bluuebunny/crossref_metadata_2025_split huggingface dataset:
Constructing Activatable Photosensitizers Using Covalently Modified Mesoporous Silica
Authors: Liu Yan , Wang Xiang , Wang Ben , Lu Zhenni , Wu Changru , He Zhanghao , Jiang Libo , Wei Peng , Yi Tao 
Published: January 2025

AbstractThe combination of photosensitizers (PSs) and nanomaterials is a widely used strategy to enhance PS efficacy and broaden their applicability. However, the current nanocarrier‐based delivery strategies focus on conventional PSs, neglecting the critical issue of PS phototoxicity. In this study, DHUOCl‐25, an activatable PS (aPS) activated by hypochlorous acid, is synthesized by combining a silicon source structure and an activation unit. DHUOCl‐25 functions as a silica source for synthesizing activatable mesoporous silica nanostrctures (MSNs) using a standardized protocol, enabling the synthesis of aPS‐covalently modified MSNs for a variety of biologic therapeutic applications. On one hand, the resulting nano‐aPS maintains aPS functionality for antibacterial application by achieving synergistic antibacterial action via MB PDT and retained cetyltrimethylammonium bromide (CTAB) (antibacterial agent) (DHU–MSNs‐2). On the other hand, the nano‐aPS exhibits MSN properties for drug loading, facilitating the synergistic integration of photodynamic therapy with chemotherapy (DHU–MSNs‐6) of tumors and demonstrating efficacy against the spinal metastases of lung cancer. These results validate this strategy for developing novel aPSs and expanding the application of aPSs and MSNs.
Functionally Graded Oxide Scale on (Hf,Zr,Ti)B2 Coating with Exceptional Ablation Resistance Induced by Unique Ti Dissolving
Authors: Lv Junshuai , Li Wei , Fu Yanqin , Zhang Menglin , Guo Lingxiang , Lu Fanyu , Li Jiachen , Li Tao , Zhang Yulei , Li Hejun 
Published: January 2025

AbstractMulticomponent Ti‐containing ultra‐high temperature ceramics (UHTCs) have emerged as more promising ablation‐resistant materials than typical UHTCs for applications above 2000 °C. However, the underlying mechanism of Ti improving the ablation performance is still obscure. Here, (Hf,Zr,Ti)B2 coatings are fabricated by supersonic atmospheric plasma spraying, and the effects of Ti content on the ablation performance under an oxyacetylene flame are investigated. The (Hf0.45Zr0.45Ti0.10)B2 coating shows superior ablation resistance and cycling reliability at ≈2200°C. A functionally graded oxide scale comprising an outer dense layer and an underlying fine granular layer formed. The former is a better oxygen barrier owing to fewer cracks and the latter has high strain tolerance due to finer grain size. The uniform dissolving of ≈4 mol% Ti in the inner layer results in grain refinement via sluggish diffusion and thus stress release. For the outer layer, Ti segregation at the nanoscale leads to a metastable cubic (Hf,Zr,Ti)O2 and local severe lattice distortion, inhibiting the propagation of cracks. Ti ions’ unique dissolving in the oxide scale enables a strong oxygen diffusion barrier with high strain tolerance, which is responsible for superior performance. This study provides new insights into the ablation behavior of Ti‐containing multicomponent UHTCs.
Lightweight MXene Composite Films with Hollow Egg‐Box Structures: Enhanced Electromagnetic Shielding Performance Beyond Pure MXene
Authors: Wang Yijie , Zhao Chenxiang , Tian Yunze , Sun Yue , Zhang Mengfei , Wang Kangjing , Xia Bihua , Wang Yang , Li Ting , Zhang Xuhui , Huang Jing , Wang Shibo , Dong Weifu , Qiao Jinliang 
Published: January 2025

AbstractMXene is widely used in the electromagnetic interference (EMI) shielding field. However, the high electromagnetic reflectivity of pure MXene causes potential secondary EMI pollution. This study presents a hollow egg‐box structure used in MXene composite film, by which the reflectivity (R) could decrease from 0.98 to 0.54 and absorbance (A) increased from 0.02 to 0.45, effectively decreasing the high electromagnetic reflectivity of pure MXene. Additionally, compared to pure MXene films, the MXene composite films exhibit improved electromagnetic interference shielding effectiveness (EMI SE) and SSE/t. The prepared films achieve a peak EMI SE of 69.19 dB at 12.4 GHz, which is 1.3 times higher than pure MXene, and a peak SSE/t of 27 888 dB cm2 g⁻¹ at 12.4 GHz, 1.4 times that of pure MXene. The hollow egg‐box structure not only enhances the electromagnetic shielding performance beyond pure MXene but also demonstrates outstanding performance compared to most reported MXene films, balancing lightweight material properties with effective shielding. Furthermore, the prepared MXene composite films with the hollow egg‐box structure show improved water resistance. Therefore, MXene composite films with hollow egg‐box structures are promising candidates for advanced EMI devices in future lightweight materials.
In Vivo Nanodiamond Quantum Sensing of Free Radicals in Caenorhabditis elegans Models
Authors: Fan Siyu , Zhang Yue , Ainslie Anna P. , Seinstra Renée , Zhang Tao , Nollen Ellen , Schirhagl Romana 
Published: January 2025

AbstractFree radicals are believed to play a secondary role in the cell death cascade associated with various diseases. In Huntington's disease (HD), the aggregation of polyglutamine (PolyQ) not only contributes to the disease but also elevates free radical levels. However, measuring free radicals is difficult due to their short lifespan and limited diffusion range. Here, a quantum sensing technique (T1 relaxometry) is used that involves fluorescent nanodiamonds (FND). Nitrogen vacancy (NV) centers within these nanodiamonds change their optical properties in response to magnetic noise, which allows detecting the unpaired electron from free radicals. This method is used to monitor the production of free radicals inside Caenorhabditis elegans models of Huntington's disease in vivo and in real‐time. To investigate if radical generation occurs near polyglutamine expansions, a strain expressing Q40 yellow fluorescent protein (Q40::YFP, polyglutamine expansion overexpressed in the muscle) is used. By applying T1 relaxometry on FNDs in the body wall muscle, it is found that the production of free radicals significantly increase when PolyQ is expressed there (compared to the FNDs in intestine). The technique demonstrates the submicrometer localization of free radical information in living animals and direct measurement of their level, which may reveal the relation between oxidative stress and Huntington's disease.
Development of a Nb‐Based Semiconductor‐Superconductor Hybrid 2DEG Platform
Authors: Telkamp Sjoerd , Antonelli Tommaso , Todt Clemens , Hinderling Manuel , Coraiola Marco , Haxell Daniel , Kate Sofieke C. ten , Sabonis Deividas , Zeng Peng , Schott Rüdiger , Cheah Erik , Reichl Christian , Nichele Fabrizio , Krizek Filip , Wegscheider Werner 
Published: January 2025

AbstractSemiconductor‐superconductor hybrid materials are used as a platform to realize Andreev bound states, which hold great promise for quantum applications. These states require transparent interfaces between the semiconductor and superconductor, which are typically realized by in‐situ deposition of an Al superconducting layer. Here a hybrid material is presented, based on an InAs 2D electron gas (2DEG) combined with in‐situ deposited Nb and NbTi superconductors, which offer a larger operating range in temperature and magnetic field due to their larger superconducting gap. The inherent difficulty associated with the formation of an amorphous interface between III‐V semiconductors and Nb‐based superconductors is addressed by introducing a 7 nm Al interlayer. The Al interlayer provides an epitaxial connection between an in‐situ magnetron sputtered Nb or NbTi thin film and a shallow InAs 2DEG. This metal‐to‐metal epitaxy is achieved by optimization of the material stack and results in an induced superconducting gap of approximately 1 meV, determined from transport measurements of superconductor‐semiconductor Josephson junctions. This induced gap is approximately five times larger than the values reported for Al‐based hybrid materials and indicates the formation of highly‐transparent interfaces that are required in high‐quality hybrid material platforms.
What Control Measures Should I Use? Applying the Total Worker Health Hierarchy of Controls to Manage Workplace Fatigue
Authors: Wong Imelda S. , Dawson Drew , Pandalai Sudha , Sprajcer Madeline 
Published: January 2025

ABSTRACTIncreased fatigue risk has been associated with safety‐critical events such as work‐related injuries. While control measures are needed to reduce these risks, the wide range and complexities of fatigue risk management strategies can make it difficult for organizations to prioritize efforts given limited resources and time. Given these challenges, the aims of this commentary are two‐fold. The first is to conceptualize fatigue risk management strategies within the Total Worker Health (TWH) Hierarchy of Controls, a conceptual framework used to prioritize strategies to advance worker safety, health, and wellbeing. As an extension to the traditional Hierarchy of Controls, the TWH version presents strategies in order of effectiveness, ranging from “eliminate,” “substitute,” “redesign,” “educate,” and “encourage” categories. The second aim of this paper is to use the TWH Hierarchy of Controls to identify control measures which reflect the level of fatigue risk for adverse safety and health outcomes.
Interfacial Water Orientation in Neutral Oxygen Catalysis for Reversible Ampere‐Scale Zinc‐Air Batteries
Authors: Hao Yixin , Wang Luqi , Huang Hongjiao , Zhou Hao , Xing Gengyu , Ji Dongxiao , Zhang Tianran , Huang Aoming , Wang Ai‐Yin , Chen Xiang‐Rong , Chen Tsung‐Yi , Chen Han‐Yi , Ramakrishna Seeram , Peng Shengjie 
Published: January 2025

AbstractThe neutral oxygen catalysis is an electrochemical reaction of the utmost importance in energy generation, storage application, and chemical synthesis. However, the restricted availability of protons poses a challenge to achieving kinetically favorable oxygen catalytic reactions. Here, we alter the interfacial water orientation by adjusting the Brønsted acidity at the catalyst surface, to break the proton transfer limitation of neutral oxygen electrocatalysis. An unexpected role of water molecules in improving the activity of neutral oxygen catalysis is revealed, namely, increasing the H‐down configuration water in electric double layers rather than merely affecting the energy barriers for reaction limiting steps. The proposed porous nanofibers with atomically dispersed MnN3 exhibit record‐breaking activity (EORR@1/2/EOER@10 mA = 0.85/1.65 V vs. RHE) and reversibility (2500 h), outperforming all previously reported neutral catalysts and rivaling conventional alkaline systems. In particular, practical ampere‐scale zinc‐air batteries (ZABs) stack are constructed with a capacity of 5.93 Ah and can stably operate under 1.0 A and 1.0 Ah conditions, demonstrating broad application prospects. This work provides a novel and feasible perspective for designing neutral oxygen electrocatalysts and reveals the future commercial potential in mobile power supply and large‐scale energy storage.
Ultrafast Synthesis of Nanoscale Metal Borides for Efficient Hydrogen Evolution
Authors: Liu Tingting , Chen Chen , Pu Zonghua , Huang Qiufeng , Jiang Jiadong , Han Min , Chen Wei , Yu Guangtao , Sun Yuzhi , Huang Shengyun , Chen Qingjun , Al‐Enizi Abdullah M. , Nafady Ayman , Mu Xueqin , Mu Shichun 
Published: January 2025

AbstractNanoscale metal borides, with exceptional physicochemical properties, have been attracted widespread attention. However, traditional synthesis methods of metal borides often lead to surface coking and large particle sizes. Herein, we have employed a flash Joule heating (FJH) technique to enable the ultrafast synthesis of metal boride nanomaterials. The synthesized materials encompass a wide range of diverse categories, including alkaline‐earth metal borides (CaB6), transition metal borides (TiB2, VB2, CrB2, MoB, MoB2, MnB2, MnB4, FeB, CoB, NiB), noble‐metal borides (RuB2, RuB1.1), and rare‐earth metal borides (LaB6, CeB6). As an example, the RuB2 demonstrates highly desirable electrocatalytic performance for all‐pH hydrogen evolution reaction (HER). Especially, under the acidic condition, it exhibits an overpotential as low as 15 mV at a current density of 10 mA cm−2, with a nearly 100 % faradic efficiency. Additionally, in situ Raman spectra confirm that both Ru and B sites serve as active sites for the HER. Moreover, the stability of RuB2 can be further enhanced by optimizing the microenvironments of the anolyte composition (H+, K+). More importantly, the experimental and density functional theory (DFT) calculations reveal that the co‐existence of H+ and K+ localized around the RuB2 plays a crucial role in further enhancing the stability.
Semirational Protein Engineering of a Decarboxylative Aldolase for the Regiodivergent and Stereodivergent Synthesis of Cyclic Imino Acids
Authors: Lan Yuqiu , Zhang Chenghua , Tang Chunping , Ye Yang , Zhang Rui , Sheng Xiang , Liao Cangsong 
Published: January 2025

AbstractAldolases are powerful C−C bond‐forming enzymes for asymmetric organic synthesis because of their supreme stereoselectivity, compatibility with diverse electrophiles and nucleophiles, and promising scalability. Stereodivergent engineering of aldolases to tune the selectivity for the synthesis of stereoisomers of chiral molecules is highly desirable but has rarely been reported. Herein we report the semirational engineering of the decarboxylative aldolase UstD with a focused rational iterative site‐specific mutagenesis (FRISM) strategy to perform a C−C bond‐forming reaction with dione electrophiles. The variant obtained from a small mutant library showed divergent regioselectivity and diastereoselectivity compared to the wild‐type enzyme, resulting in the production of 30 cyclic imino acids with stereocenters at the α and γ positions. Molecular dynamics simulation and kinetic data revealed the basis of selectivity.
Influence of Graphene, Hydroxyapatite, and Hydroxyapatite‐Niobium Pentoxide Nanoparticles on Polycaprolactone Electrospun Fibers Mats Properties
Authors: de Moraes Elisângela Guzi , Andrade Karina Luzia , Ribeiro Luiz Fernando Belchior , da Costa Laqua Letícia Alves , da Silva Daiara Floriano , Arcaro Sabrina , Hiratsuka Larissa Shinju , Tada Dayane , Faita Fabrício Luiz , de Oliveira Antonio Pedro Novaes , Machado Ricardo Antonio Francisco 
Published: January 2025

ABSTRACTPolycaprolactone (PCL) electrospun fiber mats containing varying concentrations of graphene flakes (GF), hydroxyapatite (HAp), and hydroxyapatite with niobium pentoxide (HAp5Nb) were successfully prepared by electrospinning. These composites exhibit great potential in biomedical applications, particularly as scaffolds for bone tissue engineering. The addition of GF enhances the rheological properties of the PCL solution due to the intrinsic properties resulting from their interactions. Additionally, incorporating HAp and HAp5Nb nanoparticles increases the viscosity of PCL‐based solutions, leading to the formation of thinner fiber diameters. The GF, HAp, and HAp5Nb nanoparticles were characterized using transmission electron microscopy (TEM) and x‐ray diffractometry (XRD), while the degree of disorder and heterogeneity of GF was assessed using Raman spectroscopy. The physical and chemical properties of the electrospun fiber mats were also characterized by scanning electron microscopy (SEM), XRD, fourier‐transform infrared spectroscopy (FTIR), and contact angle measurements. The cytotoxicity of PCL‐based electrospun fiber mats containing GF, HAp, and HAp5Nb nanoparticles was evaluated using mouse fibroblasts. Results showed that cell viability with 100% extract from the fiber mats was higher than with pure PCL or Dulbecco's modified Eagle's medium DMEM control, indicating that the samples were non‐toxic and promoted cell growth. This highlights their potential as scaffolds for bone tissue engineering.
Dually Modified Starch‐Based Coating for Improving Barrier and Mechanical Performances of Paper Toward Food Packaging
Authors: Zhang Yazeng , Zhao Wenguang , Lin Benping , Zhu Hongwei , Deng Fengwei , Chen Qijie 
Published: January 2025

ABSTRACTPaper is a promising packaging material, while raw paper always presents poor barrier and mechanical performances. Developing high‐performance coating is an effective strategy to expand its applications. In this paper, a biobased high‐performance coating was developed via dual modifications on starch. Specifically, starch was first modified using polyethylenimine (PEI), and then grafted using the hydrophobic methyltrimethoxysilane (MTMS). The finally obtained dually modified starch (PM‐St) enabled paper to display favorable barrier properties, including excellent water resistance (static contact angle of ~128°) and oil‐proof performance (oil‐proof grade > 7). Furthermore, the coated paper also exhibited obviously enhanced mechanical performances, including improved tensile index of 46.88% and improved burst index of 81.69% for coated paper. In conclusion, this biobased coating has the potential for application in paper coating toward food packaging and thus reduces the use of plastic materials.
Study on the Prediction Model of Swelling Response of EPDM in Liquid Mixture by Using the Modified Flory–Huggins Interaction Parameter (χHSP)
Authors: Li Zhuozhuo , Liu Guangyong 
Published: January 2025

ABSTRACTThe swelling responses of ethylene propylene diene monomers (EPDM) in cyclohexane/xylene (CYH/X) and cyclohexane/cyclohexanone (CYH/C) binary systems were studied by using equilibrium swelling method, and the co‐solvent effect was further analyzed. The results show that the swelling responses of EPDM in CYH/X and CYH/C binary systems are significantly different. EPDM exhibits more obvious co‐solvent effect in CYH/C binary system which may be generated by the self‐association of cyclohexanone. In addition, the modified Flory–Huggins interaction parameter (χHSP) calculated by three‐dimensional solubility parameters (HSP) was used to establish the prediction model from the correlation with the swelling ratio (qm) of EPDM. The prediction model can be represented by an exponential equation with high degree of fitting, and the calculated qm values from this model are comparable with the experimental values. The prediction model has been employed to evaluate the swelling responses (q‐fitting) of EPDM in IRM 903 test oil/ethanol mixtures theoretically. It reveals that lower χHSP values result in higher swelling responses of EPDM, following the same rule of q–χHSP. Potentially, the prediction model based on χHSP provides a new way to determine the swelling responses of EPDM based rubber parts in any possible fluids.
Photoinduced Azidoamination of Styrenes Using Sodium Azide and (Diphenylmethylene)amino Benziodoxolone
Authors: Kiyokawa Kensuke , Nakano Koki , Okumatsu Daichi , Minakata Satoshi 
Published: January 2025

AbstractHerein, we report the radical azidoamination of styrenes via the use of a combination of sodium azide and (diphenylmethylene)amino benziodoxolone under visible‐light irradiation. This approach to unsymmetrical diamination provides a simple and practical method for constructing vicinal diamine scaffolds with two distinct and easily modifiable amino functionalities.
Rational Design of Porous Organic Framework (POF) for Efficient Conversion of CO2 to Cyclic Carbonates and 2‐Oxazolidinones at Atmospheric Pressure Conditions
Authors: Parihar Vaibhav , Kumar Bharat , Singh Gulshan , Nagaraja C. M. 
Published: January 2025

AbstractCarbon dioxide (CO2) capture and its subsequent catalytic fixation into usable compounds represent a potential approach for addressing the energy problem and the implications of global warming. Hence, it is necessary to develop effective catalytic systems required for the transformation of CO2 into valuable chemicals/fuels. Herein, we rationally designed a hydroxyl‐functionalized porous organic framework (OH‐POF) consisting of both acidic (OH) as well as basic N sites for the transformation of CO2 using epoxides for the production of cyclic carbonates (CCs), a useful commodity chemical under environmental‐friendly, metal/solvent/co‐catalyst‐free conditions. Moreover, OH‐POF was post‐synthetically modified to anchor non‐noble metal, Zn(II) to generate Zn‐POF and further explored it for the efficient functionalization of CO2 with propargylic amines to generate valuable bioactive 2‐oxazolidinones. Significantly, both OH‐POF and Zn‐POF demonstrated exceptional reusability with catalytic efficacy retained across numerous cycles of use. Notably, this study showcases a green and sustainable process for utilization of CO2 under environmentally favorable ambient conditions into two highly valuable compounds, viz cyclic carbonates and 2‐oxazolidinones.
Utilization of orange peel waste for activated carbon production and its application in particleboard for formaldehyde emission reduction
Authors: Ergun Mehmet Emin , Koyuncu Filiz , Istek Abdullah , Özlüsoylu İsmail , Bülbül Şaban , Kılıç‐Pekgözlü Ayben 
Published: January 2025

AbstractActivated carbon (AC) is valued for its large surface area, porosity, and chemical adsorption properties, making it suitable for a wide range of industrial applications. Its most common sources are coconut shells, wood, and coal – all of which are costly or harmful to the environment. It is thus important to finding sustainable feedstock, such as agricultural waste. Inexpensive materials like waste orange peel have been used in the production of AC. This study explores the synthesis of AC from orange peel waste through phosphoric acid (H3PO4) activation for potential applications in reducing volatile organic compounds such as formaldehyde emissions in particleboard production. Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), nitrogen adsorption/desorption isotherms, and Fourier transform infrared (FTIR) spectroscopy were used to examine AC. The Brunauer–Emmett–Teller (BET) surface area of AC was 497 m2·g⁻¹. The addition of AC to urea‐formaldehyde (UF) adhesive enhanced cross‐linking and condensation reactions, improving the mechanical and physical properties of particleboards without compromising integrity. The effects of AC on formaldehyde emissions were assessed at 0 and 3 months. Compared to the control group, particleboards with AC showed a 28.98% reduction in free formaldehyde emissions at 0 months and a 45.25% reduction at 3 months. Activated carbon derived from orange peels can thus improve particleboard properties while reducing formaldehyde emissions in an environmentally sustainable way.