bluuebunny/crossref_metadata_2025 huggingface dataset:
Incorporating MIL‐125 Metal‐Organic Framework for Flexible Triboelectric Nanogenerators and Self‐Powered Sensors for Robotic Grippers
Authors: Kakim Alibek , Nurkesh Ayan , Sarsembayev Bayandy , Dauletiya Daniyar , Balapan Azat , Bakenov Zhumabay , Yeshmukhametov Azamat , Kalimuldina Gulnur
Published: April 2024

Triboelectric nanogenerators (TENGs) are getting popular as biomechanical energy harvesters to power small electronic devices and as self‐powered sensors for pressure, motion, vibration, wind, waves, biomedical information, and chemical substance detections. In this study, the TENG is designed with biocompatible materials, and concentrations of its components have been optimized to generate higher power for application as an energy source and tactile sensor. The process involves using metal‐organic frameworks (MOFs), namely MIL‐125, with high charge‐inducing and charge‐trapping capabilities incorporated into the commercial Ecoflex matrix. Electrical characterization demonstrated that the sample with 0.25 wt% MIL‐125 (0.25%MOF/Ecoflex) is the optimal concentration in the matrix with an output of up to 305 V and 13 µA, respectively. Moreover, the proposed flexible TENG converts mechanical energy to electrical, with a maximum power density of 150 µW cm−2(1.5 W m−2), which is more than twice superior to the pristine Ecoflex‐based counterparts. The TENG shows robust and stable performance without noticeable degradation during continuous 200,000 cyclic testing. Furthermore, 0.25%MOF/Ecoflex TENG can power small electronic devices such as calculators, humidity sensors, and cardiac pacemakers. A robotic gripper trained via machine learning to identify various objects is also successfully developed with a self‐powered 0.25%MOF/Ecoflex TENG sensor.
PXR Activation Relieves Deoxynivalenol‐Induced Liver Oxidative Stress Via Malat1 LncRNA m6A Demethylation
Authors: Feng Yue , Shen Jiakun , Lin Zishen , Chen Zeyi , Zhou Min , Ma Xi
Published: April 2024

Deoxynivalenol (DON) is a prevalent toxin causing severe liver damage through hepatocellular oxidative stress. However, the underlying mechanisms and effective therapeutic approaches remain unknown. Here, the unique role of the xenobiotic metabolism factor pregnane X receptor (PXR) in mediating DON‐induced hepatocellular oxidative stress is investigated. Treatment with the PXR agonist 3‐indole‐propionic acid (IPA) alleviates DON‐induced oxidative stress and liver injury both in vitro and in vivo. Mechanistically, it is discovered for the first time that PXR agonist IPA directly transactivates the m6A demethylase FTO expression, leading to site‐specific demethylation and decreased abundance of YTHDC1‐bound Malat1 lncRNA at single‐nucleotide resolution. The diminished m6A modification of Malat1 lncRNA reduces its stability and augments antioxidant pathways governed by NRF2, consequently mitigating DON‐induced liver injury. Furthermore, Malat1 knockout mice exhibit decreased DON‐induced liver injury, emphasizing the role of Malat1 lncRNA in oxidative stress. Collectively, the findings establish that PXR‐mediated m6A‐dependent Malat1 lncRNA expression determines hepatocyte oxidative stress via m6A demethylase FTO, providing valuable insights into the potential mechanisms underlying DON‐induced liver injury and offers potential therapeutic strategies for its treatment.
Extrusion Printing of Surface‐Functionalized Metal‐Organic Framework Inks for a High‐Performance Wearable Volatile Organic Compound Sensor
Authors: Wang Xiao , Qi Hao , Shao Yuzhou , Zhao Mingming , Chen Huayun , Chen Yun , Ying Yibin , Wang Yixian
Published: April 2024

Wearable sensors hold immense potential for real‐time and non‐destructive sensing of volatile organic compounds (VOCs), requiring both efficient sensing performance and robust mechanical properties. However, conventional colorimetric sensor arrays, acting as artificial olfactory systems for highly selective VOC profiling, often fail to meet these requirements simultaneously. Here, a high‐performance wearable sensor array for VOC visual detection is proposed by extrusion printing of hybrid inks containing surface‐functionalized sensing materials. Surface‐modified hydrophobic polydimethylsiloxane (PDMS) improves the humidity resistance and VOC sensitivity of PDMS‐coated dye/metal‐organic frameworks (MOFs) composites. It also enhances their dispersion within liquid PDMS matrix, thereby promoting the hybrid liquid as high‐quality extrusion‐printing inks. The inks enable direct and precise printing on diverse substrates, forming a uniform and high particle‐loading (70 wt%) film. The printed film on a flexible PDMS substrate demonstrates satisfactory flexibility and stretchability while retaining excellent sensing performance from dye/MOFs@PDMS particles. Further, the printed sensor array exhibits enhanced sensitivity to sub‐ppm VOC levels, remarkable resistance to high relative humidity (RH) of 90%, and the differentiation ability for eight distinct VOCs. Finally, the wearable sensor proves practical by in situ monitoring of wheat scab‐related VOC biomarkers. This study presents a versatile strategy for designing effective wearable gas sensors with widespread applications.
A Giant Magneto‐Superelasticity of 5% Enabled by Introducing Ordered Dislocations in Ni34Co8Cu8Mn36Ga14 Single Crystal
Authors: Yu Qijia , Wang Jingmin , Liang Chuanxin , Meng Jiaxi , Xu Jinyue , Liu Yang , Zhao Shiteng , Xi Xuekui , Xi Chuanying , Yang Ming , Si Chen , He Yangkun , Wang Dong , Jiang Chengbao
Published: April 2024

Elasticity, featured by a recoverable strain, refers to the ability that materials can return to their original shapes after deformation. Typically, the elastic strains of most metals are well‐known 0.2%. In shape memory alloys and high entropy alloys, the elastic strains can be several percent, as called superelasticity, which are all triggered by external stresses. A superelasticity induced by magnetic field, termed as magneto‐superelasticity, is extremely important for contactless work of materials and for developing brand‐new large stroke actuators and high efficiency energy transducers. In magnetic shape memory alloys, the twin boundary motion driven by magnetic field can output a strain of several percent. However, this strain is unrecoverable when removing the magnetic field and hence it is not magneto‐superelasticity. Here, a giant magneto‐superelasticity of 5% in a Ni34Co8Cu8Mn36Ga14 single crystal is reported by introducing arrays of ordered dislocations to form preferentially oriented martensitic variants during the magnetically induced reverse martensitic transformation. This work provides an opportunity to achieve high performance in functional materials by defect engineering.
On‐Chip Neural Induction Boosts Neural Stem Cell Commitment: Toward a Pipeline for iPSC‐Based Therapies
Authors: Jain Saumey , Voulgaris Dimitrios , Thongkorn Surangrat , Hesen Rick , Hägg Alice , Moslem Mohsen , Falk Anna , Herland Anna
Published: April 2024

The clinical translation of induced pluripotent stem cells (iPSCs) holds great potential for personalized therapeutics. However, one of the main obstacles is that the current workflow to generate iPSCs is expensive, time‐consuming, and requires standardization. A simplified and cost‐effective microfluidic approach is presented for reprogramming fibroblasts into iPSCs and their subsequent differentiation into neural stem cells (NSCs). This method exploits microphysiological technology, providing a 100‐fold reduction in reagents for reprogramming and a ninefold reduction in number of input cells. The iPSCs generated from microfluidic reprogramming of fibroblasts show upregulation of pluripotency markers and downregulation of fibroblast markers, on par with those reprogrammed in standard well‐conditions. The NSCs differentiated in microfluidic chips show upregulation of neuroectodermal markers (ZIC1, PAX6, SOX1), highlighting their propensity for nervous system development. Cells obtained on conventional well plates and microfluidic chips are compared for reprogramming and neural induction by bulk RNA sequencing. Pathway enrichment analysis of NSCs from chip showed neural stem cell development enrichment and boosted commitment to neural stem cell lineage in initial phases of neural induction, attributed to a confined environment in a microfluidic chip. This method provides a cost‐effective pipeline to reprogram and differentiate iPSCs for therapeutics compliant with current good manufacturing practices.
Fast Room‐Temperature Mg‐Ion Conduction in Clay‐Like Halide Glassy Electrolytes
Authors: Yang Xiaochen , Gupta Sunny , Chen Yu , Sari Dogancan , Hau Han‐Ming , Cai Zijian , Dun Chaochao , Qi Miao , Ma Lu , Liu Yi , Urban Jeffrey J. , Ceder Gerbrand
Published: April 2024

The discovery of mechanically soft solid‐state materials with fast Mg‐ion conduction is crucial for the development of solid‐state magnesium batteries. In this paper, novel magnesium gallium halide compounds are reported that achieve high ionic conductivity of 0.47 mS cm−1 at room temperature. These Mg‐ion conductors obtained by ball milling Mg and Ga salts exhibit clay‐like mechanical properties, enabling intimate contact at the electrode–electrolyte interface during battery cycling. With a combination of experimental and computational analysis, this study identifies that the soft‐clay formation is induced by partial anion exchange during milling. This partial anion exchange creates undercoordinated magnesium ions in a chlorine‐rich environment, yielding fast Mg‐ion conduction. This work demonstrates the potential of clay‐like halide electrolytes for all‐solid‐state magnesium batteries, with possible further extension to other multivalent battery systems.
Electrocatalysis for Green(er) Chemistry: Limitations and Opportunities with Traditional and Emerging Characterization Methods for Tangible Societal Impact
Authors: Sherrell Peter C. , Iesalnieks Mairis , Ehrnst Yemima , Rezk Amgad R. , Šutka Andris
Published: April 2024

The world is facing grand challenges in energy security, environmental pollution, and sustainable use (and re‐use) of resources. Electrochemical processes, incorporating electrosynthesis, electrochemical catalysis, and electrochemical energy storage devices, provide pathways to address these challenges via green chemistry. However, the applicability of electrochemical processes for these systems is limited by the required energy input, the “electrons” in electrochemistry. Electrocatalysis as a subset of electrochemistry is set to underpin many of the United Nations Sustainable Development Goals, including “Affordable and Clean Energy” through the production of future fuels and abatement of carbon emissions; “Responsible Consumption and Production” through recycling and degradation of waste; and “Climate Action” through CO2 (and other greenhouse gas) remediation. The rise of green photovoltaic power has lowered the carbon cost of these electrons, making electrocatalysis an even more viable, green(er), chemical conversion pathway. This perspective highlights the need for comprehensive understanding of catalyst structure via in situ and operando analysis to complement device design considerations. The challenges faced by the field of electrocatalysis in data reporting, elimination of electrochemical artifacts, catalyst stability, and scaling to industrial relevance, along with opportunities, emerging tools, are discussed with a view to achieve the maximum ‘potential’ of electrocatalysis.
All together now: Assessing variation in maternal and nonmaternal handling of wild Colobus vellerosus infants
Authors: King Allyson G. , Rissling Tianna , Cote Susanne , Sicotte Pascale
Published: April 2024

Primatologists have a long‐standing interest in the study of maternal care and nonmaternal handling (NH) of infants stemming from recognition that early social relationships can have enduring consequences. Though maternal care and NH often include expression of similar behaviors, they are regularly studied in isolation from each other with nonoverlapping terminology, thereby overlooking possible interplay between them and obfuscating potential developmental ramifications that ensue from trade‐offs made between maternal (MH) and NH during infancy. To that end, identifying how MH and NH patterns interact and contribute to the total handling (TH) infants receive is a critical first step. We present durational handling data collected from 25 wild Colobus vellerosus infants from 2016 to 2017 and assess the relationships between TH, MH, and NH. Patterns of social affiliation are shaped in part by surrounding context, and therefore, we also assess whether NH and TH differ in their responsivity to various infant and social group characteristics. Ninety‐four percent of observed handling was MH, while just 5.5% was NH. Young infants who received more MH (excluding nursing) also received more NH; there was no relationship between the two in older infants. Infants in larger groups participated in more handling of all types. Additionally, NH time was associated with infant sex and group stability. Non‐nursing TH time was associated with group stability and infant cohort size. Though NH variation likely confers social‐networking advantage, in this population NH is not a major contributor to TH and would not effectively replace reduced MH. The positive association between MH and NH during early infancy suggests that colobus mothers may play a mediating role in shaping infant socialization. This is a first step in elucidating how different forms of handling relate to one another in wild primates and in identifying the impact of handling on infant socialization.
Prevalence of and Annual Conversion Rates to Mild Cognitive Impairment and Dementia: Prospective, Longitudinal Study of an Essential Tremor Cohort
Authors: Ghanem Ali , Berry Diane S. , Burkes Allison , Grill Natalie , Hall Talía M. , Hart Kira A. , Hernandez Nora C. , Chapman Silvia , Sharma Vibhash D. , Huey Edward D. , Cosentino Stephanie A. , Louis Elan D.
Published: April 2024

Objective

Despite recent attention to cognitive impairment in essential tremor, few studies examine rates of conversion to diagnoses of mild cognitive impairment and dementia. Development of dementia in essential tremor is associated with loss of functional ability and a doubling of mortality rate. This prospective, longitudinal study comprehensively reports the prevalence and incidence of, and the annual rates of conversion to, mild cognitive impairment and dementia in an essential tremor cohort.

Methods

Patients underwent detailed cognitive assessments and were assigned diagnoses of normal cognition, mild cognitive impairment, or dementia. There were 222 patients at baseline (mean age = 79.3 ± 9.7 years), and 177 patients participated in follow‐up evaluations at 18, 36, 54, and 72 months (mean years of observation = 5.1 ± 1.7). Data were compared to those of historical controls and Parkinson disease patients.

Results

The cumulative prevalence of dementia and average annual conversion rate of mild cognitive impairment to dementia were 18.5% and 12.2%, nearly three times higher than rates in the general population, and approximately one half the magnitude of those reported for Parkinson disease patients. The cumulative prevalence of mild cognitive impairment (26.6%) was almost double that of the general population, but less than that in Parkinson disease populations.

Interpretation

We present the most complete exposition of the longitudinal trajectory of cognitive impairment in an essential tremor cohort yet presented. The prevalence of and conversion rates to dementia in essential tremor fall between those associated with the natural course of aging and the more pronounced rates observed in Parkinson disease. ANN NEUROL 2024;95:1193–1204
A Photodynamic and Photochemotherapeutic Platinum‐Iridium Charge‐Transfer Conjugate for Anticancer Therapy
Authors: Shi Huayun , Carter Oliver W. L. , Ponte Fortuna , Imberti Cinzia , Gomez‐Gonzalez Miguel A. , Cacho‐Nerin Fernando , Quinn Paul D. , Parker Julia E. , Sicilia Emilia , Huang Huaiyi , Sadler Peter J.
Published: April 2024

The novel hetero‐dinuclear complex trans,trans,trans‐[PtIV(py)2(N3)2(OH)(μ‐OOCCH2CH2CONHCH2‐bpyMe)IrIII(ppy)2]Cl (Pt‐Ir), exhibits charge transfer between the acceptor photochemotherapeutic Pt(IV) (Pt‐OH) and donor photodynamic Ir(III) (Ir‐NH2) fragments. It is stable in the dark, but undergoes photodecomposition more rapidly than the Pt(IV) parent complex (Pt‐OH) to generate Pt(II) species, an azidyl radical and 1O2. The Ir(III)* excited state, formed after irradiation, can oxidise NADH to NAD⋅ radicals and NAD+. Pt‐Ir is highly photocytotoxic towards cancer cells with a high photocytotoxicity index upon irradiation with blue light (465 nm, 4.8 mW/cm2), even with short light‐exposure times (10–60 min). In contrast, the mononuclear Pt‐OH and Ir‐NH2 subunits and their simple mixture are much less potent. Cellular Pt accumulation was higher for Pt‐Ir compared to Pt‐OH. Irradiation of Pt‐Ir in cancer cells damages nuclei and releases chromosomes. Synchrotron‐XRF revealed ca. 4× higher levels of intracellular platinum compared to iridium in Pt‐Ir treated cells under dark conditions. Luminescent Pt‐Ir distributes over the whole cell and generates ROS and 1O2 within 1 h of irradiation. Iridium localises strongly in small compartments, suggestive of complex cleavage and excretion via recycling vesicles (e.g. lysosomes). The combination of PDT and PACT motifs in one molecule, provides Pt‐Ir with a novel strategy for multimodal phototherapy.
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

A 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

Hierarchical 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

Artificial 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

A 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

A 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

The 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

Repurposing 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

Positron 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

The 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

Vitamin 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

Although 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

Co‐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

In 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

Nowadays, 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

In 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

A 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.
Identification of percolation threshold of spray‐dried cellulose nanocrystals in homopolymer polypropylene composites
Authors: Wang Xueqi , Wang Pixiang , Liu Shaoyang , Zhan Ke , Via Brian , Gallagher Tom , Smidt Mathew , Gardner Douglas J. , Elder Thomas , Peng Yucheng
Published: April 2024

Understanding the percolation threshold is essential for determining the performance of particle‐reinforced polymer composites. Spray‐dried cellulose nanocrystals (SDCNC) of micrometer size reinforced homopolymer polypropylene (HPP) composites at 20, 30, 40, and 50 wt.% were prepared to investigate the percolation threshold of SDCNC particles in HPP. The effect of a compatibilizer (maleic anhydride polypropylene (MAPP)) at 3, 5, and 7 wt.%, on the SDCNC percolation networks and composites performance were also studied. The results indicated that SDCNC particle percolation networks in HPP were established between 30 and40 wt.%. For composites without MAPP, the impact strength significantly increased by up to 23% below the percolation threshold and declined beyond it. The peak crystallization temperature of HPP was steadily increased until 30 wt.% SDCNC particles were added due to the SDCNC saturated nucleation function at the threshold. Introducing MAPP significantly improved tensile strength (58%), tensile strain (61%), flexural strength (45%), and impact strength (91%) compared with the corresponding composites without MAPP, attributed to the enhanced interfacial adhesion between the SDCNC particles and HPP. Water absorption results indicated that adding MAPP changed the SDCNC particle distribution networks within the matrix above the percolation threshold but did not change it below the threshold.
Design and synthesis of phenoxy methyl‐oxadiazole compounds against Alzheimer's disease
Authors: Evren Asaf E. , Nuha Demokrat , Özkan Begüm N. S. , Kahraman Çiğdem , Gönülalan Ekrem M. , Yurttaş Leyla
Published: April 2024

This study examines the synthesis and evaluation of 11 newly developed compounds as potential anti‐Alzheimer's agents that occur via cholinesterase and β‐secretase inhibition. The compounds were tested for their inhibitory activity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) using the modified Ellman method. The results showed that several compounds exhibited significant inhibition of AChE, particularly compounds 6d, 7a, and 7e, which demonstrated high inhibitory activity at lower concentrations, with IC50 values of 0.120, 0.039, and 0.063 µM, respectively. However, the compounds showed limited effectiveness against BChE, with only a few compounds exhibiting moderate inhibition. Compound 7e showed an inhibitory effect against BACE‐1 close to that of the standard drug. Structural analysis revealed that the compounds with substituted benzothiazole and thiazole moieties exhibited the most promising inhibitory activity. This study provides valuable insights into the potential of these synthesized derivatives as a treatment against Alzheimer's disease. Moreover, the structure, stability, and properties of the active compounds were further investigated using density functional theory calculations. As a final note, the utilization of molecular docking and molecular dynamics simulation studies allowed us to elucidate the action mechanism of the active compounds and gain insights into the structure–activity relationship against AChE and β‐secretase proteins. These computational techniques provide valuable information on the binding modes, interactions with target enzymes, dynamic behavior, and conformational changes of the compounds, enabling a comprehensive understanding of their biological activity.
Anatomical variation is the norm: A novel curriculum framework
Authors: Kimmorley Annabelle L. , Reynolds Mikaela S. , Gregory Laura S.
Published: April 2024

Anatomical variation is an inherent part of every health curriculum, due in large to the negative clinical consequences that can ensue if anatomical variation is not thoroughly understood. However, current literature fails to describe any structured whole‐of‐course pedagogy for the teaching of anatomical variation in higher education. This study therefore aimed to (i) propose a whole‐of‐course curriculum framework to guide academic development and implementation of anatomical variation resources and assessment; and (ii) assess the depth of anatomical variation knowledge in a multiyear undergraduate health‐science cohort (n = 152) at the Queensland University of Technology. Current anatomical variation pedagogy, and subsequently the need for the curriculum framework, were explored using a scoping review protocol. As part of this study, anatomical variation was novelly defined as macroscopic differences in morphology (shape and size), topography (location), developmental timing, or frequency (number) of an anatomical structure between individuals that form during embryological or subadult development and result in no substantive, observable interruption to physiological function. The framework incorporated three themes of anatomical variation learning outcomes: description of anatomical variation, theories of the professional implications of variation, and investigation of variant formation. These themes were strongly aligned with the concepts recommended for teaching identified through the scoping review. Significant deficits in anatomical variation student knowledge were identified, with the third‐year cohort recording a mean total score of only 54.6%. A strong recommendation to implement the anatomical variation curriculum framework in all medical and health‐science curricula is made to intentionally develop student understanding of anatomical variation and improve future clinical practice.
Parameterization to fault detection filtering for Itô stochastic T‐S fuzzy systems
Authors: Han Yingying , Zhou Shaosheng
Published: April 2024

This article focuses on the fault detection filtering problem for Itô stochastic Takagi–Sugeno (T‐S) fuzzy systems. In terms of line integral Lyapunov function, a sufficient condition of exponential stability in mean square and extended dissipativity for the systems under consideration is established which has less conservatism than the one based on quadratic Lyapunov function. The obtained sufficient condition is nonlinear, which makes the synthesis of fault detection filter being difficult and challenging. By choosing general matrix variables and constructing the appropriate orthogonal complement matrices, the nonlinear sufficient condition can be converted into linear one ingeniously via utilizing Finsler's lemma twice. Thus, the fault detection filter can be developed by virtue of parameterization. It should be pointed out that our filter determined by the parameterization approach includes the one obtained by the equivalent transformation method as a special case. Finally, we demonstrate the feasibility and superiority of our proposed approach through three numerical examples.
Design of finite‐time convergent functional observer for descriptor systems: Application to fault estimation
Authors: Ríos‐Ruiz Carlos , Osorio Gordillo Gloria Lilia , Darouach Mohamed , Souley Ali Harouna , Astorga‐Zaragoza Carlos Manuel
Published: April 2024

In this paper, a finite‐time functional observer design for linear time‐invariant descriptor systems is presented. A generalized observer based on additional degrees of freedom is developed. This observer can be considered of a general structure since the existing proportional observer (PO) and proportional‐integral observer (PIO) constitute its particular cases. The main contribution is to generate a finite‐time convergent functional observer for descriptor systems by combining two generalized functional observers. The obtained results are applied to the simultaneous state, sensor, and actuator faults estimation. A numerical example is given to illustrate the approach. The obtained results show that the observer is robust in presence of uncertainties, compared to its particular cases.