phr by weight loading level of MDH. Volume resistivity of 9.71 E14 Ω‐cm is obtained at 30 phr weight loading of MDH and 5 phr of nH‐AlN. AC, +DC, and −DC dielectric strength improved by 1.09, 2.06, and 1.08 times for co‐filled composites at 30 phr MDH and 5 phr nH‐AlN loading levels over unitary filled composite. Effect of dielectric polarization on dielectric constant and dissipation factor is studied at various frequencies. Limitations while conducting dry arc resistance test at standard voltage of 12.50 kV is discussed, with modification in dry arc resistance test voltage to 16.95 kV. The results are presented and discussed here.
Thermally conductive high‐voltage insulation composites with outstanding comprehensive properties through particle grading design
Authors: Feng Zun‐Peng , Hao Ya‐Nan , Song Yan‐Hui , Feng Qi‐Kun , Xu Hai‐Ping , Dang Zhi‐Min 
Published: April 2024

AbstractIn order to meet the requirements of practical applications, the comprehensive performance of thermally conductive high‐voltage insulating composites is worth evaluating. Guided by the particle packing theory, spherical alumina particles with different particle size distributions were compounded and filled into low‐density polyethylene (LDPE), and the thermal conductivity (TC) and mechanical breakdown of different compound systems were systematically investigated. The results show that the particle grading design of small‐particle filled composites has better comprehensive properties than that of single‐scale or large‐particle filled composites, which proves the superiority and feasibility of particle grading design. The 110–40 wt.% composite has a higher TC (0.47 W/(m K)) compared with LDPE, while maintaining excellent insulation properties (227 kV/mm) and mechanical properties (tensile strength of 10 MPa and elongation at break of 720%). Finally, studies on the application of composite materials in the field of thermal management and ice melting of steel‐core aluminum insulated wires were applied, and both studies show good prospects for the applications of Al2O3/LDPE thermal conductive high‐voltage insulation composites.
Recycling of polyester bottle waste to generate functional acid dye in situ on wool
Authors: Singh Ankit , Sheikh Javed 
Published: April 2024

AbstractNowadays, waste management is gaining popularity to reduce the environmental impact made by human beings. There is a dire need to decrease the pollution caused by plastic materials. A gradual rise in the demand for polyester bottles has generated a need to recycle these materials. In the present work, an aromatic amine (4,4′‐(1,4‐phenylenebis(1,3,4‐oxadiazole‐5,2‐diyl)) dianiline) was prepared from the polyester bottle waste. The successful synthesis and chemical structure of the amine was confirmed by various characterization techniques such as Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR), and 13C NMR. The amine was diazotized and coupled with H‐acid (4‐amino‐5‐hydroxy‐2,7‐naphthalene disulfonic acid)‐treated wool fabric to generate acid dye in situ on the fabric. The coloration (L*, a*, b*, and K/S) and fastness properties of dyed wool were evaluated, and the samples were further analyzed for antibacterial and UV‐protective properties. The dyed wool was also characterized by FTIR to confirm the presence of the aromatic group of the dye. The introduction of dye structure on the wool increased the thermal stability of the fabric, which was confirmed through thermogravimetric analysis analysis. Antibacterial activity (>70%) and excellent UV protection were retained by dyed wool after 20 washes. Furthermore, the dyed wool was found nontoxic under the cytotoxicity evaluation test.
Sugar‐template method to construct a boron nitride filler network to enhance the thermal conductivity of epoxy composites
Authors: Wang Yifan , Yu Zhiqiang 
Published: April 2024

AbstractIn this work, a technique for constructing a three‐dimensional (3D) skeleton of hexagonal boron nitride (h‐BN) using sugar as the fulcrum and preparing composites by embedding in the epoxy (EP) in a vacuum environment is proposed. The study of thermal conductivity (TC) in polymer composites is conducted through a blend of techniques: laser flashing, theoretical modeling, and finite element simulation. The h‐BN skeleton exhibits a honeycomb structure through the scanning electron microscopy findings. Further investigation using finite element simulation demonstrates that conductive networks are formed by the h‐BN skeleton within the composites, leading to a notable enhancement in TC. Specifically, the composite for h‐BN/EP reaches a TC of 2.25 W/m K when composed of 52 vol% h‐BN. A dielectric loss of 0.008 for the composite with the same h‐BN loading shows a considerable improvement. The compressive yield strength of the 3D h‐BN/EP composites reached 312 MPa at 5 vol% h‐BN loading.
Modification of discarded polypropylene mask and its utilization as crude oil flow improver
Authors: Zang Yunlei , Wentao Ji , Ying Wang , Xiaoli Dong , Li Yongfei , Chen Shijun , Chen Gang 
Published: April 2024

AbstractA method was investigated for the treatment and utilization of large quantities of polypropylene (PP)‐based wastes, such as discarded masks, generated by the COVID‐19 pandemic. A novel crude oil flow improver (named as MPP) was synthesized by modifying waste PP masks with maleic anhydride. The structure and properties of PP and MPP were characterized using Fourier transform infrared and differential scanning calorimetry (DSC). The optimal reaction ratio was determined to be npolypropylene:nmaleic anhydride = 1:2 and nBPO = 0.2%. When the concentration of MPP is 500 ppm, the viscosity of the YL crude oil samples is reduced by 92.48%, and the pour point is reduced by 4.2°C. In addition, MPP2 can significantly reduce the viscosity of CQ oil sample by 87.62%. The mechanism of MPP was investigated by DSC and polarized light microscopy (PLM) analysis of YL oil samples before and after the addition of MPP2. Finally, the total cost of this new crude oil flow improver is estimated and its market feasibility is analyzed. The study not only realizes resource utilization but also achieves the cycle of returning oil from oil to oil, which contributes to the implementation of resource circular economy and is of positive significance in promoting the petrochemical industry.