bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chemically Recyclable Dithioacetal Polymers via Reversible Entropy‐Driven Ring‐Opening Polymerization**
Authors: Kariyawasam Lasith S. , Highmoore Julian F. , Yang Ying 
Published: March 2023

AbstractIn a sustainable circular economy, polymers capable of chemical recycling to monomers are highly desirable. We report an efficient monomer‐polymer recycling of polydithioacetal (PDTA). Pristine PDTAs were readily synthesized from 3,4,5‐trimethoxybenzaldehyde and alkyl dithiols. They then exhibited depolymerizability via ring‐closing depolymerization into macrocycles, followed by entropy‐driven ring‐opening polymerization (ED‐ROP) to reform the virgin polymers. High conversions were obtained for both the forward and reverse reactions. Once crosslinked, the network exhibited thermal reprocessability enabled by acid‐catalyzed dithioacetal exchange. The network retained the recyclability into macrocyclic monomers in solvent which can repolymerize to regenerate the crosslinked network. These results demonstrated PDTA as a new molecular platform for the design of recyclable polymers and the advantages of ED‐ROP for which polymerization is favored at higher temperatures.
Exposed Zinc Sites on Hybrid ZnIn2S4@CdS Nanocages for Efficient Regioselective Photocatalytic Epoxide Alcoholysis
Authors: Li Jing‐Yu , Tan Chang‐Long , Qi Ming‐Yu , Tang Zi‐Rong , Xu Yi‐Jun 
Published: March 2023

AbstractPhotocatalytic epoxide alcoholysis through C−O bond cleavage and formation has emerged as an alternative to synthesizing anti‐tumoral pharmaceuticals and fine chemicals. However, the lack of crucial evidence to interpret the interaction between reactants and photocatalyst surface makes it challenging for photocatalytic epoxide alcoholysis with both high activity and regioselectivity. In this work, we report the hierarchical ZnIn2S4@CdS photocatalyst for epoxide alcoholysis with high regioselectivity nearly 100 %. Mechanistic studies unveil that the precise activation switch on exposed Zn acid sites for C−O bond polarization and cleavage has a critical significance for achieving efficient photocatalytic performance. Furthermore, the establishment of Z‐scheme heterojunction facilitates the interface charge separation and transfer. Remarkably, the underlying regioselective photocatalytic reaction pathway has been distinctly revealed.
Weakened Crystalline SnNb2O6 for Enhanced Performance in Photocatalytic H2 Production and CO2 Reduction
Authors: Li Hui , Tong Haojie , Gao Hongyu , Wang Yinshu , He Jinwei , Wang Zelin , Wang Xiaojing , Chai Zhanli 
Published: March 2023

AbstractLow crystalline photocatalysts with unsaturated active sites, such as oxygen vacancy (Ov), is reported to exhibit enhanced adsorption and activation of oxygen‐containing small molecules, such as H2O and CO2, thus boosting the activity in photocatalytic H2 evolution and CO2 reduction. However, numerous low‐crystalline photocatalysts show unsatisfactory stability due to the easily repaired surface Ov. Herein, three SnNb2O6 with different crystallinity were prepared by hydrothermal approach with similar precursors. Compared with bulk SnNb2O6 and ultra‐thin layered SnNb2O6, low‐crystalline SnNb2O6 (SNA) exhibits optimal visible‐light‐driven evolution rates of H2 (86.04 μmol g−1 h−1) and CO from CO2 (71.97 μmol g−1 h−1), which is mainly ascribed to the fast separation of the photogenerated carriers and enhanced photoreduction power caused by the surface Ov. More importantly, the sharp decrease of photocatalytic activity of SNA after seven cycles is well restored by the hydrothermal treatment of recycled SNA, ascribed to the reactivated surface Ov with the recovered low‐crystalline structure. These works thus offer a promising strategy for developing low‐crystalline and amorphous photocatalysts with high activity and stability.
Heritability of human “directed” functional connectome
Authors: Bianco Maria Giovanna , Duggento Andrea , Nigro Salvatore , Conti Allegra , Toschi Nicola , Passamonti Luca 
Published: March 2023

AbstractIntroductionThe functional connectivity patterns in the brain are highly heritable; however, it is unclear how genetic factors influence the directionality of such “information flows.” Studying the “directionality” of the brain functional connectivity and assessing how heritability modulates it can improve our understanding of the human connectome.MethodsHere, we investigated the heritability of “directed” functional connections using a state‐space formulation of Granger causality (GC), in conjunction with blind deconvolution methods accounting for local variability in the hemodynamic response function. Such GC implementation is ideal to explore the directionality of functional interactions across a large number of networks. Resting‐state functional magnetic resonance imaging data were drawn from the Human Connectome Project (total n = 898 participants). To add robustness to our findings, the dataset was randomly split into a “discovery” and a “replication” sample (each with n = 449 participants). The two cohorts were carefully matched in terms of demographic variables and other confounding factors (e.g., education). The effect of shared environment was also modeled.ResultsThe parieto‐ and prefronto‐cerebellar, parieto‐prefrontal, and posterior‐cingulate to hippocampus connections showed the highest and most replicable heritability effects with little influence by shared environment. In contrast, shared environmental factors significantly affected the visuo‐parietal and sensory‐motor directed connectivity.ConclusionWe suggest a robust role of heritability in influencing the directed connectivity of some cortico‐subcortical circuits implicated in cognition. Further studies, for example using task‐based fMRI and GC, are warranted to confirm the asymmetric effects of genetic factors on the functional connectivity within cognitive networks and their role in supporting executive functions and learning.
Negative Homotropic Cooperativity in Guest Binding of a Trisporphyrin Double Cleft
Authors: Hisano Naoyuki , Kodama Tomoki , Haino Takeharu 
Published: March 2023

AbstractThe negative homotropic allostery of a triple‐layered trisporphyrin cleft with two guest binding sites is confirmed. The X‐ray crystal structures of the 1 : 2 host‐guest complexes showed that the trisporphyrin accommodated two guest molecules within the cleft through π–π stacking and donor‐acceptor interactions. In solution, 1H NMR and Job plots showed 1 : 2 host‐guest complexes. Isothermal titration calorimetry (ITC) and UV/vis absorption spectroscopy were employed to evaluate the binding constants and cooperativities. The guest binding of the trisporphyrin showed negative cooperativity and non‐cooperativity depending on the structures of the guest molecules. The correlations between the interaction parameters (α) and Hill constants were determined. ITC experiments showed that the host‐guest complexation of trisporphyrin with electron‐deficient guests incurred an enthalpy penalty in the successive guest binding process. DFT calculations revealed that binding of the first guest reduced the electron density of the central porphyrin plane, which led to an energetic penalty that weakened the successive binding process.
Precisely Designed Difunctionalized Cyclodextrin Produces a Solid‐State Organic Porous Hierarchical Supramolecular Assembly
Authors: Colesnic Dmitri , Hernando Pedro J. , Chamoreau Lise‐Marie , Bouteiller Laurent , Ménand Mickaël , Sollogoub Matthieu 
Published: March 2023

AbstractRegioselective di‐functionalization of a cyclodextrin allows hydrophobic domains to be directed in a geometrically controlled manner. This controlled orientation ultimately gives access to an original hierarchical assembly in the solid state. This assembly spans over three levels of hierarchy which are governed by synergistic host‐guest inclusions, directed hydrophobic effect and hydrogen bonding. This combination of interactions precisely positioned in space through regioselective functionalization of a cyclodextrin creates a porous organic architecture.
(3+2)‐Cyclization Reactions of Unsaturated Phosphonites with Aldehydes and Thioketones
Authors: Munasinghe Don S. , Kasper Marc‐André , Jasiński Radomir , Kula Karolina , Palusiak Marcin , Celeda Małgorzata , Mlostoń Grzegorz , Hackenberger Christian P. R. 
Published: March 2023

AbstractBy exploiting the unique reactivity of ethynyl‐phosphonites we obtain novel P(V)‐containing five‐membered heterocycles via (3+2)‐cyclization reactions with aldehydes or cycloaliphatic thioketones in satisfactory to excellent yields. Whereas reactions with thioketones to yield 1,3‐thiaphospholes‐3‐oxides occur smoothly at room temperature with equimolar amounts of the starting materials in absence of any catalyst, the analogous conversions with aldehydes to generate 3‐oxides of 1,3‐oxaphospholes require addition of triethylamine as a base. We postulate a step‐wise (3+2)‐cyclization mechanism for the formation of the 1,3‐thiaphosphole ring based on DFT quantum chemical calculations. With this study, we introduce new cyclization reactions originating from unsaturated phosphonites as central synthetic building blocks to yield previously inaccessible stable phosphorus‐containing heterocycles with unexplored potential for the molecular sciences.
An Intelligent Laser‐Free Photodynamic Therapy Based on Endogenous miRNA‐Amplified CRET Nanoplatform**
Authors: Weng Benrui , Wang Yifei , Wang Siyuan , Liu Yaqi , Kang Nana , Liu Sijia , Ran Jiabing , Deng Zhangshuang , Yang Changying , Wang Decheng , Wang Huimin , Wang Fuan 
Published: March 2023

AbstractLaser‐free photodynamic therapy (PDT) is a promising noninvasive therapeutic modality for deep‐seated tumor, yet is constrained by low efficiency due to the limited stimulation strategies. Herein, a novel miRNA‐responsive laser‐free PDT was developed through metal‐organic frameworks (MOFs)‐mediated chemiluminescence resonance energy transfer (CRET) nanoplatform. The photosensitizer chlorin e6 (Ce6)‐loaded MOFs were functionalized with hairpin nucleic acids for sensitive responsiveness of tumor biomarker miRNA through catalytic hairpin assembly (CHA), which enabled the amplified assembly of horseradish peroxidase (HRP)‐mimicking hemin/G‐quadruplex DNAzyme on MOFs. Simultaneously, the on‐MOF assembled DNAzymes efficiently catalyzed chemiluminescence reaction to stimulate adjacent Ce6 in the presence of luminol and H2O2, thus allowing the CRET‐mediated Ce6 luminescence and reactive oxygen species (ROS) generation for self‐illuminating PDT. The CRET nanoplatform achieved significant malignant cell apoptosis and tumor inhibition effects without external laser irradiation. It is envisioned that the miRNA‐amplified CRET nanoplatform might be a selective and highly efficient antitumor nanomedicine for precise theranostic.
The photoreceptor protective cGMP‐analog Rp‐8‐Br‐PET‐cGMPS interacts with cGMP‐interactors PKGI, PDE1, PDE6, and PKAI in the degenerating mouse retina
Authors: Rasmussen Michel , Tolone Arianna , Paquet‐Durand Francois , Welinder Charlotte , Schwede Frank , Ekström Per 
Published: March 2023

AbstractThe inherited eye disease retinitis pigmentosa (RP) causes the loss of photoreceptors by a still unknown cell death mechanism. During this degeneration, cyclic guanosine‐3′,5′‐monophosphate (cGMP) levels become elevated, leading to over‐activation of the cGMP‐binding protein cGMP‐dependent protein kinase (PKG). cGMP analogs selectively modified to have inhibitory actions on PKG have aided in impeding photoreceptor death, and one such cGMP analog is Rp‐8‐Br‐PET‐cGMPS. However, cGMP analogs have previously been shown to interact with numerous targets, so to better understand the therapeutic action of Rp‐8‐Br‐PET‐cGMPS, it is necessary to elucidate its target‐selectivity and hence what potential cellular mechanism(s) it may affect within the photoreceptors. Here, we, therefore, applied affinity chromatography together with mass spectrometry to isolate and identify Rp‐8‐Br‐PET‐cGMPS interactors from retinas derived from three different murine RP models (i.e., rd1, rd2, and rd10 mice). Our findings revealed that Rp‐8‐Br‐PET‐cGMPS bound seven known cGMP‐binding proteins, including PKG1β, PDE1β, PDE1c, PDE6α, and PKA1α. Furthermore, an additional 28 proteins were found to be associated with Rp‐8‐Br‐PET‐cGMPS. This latter group included MAPK1/3, which is known to connect with cGMP/PKG in other systems. However, in organotypic retinal cultures, Rp‐8‐Br‐PET‐cGMPS had no effect on photoreceptor MAPK1/3 expression or activity. To summarize, Rp‐8‐Br‐PET‐cGMPS is more target specific compared to regular cGMP.
Transitions of Collective Motions Driven by Phase Resetting
Authors: Teng Rui , Li Yang , Ren Lin , Ma Juan , Epstein Irving R. , Gao Qingyu 
Published: March 2023

AbstractAbrupt (i. e. step) environmental changes, such as natural disasters or the intervention of predators, can alter the internal dynamics of groups with active units, leading to the rapid destruction and/or restructuring of the group, with the emergence of new collective structures that endow the system with adaptability. Few studies, to date, have considered the influence of abrupt environmental changes on emergent behavior. Here, we use a model of active matter, the Belousov‐Zhabotinsky (BZ) self‐oscillating gel, to study the mechanism of formation and transition between modes of collective locomotion caused by changes of illumination intensity in arrays of interacting photosensitive active units. New forms of collective motion can be generated by step changes of illumination intensity. These transformations arise from the phase resetting and wave‐signal regeneration induced by the abrupt parameter variation, while gradual change results in different evolution of collective motion. Our results not only suggest a novel mechanism for emergence, but also imply that new collective behaviors could be accessible via discontinuous parameter changes.
Crushing It: Can Ground‐Up Rock Help Save the Earth?
Authors: Coyne Kristen 
Published: March 2023

AbstractNature perfected the carbon cycle a long time ago, and rock weathering plays a key role by helping capture atmospheric carbon dioxide through a chemical reaction that occurs when silicate rocks are exposed to air and water. Crushing up the right kind of rocks and spreading them on land could help humans ratchet up nature’s process significantly, capturing some of the excess carbon dioxide we’ve released into the atmosphere. The promising idea has attracted not only a growing number of scientists, but also environmental entrepreneurs who are turning the research into action, albeit at a pace not everyone is comfortable with. While the scientific and business approaches operate under different rules, there’s room for cooperation, data sharing, and innovation as they target the common enemy of climate change.
Clinical application of pancreatic juice‐derived small extracellular vesicles of pancreatic ductal adenocarcinoma
Authors: Tsutsumi Koichiro , Otsuka Motoyuki 
Published: March 2023

AbstractBackgroundRecent imaging modalities have helped inthe early detection of pancreatic ductal adenocarcinoma (PDAC), resulting inimproved survival rates for patients with early‐stage PDAC. However, preoperative pathological diagnosis of early‐stage PDAC remains a challenge, particularly for small PDAC that is difficult to diagnose through standardendoscopic ultrasound‐guided fine‐needle biopsy. In this context, pancreaticjuice cytology has been re‐evaluated as an important tool for the preoperativediagnosis of early‐stage PDAC.MainPancreatic juice (PJ) comes in directcontact with PDAC lesions in the pancreatic duct and thus may contain a fewHG‐PanIN/PDAC cells and specific molecules. Additionally, the PJ may containconcentrated small extracellular vesicles (sEVs) that are released from cancerlesions. sEVs are double‐layered lipid‐bound particles that contain cargoassociated with the cell‐of‐origin, including proteins, microRNA, and RNA. sEVsreleased from cancer lesions found in body fluids, such as blood, urine, andsaliva, have already been studied as potential sources of diagnostic biomarkersfor cancer. PJ‐derived sEVs could serve as a “liquid biopsy” for theearly diagnosis of PDAC. However, little is known about the existence,physiological status, and function of PJ‐derived sEVs and their potentialutility as biomarkers for diagnostic, surveillance, and monitoring purposes oras therapeutic targets.ConclusionPJ‐derived sEVs represent a promisingavenue for the early diagnosis of PDAC. The utility of these particles as biomarkersfor diagnostic, surveillance, and monitoring purposes, or as therapeutictargets, warrants further research. Understanding the existence, physiologicalstatus, and function of PJ‐derived sEVs is crucial to unlocking their potentialas a valuable tool for overcoming PDAC.
Cinepazide maleate promotes recovery from spinal cord injury by inhibiting inflammation and prolonging neuronal survival
Authors: Li Dadi , Zhao Shuxian , Zhu Bin , Zhao Wanmin , Ding Ya , Li Xuejun , Fu Donglin , Yu Haiyang , Wang Baogui , Pan Tan 
Published: March 2023

AbstractThis study aimed to investigate the therapeutic effects of cinepazide maleate (CM) on spinal cord injury (SCI) in rats, thereby providing an experimental basis for the use of CM as a preventative and therapeutic strategy for SCI. Terminal deoxynucleotidyl transferase dUTP nick end labeling staining and western blot analysis were used to assess neural cell apoptosis. enzyme‐linked immunosorbent assay was used to analyze the expression of interleukin (IL)‐1β, IL‐6, and tumor necrosis factor‐α (TNF‐α) in spinal cord tissues and cerebrospinal fluid. CD68 staining and western blot analysis were used to investigate the effect of CM on microglia activation. The effects of CM on motor function and histological damage in rats after SCI were investigated using the Basso‐Beattie‐Bresnahan (BBB) score, footprint assay, hematoxylin and eosin staining, and NeuN staining. In vitro models of neuronal cell injury and microglial inflammation were developed to investigate the effects of CM on apoptosis and inflammation. Functional tests (BBB score and footprint test) revealed that CM‐treated rats had significantly improved motor function. In vivo CM treatment reduced the number of apoptotic cells at the site of injury. Similarly, in vitro CM treatment reduced H2O2‐induced neuronal apoptosis. In vivo CM treatment reduced the number of CD68‐positive microglia and the expression levels of TNF‐α, IL‐1β, and IL‐6. Similarly, in vitro CM treatment reduced LPS‐induced pro‐inflammatory cytokines in microglia. CM promotes the recovery of motor function by inhibiting SCI‐induced apoptosis and inflammatory responses and reducing the area of the post‐SCI cavity in rats. These findings indicate that CM is a potential drug worthy of translational studies for SCI treatment.
The promise of single session interventions for eating disorders: Lessons to be learned from research on digital mental health. Commentary on Schleider et al. (2023)
Authors: Linardon Jake , Fuller‐Tyszkiewicz Matthew 
Published: March 2023

AbstractSchleider et al. propose that single session interventions (SSIs) could be a promising path toward catalyzing innovation in the development of accessible interventions for eating disorders (EDs). In this commentary, we contend that the arguments made by Schleider et al. raise many unresolved questions that continue to arise in the broader field. Drawing from our experiences with—and lessons learned from—developing, evaluating, and disseminating digital health interventions, we discuss four key empirical questions that should be addressed in order to realize the full potential of SSIs and other innovations in intervention delivery. These include: (i) for whom do we deliver an SSI; (ii) what are the optimal treatment mechanisms to target; (iii) what constitutes a “good” outcome; and (iv) where and how might we embed innovations like these. The SSI approach is a fruitful area of research enquiry, and we hope that this commentary generates further discussion and high‐quality, collaborative work related to improving treatment accessibility and clinical outcomes among people with EDs.
A review on QST–FST comparisons of seed plants: Insights for conservation
Authors: Chung Mi Yoon , Merilä Juha , Kim Yuseob , Mao Kangshan , López‐Pujol Jordi , Chung Myong Gi 
Published: March 2023

AbstractIncreased access to genome‐wide data provides new opportunities for plant conservation. However, information on neutral genetic diversity in a small number of marker loci can still be valuable because genomic data are not available to most rare plant species. In the hope of bridging the gap between conservation science and practice, we outline how conservation practitioners can more efficiently employ population genetic information in plant conservation. We first review the current knowledge about neutral genetic variation (NGV) and adaptive genetic variation (AGV) in seed plants, regarding both within‐population and among‐population components. We then introduce the estimates of among‐population genetic differentiation in quantitative traits (QST) and neutral markers (FST) to plant biology and summarize conservation applications derived from QST–FST comparisons, particularly on how to capture most AGV and NGV on both in‐situ and ex‐situ programs. Based on a review of published studies, we found that, on average, two and four populations would be needed for woody perennials (n = 18) to capture 99% of NGV and AGV, respectively, whereas four populations would be needed in case of herbaceous perennials (n = 14). On average, QST is about 3.6, 1.5, and 1.1 times greater than FST in woody plants, annuals, and herbaceous perennials, respectively. Hence, conservation and management policies or suggestions based solely on inference on FST could be misleading, particularly in woody species. To maximize the preservation of the maximum levels of both AGV and NGV, we suggest using maximum QST rather than average QST. We recommend conservation managers and practitioners consider this when formulating further conservation and restoration plans for plant species, particularly woody species.
Chemistry and Applications of Functionalized 2,4‐Thiazolidinediones
Authors: Ibrahim Ayman M. , Shoman Mai E. , Mohamed Mamdouh F. A. , Hayallah Alaa M. , El‐Din A. Abuo‐Rahma Gamal 
Published: March 2023

AbstractThiazolidinedione (TZD) is one of the privileged heterocyclic rings and has shown many biological applications in medicinal chemistry and drug discovery. This review covers the synthetic approaches of TZD and its derivatives, different synthetic techniques for affording the desired regioselectivity and stereoselectivity, and the techniques that would enhance reaction conditions such as microwave, one‐pot, or ultrasound synthesis. It focuses on synthetic challenges of glitazones and the transformation of other heterocycles to TZD. Moreover, the chemical and biological behavior of TZD through the substitution in the N3 position, modification of the C5 position, annealing in complex heterocyclic systems, and hybridization with other pharmacologically attractive moieties are discussed. All reactions mentioned are provided as possible with different reaction conditions, mechanisms, derivatives scope, yield and clarified by applications of such reactions in the construction of potential medicinal agents. The review also answers questions about rapid racemization of glitazones, their toxicity, considering TZD as pan‐assay interference compounds (PAINS) or not, and the influence of saturation of 5‐position of TZD in their biological activities. This review is a comprehensive guide to make informed decisions for construction of TZD derivatives with biological potentials.