bluuebunny/crossref_metadata_2025_split huggingface dataset:
Solvent‐Controlled Separation of Integratively Self‐Sorted Pd2LA2LB2 Coordination Cages
Authors: Ebbert Kristina E. , Sendzik Fabian , Neukirch Laura , Eberlein Lukas , Platzek André , Kibies Patrick , Kast Stefan M. , Clever Guido H. 
Published: October 2024

AbstractThe integrative implementation of multiple different components into metallosupramolecular self‐assemblies requires sophisticated strategies to avoid the formation of statistical mixtures. Previously, the key focus was set on thermodynamically driven reactions of simple homoleptic into complex heteroleptic structures. Using Pd2LA2LB2‐type coordination cages, we herein show that integrative self‐sorting can be reversed by a change of solvent (from DMSO to MeCN) to favor narcissistic re‐segregation into coexisting homoleptic species Pd2LA4 and Pd3LB6. Full separation (“unsorting”) back to a mixture of the homoleptic precursors was finally achieved by selective precipitation of Pd3LB6 with anionic guest G1 from MeCN, keeping pure Pd2LA4 in solution. When a mixture of homoleptic Pd3LB6 and heteroleptic Pd2LA2LB2 is exposed to a combination of two different di‐anions (G1 and G2) in DMSO, selective guest uptake gives rise to two defined coexisting host–guest complexes. A joint experimental and deep theoretical investigation via liquid‐state integral equation theory of the reaction thermodynamics on a molecular level accompanied by solvent distribution analysis hints at solvent expulsion from Pd2LA4 to favor the formation of Pd2LA2LB2 in DMSO as the key entropic factor for determining the solvent‐specific modulation of the cage conversion equilibrium.
Supramolecular Reconstruction of Self‐Assembling Photosensitizers for Enhanced Photocatalytic Hydrogen Evolution
Authors: Bu Seok Hyeong , Cho Wansu , Ham Gayoung , Yang Beomjoo , Jung Jongwon , Cha Hyojung , Park Chiyoung 
Published: October 2024

AbstractNatural photosynthetic systems require spatiotemporal organization to optimize photosensitized reactions and maintain overall efficiency, involving the hierarchical self‐assembly of photosynthetic components and their stabilization through synergistic interactions. However, replicating this level of organization is challenging due to the difficulty in efficiently communicating supramolecular nano‐assemblies with nanoparticles or biological architectures, owing to their dynamic instability. Herein, we demonstrate that the supramolecular reconstruction of self‐assembled amphiphilic rhodamine B nanospheres (RN) through treatment with metal‐phenolic coordination complexes results in the formation of a stable hybrid structure. This reconstructed structure enhances electron transfer efficiency, leading to improved photocatalytic performance. Due to the photoluminescence quenching property of RN and its electronic synergy with tannic acid (T) and zirconium (Z), the supramolecular complexes of hybrid nanospheres (RNTxZy) with Pt nanoparticles or a biological workhorse, Shewanella oneidensis MR‐1, showed marked improvement in photocatalytic hydrogen production. The supramolecular hybrid particles with a metal‐phenolic coordination layer showed 5.6‐ and 4.0‐fold increases, respectively, in the productivities of hydrogen evolution catalyzed by Pt (Pt/RNTxZy) and MR‐1 (M/RNTxZy), respectively. These results highlight the potential for further advancements in the structural and photochemical control of supramolecular nanomaterials for energy harvesting and bio‐hybrid systems.
Bifunctional Metal–Organic Framework Synergistically Enhances Radiotherapy and Activates STING for Potent Cancer Radio‐Immunotherapy
Authors: Wang Chaoyu , Li Jinhong , Jiang Xiaomin , Ma Xin , Zhen Wenyao , Tillman Langston , Weichselbaum Ralph R. , Lin Wenbin 
Published: October 2024

AbstractThe activation of the stimulator of interferon genes (STING) protein by cyclic dinucleotide metabolites plays a critical role in antitumor immunity. However, synthetic STING agonists like 4‐(5,6‐dimethoxybenzo[b]thiophen‐2‐yl)‐4‐oxobutanoic acid (MSA‐2) exhibit suboptimal pharmacokinetics and fail to sustain STING activation in tumors for effective antitumor responses. Here, we report the design of MOF/MSA‐2, a bifunctional MSA‐2 conjugated nanoscale metal–organic framework (MOF) based on Hf6 secondary building units (SBUs) and hexakis(4′‐carboxy[1,1′‐biphenyl]‐4‐yl)benzene bridging ligands, for potent cancer radio‐immunotherapy. By leveraging the high‐Z properties of the Hf6 SBUs, the MOF enhances the therapeutic effect of X‐ray radiation and elicits potent immune stimulation in the tumor microenvironment. MOF/MSA‐2 further enhances radiotherapeutic effects of X‐rays by enabling sustained STING activation and promoting the infiltration and activation of immune cells in the tumors. MOF/MSA‐2 plus low‐dose X‐ray irradiation elicits strong STING activation and potent tumor regression, and when combined with an immune checkpoint inhibitor, effectively suppresses both primary and distant tumors through systemic immune activation.
Building Asymmetric Zn−N3 Bridge between 2D Photocatalyst and Co‐catalyst for Directed Charge Transfer toward Efficient H2O2 Synthesis
Authors: Wang Weikang , Liu Rong , Zhang Jianjun , Kong Tingting , Wang Lele , Yu Xiaohui , Ji Xiaomin , Liu Qinqin , Long Ran , Lu Zhou , Xiong Yujie 
Published: October 2024

AbstractTwo‐dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in‐plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π–π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn−N3 units that can bridge nitrogen (N)‐doped carbon layers with polymeric carbon nitride nanosheets (C3N4−Zn−N(C)) to address this challenge. The symmetry‐breaking Zn−N3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C3N4 photocatalyst and the N‐doped carbon co‐catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn−N3 bonding bridges. As a result, the designed C3N4−Zn−N(C) catalyst exhibits dramatically enhanced H2O2 photosynthesis activity, outperforming most of the reported C3N4‐based catalysts. This work highlights the importance of tailoring interfacial chemical bonding channels in polymeric photocatalysts at the molecular level to achieve effective spatial charge separation.
Long‐Lifespan 522 Wh kg−1 Lithium Metal Pouch Cell Enabled by Compound Additives Engineering
Authors: Tang Tingxuan , Sun Chuang , Li Yong , Tong Minman , Lu Jun , Lai Chao 
Published: October 2024

AbstractMatching high‐voltage cathodes with lithium metal anodes represents the most viable technological approach for developing secondary batteries with ultra‐high energy density exceeding 500 Wh kg−1. Nevertheless, the instability of electrolyte/electrode interface film and commercial electrolytes with cut‐off voltage above 4.3 V is still a major concern. Herein, we present that excellent cycling stability with an ultra‐high cut‐off voltage of up to 5.0 V can be obtained by using three‐component additives containing fluoroethylene carbonate (FEC), hexadecyl trimethylammonium chloride (CTAC), and tri(pentafluorophenyl)borane (TPFPB). Excellent ionic conductivity, robust interfacial films on both electrodes, and long‐lasting uniform Li+ regulation ability can be obtained in the modifying electrolyte. Consequently, using a high plating/stripping capacity of 3 mAh cm−2 under the current density of 1 mA cm−2, lithium symmetric cells demonstrate stable cycling performance exceeding 800 hours. Meanwhile, the 7.3 Ah‐class Li[NixCoyMn1‐x‐y]O2 (x=0.83, NCM83)|Li pouch cells are assembled, which show a high energy density of 522 Wh kg−1 and present excellent stability over 178 cycles with a high initial coulombic efficiency (CE) of 98.0 %.
Crystallization‐Induced Dimerization and Solution‐Phase Bond Dissociation of Stable Dibenzoolympicenyl Radicals
Authors: Zhang Xin , He Huijie , Ge Chang , Xiang Qin , Sato Sota , Lv Menglan , Chen Xing , Sun Zhe 
Published: October 2024

AbstractCrystallization of organic materials can lead to different assembly structure with different reactivity, but this phenomenon is rarely observed for delocalized hydrocarbon radicals. This report introduces a crystallization‐induced radical–radical coupling reaction, which employs a series of stable nonplanar organic π‐radicals as reactants. Six stable radical congeners are synthesized, resulting in radical–radical coupling at the allenyl radical site during crystallization to produce close‐shell dimers. This coupling reaction is absent in the solution phase, which highlights the importance of preorganization in the lattice. Remarkably, the attempts of cocrystallization of different congeners yielded homocoupling products instead of cross‐coupling products. In specific cases, two distinct polymorphs are observed and their reactivity is different according to the distance of the reaction sites. Theoretical calculations indicate that the transition from a metastable preorganized monomer to a dimer is barrierless and spontaneous. The dimer could regenerate free radicals by heating or photoirradiation in the solution phase. This discovery may lead to controllable molecular switches.
Determining the Absolute Configuration of Small Molecules by Diffusion NMR Experiments
Authors: Cabral Tadeu Luiz Gomes , Poggetto Guilherme Dal , Brussolo da Silva João Pedro , Nilsson Mathias , Tormena Claudio F. 
Published: October 2024

AbstractEnantiomers are ubiquitous in many areas of science, such as pharmaceuticals, agriculture, and food. Nuclear magnetic resonance (NMR) alone is not able to differentiate enantiomers as their spectra are identical. However, these can be distinguished using chiral auxiliaries (such as chiral complexing agents) that form diastereomeric complexes, but absolute identification is still troublesome, usually requiring a chemical reaction with a chiral derivatizing agent. Here, we propose a new method that uses a hybrid mixture of solvating agents in a simple comparison of diffusion NMR experiments, which can discriminate enantiomers in both frequency and diffusion domains, dubbed CHIMERA (CHIral Micelle Enantiomer Resolving Agent). The new method was assessed for twenty‐three small chiral molecules using a combination of BINOL and (−)‐DMEB, a chiral surfactant, and initial results indicate that absolute configuration can be obtained from a simple experiment.
Unveiling the NLO Potential of New Zn (II) Complex of 6‐Methylpyridine‐2‐Carboxaldehyde: Experimental/DFT Study on Spectral, Static, and Frequency‐Dependent Linear/Nonlinear Optical Parameters
Authors: Şimşek Merve , Avcı Davut , Sönmez Fatih , Başoğlu Adil , Tamer Ömer , Atalay Yusuf 
Published: October 2024

ABSTRACTOngoing exploration focuses on synthesizing and characterizing coordination compounds to improve the design of nonlinear optical (NLO)‐based materials. In this regard, to examine spectral and static/frequency–dependent linear/NLO parameters, the new Zn (II) complex {[Zn(6‐MePyAld)2(Cl)]; 6‐MePyAld: 6‐methylpyridine‐2‐carboxaldehyde} was synthesized and characterized by using 1H and 13C NMR, mass (LC‐HRMS), powder XRD, and FTIR spectra. The electronic features of synthesized complex were investigated by considering the TD‐CAM‐B3LYP/ and TD‐M06L/6‐311G(d,p)//LanL2DZ levels of time‐dependent density functional theory (TD‐DFT). Moreover, the theoretical linear optical (LO), second‐, and third‐order NLO susceptibility tensors/polarization (χ(1)/P(1), χ(2)/P(2), χ(3)/P(3)) parameters for the Zn (II) complex were computed using the DFT/M06L and DFT/CAM‐B3LYP levels. The external electric field (E), polarization (P), and electric displacement (D) values of the Zn (II) complex were also calculated using the same DFT levels. To investigate microscopic LO (isotropic polarizability <α(0;0)>/<α(−ω;ω)>, and anisotropic polarizability (∆α (0;0)/∆α (−ω;ω)) and second‐/third‐order NLO (<β(0;0,0)>/<β(−ω;ω,0), <β(−2ω;ω,ω)>/<γ(0;0,0,0)>/<γ(−ω;ω,0,0)> and <γ(−2ω;ω,ω,0)>) parameters for the Zn (II) complex, the DFT/M06L and DFT/CAM‐B3LYP levels in the gas phase were used. The ∆α (0;0), ∆α (−ω;ω), <β(0;0,0)>, <β(−ω;ω,0)>, and <β(−2ω;ω,ω)> for Zn (II) complex were computed at 17.288 × 10−24, 21.782 × 10−24, 14.692 × 10−30, 466.80 × 10−30, and 210.79 × 10−30 esu, respectively, by using the DFT/CAM‐B3LYP level. Moreover, the <γ(0;0,0,0)>/<γ(−ω;ω,0,0)> and <γ(−2ω;ω,ω,0)> in the gas phase computed at the DFT/CAM‐B3LYP level for Zn (II) complex were obtained at 129.74 × 10−36, 3997.6 × 10−36, and −886.60 × 10−36 esu, in turn. According to the CAM‐B3LYP level, the <γ(0;0,0,0)> value is 8.65 and 18.53 times higher than the values of para‐nitroaniline (pNA) and urea, respectively. The obtained static/dynamic β and γ values of Zn (II) complex are greater than those of urea and pNA. Zn (II) complex exhibited remarkably microscopic second‐order and particularly third‐order NLO features. It is predicted that our study will shed light on NLO materials that might be used in telecommunication and optoelectronics.
Effect of succinonitrile on the structural, ion conductivity, and dielectric properties of PVDF‐HFP based solid polymer electrolytes
Authors: Rani Iqra , Arwish Sajal , Khan Khizar Hayat , Zamurad Muddassir , Shah Syed Mujtaba , Hussain Hazrat 
Published: October 2024

AbstractA detailed account of the poly(vinylidene difluoride‐co‐hexafluoropropylene) (PVDF‐HFP)/succinonitrile (SN)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) based solid polymer electrolytes (SPEs) of various compositions is reported. SN is incorporated as plasticizer, while LiTFSI is employed as the source of lithium ions. Fourier transfer infrared (FTIR) spectroscopy reveals the formation of polar and electroactive γ crystal phase by PVDF in pristine PVDF‐HFP and the prepared SPE films. FTIR further confirms the interaction between the host polymer and the salt and between the salt and the plasticizer. The interaction between the salt and plasticizer suggests that SN not only offers the plasticization effect but also facilitates salt dissociation. The ion conductivity increases with increasing salt content up to 20 wt% but beyond that concentration a decline in ion conductivity is observed, which could be attributed to the ion pair association or cluster formation due to the excess salt concentration that reduces the availability of free ions and ultimately leads to the reduction in ion conductivity. After including SN in the SPE formulation, electrochemical impedance spectroscopy reveals a substantial increase in room temperature ion conductivity of the SPE from ~1.08 × 10−5 S cm−1 for pristine SPE with 20 wt% salt to ~2.7 × 10−4 S cm−1 for plasticized SPE with 40 wt% SN and 20 wt% salt. This is attributed to the plasticizing effect of SN that enhances ion mobility through the matrix and to the increased charge carrier concentration (SN facilities salt dissociation). The fabricated SPEs exhibit a significant enhancement in ion conductivity with increasing temperature and the maximum ion conductivity of 1.1 × 10−3 S cm−1 is attained at 393 K by plasticized SPE with 40 wt% SN content. The ion conductivity of all the prepared SPEs follows the temperature dependent Arrhenius behavior, suggesting the thermally activated ion hopping mechanism of ionic conduction. Further, the plasticized SPEs display near unity ion transference number indicating the predominance of the ionic mode of conduction. The dielectric and electric modulus analysis reveal a faster relaxation phenomenon and hence higher ion conductivity of the prepared SPEs with increasing salt and plasticizer content.
Crystallization‐correlated phase separation of polypropylene random copolymers
Authors: Guo Jiajun , Liu Liuxin , Lu Xiaoying , Nie Min , Wu Ying , Wu Jinyu , Gao Yuan 
Published: October 2024

AbstractEthylene segments are incorporated into stereoregular propylene‐propylene‐propylene (PPP) homo‐sequences to create locally disordered ethylene‐propylene (EP) segments in polypropylene random copolymer (PPR) through a phase separation process, resulting in large quantities of spherical EP rubbery particles for improving impact toughness. However, the manipulation on size and distribution of these spherical EP rubbery phases remains insufficiently understood. In this study, the phase separation of PPR and the influence of crystallization on phase separation were investigated using rheological measurements and small‐angle x‐ray scattering (SAXS) methods. Combined with the isothermal crystallization method, phase separation was differentiated by the crystallization rate. The molecular chain states corresponding to different crystallization conditions were studied to interpret the varying rubbery particle sizes resulting from phase separation. The results showed that phase separation of EP segments from PPP is highly related to crystallization. Isothermal crystallization at temperatures ranging from 110 to 130°C leads to a high degree of phase separation due to the fast crystallization rate, as evidenced by the presence of small quantities of large pores in microscopic observations. This work provides insights into the phase separation of random copolymers and establishes correlations for manipulating the low‐temperature toughness of PPR.
Post‐Functionalization of Fluorinated Dibenzosulfone‐Based Conjugated Polymer for Smart ‘Turn‐off’ Sensing of Cu2+ Ions
Authors: Maity Krishnendu , Sau Soumitra , Samanta Suman Kalyan 
Published: October 2024

AbstractPost‐functionalization of conjugated polymeric backbone with various N‐containing heterocycles through nucleophilic aromatic substitution reaction (SNAr) demonstrates crucial tailoring of their photophysical properties. This study explores an approach of post‐polymerization modification of a fluorinated dibenzosulfone‐based conjugated polymer aiming to incorporate functional groups having coordinating sites to bind metal ions. The resulting polymers, namely BDT‐DBTS‐IM, BDT‐DBTS‐TR, and BDT‐DBTS‐PY revealed successful substitution reactions with imidazole, triazole, and pyridine respectively, and showed significant changes in their absorption and emission properties. Notably, BDT‐DBTS‐IM demonstrated exceptional performance as a chemosensor, exhibiting a dramatic fluorescence turn‐off response specifically to copper ions (Cu2+) with the limit of detection of 26 nM and Stern‐Volmer quenching constant (KSV) of 8.2×105 Lmol−1. This high selectivity and sensitivity are attributed to the ability of the imidazole group to form a stable complex with Cu2+, resulting in both static and dynamic quenching efficiently. Our findings underscore the potential of post‐polymerization modifications to significantly enhance the functionality of conjugated polymers. The ability of BDT‐DBTS‐IM to detect trace levels of copper ions with high precision highlights its practical utility in environmental and biological monitoring. This research not only demonstrates an approach for post‐polymeric modification through SNAr reaction but also opens new avenues for developing sensors.
Enhancement of Growth and Lipid Production in Microalgae Using Aggregation‐Induced Emission Based Luminescent Material for Sustainable Food and Fuel
Authors: Ferdewsi Rakhi Sharmin , Mohammad Mohsinul Reza Abdul Hakim , Wang Jianzhong , Tang Youhong , Qin Jianguang 
Published: October 2024

AbstractAggregation‐Induced Emission (AIE) based nanomaterials are progressively gaining momentum owing to their evolvement into an interdisciplinary field ranging from biomass and biomolecule yield to image‐guided photodynamic therapy. This study focuses on a novel strategy to enhance growth, lipid accumulation, and in vivo fluorescence visualisation in green microalgae Chlamydomonas reinhardtii using AIE nanoparticles to quantify radical changes. The absorption of AIE photosensitiser (PS), TTMN (C26H17N3S[M]+) was recorded from 420 to 570 nm with a peak at 500 nm, and the emission ranged from 550 to 800 nm with a peak at 650 nm. As a reactive oxygen species (ROS) molecule, H2O2 generation of TTMN in C. reinhardtii cells was detected with AIE nanoprobes TPE‐BO (C38H42B2O4). H2O2 accumulation increased with the increase of TTMN concentrations. The maximum growth (2.1×107 cell/mL) was observed at 10 μM TTMN‐exposed C. reinhardtii cells. Significant lipid accumulation was found in both 10 and 15 μM TTMN‐treated cells. For lipid visualisation, an AIE nanoprobe, 2‐DPAN (C24H18N2O) was used, and superior fluorescence was determined and compared with the traditional BODIPY dye. Cytotoxicity analysis of 10 μM TTMN on the HaCat cell line with 86.2 % cell viability revealed its high biocompatibility on living cells. This AIE‐based nanotechnology provides a novel approach for microalgae‐derived sustainable biomass and eco‐friendly biofuel production.
Can Residual Inhibition Predict the Success of Sound Enrichment Treatment for Tinnitus?
Authors: Sendesen Eser , Turkyilmaz Didem 
Published: October 2024

ABSTRACTObjectivesThe objective of this study was to investigate whether residual inhibition (RI), which provides information on the relationship between tinnitus and increased spontaneous activity in the auditory system, is a predictor for the success of sound enrichment treatment.DesignTinnitus patients were divided into two groups based on whether RI was achieved (RI+) or not (RI−). All participants underwent sound enrichment. Psychosomatic measures (for tinnitus severity, discomfort, attention deficit and sleep difficulties), Tinnitus Handicap Inventory (THI), minimum masking level (MML), and tinnitus loudness level (TLL) results were compared before and at 1, 3, and 6 months after treatment.Study sampleSixty‐seven chronic tinnitus patients were divided into two groups based on whether RI was achieved (RI+) or not (RI−). There were 38 patients in the RI+ group and 29 in the RI− group.ResultsThere was a statistically significant difference between the groups in psychosomatic measures, THI, MML and TLL scores at the post‐treatment 6 months after treatment (p <.05). There was a statistically significant decrease in psychosomatic measures, THI, MML and TLL scores during the treatment period in the RI+ group, but not in the RI− group.ConclusionRI may predict the prognosis of tinnitus treatments used in clinics to reduce the spontaneous firing rate of neurons in the central auditory system, and that RI positivity may be a predictor of treatment success in sound enrichment.