bluuebunny/crossref_metadata_2025 huggingface dataset:
Dexamethasone Delivery via Amphiphilic, Low‐swelling Hydrogels Treats Postoperative Inflammation in Cervical Spine Applications
Authors: Linderman Stephen W. , Barber Graham F. , DeVeaux S'Dravious A. , Botchwey Edward A. , Refai Daniel , Klein Adam M. , García Andrés J.
Published: January 2025

Anterior cervical spine surgeries are often complicated by difficulty swallowing due to local postoperative swelling, pain, scarring, and tissue dysfunction. These postoperative events lead to systemic steroid and narcotic use. Local, sustained drug delivery may address these problems, but current materials are unsafe for tight surgical spaces due to high biomaterial swelling, especially upon degradation. To address these shortcomings, a low‐swelling, amphiphilic hydrogel system termed DexaPatch is developed containing dexamethasone‐poly(lactic‐co‐glycolic acid) (PLGA) microparticles for sustained release upon local implantation in the surgical site. The bulk amphiphilic hydrogel, comprised of 4‐arm poly(ethylene glycol) (PEG)‐maleimide macromer cross‐linked with triblock dithiolated PEG‐poly(propylene glycol)‐PEG (poloxamer a.k.a. Pluronic), achieves consistent and tunable mechanical and low‐swelling properties. Dexamethasone is released in a burst, followed by a sustained release over 40 days, similar to the release from microparticles alone. The DexaPatch system is lyophilized for shelf stability and surgical handling properties, sterilized, and briefly rehydrated in the operating room prior to surgical implantation in a rabbit model of anterior spinal surgery. DexaPatch results in significantly reduced prevertebral edema radiographically and decreased fibrosis in prevertebral muscles compared to sham surgery. This implantable biomaterial platform reduces local postoperative inflammation with potential surgical applications throughout the body.
Creating Single Atomic Coordination for Hypoxia‐Resistant Pyroptosis Nano‐Inducer to Boost Anti‐Tumor Immunotherapy
Authors: Li Wenshuai , Li Hongyuan , Jiang Guangwei , Yang Lan , Nie Huifang , Lin Chenteng , Gao Wenjia , Huang Rongqin
Published: January 2025

General synthesis and mechanical understanding of type I nano‐photosensitizers are of great importance for hypoxia‐resistant pyroptosis inducers. Herein, a simple solvothermal treatment is developed to convert non‐photosensitive small molecules (hemin) into uniform carbon nanodots (HNCDs) with strong type I photodynamic activity and red fluorescence emission. These HNCDs inherit the single atomic Fe–N4 center of hemin while creating sp2‐hybridized carbon surroundings, which synergistically modulated the energy level and electron transfer for converting the type II photodynamic process to type I. After encapsulating HNCDs with bovine serum albumin (BSA) to facilitate in vivo applications, the resulting BSA nanoparticles (HB) can image tumors and significantly induce the pyroptosis of tumor cells even under an extremely hypoxic environment (2% O2). This evokes a strong antitumor immune response, effectively restraining tumor growth and lung metastasis in triple‐negative breast cancer mice, with good biocompatibility. This work introduces an applicable pyroptosis nano‐inducer to combat hypoxic tumors and highlights the regulation of Fe–N4 centers to develop hypoxia‐resistant type I nano‐photosensitizers for cancer treatment.
Hybrid Soft Segments Boost the Development of Ultratough Thermoplastic Elastomers with Tunable Hardness
Authors: Zhang Xingxue , Wang Luping , Zhang Kaiqiang , Zhou Kunyang , Hou Kaiyang , Zhao Zhixun , Li Guiliang , Yao Qing , Sun Nan , Wang Xu
Published: January 2025

The hardness of thermoplastic elastomers (TPEs) significantly influences their suitability for various applications, but traditionally, enhancing hardness reduces toughness. Herein a method is introduced that leverages hybrid soft segments to fine‐tune the hardness of TPEs without compromising their exceptional toughness. Through the selective copolymerization of polytetramethylene ether glycols (PTMEGs) at various molecular weights, supramolecular poly(urethane‐urea) TPEs are molecularly engineered to cover a wide spectrum of hardness while retaining good toughness. It is achieved through the formation of graded functional zones—densely packed for enhanced hardness and strength, and loosely packed for greater extensibility and toughness—driven by variations in PTMEG chain length and mismatched supramolecular interactions. Through the establishment and systematic investigation of a TPE library, the intricate interplay between design, structure, and performance of these materials is elucidated, refining the optimization techniques. The TPEs demonstrate exceptional mechanical properties, including a variant with a Shore hardness of 86A and a toughness of 819 MJ m−3, alongside a softer variant with a 59A hardness and a 786 MJ m−3 toughness. The innovation extends to a scalable solvent‐based TPE production line, promising widespread industrial application. This advancement reimagines the potential of high‐performance TPEs and composites, offering versatile materials for demanding applications.
Enhanced Photocatalytic Efficiency Through Oxygen Vacancy‐Driven Molecular Epitaxial Growth of Metal–Organic Frameworks on BiVO4
Authors: Xin Yulei , Tian Jian , Xiong Xianqiang , Wu Chenglin , Carabineiro Sónia A.C. , Yang Xiaogang , Chen Zhangxing , Xia Yang , Jin Yanxian
Published: January 2025

Efficient charge separation at the semiconductor/cocatalyst interface is crucial for high‐performance photoelectrodes, as it directly influences the availability of surface charges for solar water oxidation. However, establishing strong molecular‐level connections between these interfaces to achieve superior interfacial quality presents significant challenges. This study introduces an innovative electrochemical etching method that generates a high concentration of oxygen vacancy sites on BiVO4 surfaces (Ov‐BiVO4), enabling interactions with the oxygen‐rich ligands of MIL‐101. This reduces the formation energy and promotes conformal growth on BiVO4. The Ov‐BiVO4/MIL‐101 composite exhibits an ideal semiconductor/cocatalyst interface, achieving an impressive photocurrent density of 5.91 mA cm−2 at 1.23 VRHE, along with excellent stability. This high‐performing photoanode enables an unbiased tandem device with an Ov‐BiVO4/MIL‐101‐Si solar cell system, achieving a solar‐to‐hydrogen efficiency of 4.33%. The molecular‐level integration mitigates surface states and enhances the internal electric field, facilitating the migration of photogenerated holes into the MIL‐101 overlayer. This process activates highly efficient Fe catalytic sites, which effectively adsorb water molecules, lowering the energy barrier for water oxidation and improving interfacial kinetics. Further studies confirm the broad applicability of oxygen vacancy‐induced molecular epitaxial growth in various MOFs, offering valuable insights into defect engineering for optimizing interfaces and enhancing photocatalytic activity.
Boosting Thermoelectric Performance of Semicrystalline Conducting Polymers by Simply Adding Nucleating Agent
Authors: Chen Chen , Ma Haibao , Lu Kaiqing , Zhang Xiaoxuan , Yue Baiqiao , Song Ce , Huang Pochong , Cheng Haifeng , Lin Yue
Published: January 2025

Controlling the microstructure of semiconducting polymers is critical for optimizing thermoelectric performance, yet remains challenging, requiring complex processing techniques like alignment. In this study, a straightforward strategy is introduced to enhance the thermoelectric properties of semi‐crystalline polymer films by incorporating minimal amounts of nucleating agents, a method widely used in traditional polymer industries. By blending less than 1 wt% of N,N′‐(1,4‐phenyl)diisonicotinamide (PDA) into poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT‐C14), controlled modulation of crystallization behavior is achieved, resulting in reduced structural disorder and enhanced charge carrier mobility. Systematic investigations reveal that an optimal PDA loading of 0.9 wt% increases the crystallization degree by 45% compared to pristine PBTTT‐C14 films. Under these optimized conditions, the PDA‐modified PBTTT‐C14 films exhibit a maximum electrical conductivity of 1,894 S cm−1 and a maximum power factor of 176 µW m−1 K−2, showing improvements of 96% and 433%, respectively, over doped pristine PBTTT‐C14 films. These gains are attributed to the synergistic effects of polymer chain extension and reduced grain boundary resistance, which collectively enhance charge transport efficiency. Additionally, ion exchange doping is found to maintain a high charge carrier concentration while preserving the crystallinity introduced by PDA, paving the way for advanced thermoelectric materials and next‐generation polymer‐based electronics.
IR Spectroscopic Studies on Water Confined in an Isoreticular MOF Series–Influence of the Metal and Linker Functionality
Authors: Haug Tabea C. V. , Hoffmann Frank , Tasova Merve N. , Heffels Roy , Fröba Michael
Published: January 2025

Mono‐ and bimetallic MOF‐74 samples with different ratios of Mg2+ and Ni2+ (9:1, 7:3, and 1:1), as well as Ni‐MOF‐74 analogs with different pore sizes and functionalities, were loaded with water through the exposure to a controlled relative humidity. To get information on the influence of the metal, pore size (1.2–3.6 nm), and functionality on the confined water, all samples were analyzed through infrared spectroscopy and the results were correlated to corresponding water sorption isotherms. Deconvolution of the O‐H stretching vibrational band made it possible to draw conclusions about differently ordered water species inside the pores. In all samples, it was visible that at lower pore loadings, the MOFs mostly comprised of less ordered water species, while higher pore loadings led to an increased formation of a more ordered, tetrahedral phase. Increasing amounts of Ni2+ within the series of bimetallic Mg/Ni‐MOF‐74 samples gave the hydrated systems a more hydrophilic behavior and favored the growth of more ordered species. Moreover, larger pores favored the less ordered water species, while hydrophilic functionalities led to the growth of water with a higher tetrahedrality and hydrophobic groups led to pores dominated by less ordered water species but can also have an ordering effect.
Hybrid Contact for High‐Performance MoS2 Transistors via Hard‐Mask Scanning Probe Lithography
Authors: Chen Zhe , Zhu Wen , Xu Lanxin , An Minghao , Zheng Xiaorui
Published: January 2025

The scaling down of transistors in silicon‐based complementary metal‐oxide‐semiconductor (CMOS) technology has reached critical limits, necessitating the exploration of novel materials and architectures. 2D semiconductors have emerged as promising candidates for continuing Moore's law beyond traditional silicon due to their atomic‐scale thickness and superior electrostatic control, which mitigate short channel effects. However, realizing the full potential of 2D materials in industrial applications requires overcoming challenges in fabricating scalable and CMOS‐compatible devices, particularly concerning metal‐semiconductor contacts. Here, a hybrid‐contact configuration is presented by developing a hard‐mask scanning probe lithography (SPL) for high‐performance molybdenum disulfide (MoS2) field‐effect transistors (FETs). After systematically comparing with the fabricated top‐contact and edge‐contact configurations, the hybrid‐contact substantially improves carrier injection efficiency, enabling an enhanced on‐current of 50.5 µA·µm⁻¹, an on/off ratio exceeding 5 × 1010, a reduced contact resistance of 2.14 kΩ·µm, and a Schottky barrier height of 26 meV, which is evidently illustrated by using the equivalent resistor network. The hard‐mask SPL also facilitates the high‐resolution nanoscale patterning on MoS2 flakes with a feature size of ≈18 nm. This hybrid‐contact configurations along with hard‐mask SPL demonstrate potentials in fabricating high‐performance 2D FETs, paving the way for their practical application in future electronic devices.
Pathophysiology of IBD as a Key Strategy for Polymeric Nanoparticle Development
Authors: Gardey Elena , Brendel Johannes C. , Stallmach Andreas
Published: January 2025

Inflammatory bowel disease (IBD) is a complex chronic inflammatory disorder of the gastrointestinal (GI) tract with an uncertain etiology. Currently, IBD therapy relies on the induction of clinical remission followed by maintenance therapy using anti‐inflammatory drugs and immunosuppressants; however, a definite cure of the disease is still out of scope. Established approaches are characterized by adverse drug‐related side effects that can even be potentially life‐threatening. In contrast, increased interest and remarkable scientific progress in targeted drug delivery systems offer a promising approach to reduce systemic adverse events, delivering the therapeutic substances only to inflamed tissue. All alteration in gastrointestinal barrier integrity, especially a disturbed epithelial barrier, a unique pattern of the receptors on cell surface and/or an oxidative stress milieu in inflamed areas can be used as effective approaches for targeted and controlled drug delivery. Hence, this review focuses on the pathophysiology of the inflamed GI tract as a potential strategy for targeted polymeric nanoparticles for IBD treatment. Interdisciplinary efforts between the polymeric chemistry and gastroenterology/immunology promise to create novel synergies that improve the development of effective nanoparticle systems with significant clinical impact. In this regard, the current challenges in the clinical translation of promising nanomedicine are also discussed.
Lipopeptide 01 from Staphylococcus Epidermidis Resists Pathogenic Bacteria and Promotes Bone Healing in Implant‐Associated Infections
Authors: Wang Shengjie , Liu Wei , Yang Chao , Li Changwei , Zhang Xianlong
Published: January 2025

Implant‐associated infections (IAI) present a significant clinical challenge. Effective prevention of and recovery from IAI is complex, involving antibacterial treatment and the promotion of bone integration. However, the current artificial implants used in clinics often lack effective antibacterial properties and have limited functionality. In this study, Lipopeptide 01 (LP01), a lipopeptide derived from the skin commensal Staphylococcus epidermidis is successfully immobilized, onto the porous surface of sulfonated Poly (ether‐ether‐ketone) (SPEEK) to create a novel artificial implant, LP01‐PS. Both in vivo and in vitro experiments demonstrates that LP01‐PS displays favorable material properties, biocompatibility, outstanding antibacterial characteristics, and the ability to promote bone formation. Mechanistically, LP01‐PS enhances antibacterial activities by triggering TLR2/P65 signaling, upregulating the expression of LL37 and β‐defensins in macrophages. Furthermore, it can boost the osteogenic differentiation capability of bone marrow mesenchymal stem cells (BMSCs) through the β‐catenin signaling pathway, thereby facilitating bone formation. The discovery of LP01‐PS with dual antibacterial and osteogenic effects, coupled with insights into its mode of action, suggests that LP01‐PS can serve as a promising implant material to enhance the success rates of total joint replacement surgeries, mitigate the risks of infection and prosthetic loosening, and foster the repair and regeneration of bone tissue.
Ethynyl‐Linked Donor–Acceptor Covalent Organic Framework for Highly Efficient Photocatalytic H2O2 Production
Authors: Li Bowen , Chen Junjin , Wang Kang , Qi Dongdong , Wang Tianyu , Jiang Jianzhuang
Published: January 2025

Photocatalytic H2O2 synthesis from H2O and O2 is considered to be one of the most promising alternative approaches for manufacturing H2O2. Developing highly active and selective photocatalysts is of significant in achieving efficient H2O2 photosynthesis. Herein, an ethynyl‐linked donor–acceptor covalent organic framework (COF), named EBBT‐COF, is prepared from the condensation reaction between an electron‐deficient unit 4,4′,4″‐(1,3,5‐benzenetriyltri‐2,1‐ethynediyl)tris‐benzenamine and an electron‐rich unit benzo[1,2‐b:3,4‐b′:5,6‐b″]trithiophene‐2,5,8‐tricarboxaldehyde. Powder X‐ray diffraction and N2 adsorption isotherm unveil the crystalline porous hcb network of EBBT‐COF with pores size centered at ca. 2.3 nm. Spectroscopic characterizations demonstrate the excellent visible‐light absorption capacity and enhanced photo‐induced charge separation and transport efficiency of EBBT‐COF owing to its donor–acceptor architecture. Density functional theory calculations and electrochemical tests indicate the high activity and selectivity of EBBT‐COF toward 2e− O2 reduction reaction and 2e− water oxidation reaction with triethynylbenzene and trithiophene moieties to accelerate O2‐to‐H2O2 and H2O‐to‐H2O2 conversion, respectively. These merits enable EBBT‐COF to be a promising photocatalyst toward H2O2 generation from H2O and O2 with a H2O2 yield rate of 5 686 µmol g−1 h−1, an optimal apparent quantum yield of 15.14%, a solar‐to‐chemical conversion efficiency of 1.17% (λ > 400 nm), representing one of the best performance among COF‐based photocatalysts reported thus far.
Homogeneously Blended Donor and Acceptor AgBiS2 Nanocrystal Inks Enable High‐Performance Eco‐Friendly Solar Cells with Enhanced Carrier Diffusion Length
Authors: Kim Hae Jeong , Park Jin Young , Choi Ye‐Jin , Kim Soo‐Kwan , Yong Taeyeong , Lee Wonjong , Seo Gayoung , Lee Eon Ji , Choi Seongmin , You Hyung Ryul , Park Won‐Woo , Yoon Soojin , Kim Wook Hyun , Lim Jongchul , Kim Younghoon , Kwon Oh‐Hoon , Choi Jongmin
Published: January 2025

Colloidal semiconductor nanocrystals (NCs) have garnered significant attention as promising photovoltaic materials due to their tunable optoelectronic properties enabled by surface chemistry. Among them, AgBiS2 NCs stand out as an attractive candidate for solar cell applications due to their environmentally friendly composition, high absorption coefficients, and low‐temperature processability. However, AgBiS2 NC photovoltaics generally exhibit lower power conversion efficiency (PCE) compared to other NC‐based devices, primarily due to numerous surface traps that serve as recombination sites, leading to a short diffusion length for free carriers. To address this challenge, this work develops donor and acceptor blended (D/A) AgBiS2 films. Through ligand modulation, this work formulates acceptor and donor AgBiS2 NC inks with suitable electrical band alignment for charge separation, while ensuring that they are fully miscible in the same solvent. This enabled the fabrication of high‐quality, thickness‐controllable D/A‐blended junction films. This work finds that this approach effectively facilitates carrier separation, leading to an enhanced carrier lifetime and diffusion length. As a result, using this approach, this work achieves AgBiS2 films that are twice as thick in solar cell applications compared to conventional devices, leading to improvements in current density and a solar cell PCE of 8.26%.
Gyro‐Multigrid Triboelectric Nanogenerator via Topological Defects Strategy for Efficiently Harvesting Low‐Grade Wave Energy
Authors: Gao Wei , Gao Xiaobo , Su Juan , Cai Huisheng , Li Hao , Chen Baodong , Wang Zhong Lin
Published: January 2025

Wave energy is a promising sustainable energy yet to be fully exploited due to the low frequency and broad‐banded wave fields, so much so that difficult to capture, resulting in low efficiency and limited power output from current many wave energy harvesters. Here, a topological defect gyro‐multigrid triboelectric nanogenerator (TD‐GM‐TENG) is proposed that harnesses the mechanical energy of ocean waves to generate electricity and promotes the accumulation of triboelectric charge on the basis of realized from low to high rotation speed under the precession and gravitation acceleration effects. It benefited from topological defect strategy, TD‐GM‐TENG offers a charge transfer rate of 3.1 µC s−1 that when can reach to a speed of nearly 1000 rpm at the wave frequency of 1 Hz. Furthermore, the charge density reaches 90 µC m−2 in a cycle of 0.06 s, which is 1.6 times higher than the same kind of spherical‐TENGs in the field of ocean energy harvesting. Finally, TD‐GM‐TENG unit outputs a peak power of 3.7 mW at the simulated water wave environment of 1 Hz and demonstrates its applicability and feasibility of being used as a distributed emergency power supply in the offshoring observation and early warning services.
Cu‐Driven Active Cu2Se@MXene Heterointerface Reconstruction and Co Electron Reservoir Toward Superior Sodium Storage
Authors: Lu Chengxing , Li Boyu , Shi Mengjie , Li Qun , Liu Kun , Lu Cuiyun , Liao Jingwen , Hu Ziyue , Wei Xiaoyan , Li Chunsheng , Sun Yan , Liu Tong , Liu Ronghui , Zhao Qing
Published: January 2025

Heterostructure engineering and active component reconstruction are effective strategies for efficient and rapid charge storage in advanced sodium‐ion batteries (SIBs). Herein, sandwich‐type CoSe2@MXene composites are used as a model to reconstruct new active Cu2Se@MXene heterostructures by in situ electrochemical driving. The MXene core provides interconnected pathways for electron and ion conduction, while also buffering volumetric expansion to stabilize the structure. This reconstructed Cu2Se@MXene heterointerface features abundant sodium storage active sites, enhanced Na+ adsorption, and diffusion kinetics, thus increasing sodium storage capacity. Moreover, the elevated Co valence state during the discharge process allows it to act as an electron reservoir to provide additional electron supply for Cu2Se conversion and accelerate the sodium storage kinetics. When employed as an anode in SIBs, the CoSe2@MXene electrode exhibits high capacity (694 mAh g−1 at 0.1 A g−1), excellent rate performance (425 mAh g−1 at 20 A g−1), and exceptional durability (437 mAh g−1 after 10 000 cycles at 5 A g−1 with a 0.0014% capacity decay per cycle). The electrochemical reconstruction and sodium storage mechanism of Cu2Se@MXene anode is further revealed through ex situ characterization and theoretical calculations. This work provides a new approach for designing advanced conversion‐type anodes for SIBs.
Impact of index insurance on downside income risk: Evidence from northern Kenya
Authors: Shikuku Kelvin Mashisia , Ochenje Ibrahim
Published: January 2025

We assessed the impact of index‐based livestock insurance (IBLI) on household income and its higher‐order moments (i.e., variance and skewness). The study uses four waves of panel survey data from northern Kenya and applies a two stage least squares (2SLS) instrumental variables regression to estimate the causal impacts. We found that uptake of IBLI increased household income and reduced pastoralists' exposure to downside risk. Our results imply that policies and investments promoting the scaling of index insurance will be effective for climate risk management and welfare improvement in Sub‐Saharan Africa by increasing income and reducing exposure to downside risk.
Comparative Evaluation of HFC‐134a Decompositions Over Metal‐Impregnated γ‐Al2O3 Catalysts (M/γ‐Al2O3) (M = Mg, Ni, Co, Zn, Cu)
Authors: Yoo Myeong‐Heon , Yoo Hyeonsuk , Lee Yongjin , Lee Seok‐Goo , Moon Seung‐Hyun , Jung Tae‐Sung , Cho Churl‐Hee , Jeong Heon‐Do , Cho Dong‐Woo
Published: January 2025

Al2O3, widely used in the catalytic decomposition of fluorocarbons, is known to be rapidly deactivated owing to its transformation to AlF3. Accordingly, in this study, metal‐impregnated γ‐Al2O3 catalysts (M/γ‐Al2O3) were synthesized and their long‐term stabilities for HFC‐134a decomposition were investigated under the conditions of 10,000 ppm HFC‐134a in air balance. Although γ‐Al2O3 and Mg/γ‐Al2O3 demonstrated long‐term activities, significantly longer than those of the other catalysts, activity of γ‐Al2O3 rapidly decreased, whereas that of Mg/γ‐Al2O3 gradually decreased. Although Mg/γ‐Al2O3 exhibited the smallest Brunauer‐Emmett‐Teller specific surface area among those of the synthesized catalysts, it demonstrated excellent long‐term stability and the lowest deactivation rate due to the high total amount of weak acid sites. Mg/γ‐Al2O3 exhibited considerably smaller crystal size of AlF3 compared to other catalysts. Additionally, after HFC‐134a decomposition, the morphology of Mg/γ‐Al2O3 was clearly less modified and metal agglomeration was lower than those of other catalysts. Finally, this was caused by the reaction of Mg with HF, forming MgF2, which inhibited the complete conversion of γ‐Al2O3 to AlF3 and produced AlOFX, an intermediate compound. These results suggest that Mg impregnation in γ‐Al2O3‐based catalysts is a suitable method for enhancing the performances of these catalysts in the long‐term decomposition of HFC‐134a.
Performance and legacy effect of crop rotations on eastern Canadian dairy farms
Authors: Khechine Mohamed Taher , Thivierge Marie‐Noëlle , Chantigny Martin H. , Bélanger Gilles , Hassanat Fadi , Charbonneau Édith , Brégard Annie , Vanasse Anne , Royer Isabelle , Jégo Guillaume , Maillard Émilie , Tremblay Gaëtan F. , Angers Denis A. , Halde Caroline
Published: January 2025

Crop rotations on dairy farms in eastern Canada nowadays include fewer perennial crops and more nitrogen‐demanding annual crops. This study compared, over a 7‐year rotation cycle, the agronomic performance and the legacy effect of six crop rotations that varied in crop types (perennial or annual) and nutrient sources (mineral or organic). Crop yield and nutritive value were determined on a yearly basis and cumulated over the rotation cycle. The legacy effect was assessed by growing forage corn (Zea mays L.) in year 6 and soybean [Glycine max (L.) Merr.] in year 7 in all rotations. The legacy effect of perennial forage crops manifested with a 78% lower weed biomass at harvest of forage corn in year 6 and a 14% greater soybean yield in year 7. A greater soil‐derived corn nitrogen uptake in year 6 after repeated slurry applications indicated a modest legacy effect of organic fertilization on soil N supply capacity. The presence of perennial forage crops or the use of organic fertilization did not affect cumulative dry matter or crude protein production over the 7‐year rotation cycle. The addition of alfalfa (Medicago sativa L.) in mixture with perennial grasses improved forage yield (+26%) and nutritive value (greater digestible energy and crude protein concentration) in post‐seeding years. In perennial‐based rotations, adding alfalfa to grasses resulted in greater dry matter (+22%) and crude protein (+46%) productions over the 7‐year cycle despite a fourfold reduction in N fertilizer input, attesting to the high N use efficiency of perennial legume‐based cropping systems.
Coumestans: Synthesis, Isolation, and Bioactivity
Authors: Naik Mayuri M. , Patre Rupesh E. , Tilve Santosh G.
Published: January 2025

Coumestans are tetracyclic heterocycles having a coumarin ring and a benzofuran ring fused together, sharing a common C=C bond. A large number of oxygenated coumarins have been isolated from nature. In this review, we have compiled information to date on the natural occurrences of coumestans, their biological activity, and methods for their synthesis. We have further categorized the synthetic methods according to how the tetracycle is built, whether using the preformed coumarin ring, the furan ring, the flavonoid or by other diverse pathways.
Visible‐Light Induced Three‐Component Dearomatization of Phenols with Oxime Ester and DABSO
Authors: Wei Hu , Liu Hongyuan , Zhang Zhen‐Dong , Li Zhi‐Kai , He Yong‐Ke , Li Shaoyu , Yu Weijie
Published: January 2025

In this work, a visible‐light‐induced three‐component dearomatization of phenols with oxime ester and DABSO has been developed for the efficient assembly of various sulfone‐substituted cyclohexadienones under mild conditions. This dearomatization process is devoid of oxidants and does not necessitate transition metals. On the basis of mechanistic investigations, a radical tandem reaction process is proposed for the transformation.
High‐Energy‐Density Li‐CO2 Battery at Elevated Temperatures: Advances with Fluorine‐Substituted Graphdiyne and Ionic Liquid
Authors: Zhang Junxiang , Ding Ding , Fang Qisheng , Cheng Jianli , Xiao Heyu , Wang Bin
Published: January 2025

Li‐CO2 batteries demonstrate promising prospects in terms of high‐density energy storage and efficient CO2 fixation. However, their practical application is impeded by sluggish reaction kinetics and leakage of volatile and flammable organic electrolytes, especially for high temperature application scenarios, leading to large polarization and limited cycling stability. Herein, we fabricate a highly rechargeable and stable Li‐CO2 battery with high temperature adaptability by employing fluorine‐substituted graphdiyne (FGDY) as cathode catalysts and imidazolium‐based ionic liquid as electrolyte solvents. The employed FGDY, which possesses homogeneous sp‐hybridized carbon, high specific surface area, and uniform pores, significantly enhances the battery reaction kinetics. Consequently, the fabricated Li‐CO2 batteries operate consistently at a large current density of 5.0 A·g‐1 at 80 °C while showcasing high discharge capacity of 29050 mAh·g‐1 along with excellent cycling stability. As proof of concept, Li‐CO2 pouch cells achieve a high energy density of 536 Wh·kg‐1 based on the total mass of the device, and show outstanding cycling stability at 80 °C. This study underscores the effectiveness of graphdiyne‐derived carbon catalysts in achieving high‐performance Li‐CO2 batteries.
The Role of Open‐Shell Organic Radical in Enhancing Anti‐Tumor Photocatalysis Reaction of NIR Light‐Activated Photosensitizer
Authors: Li Heng , Gu Ying , Ding Yafei , Huang Jia , Yang Zhiqiang , Ding Pengbo , Wang Mengying , Han Liang , Yang Bing , Guo Liang , Zhang Yuanzhu , He Feng , Tian Leilei
Published: January 2025

Open‐shell radical materials, which are characterized by unpaired electrons, have led to revolutionary breakthroughs in material science due to their unique optoelectronic properties. However, the involvement of organic radicals in photodynamic therapy (PDT) has rarely been reported or discussed. This work studies two photosensitizer analogs. 4AM‐OS with extended π‐conjugation exhibits open‐shell radical characters and enhanced type‐I photodynamic activity compared with closed‐shell 2AM‐CS. 4AM‐OS displays the thermally accessible triplet‐state character, resulting in more unpaired electrons delocalized along the π‐conjugated backbone at higher temperatures. Accordingly, the temperature‐dependent photodynamic activity of 4AM‐OS confirms its association with the open‐shell electronic structure. As the unpaired electrons in open‐shell 4AM‐OS are more delocalized and generate additional electronic energy states, photo‐induced charge transfer is promoted to facilitate type‐I photodynamic reactions. This observation addresses the challenge associated with near‐infrared (NIR) photosensitizers, such as 4AM‐OS, which often demonstrate low efficacy in PDT due to the limited energy provided by NIR light despite its superior tissue penetration depth. Overall, clarifying the beneficial role of organic radicals in photodynamic reactions will bring revolutionary breakthroughs to developing high‐performance NIR photosensitizers and promoting the efficacy of PDT for deep‐seated lesions.
Reprocessable and Recyclable Materials for 3D Printing via Reversible Thia‐Michael Reactions
Authors: Su Yong‐Liang , Yue Liang , Paul McKinley K. , Kern Joseph , Otte Kaitlyn S. , Ramprasad Rampi , Qi H. Jerry , Gutekunst Will R.
Published: January 2025

The development of chemically recyclable polymers for sustainable 3D printing is crucial to reducing plastic waste and advancing towards a circular polymer economy. Here, we introduce a new class of polythioenones (PCTE) synthesized via Michael addition‐elimination ring‐opening polymerization (MAEROP) of cyclic thioenone (CTE) monomers. The designed monomers are straightforward to synthesize, scalable and highly modular, and the resulting polymers display mechanical performance superior to commodity polyolefins such as polyethylene and polypropylene. The material was successfully employed in 3D printing using fused‐filament fabrication (FFF), showcasing excellent printability and mechanical recyclability. Notably, PCTE−Ph retains its tensile strength and thermal stability after multiple mechanical recycling cycles. Furthermore, PCTE−Ph can be depolymerized back to its original monomer with a 90 % yield, allowing for repolymerization and establishing a successful closed‐loop life cycle, making it a sustainable alternative for additive manufacturing applications.
pH‐Responsive Polyglycerol Nanogels for Periodontitis Treatment through Antibacterial and Pro‐Angiogenesis Action
Authors: Ma Guoxin , Xu Ke , Yu Leixiao , Haag Rainer
Published: January 2025

Periodontitis is a microbe‐driven inflammatory disease leading to bone resorption and tissue destruction. We propose a dual‐functional nanogel complex armed with the antimicrobial drug triclosan (TCS) and the pro‐angiogenesis medication deferoxamine (DFO) for combating microbial pathogens and promoting tissue regeneration. The nanogel system (NG‐TCS‐DFO) that we fabricated from linear polyglycerol exhibits well‐defined spherical morphology and a positively charged surface for bacteria adhesion. The rapid and sustained degradation of NG‐TCS‐DFO in the acidic environment of an infection site induces the on‐demand release of TCS and DFO. The NG‐TCS‐DFO shows potent bacteria elimination of the gingivitis‐causing bacteria Porphyromonas gingivalis in both planktonic (99.9 %) and biofilm (99 %) states. Furthermore, the NG‐TCS‐DFO can promote vascularization and migration of human umbilical vein endothelial cells (HUVECs). Contributing to the synergistic effect of TCS and DFO, the NG‐TCS‐DFO demonstrates significant bone tissue regeneration and accelerated healing of periodontitis in vivo. This polyglycerol‐based nanogel may therefore offer smart combined delivery of multiple therapeutics against bacteria‐driven diseases.
Employing Octahedral Net Charge Descriptors for Designing High‐Performance Aqueous Proton Batteries
Authors: Zhao Jun , Ma Ninggui , Wang Yuhang , Wang Zhaowei , Wang Tairan , Liang Bochun , Zhang Yaqin , Han Jian , Zhi Chunyi , Fan Jun
Published: January 2025

Recently, aqueous proton batteries have shown promise for electrochemical energy storage using MXene electrodes. However, designing high‐performance MXene proton batteries remains challenging due to the inevitable hydrogen evolution reaction (HER), the vast chemical composition space of MXene, and the unclear proton transport mechanism. To tackle these challenges, we established a general descriptor based on structural units of MXenes, termed the octahedral net charge descriptor (Qoct). This descriptor correlates well with HER activity, capacity, and proton transport performance. Based on the descriptor, prediction reveals a dual‐proton storage mechanism per site in N‐functionalized MXene. Meanwhile, the accuracy of the descriptor is verified across a broader MXene chemical space. Additionally, the kinetic process shows the topological transformation energy barrier of the interfacial solution is profoundly influenced by Qoct, thereby impacting the proton transfer performance. This universal descriptor originates from the different electron filling states on the molecular orbitals of the octahedron. Overall, this work provides an efficient strategy for designing MXene proton batteries and can be extended to other battery and catalysis fields.
Tunable Organic‐Inorganic p‐π‐d Electron Conjugation Triggers d‐π Hybridization in Quinonized MnO2 Superlattice toward Ultrastable and High‐Rate Zn−MnO2 Batteries
Authors: Zhang Anqi , Chen Tiande , Zhao Ran , Wang Yahui , Yang Jingjing , Han Xiaomin , Wang Xinran , Wu Chuan , Bai Ying
Published: January 2025

Zn‐MnO2 batteries with two‐electron transfer harvest high energy density, high working voltage, inherent safety, and cost‐effectiveness. Zn2+ as the dominant charge carriers suffer from sluggish kinetics due to the strong Zn2+−MnO2 coulombic interaction, which is also the origin of pestilent MnO2 lattice deformation and performance degradation. Current studies particularly involve H+ insertion‐dominating chemistry, where the long‐term cycle stability remains challenging due to the accumulative Zn2+ insertion and structural collapse. Herein, a simultaneously enhanced and stabilized Zn2+/H+ co‐insertion chemistry is proposed by the quinone‐hybridized MnO2 superlattice, a first‐of‐this‐kind structure with a distinctive organic–inorganic‐extended p‐π‐d conjugation, which enables a tunable interlayer d‐π hybridization. Theoretical and experimental results substantiate that the interlayer d‐π hybridization triggers the enhancement of polarons occupancy near Fermi level, the downward shift of O p‐band center, the elevated Mn t2g occupation and thus improved [MnO6] stability upon unprecedentedly high Zn2+ contribution. The notable d‐π hybridization endows MnO2 superlattice an ultrahigh specific capacity (435.9 mAh g−1 at 0.25 A g−1), state‐of‐the‐art cycle stability (~100 % capacity retention after 30,000 cycles at 10 A g−1) with substantially enhanced rate performance. Our findings enlighten a new paradigm in the adjustment of Zn2+/H+ co‐insertion chemistry towards high‐performance rechargeable aqueous batteries.
COF‐Assisted Construction of Steric Mass‐Charge Channels to Boost Activity for High‐Performance Fuel Cells
Authors: Wen Guobin , Sun Liancheng , Qin Yanzhou , Liu Shengnan , Ma Luyao , Zhang Ningce , Liu Shuxuan , Yin Yan , Ren Bohua , Wang Shuangyin
Published: January 2025

The two‐dimensional lamellar materials disperse platinum sites and minimize noble‐metal usage for fuel cells, while mass transport resistance at the stacked layers spurs device failure with a significant performance decline in membrane electrode assembly (MEA). Herein, we implant porous and rigid sulfonated covalent organic frameworks (COF) into the graphene‐based catalytic layer for the construction of steric mass‐charge channels, which highly facilitates the activity of oxygen reduction reactions in both the rotating disk electrode (RDE) measurements and MEA device tests. Specifically, the normalized mass activity is remarkably boosted by 3.7 times to 1.56 A mgpt−1 after additions of suitable COF modifications in the RDE tests. Especially, an excellent maximum power density of 1.015 W cm−2 is realized on the MEA in H2/Air condition, representing a 22 % improvement through such constructions of steric mass‐charge channels. Meanwhile, the open‐circuit voltage of fuel cells demonstrates only 0.8 % reductions after 10,000 cycles of stability tests. We further extended such methodology of constructing mass‐charge channels to granular PtCo and commercial Pt/C catalysts, which demonstrates a significant impetus for stimulating the catalytic activity in fuel cells.
Theoretical Insights and Anticancer Potential of 2,6‐Bis((E)‐(2‐amino‐4‐nitrophenylimino)methyl)‐4‐methoxyphenol and Its Binuclear Cu(II) Complex
Authors: Praveen S. , Parinamachivayam G. , Jeyaraman P. , Prabakarakrishnan R. , Natarajan A. , Geetha K. , Chinnathambi Arunachalam , Alharbi Sulaiman Ali , Pugazhendhi Arivalagan , Kandasamy Sabariswaran
Published: January 2025

This study explores the synthesis and applications of a new Schiff base, 2,6‐bis((E)‐(2‐amino‐4‐nitrophenylimino)methyl)‐4‐methoxyphenol (HL), and its copper(II) complexes. The Schiff base was prepared by reacting 2‐amino‐4‐nitroaniline with 2,6‐diformyl‐4‐methoxyphenol and characterized using techniques like microanalysis, UV–Vis, IR spectroscopy, 1H‐NMR, and LC–MS, confirming its structure. Theoretical studies provided insights into its molecular geometry and electronic properties. Cyclic voltammetry of the copper complex revealed diffusion‐controlled electrochemical behavior, involving a single‐electron transfer. Both the Schiff base and its Cu(II) complexes exhibited promising anticorrosion and anticancer activities, highlighting their multifunctional potential in industrial and biomedical applications. This study emphasizes the importance of comprehensive characterization in developing innovative materials with practical uses.
Characterization of Cs2AgInCl6: Bridging Optical and Electrical Properties for Advanced Optoelectronic Applications
Authors: Jebnouni Achref , Alatawi Abdullah A. , Bouzidi Mohamed , Alshammari Ahlam F. , Aljaloud Amjad Salamah , Alshammari Mona A. F. , Jebali Maher , Bechir Mohamed Ben
Published: January 2025

Lead‐free double perovskites, such as Cs2AgInCl6, represent a promising class of materials for optoelectronic applications due to their favorable properties and environmental sustainability. This work focuses on the synthesis and comprehensive characterization of Cs2AgInCl6, employing a range of techniques including X‐ray diffraction (XRD) for structural verification, thermogravimetric analysis (TGA) to assess thermal stability, and UV–visible absorption measurements to determine the optical bandgap energy of 3.32 eV. Additionally, we explore photoluminescence (PL) and decay measurements to elucidate the luminescent properties of the compound. Complex impedance measurements are performed under both blue and red light to investigate the electrical behavior, revealing two distinct conduction mechanisms: the overlapping large–polaron tunneling (OLPT) and nonoverlapping small–polaron tunneling (NSPT). We analyze the implications of our findings on the current–voltage (I–V) behavior and trap density, further supported by Raman spectroscopy under both illumination conditions. The combined insights from optical and electrical characterizations highlight the potential of Cs2AgInCl6 in optical applications, paving the way for its use in advanced optoelectronic devices.
Investigating the Fracture Mechanisms Arising From the Inhomogeneous Shrinkage Behavior in the Anisotropic Structure of Natural Bamboo via Experimental and Numerical Methods
Authors: Ramful Raviduth
Published: January 2025

The integration of natural materials in modern designs, architecture and infrastructure is essential to enhance the standard of living, to improve aesthetic attributes and most importantly to address the issues of global crises faced in our modern times such as climate change. Modern solution is calling for alternative materials and the consideration of natural materials may provide a wide range of benefits ranging from being sustainable to having a low carbon offset. On the downside, natural materials made of organic structure, are vulnerable to diverse number of naturally occurring or externally induced factors which can affect their rate of degradation. This study was mainly focused on one aspect of degradation based on abiotic factors which affected the durability of bamboo‐based natural materials. The study probed into the mechanisms prevailing between the interlaminar layers of bamboo anisotropic structure which resulted in random crack propagation during shrinkage of the material thereby greatly affecting their durability. To achieve the aim of this study, experimental investigation was conducted in the first place on thermally modified bamboo specimens to reveal their shrinkage behavior with respect to the anisotropic nature of the material. In second instance, numerical modeling via the Finite Element Method (FEM) was conducted to further ascertain the findings observed in the experimental study. The FEM software of LS‐DYNA was considered for that purpose and the fringe plot of XY displacement was selected to assess the zone in the material most susceptible to crack initiation and propagation. The findings of this study will have a notable significance as it will shed further light on one of the main limitations of a natural material like bamboo. The established methodology and findings could also be considered to further modify the material for improved durability in modern designs and applications.
Departing from standard practices: Strategic application of value engineering in the anatomy laboratory to enhance formaldehyde extraction using high‐impact, low‐cost, and low‐maintenance solutions
Authors: Russ Jürgen , Hammer Niels
Published: January 2025

This study describes the process of developing a high‐impact, low‐cost, and low‐maintenance air ventilation system for anatomy facilities. It employed the strategic application of Value Engineering (VE), assuring that the air ventilation system meets contemporary threshold limit values (TLVs) for formaldehyde in the working zone of dissection tables. A creative–innovative construction methodology was used, combining the Theory of Inventive Problem Solving (TRIZ/TIPS) and VE for an anatomy laboratory air ventilation concept. The TRIZ/TIPS aimed to resolve conflicts that impeded progress toward higher ideality, while VE aimed to develop alternative approaches to fulfill required functions at a minimal cost. The findings were first trialed in a mockup while dissecting human tissues embalmed with two protocols. The experimental results were validated by computational fluid dynamics simulations, and then followed by a pilot and commissioning phase once the physical installation of the dissection laboratory concluded. The findings demonstrate the superiority of the combined TRIZ/TIPS and VE approach in terms of air distribution and efficient formaldehyde extraction within the breathing zone. A formaldehyde exposition below 0.1 ppm, lowered air exchange rates, and system usability proved that the given third‐generation ventilation system complies with contemporary TLVs and potential changes in user requirements. The third‐generation ventilation system offers a cost‐effective, high‐impact, and low‐maintenance solution for state‐of‐the‐art air ventilation systems in the anatomy dissection laboratory. The underlying design approach ensured that formaldehyde levels in the laboratory meet the TLV and indoor air guideline values for formaldehyde exposure, at which current knowledge indicates no increased risk of cancer.
Optimization of Polymers for Organic Solar Cells: Effects of Alkyl, Fluorinated and Thiophenated Chains
Authors: Ahmad Mustamin Kalsum , Sani Sarjadi Mohd , Sarkar Shaheen M. , Kumar Sandeep , Rahman Md Lutfor
Published: January 2025

This paper explores optimization strategies for polymeric materials in organic solar cells (OSCs) with the focus on varying alkyl side chain, addition of fluorine atom, and thiophenated derivatives onto polymer. As such, it outlines the significance of renewable energy sources and the potential of photovoltaic technologies, particularly organic photovoltaics (OPVs). Objectives include factors affecting power conversion efficiency (PCE), open‐circuit voltage (Voc), aggregation tendencies, and optoelectronic properties in OPVs. The scope encompasses the impact of alkyl as well as the comparison between fluorinated and chlorinated polymers and the role of thiophene units to obtain an efficient organic solar cell. The review examines how alkyl chain structures influence thin film morphology, packing, and device performance, comparing linear and branched configurations. It also explores the role of halogenated polymers in modifying electronic properties and stability, focusing on the comparative performance between fluorinated and chlorinated polymers. The importance of thiophene units in polymer design for OPVs is discussed, along with performance comparisons based on different architectures. The paper summarizes key findings regarding the impact of various side chain modifications for OPVs device performance and outlines future research directions to enhance efficiency, stability, and scalability. It suggests exploring novel material design to further optimize OSCs.