bluuebunny/crossref_metadata_2025_split huggingface dataset:
Exploiting Chirality in Confined Nanospaces
Authors: Begato Federico , Licini Giulia , Zonta Cristiano 
Published: September 2023

AbstractSpatial organization using confinement has been of great interest since the early ages of supramolecular chemistry. Application such as sensing, catalysis and delivery are continuously emerging. This minireview highlights the evolution of chiral supramolecular cages (CSC) applications in the fields of catalysis, sensing and chiroptical properties. More in detail, beside the description of the strategies adopted for the preparation of chiral supramolecular cages, either of purely organic supramolecular architectures or prepared using metal‐ligand coordination bonds, recent findings on their applications, with particular attention to stereodynamic systems, are presented to highlight the recent scientific interests and the future opportunities.
Microwave‐assisted fractionation and functionalization of technical lignin toward thermoset resins
Authors: Truncali Alessio , Ribca Iuliana , Yao Jenevieve , Hakkarainen Minna , Johansson Mats 
Published: September 2023

AbstractLignin is the most abundant aromatic biopolymer, with a potential to serve as a building block of rigid and thermally stable bio‐based materials. However, it is still underutilized because of the heterogeneous and not fully understood chemical structure. Here, technical softwood Kraft lignin is refined in to narrow‐dispersity and relatively low molar mass fractions by microwave‐assisted processing, followed by microwave‐assisted allylation and further application in lignin‐based thermosets. This microwave processing is carried out under non‐catalyzed conditions using a low boiling point solvent and elevated pressure. The properties of the retrieved fractions are investigated by 31P‐NMR, heteronuclear single quantum coherence spectroscopy‐NMR, SEC, differential scanning calorimetry, and thermogravimetric analysis. The extraction yield of the selected lignin fraction is around 25%, with the number‐average molar mass (Mn), weight‐average molar mass (Mw), and dispersity (Đ) significantly reduced. The chemically modified lignin is characterized by 31P NMR and FTIR, which provides evidence of the introduction of the allyl moieties. The analyses demonstrate that 90 ± 3% of the hydroxyl groups in fractionated lignin are successfully allylated. Subsequently, the allylated lignin is cross‐linked through thermally induced thiol‐ene chemistry to produce lignin‐based thermosets. The final thermosets exhibit a storage modulus of 4050 ± 60 MPa and a Tg of 105 ± 5°C.
Drug design education in China
Authors: Fu Wei , Li Wei , Chen Boyu , Zhang Junjie , Xie Qiong , Zhou Lu , Zhang Xuemei 
Published: September 2023

AbstractWith the emergence of innovative technologies, including combinatorial chemistry, high‐throughput screening, computer‐aided drug design (CADD), artificial intelligence (AI) and big data, the importance of drug design in the field of drug discovery and development is increasing. Additionally, education in drug design plays an important role in the training of pharmaceutical talent. Starting with undergraduates, cultivating pharmaceutical design thinking, developing innovation and creativity, and establishing an interdisciplinary knowledge system will not only provide students with a solid knowledge basis but also promote the development of the pharmaceutical industry in China. This article presents the current status of pharmaceutical education and the distribution of drug design courses in China and summarizes the employment prospects of graduates, thus providing valuable references and evidence for global pharmaceutical design education.
Evaluating the neuroprotective effects of progesterone receptors on experimental traumatic brain injury: The PI3K/Akt pathway
Authors: Amirkhosravi Ladan , khaksari Mohammad , Amiresmaili Sedigheh , Sanjari Mojgan , Khorasani Parisa , Hashemian Morteza 
Published: September 2023

AbstractBackgroundStudies have confirmed the salutary effects of progesterone (P4) on traumatic brain injury (TBI). This study investigated the beneficial effects of P4 via its receptors on TBI, and also whether progesterone receptors (PRs) can modulate TBI through PI3K/Akt pathway.Material and methodsMarmarou method was utilized to induce diffuse TBI in ovariectomized rats. P4 (1.7 mg/kg) or the vehicle (oil) was administered 30 min after TBI induction. Moreover, RU486 (PR antagonist) and its vehicle (DMSO) were injected before TBI induction and P4 injection. Brain Evans blue content, brain water content (WC), various oxidative stress parameters, IL‐1β levels, tumor necrosis factor‐α (TNF‐α), histopathological alterations, and also phosphorylated Akt (p‐Akt) and PI3K expressions in the brain were assessed 24 h after TBI. The veterinary comma scale (VCS) was measured before and after TBI at different times.ResultsThe findings revealed that P4 caused an increase in VCS and a decrease in brain WC, oxidative stress, TNF‐α and IL‐1β levels. RU486 inhibited the beneficial effects of P4 on these indices. Moreover, RU486 prevented the reduction of brain edema, inflammation, and apoptosis caused by P4. Moreover, P4 following TBI increased the expression of PI3K/p‐Akt protein in the brain. RU486 eliminated the effects of P4 on PI3K/p‐Akt expression.ConclusionAccording to these findings, PRs are acting as critical mediators for the neuroprotective properties of P4 on oxidative stress, pro‐inflammatory cytokine levels, and neurological outcomes. PRs also play an important role in regulating the PI3K/p‐Akt expression and nongenomic function of P4.
Isolation of (Aryl)‐(Imino) Phosphide and (Aryl)‐(Phosphaalkene) Amide Complexes of Alkali Metals from Carbene‐Phosphinidenes under Reductive‐Thermal Rearrangements
Authors: Nag Ekta , Francis Maria , Putta Divya , Roy Sudipta 
Published: September 2023

AbstractTwo‐electron reduction of cyclic alkyl(amino) carbene (cAAC)‐supported chloro‐phosphinidene cAAC=P−Cl (1) followed by unprecedented thermal rearrangements afforded the alkali metal complexes of (aryl)‐(cyclic alkyl(imino)) phosphides 3 a–3 c, 4 a–4 b through migration of the 2,6‐diisopropylphenyl (dipp) group from N to the P centre, and the (aryl)‐(cyclic alkyl(phosphaalkene)) amide 5 through cleavage of the CMe2−N bond followed by energetically favoured 5‐exo‐tet ring‐closure in the presence of the alkali metals Cs (3 a–3 c), K (4 a, 4 b), and Li (5). Compound 3 a was found to be photoluminescent (PL), emitting bright orange light under a laboratory UV lamp of wavelength 365 nm with PL quantum yield (ϕPL) of 2.6 % (λem=600 nm), and an average lifetime (τ) of 4.8 μs. Reaction of 3 a with CuCl and AgOTf afforded (aryl)‐(cyclic alkyl(imino)) phosphide‐stabilized tetra‐nuclear CuI (6), and octa‐nuclear AgI (7) clusters, respectively. Moreover, complexes 3 a–3 c provided a direct route for the stabilization of cyclic alkyl(aminoboryl) phosphaalkenes 8 a‐8 c when treated with 1‐bromo‐N,N,N′,N′‐tetraisopropylboranediamine.
Localized Crystallization of Calcium Phosphates by Light‐Induced Processes
Authors: Besirske Patricia , Menichetti Arianna , Montalti Marco , García‐Ruiz Juan Manuel , Winterhalder Martin , Boneberg Johannes , Cölfen Helmut 
Published: September 2023

AbstractMedical treatment options for bones and teeth can be significantly enhanced by taking control over the crystallization of biomaterials like hydroxyapatite in the healing process. Light‐induced techniques are particularly interesting for this approach as they offer tremendous accuracy in spatial resolution. However, in the field of calcium phosphates, light‐induced crystallization has not been investigated so far. Here, proof of principle is established to successfully induce carbonate‐hydroxyapatite precipitation by light irradiation. Phosphoric acid is released by a photolabile molecule exclusively after irradiation, combining with calcium ions to form a calcium phosphate in the crystallization medium. 4‐Nitrophenylphosphate (4NPP) is established as the photolabile molecule and the system is optimized and fully characterized. A calcium phosphate is crystallized exclusively by irradiation in aqueous solution and identified as carbonate apatite. Control over the localization and stabilization of the carbonate apatite is achieved by a pulsed laser, triggering precipitation in calcium and 4NPP‐containing gel matrices. The results of this communication open up a wide range of new opportunities, both in the field of chemistry for more sophisticated reaction control in localized crystallization processes and in the field of medicine for enhanced treatment of calcium phosphate containing biomaterials.
Dynamic chaos of imaging measurements for characterizing gas–liquid nonlinear flow behaviour in a metallurgical reactor stirred by top‐blown air
Authors: Yang Kai , Zhang Xiaoxue , Yang Guiyan , Li Meng , Wang Hua , Xiao Qingtai 
Published: September 2023

AbstractA modern chaos detection strategy for imaging measurements is proposed in this work to quantify the thermal mixing state quality in a metallurgical reactor stirred by top‐blown air. Specifically, the improved C‐C algorithm is proposed to reconstruct the phase space of the nonlinear time series of the bubble characteristics under thermal conditions. Moreover, a chaos decision tree algorithm is introduced to extract the chaotic mixing characteristics of the thermal two‐phase mixing system for the first time. Experimental and calculated results show that all the possible mixing states of the mixing system are visualized by reconstructing the phase space with the help of the visualization technique of the thermal gas–liquid two‐phase flow. It is found that the attractor of the nonlinear time series of bubbles exhibited more serious variations while the chosen working condition was optimal. Furthermore, the obtained parameter represents the chaotic characteristics of the thermal gas–liquid two‐phase mixing system which has chaotic characteristics under various experimental conditions. Hence, the new strategy would be helpful and effective in beneficial exploration for understanding the nonlinear intensification mechanism of metallurgical thermal processes.
Ionothermal Synthesis and Photoactivity of Ti17 and Ti19‐Oxo Clusters Functionalized by Sulfate and 1,10‐Phenanthroline Ligands
Authors: Chintakrinda Kalpana , Narayanam Nagaraju , Chen Guang‐Hui , Zhang Jian , Zhang Lei 
Published: September 2023

Comprehensive SummaryIn this study, we successfully synthesized two titanium‐oxo clusters, namely Ti19(μ3‐O)19(μ2‐O)10(1,10‐phn)2(OiPr)18] (PTC‐178) and (EMIm)3[Ti17(μ4‐O)4(μ3‐O)16(μ2‐O)4(SO4)3(μ2‐OiPr)4(OiPr)13] (PTC‐179). These clusters were synthesized using an ionothermal reaction and possess similar nuclearity (Ti19 vs. Ti17) moieties. Additionally, we observed that these complexes exhibit varying activities for photocatalytic degradation of Methylene Blue (MB) dye and distinct photocurrent responses for photoelectrochemical studies due to their different surface‐decorated ligands. This study provides valuable insights into the design of Ti‐oxo molecular clusters with similar nuclearity but different surface environments, allowing for the establishment of critical structure‐property relationships. Furthermore, our research contributes to the exploration of sustainable synthetic methods for high nuclearity TOCs using ionic liquids.
Copper‐Catalyzed Highly Stereoselective Hydrodifluoroallylation of Cyclopropenes and Alkenyl Boronates with 3,3‐Difluoroallyl Sulfonium Salts†
Authors: Gao Xing , Ren Xiaoxiao , Deng Wei , Zhang Xingang 
Published: September 2023

Comprehensive SummaryDespite the paramount applications of organofluorine compounds in life and materials sciences, efficient strategies for stereoselectively constructing the C(sp3)‐CF2R bond at the stereogenic center remain limited. Here, we report a copper‐catalyzed hydrodifluoroallylation of cyclopropenes and alkenyl boronates with 3,3‐difluoroallyl sulfonium salts (DFASs). The use of DFASs overcomes the previous challenge of suppressing the reduction of fluoroalkylating reagents with M‐H species. The reaction provides an array of gem‐difluoroallyl cyclopropanes and borylalkanes with high efficiency and stereoselectivity under mild reaction conditions. Using chiral phosphine ligand could provide gem‐difluoroallyl borylalkanes with high enantioselectivities, paving a new way for the catalytic asymmetric fluoroalkylation with ubiquitous alkenes. The advantages of this protocol are synthetic convenience, high functional group tolerance, and the synthetic versatility of the resulting gem‐difluoroallyl cyclopropanes and borylalkanes. The synthetic utility of this approach has also been demonstrated by the diversified transformations of the gem‐difluoroallylated products and the rapid synthesis of bioactive molecule analogs.
In‐situ Generation of Hydroxyl Layers in CoO@FeSe2 Catalyst for High Selectivity Seawater Electrolysis
Authors: Feng Suyang , Rao Peng , Wu Xiao , Li Ke , Qi Anyuan , Yu Yanhui , Li Jing , Deng Peilin , Yuan Yuliang , Wang Shaolei , Tian Xinlong , Kang Zhenye 
Published: September 2023

Comprehensive SummarySeawater electrolysis holds great promise for hydrogen production in the future, while the development of anodic catalysts has been severely hampered by the side‐reaction, chloride evolution reaction. In this work, nano‐flower‐cluster structured CoO@FeSe2/CF catalysts are synthesized via a scalable electrodeposition technique, and the performance is systematically studied. The oxygen evolution reaction (OER) overpotential of CoO@FeSe2/CF is 267 mV at 100 mA·cm−2, which is significantly lower than that of the IrO2 catalyst (435 mV). Additionally, the catalyst shows high selectivity for OER (97.9%) and almost no loss of activity after a durability test for 1100 h. The impressive performance is attributed to the dense rod‐like structure with abundant active centers after electrochemical activation and the in‐situ generated CoOOH and FeOOH that improve the catalytic activity of the catalyst. The synergistic effect induced by the non‐uniform structure endows the catalyst with excellent stability.
Construction of a Metallacyclopentadiene Ring through the Attack of Carbanions to M≡C Bond Followed by C—H Activation†
Authors: Tang Chun , Zhang Shengjie , Lu Zhengyu , Li Qian , Luo Ming , Chen Dafa , Xia Haiping 
Published: September 2023

Comprehensive SummaryMetallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions, therefore, new methods to achieve them are anticipated. In this study, a formal [3+2] method, through the reactions of an osmapentalyne with benzyl carbanions, was developed. The reactions underwent a nucleophilic attack of carbanions to the Os≡C bond, followed by C—H activation to form the five‐membered osmacyclopentadiene ring. Most of the reactions were carried out at room temperature, the substituents on the aromatic rings of benzyl carbanions are diverse, and the resulting products contain an Os—H bond, representing a novel type of 10C‐carbolong complexes. This work provides a new convenient route to construct metallacyclopentadienes, which is expected to further promote the development of such a type of substances.
Long‐term safety of ultrathin bioabsorbable‐polymer sirolimus‐eluting stents versus thin durable‐polymer drug‐eluting stents in acute coronary syndrome: A systematic review and meta‐analysis
Authors: Li Fadong , Wang Shen , Wang Yue , Wei Can , Wang Yue , Liu Xinyan , Sun Shuaifeng , Zhao Wenxin , Guo Pengrong , Wu Xiaofan 
Published: September 2023

AbstractBackgroundBecause of the advancement of bioabsorbable polymers and thinner struts, bioabsorbable‐polymer sirolimus‐eluting stents (BP‐SES) with ultrathin struts may be related to superior performance when compared to durable‐polymer drug‐eluting stents (DP‐DES) with thin struts. Nonetheless, the long‐term safety of ultrathin BP‐SES in acute coronary syndrome (ACS) remains unknown.MethodsWe sought to assess the long‐term safety of ultrathin BP‐SES in ACS patients, conducting a thorough meta‐analysis of all relevant trials drawing a comparison between ultrathin BP‐SES and contemporary thin DP‐DES. Target lesion failure (TLF), which includes cardiac death (CD), target‐vessel myocardial infarction (TV‐MI), and clinically driven target lesion revascularization (CD‐TLR) was considered the primary endpoint. Multiple databases comprising Embase, MEDLINE, Cochrane Library, and Pubmed were all thoroughly searched.ResultsThere were seven randomized controlled trials included in our study with 7522 randomized patients with ACS (BP‐SES = 3888, DP‐DES = 3634). TLF occurred in 371 (9.5% in BP‐SES) and 393 (10.8% in DP‐DES) patients, respectively, across a 40.7‐month weighted mean follow‐up, with no statistically significant group differences (risk ratio [RR]: 0.87; 95% confidence interval [CI]: 0.73–1.04; p = .12). Furthermore, no significant differences in cardiac death (RR: 0.96; 95% CI: 0.68–1.35; p = .81), TV‐MI (RR: 0.63; 95% CI: 0.36–1.10; p = .10) and CD‐TLR (RR: 0.77; 95% CI: 0.46–1.29; p = .32) were detected between two groups.ConclusionDuring a follow‐up of 40.7 months, ultrathin BP‐SES and thin DP‐DES had a comparable risk of TLF and its individual components (CD, TV‐MI, and CD‐TLR), indicating that ultrathin BP‐SES held at least the same safety and efficiency as thin DP‐DES presented in patients with ACS.
Simple Hydrothermal Synthesis of Molybdenum Disulfide and Its Application for a Large‐Area Photodetector
Authors: Hou Kaiqiang , Liu Shengqian , Liao Gengcheng , Qiao Hui , Li Jun , Qi Xiang 
Published: September 2023

AbstractHere, molybdenum disulfide with graphene‐like structure is prepared by a feasible and simple hydrothermal method. It is also characterized by X‐ray diffraction and a scanning electron microscope to verify the yield and quality of the prepared molybdenum disulfide (MoS2). In addition, a type of photodetector is prepared from the prepared MoS2 as a photosensitive material, and its light response characteristics are explored. The experimental results show that the prepared MoS2 has good photoresponse performance, and it can achieve a photocurrent of 2.40 µA under 660 nm light of 9.85 mW mm−2. At the same time, it shows stable and repeatable light response characteristics at different bending angles. This work is considered as a way to construct a new type of photodetector with a simple manufacturing process and low cost.
Growth and Various Characterizations of Lithium Sulfate Monohydrate Single Crystals after Eu3+ and Tb3+ Ion Doping
Authors: Najar Fayaz A. , Naik Mudassar M. , Mir Feroz A. , Vakil Gowher B. , Want Basharat 
Published: September 2023

AbstractA slow evaporation solution growth technique is used to grow rare earth (Eu3+ and Tb3+) doped lithium sulfate monohydrate (LSMH) single crystals. X‐ray diffraction analysis of these crystals confirms the monoclinic crystal structure with P21 space group. Energy dispersive X‐ray spectroscopy is used to check the incorporation of dopants into the crystal lattice of these LSMH crystals. Dielectric, UV–vis photoluminescence spectroscopy studies are carried out to study the electrical and optical behavior of these crystals. The optical bandgap decreases by doping and the current material follows the direct allowed transition. The dielectric constant and ac conductivity slightly increase with the incorporation of Eu3+ and Tb3+ ions in the crystal matrix. The effect of doping on the functional groups of LSMH crystals is confirmed by Fourier transform infrared spectroscopy. The micro‐Raman spectroscopic technique is carried out on these samples, confirming the stress experienced by the crystal with dopants, and further leading to the degradation of the crystal structure. The photoluminescence emission with a large decay time of the as‐grown crystals is dominated by the 5D0 → 7Fj transitions of Eu3+ and 5D4 → 7Fj transitions of Tb3+ ions, and further provides a possibility of using them as potential optical materials.
Constructing Z‐Scheme Bi2O3/In2O3 Heterojunction for Efficient Photocatalytic Degradation of Rhodamine B
Authors: Chen Hongjun , Wang Zi , Xue Zeyang , Yu Chunhu , Pei Lizhai , Fan Chuangang 
Published: September 2023

AbstractA Bi2O3/In2O3 heterojunction is successfully fabricated via a facile hydrothermal method using sodium bismuthate and indium nitrate as the source materials. The crystal structure, composition, micromorphology, and optical property of the Bi2O3/In2O3 heterojunction are analyzed by X‐ray diffraction, X‐ray photoelectron spectroscopy, Fourier transform infrared spectrum, scanning electron microscopy, transmission electron microscopy, and solid ultraviolet‐visible (UV‐vis) diffuse reflectance spectra. The Bi2O3/In2O3 heterojunction exhibits a remarkable photocatalytic degradation capacity for Rhodamine B, which is better than that of pure Bi2O3 and In2O3. The photogenerated charges separation and transfer process of the Bi2O3/In2O3 heterojunction follows a direct Z‐scheme mechanism under UV–vis light irradiation. The trapping experiment indicates that oxidative radicals including •OH, h+, and •O2− play crucial roles in the photodegradation process. The outstanding photodegradation capacity is ascribed to spatially separated charge carriers, fast‐charge transportation characteristic, and special bandgap structure of the Bi2O3/In2O3 heterojunction. The introduction of H+ and OH− ions into the reaction system promotes the formation of •OH and •O2− radicals, significantly enhancing the photodegradation rate of RhB. This study presents a new insight into the construction of the Z‐scheme Bi2O3/In2O3 heterojunction photocatalyst with potential application in wastewater treatment.
Lattice‐Strained Metallic Aerogels as Efficient and Anti‐Poisoning Electrocatalysts for Oxygen Reduction Reaction
Authors: Fu Hui , Huang Honggang , Chen Yao , Jiang Kezhu , Lai Feili , Chen Cun , Zhang Zhe , Li Hanjun , Zhang Nan , Liu Tianxi 
Published: September 2023

AbstractLattice strain engineering optimizes the interaction between the catalytic surface and adsorbed molecules. This is done by adjusting the electron and geometric structure of the metal site to achieve high electrochemical performance, but, to date, it has been rarely reported on anti‐poisoned oxygen reduction reaction (ORR). Herein, lattice‐strained Pd@PdBiCo quasi core‐shell metallic aerogels (MAs) were designed by “one‐pot and two‐step” method for anti‐poisoned ORR. Pd@PdBiCo MAs/C maintain their original activity (1.034 A mgPd−1) in electrolytes with CH3OH and CO at 0.85 V vs. reversible hydrogen electrode (RHE), outperforming the commercial Pd/C (0.156 A mgPd−1), Pd MAs/C (0.351 A mgPd−1), and PdBiCo MAs/C (0.227 A mgPd−1). Moreover, Pd@PdBiCo MAs/C also show high stability and anti‐poisoning with negligible activity decay after 8000 cycles in 0.1 m KOH+0.3 m CH3OH. These results of X‐ray photoelectron spectroscopy, CO stripping, and diffuses reflectance FTIR spectroscopy reveal that the tensile strain and strong interaction between different elements of Pd@PdBiCo MAs/C effectively optimize the electronic structure to promote O2 adsorption and activation, while suppressing CH3OH oxidation and CO adsorption, leading to high ORR activity and anti‐poisoning property. This work inspires the rational design of MAs in fuel cells and beyond.