bluuebunny/crossref_metadata_2025 huggingface dataset:
Programmable Circular Multivalent Nanobody‐Targeting Chimeras (mNbTACs) for Multireceptor‐Mediated Protein Degradation and Targeted Drug Delivery
Authors: Jiang Shiqi , Lv Xinru , Ouyang Zhenlin , Chi Hongli , Zeng Yuchen , Wang Yani , He Jiaxuan , Chen Jinling , Chen Jingyi , An Keli , Cheng Ming , Wen Yurong , Li Juan , Zhang Penghui
Published: October 2024

Multispecific therapeutics hold significant promise in drug delivery, protein degradation, and cell recruitment to address clinical issues of tumor heterogeneity, resistance, and immune evasion. However, their modular engineering remains challenging. We developed a targeted degradation platform, termed multivalent nanobody‐targeting chimeras (mNbTACs), by encoding diverse nanobody codons on a circular template using DNA printing technology. The homo‐ or hetero‐ mNbTACs specifically recognized membrane targets in a multivalent manner and simultaneously recruited scavenger receptors to favor clathrin‐/caveolae‐dependent endocytosis and lysosomal degradation of multiple proteins with high efficiency and selectivity. We demonstrated that a bispecific doxorubicin‐loaded mNbTAC, named Doxo‐mvNbsPPH, passively accumulated at tumor sites, specifically interacted with PD−L1 and HER2 targets, and was rapidly transported into lysosome, inducing potent immunogenic cell death and alleviating immune checkpoint evasion. The synergistic boosting of innate and adaptive immunity promoted the infiltration and proliferation of CD8+ T cells in tumor microenvironment (an 11‐fold increase) with high toxicity and low exhaustion, eventually enhancing antitumor efficacy. Our mNbTAC platform provides multispecific therapeutics with variable valences and programmed species, whereas it induces targeted protein degradation through multireceptor‐mediated endocytosis and lysosomal degradation without the need for lysosome‐targeting receptors, representing a general and modular tool to harness extracellular proteome for disease treatment.
A Covalent Triazine Framework for Photocatalytic Anti‐Markovnikov Hydrofunctionalizations
Authors: Maiti Rakesh , Chakraborty Jeet , Kumar Sahoo Prakash , Nath Ipsita , Dai Xingchao , Rabeah Jabor , De Geyter Nathalie , Morent Rino , Van Der Voort Pascal , Das Shoubhik
Published: October 2024

Porous materials‐based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)‐based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C−N and C−O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron‐donating and ‐withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late‐stage functionalization of bio‐active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provide mechanistic insights into these reactions.
Novel Silicate Platform as Weakly‐Coordinating Anions for Diverse Organometallic and Electrochemical Applications
Authors: He Tianyi , Bruening Meaghan A. , Espinosa Matthew , Agapie Theodor
Published: October 2024

Weakly‐coordinating anions (WCAs) are employed in a wide range of applications, but limitations remain, including high reactivity, limited redox window, complicated synthesis, high cost, low solublity, and low structural tunabililty. Herein, we report a new class of WCA based on alkyl or aryl (R) substituted silicates bearing fluorinated pinacolate ligands, “[RSiF24]−”. Anions bearing a variety of R groups were prepared, enabling facile tuning of sterics and solubility. A range of cations employed in chemical reactivity has been supported by these anions, including ether‐free alkali cations, Ag+, Ph3C+, Fc+, [NiI(COD)2]+. [Pd(dppe)(NCMe)Me]+ has been generated by salt metathesis or protonation of a metal‐alkyl bond, showcasing the ability of the [RSiF24]− anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu4N]+ variant show an exceptionally wide stability window for the [MeSiF24]− anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.
Triplet Energy Gap‐Regulated Room Temperature Phosphorescence in Host–Guest Doped Systems
Authors: Li Jiayu , Hao Subin , Li Mengke , Chen Yanqi , Li Hailin , Wu Shiqi , Yang Sirui , Dang Li , Su Shi‐Jian , Li Ming‐De
Published: October 2024

The organic room temperature phosphorescence (RTP) materials via host–guest doped method receive considerable attention in the fields of optoelectronics, bioimaging, and information encryption. Despite many host–guest doped materials with excellent RTP properties have been developed, their luminous mechanism is still limited. Here, a series of host–guest doped materials, using benzophenone as the host and quinone compounds as the guests, were constructed to investigate the effect of the triplet energy gap (ΔET) between the host and guest on triplet states population. The guest's triplet state is proposed to be a “triplet energy reservoir”, gathering the triplet excitons to emit RTP when ΔET is large and returning triplet excitons to the host when ΔET is small. By combining the results of steady‐state and delayed emission spectra, time‐resolved transient absorption spectra, and theoretical calculations, a bidirectional energy transfer process is proved, which are triplet‐triplet energy transfer and reverse triplet‐triplet energy transfer processes. The thermal equilibrium of these two energy transfer processes can be regulated by the ΔET and temperature. The potential applications of these RTP properties are also realized in data encryption and anti‐counterfeiting. This work provides valuable insight into the design of host–guest doped materials based on energy transfer mechanisms.
Multi‐branched octopus‐like plasticizers with excellent plasticizing performance in poly(vinyl chloride)
Authors: Tang Hao , Du Yicheng , Ying Jiaying , Shen Yirui , Zhu Xiaoyuan , Liu Dekai , Lang Bo , Jiang Pingping
Published: October 2024

The development of alternatives is a priority issue for the plasticizer industry due to the reproductive toxicity and potential carcinogenicity of phthalate plasticizers. Herein we demonstrate the synthesis and characterization of multi‐branched octopus‐like plasticizers applied in poly(vinyl chloride) (PVC). The plasticizers were achieved through a straightforward one‐step esterification reaction, resulting in four polyol ester plasticizers (glyceryl tri‐n‐octanoate [GTOE], pentaerythritol tetra‐n‐octanoate [PQOE], xylitol penta‐n‐octanoate [XPOE], and mannitol hexa‐n‐octanoate [MHOE]). The multi‐branched structure enhances the interactions between plasticizers and PVC molecules leading to superior plasticizing properties, particularly mechanical properties, thermal stability, and migration resistance compared with commercial plasticizers di(2‐ethylhexyl) phthalate (DEHP), dioctyl terephthalate (DOTP), and acetyl tributyl citrate (ATBC). Concretely, the elongation at break of MHOE/PVC (825%) and PQOE/PVC (814.63%) was better than that of DEHP/PVC (670.02%), DOTP/PVC (490.62%) and ATBC/PVC (566.78%). The T5% of GTOE/PVC, PQOE/PVC, XPOE/PVC, and MHOE/PVC were 46.97, 67.24, 60.09 and 48.14°C higher than ATBC/PVC respectively. In the volatility resistance testing after 48 h, the weight loss of GTOE/PVC, PQOE/PVC, XPOE/PVC, and MHOE/PVC was 5.63%, 3.64%, 2.95%, and 8.88% respectively, which was far less than DEHP/PVC (15.58%), DOTP/PVC (11.83%) and ATBC/PVC (18.15%). Consequently, the obtained plasticizers demonstrate enhanced plasticizing efficiency, presenting promising alternatives to phthalate plasticizers and expanding the repertoire of choices within the plasticizer industry.
Organocatalyzed Asymmetric Conjugate Addition of Cyclic β‐Keto Esters to (E)‐β‐Nitroacrylate Derivatives
Authors: Matsushima Yasuyuki , Iijima Yoshiyuki , Tanabe Chinatsu , Nakashima Kosuke , Hirashima Shin‐ichi , Miura Tsuyoshi
Published: October 2024

A diaminomethylenemalononitrile organocatalyst efficiently promoted the asymmetric conjugate addition of cyclic β‐keto esters to (E)‐β‐nitroacrylate derivatives, yielding the corresponding β‐nitro esters derivatives with excellent enantioselectivities (up to >99 % ee). This is the first successful example of highly stereoselective conjugate addition of cyclic β‐keto esters to (E)‐β‐nitroacrylate derivatives to obtain anti‐isomers.
Computational insights in design of Crimean–Congo hemorrhagic fever virus conserved immunogenic nucleoprotein peptides containing multiple epitopes
Authors: Kaushal Neha , Baranwal Manoj
Published: October 2024

Crimean–Congo hemorrhagic fever virus (CCHFV) belongs to Nairoviridae family and has tripartite RNA genome. It is endemic in various countries of Asia, Africa, and Europe and is primarily transmitted by Hyalomma ticks but nosocomial transmission also been reported. Vaccines for CCHF are in early phase of clinical trial; therefore, this work is centered on identification of potential immunogenic peptide as vaccine candidates with application of different immunoinformatics approaches. Eleven conserved (>90%) peptides of CCHFV nucleoprotein were selected for CD8+ T‐cell (NetMHCpan 4.1b and NetCTLpan 1.1 server) and CD4+ T‐cell (NetMHCIIpan‐4.0 server and Tepitool) epitope prediction. Three peptides containing multiple CD8+ and CD4+ T‐cell and B‐cell epitopes were identified on basis of consensus prediction approach. Peptides displayed good antigenicity score of 0.45–0.68 and predicted to bind with diverse human leukocyte antigen (HLA) alleles. Molecular docking was performed with epitopes to HLA and HLA‐epitopes complex to T‐cell receptor (TCR). In most of the cases, docked complex of HLA‐epitope and HLA‐epitopes‐TCR have the binding energy close to respective natural bound peptide complex with HLA and TCR. Molecular dynamic simulation also revealed that HLA‐peptide complexes have minimum fluctuation and deviation than HLA‐peptide‐TCR docked over 50 ns simulation run. Considering these findings, identified peptides can serve as potential vaccine candidates for CCHFV disease.
Photovoltaic Molecule‐Based Phototheranostics With A‐D‐A Structure for Near‐Infrared Fluorescence Imaging‐Guided Synergetic Photodynamic and Photothermal Therapy of Tumors
Authors: Chen Liang , Huang Jierou , Tong Ming , He Xinchun , Liu Li , Chen Haiou , Yi Jianing
Published: October 2024

Phototheranostics with near‐infrared fluorescence and reactive oxygen species generation ability and high photothermal conversion efficiency (PCE) plays a significant role in fluorescence imaging‐guided synergetic photodynamic and photothermal therapy of tumors. Here, a star molecule in organic photovoltaic materials, NCBDT‐4C with an A‐D‐A conjugated structure, was assembled with DSPE‐PEG‐NH2 to prepare water dispersive nanoparticles (NPs). The prepared NCBDT‐4Cl NPs exhibited a maximum NIR absorption peak at 764 nm and a maximum fluorescence peak at 798 nm. These NPs could generate superoxide anion, singlet oxygen (1O2), and heat under 808 nm laser irradiation. The 1O2 generation quantum yield and PCE of the NPs were 37.5% and 53.6%, respectively. The combination of photodynamic and photothermal therapy of cancer was demonstrated in vitro and in vivo. This work presents the advanced application of organic photovoltaic materials in cancer phototherapy.
On the Architecture of Starch Granules Revealed by Iodine Binding and Lintnerization. Part 2: Molecular Structure of Lintnerized Starches
Authors: Bertoft Eric , Annor George , Vamadevan Varatharajan , Lin Amy Hui‐Mei
Published: October 2024

This investigation validated iodine binding in combination with lintnerization for studying the structural nature of the amorphous areas in starch granules. Lintners of four iodine vapor‐stained and non‐stained amylose‐containing starches and their waxy counterparts were analyzed by high‐performance anion‐exchange chromatography (HPAEC). The composition of the lintners was strongly affected by the absence of amylose in barley and potato starch but not in maize and cassava starch. Iodine‐stained waxy lintners possessed increased number of long B2 chains. β‐Limit dextrins of the lintners were very variable in composition. Iodine inclusion complexes washed out from the granular residues in the lintners (mostly from amylose‐containing barley and maize starches) were also analyzed. Acid‐soluble complexes from both amylose‐containing and waxy starches possessed a lot of material with a degree of polymerization (DP) around 60 and a periodicity in size of DP 8–12. Such long chains were only minor components in water‐soluble complexes of amylose‐containing barley and maize starch lintners, and they lacked the size periodicity. Models of the principal structure of the acid and water‐soluble complexes are suggested. It is concluded that acid hydrolysis of iodine‐stained starch granules is a useful tool in structural analyses of the molecular composition of amorphous parts of starch granules.
Application and progress of 3D tumor models in breast cancer
Authors: Xu Jiaojiao , Fang Wanxia , Zhou Huanhuan , Jiang Ruiyuan , Chen Zhanhong , Wang Xiaojia
Published: October 2024

Due to its high heterogeneity and significant impact on women's health globally, breast cancer necessitates robust preclinical models to understand tumor biology and guide personalized treatment strategies. Three‐dimensional (3D) in vitro tumor models hold immense promise in this regard. These tumor models not only mimic the spatial structure and growth environment of tumors in vivo, but also retain the pathological and genetic characteristics of solid tumors. This fidelity makes them powerful tools for accelerating advancements in fundamental research and translational medicine. The diversity, modularity, and efficacy of 3D tumor models are driving a biotechnological revolution. As these technologies become increasingly sophisticated, 3D tumor models are poised to become powerful weapons in the fight against breast cancer. This article expounds on the progress made in utilizing 3D tumor models for breast cancer research.
Parallel Mediating Effects of Sleep Quality, Psychological Distress, and Self‐Stigma in the Associations Between Long COVID Symptoms and Quality of Life Among Taiwanese Individuals With Mental Health Illness
Authors: Chang Kun‐Chia , Ahorsu Daniel Kwasi , Tsai Hsin‐Chi , Strong Carol , Ko Nai‐Ying , Chen Jung‐Sheng , Yen Cheng‐Fang , Üztemur Servet , Griffiths Mark D. , Lin Chung‐Ying
Published: October 2024

Background

Long COVID symptoms (i.e., experiencing symptoms of COVID‐19 for 3 months post‐COVID‐19) affect individuals’ health and their quality of life (QoL). However, the pathways through which it does so are not fully known.

Aim

The present study examined the mediating roles of sleep quality, psychological distress, and self‐stigma in the associations between long COVID symptoms and QoL among individuals with mental illness.

Method

Individuals with mental illness (n = 333) were recruited from a psychiatric center in southern Taiwan to participate in the study. Data were collected regarding sleep quality, psychological distress, self‐stigma, and QoL. Independent t‐tests, Pearson correlations, and regression with Hayes’ Process Macro were used to compare groups, examine relationships, and parallel mediation models, respectively.

Results

Participants with long COVID symptoms had significantly worse sleep quality, psychological distress, physical QoL, and psychological QoL compared to those without symptoms. There were significant relationships between sleep quality, psychological distress, self‐stigma, and QoL. Sleep quality significantly mediated the associations between long COVID symptoms and physical and social QoL. Psychological distress significantly mediated the associations between long COVID symptoms and all domains of QoL, but not self‐stigma.

Conclusion

There are alternative pathways (e.g., sleep quality and psychological distress) through which long COVID symptoms may affect the QoL of individuals with mental illness. The findings suggest that individuals with long COVID symptoms have a higher chance of having poor QoL. Therefore, there may be the need for counseling and possible therapy for those who contract COVID‐19, especially among individuals who already have mental illness.
Targeting the LMP1‐ALIX axis in EBV+ nasopharyngeal carcinoma inhibits immunosuppressive small extracellular vesicle secretion and boosts anti‐tumor immunity
Authors: He Fajian , Gong Yan , Tao Gan , Zhang Jianguo , Wu Qiuji , Tan Yushuang , Cheng Yajie , Wang Chunsheng , Yang Jinru , Han Linzhi , Wang Zhihao , Gao Yanping , He Jingyi , Bai Rui , Sun Peikai , Yu Xiaoyan , Zhou Yajuan , Xie Conghua
Published: October 2024

Background

Immunotherapy has revolutionized the therapeutical regimen for nasopharyngeal carcinoma (NPC), yet its response rate remains insufficient. Programmed death‐ligand 1 (PD‐L1) on small extracellular vesicles (sEVs) mediates local and peripheral immunosuppression in tumors, and the mechanism of PD‐L1 loading into these vesicles is garnering increasing attention. Latent membrane protein 1 (LMP1), a key viral oncoprotein expressed in Epstein‐Barr virus (EBV)‐positive NPC, contributes to remodeling the tumor microenvironment. However, the precise mechanisms by which LMP1 modulates tumor immunity in NPC remain unclear. Here, we aimed to investigate the roles and regulatory mechanisms of LMP1 and sEV PD‐L1 in NPC immune evasion.

Methods

We analyzed the impact of LMP1 on tumor‐infiltrating lymphocyte abundance in NPC tissues and humanized tumor‐bearing mouse models using multiplex immunofluorescence (mIF) and flow cytometry, respectively. Transmission electron microscopy and nanoparticle tracking analysis were employed to characterize sEVs. Immunoprecipitation‐mass spectrometry was utilized to identify proteins interacting with LMP1. The regulatory effects of sEVs on tumor microenvironment were assessed by monitoring CD8+ T cell proliferation and interferon‐γ (IFN‐γ) expression via flow cytometry. Furthermore, the expression patterns of LMP1 and downstream regulators in NPC were analyzed using mIF and survival analysis.

Results

High LMP1 expression in NPC patient specimens and mouse models was associated with restricted infiltration of CD8+ T cells. Additionally, LMP1 promoted sEV PD‐L1 secretion, leading to inhibition of CD8+ T cell viability and IFN‐γ expression in vitro. Mechanistically, LMP1 recruited apoptosis‐linked gene 2‐interacting protein X (ALIX) through its intracellular domain and bound PD‐L1 through its transmembrane domain, thereby facilitating the loading of PD‐L1 into ALIX‐dependent sEVs. Disruption of ALIX diminished LMP1‐induced sEV PD‐L1 secretion and enhanced the anti‐tumor immunity of CD8+ T cells both in vitro and in vivo. Moreover, increased expression levels of LMP1 and ALIX were positively correlated with enhanced immunosuppressive features and worse prognostic outcomes in NPC patients.

Conclusion

Our findings uncovered the mechanism by which LMP1 interacts with ALIX and PD‐L1 to form a trimolecular complex, facilitating PD‐L1 loading into ALIX‐dependent sEV secretion pathway, ultimately inhibiting the anti‐tumor immune response in NPC. This highlights a novel target and prognostic marker for NPC immunotherapy.
Unlocking the Potential of Origanum Grosii Essential Oils: A Deep Dive into Volatile Compounds, Antioxidant, Antibacterial, and Anti‐Enzymatic Properties within Silico Insights
Authors: Balahbib Abdelaali , Aguerd Oumayma , El Omari Nasreddine , Benali Taoufiq , Akhazzane Mohamed , Ullah Riaz , Iqbal Zafar , Zhang Wei , Shahat Abdelaaty A , Zengin Gokhan , Chamkhi Imane , Bouyahya Abdelhakim
Published: October 2024

The present study aimed to comprehensively characterize the volatile compounds from the aerial parts of Origanum grosii and evaluate their potential as antioxidants and enzyme inhibitors through both in vitro and in silico approaches. The essential oil's volatile constituents were identified using Gas Chromatography‐Mass Spectrometry (GC‐MS) analysis, revealing carvacrol (31 %), p‐cymene (18.59 %), thymol (12.31 %), and ɣ‐terpinene (10.89 %) as the major compounds. The antioxidant capacity was measured using three distinct assays. Notably, Origanum grosii essential oil (OGEO) exhibited significant antioxidant activity, with IC50 values of 55.40±2.23, 81.65±3.26, and 98.04±3.87 μg/mL in DPPH, ABTS, and FRAP assays, respectively. The antibacterial activity was evaluated against both Gram‐positive and Gram‐negative bacterial strains, including Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 29213, Pseudomonas aeruginosa IH, and Listeria monocytogenes ATCC 13932. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) were determined using the broth microdilution method. The inhibitory effects of OGEO were also assessed against enzymes implicated in human pathologies, including α‐glucosidase, α‐amylase, tyrosinase, and acetylcholinesterase (AChE). OGEO demonstrated notable inhibitory activity with IC50 values of 49.72±1.64, 60.28±2.13, 97.14±5.15, and 119.42±2.97 μg/mL against elastase, α‐glucosidase, tyrosinase, and α‐amylase, respectively. Additionally, OGEO exhibited anti‐AChE and anti‐BChE effects, with values of 7.49±0.83 and 1.91±0.77 mg GALAE/g, respectively. The MIC values were 0.125 μg/mL for E. coli, P. aeruginosa, and S. aureus, and 0.25 μg/mL for L. monocytogenes, while MBC values ranged from 0.25 to 0.5 μg/mL. Compared to chloramphenicol (MIC: 8–16 μg/mL, MBC: 32–64 μg/mL), OGEO showed significantly stronger antibacterial effects. In silico analysis further supported the strong binding affinities of the major compounds to the target enzymes. Overall, OGEO shows promise as a natural agent with potential applications in the food, pharmaceutical, and cosmetic industries.
Development and In Vitro Characterization of Azadirachta Indica Gum Grafted Polyacrylamide Based pH‐Sensitive Hydrogels to Improve the Bioavailability of Lansoprazole
Authors: Abid Mustafa Muhammad , Rashid Hussain Hafiz , Akbar Khan Jawad , Ahmad Nadeem , Bashir Sajid , Asad Muhammad , Saeed Shah Hamid , Ali Khan Azmat , Malik Abdul , Fatima Sabiha , Mehmood Yousaf Abid , Nazir Imran
Published: October 2024

The present study intended to develop a pH‐responsive hydrogel based on Neem gum (Ng) to improve Lansoprazole (LSP) oral bioavailability. Azadirachta Indica seed extract was used to obtain Ng. pH‐responsive hydrogel formulations (F1–F9) were prepared using different Ng ratios, Acrylamide (AAm), and methylene‐bis‐acrylamide (MBA). The formulated hydrogels were characterized through FTIR, thermal analysis, swelling ratio, SEM, sol‐gel ratios, In‐Vitro drug release, and cytotoxicity analysis. Azadirachta Indica was extracted to produce a powder containing 21.5 % Ng. Prepared hydrogels showed maximum swelling at pH 7.4, whereas the swelling at an acidic pH was insignificant. LSP‐loaded hydrogel demonstrated a regulated release of LSP for up to 24 h and indicated a Super Case II transport release mechanism. During the cytotoxic evaluation, the delivery system showed minimal cytotoxicity towards normal cells, while percent cytotoxicity was carried out for a longer duration (up to 96 h). The present study revealed Azadirachta indica gum‐based pH‐responsive hydrogel as a promising technique for precisely delivering LSP.
Unveiling the Biological Activities, Pharmacological Potential, and Health Benefits of Sorbifolin: A Comprehensive Review
Authors: Belmehdi Omar , Mssillou Ibrahim , Khalid Asaad , Abdalla Ashraf N. , Almalki Manal , Alqurashi Roaya S. , Bakrim Saad , Zengin Gokhan , Hing Goh Bey , Bouyahya Abdelhakim
Published: October 2024

Bioactive phytochemicals act as important factors with preventive and therapeutic potential in the pathogenesis of several disorders, often related to oxidative stress. Many dietary plant secondary metabolites could lower these conditions. Sorbifolin is one of these metabolites. This work is the first review of sorbifolin, a flavone detected in various plant matrices as a major compound. The present study discussed the natural sources, extraction, purification, quantification, and assessment of the biological activities of sorbifolin. Several databases including Google Scholar, Web of Sciences, and Science‐Direct were consulted for relevant English articles related to sorbifolin, the phytochemical profiles of several medicinal plants containing this compound, and its biological activities, such as antioxidant, anticancer, antimicrobial, anti‐inflammatory, and antidiabetic. The positive in vitro and in silico outcomes reported in the literature should be followed by additional in vivo and clinical investigations to further research the mechanisms of action, pharmacokinetic/pharmacodynamic activities, toxicological effects, pharmacological properties, and therapeutic potential of sorbifolin.
Psychopathy checklist‐youth version scores and recurring victimisation by an intimate partner in a justice‐involved sample: A comparison of young men and women using longitudinal data
Authors: Harris Michelle N. , Daigle Leah E. , Reidy Dennis , Chafin Travis , Thomson Nick D.
Published: October 2024

Background

People involved in the criminal justice system are at increased risk of recurring intimate partner violent (IPV) victimisation. Experience of trauma is linked to a variety of negative outcomes, including repeated experiences, so it is important to identify factors that may distinguish non‐victims, single‐event victims and recurring victims at an early stage as this could hold potential for intervention efforts. Research studies have identified individual‐level risk factors for IPV victimisation but have not investigated psychopathy traits or sex differences.

Aims

To examine sex differences in psychopathy scores and later IPV victimisation.

Methods

Using the Pathways to Desistance study, a longitudinal study of 1354 adjudicated adolescent offenders, relationships between psychopathy checklist‐youth version (PCL‐YV) scores measured during the baseline wave, independent/control variables in wave 6 and self‐reported IPV victimisation in wave 7 were explored using multinomial regression models.

Results

Among justice‐involved young adults (average age 19), PCL‐YV scores differentiated between non‐victims, single‐event victims and recurring victims. Higher total scores and higher ratings on the antisocial behaviours facet of psychopathy significantly increased the relative risk of recurring victimisation by an intimate partner overall, and specifically of emotional or physical intimate partner violence. For the young women but not the young men, a higher scoring on the interpersonal manipulation facet of psychopathy specifically increased the relative risk of being a recurring victim of any intimate partner violence.

Conclusions

Sex‐specific differences in relationships between high PVL‐YV scores and recurring IPV victimisation can be used to screen for risk of repeated trauma for justice‐involved young adults, which may change a trajectory of continued involvement in the criminal justice system to a trajectory of resilience and recovery.
Unveiling the Ultrafast Excitation Energy Transfer in Tetraarylpyrrolo[3,2‐b]pyrrole‐BODIPY Dyads
Authors: Gorai Sudip , Agrawal Richa , Ghosh Rajib , Mula Soumyaditya
Published: October 2024

We have synthesized two dyads (dyad 1 and 2) comprising of tetraarylpyrrolo[3,2‐b]pyrrole (TAPP) and BODIPY. In dyad 1, two BODIPYs are directly connected with TAPP moiety whereas in dyad 2, BODIPYs are connected through phenylethynyl linkers. TAPP is a blue energy donor which is easy to synthesize and functionalize as compared to other well‐known blue energy donors like pyrene, perylene etc. This is the first report of using TAPP as an energy donor in BODIPY based dyad molecules. Complete quenching of TAPP fluorescence in the dyads suggests fast energy transfer from TAPP to BODIPY unit (ETE~99.9 %). Ultrafast fluorescence and transient absorption spectroscopic studies of dyad 1 showed TAPP to BODIPY energy transfer in 125 fs (kET=8.0×1012 s−1) which is one of the fastest energy transfer events in BODIPY based dyad reported so far. Whereas, in dyad 2, energy transfer is almost four times slower (480 fs, kET=2.1×1012 s−1). These results were rationalized by theoretical Förster formulations. This study shows that suitably matched optical properties of TAPP and BODIPY dyes along with their easy syntheses will be the key to develop highly efficient energy transfer systems in future for multiple applications.
Reactivity of Polynuclear Niobium Oxynitride Cluster Anions Nb4N5‐xOx− (x=0–5) toward N2
Authors: Liu Xiao‐Xiao , Li Zi‐Yu , Liu Qing‐Yu , Zhao Xi‐Guan , Li Qian , He Sheng‐Gui
Published: October 2024

The activation of N₂ under mild conditions remains a significant challenge in chemistry. Understanding how the composition of ligands modulates the reactivity of metal centers is pivotal for the rational design of efficient catalysts for nitrogen fixation. Herein, the reactions between polynuclear niobium oxynitride anions Nb4N5‐xOx− (x=0–5) and N2 were investigated by employing mass spectrometry, photoelectron imaging spectroscopy, and theoretical calculations. The rate constants of Nb4N5‐xOx−/N2 gradually decrease for x=0 to x=4, and then increase again for x=5. The sharp increase of the rate constants of Nb4O5−/N2 corresponds to a decrease in the electron detachment energy of the Nb4O5− cluster in the photoelectron spectroscopic experiments. Theoretical calculations suggest that the low‐coordinated Nb−Nb sites in Nb4N5‐xOx− (x=0–5) behaves as the active centers to bind N2 in the side‐on/end‐on manner. Mechanistic analysis reveals that reducing the N/O ratio leads to higher electron densities on the active Nb−Nb centers and decreased positive charge on the metal atoms, which hinders the approach of N2 to the clusters. This finding discloses fundamental insights into the impact of N/O ratio in fine‐tuning the reactivity of metal centers toward N2 adsorption in related catalytic processes.
Photooxidation of Toluene Derivatives under HAT and ROS Synergy
Authors: Ma Wen‐Li , Liu Jian‐Yue , Niu Kai‐Kai , Cui Jing , Zhang Rong‐Zhen , Dong Rui‐Zhi , Liu Hui , Xing Ling‐Bao
Published: October 2024

The valorization of toluene offers a dual solution by addressing its environmental impact while also facilitating the synthesis of a diverse array of valuable fine chemicals and pharmaceutical intermediates, thus ensuring both ecological sustainability and economic viability. We report herein a synergistic approach that harmonizes hydrogen atom transfer (HAT) process with the generation of reactive oxygen species (ROS) under mild condition and low catalyst loading, which enables the efficient synthesis of a broad spectrum of esteemed benzoic acid derivatives and aryl ketones through the photocatalytic oxidation of toluene derivatives. Mechanistic elucidation reveals that the HAT reagent anthraquinone has both the capabilities to abstract hydrogen atoms and the ability to generate singlet oxygen (1O2) during energy transfer with triplet oxygen (3O2), and the combination of these two potencies significantly improves the catalytic efficiency of the reaction. This study not only introduces the amalgamation of HAT with ROS generation but also delineates a systematic approach for the selection of HAT reagents with energy transfer proficiency for ROS generation in catalytic oxidation reactions.
Heterojunction Organic Solar Cells with Efficient Charge Mobility and Separation Capabilities Studied by DFT
Authors: Huang Yuqiang , Zhang Kaiyan , Song Peng , Ma Fengcai , Li Yuanzuo
Published: October 2024

The properties of the active layer materials play a decisive role in determining the power conversion efficiency of organic solar cells (OSCs). Chlorophyll and its derivatives are abundant and environmentally friendly functional organic molecular materials. Using density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT), we have calculated the absorption spectra and their excited state properties based on optimized ground state structures. It was found that bacteriochlorin exhibits superior structural properties, a smaller energy gap and hole reorganization energy, redshifted absorption spectra, and higher hole mobility compared to the donor D18. This suggests that bacteriochlorin exhibits superior donor properties. Comparative studies between o‐AT‐2Cl and m‐AT‐2Cl showed that o‐AT‐2Cl had superior acceptor properties, implying that differences in substitution positions can influence the physicochemical properties of non‐fullerene acceptors (NFAs). Subsequently, six bulk heterojunctions (BHJs) were constructed by combining three donors with nonfused ring electron acceptors, o‐AT‐2Cl and m‐AT‐2Cl. The bacteriochlorin‐based BHJs performed well among them, with BChl3/o‐AT‐2Cl and BChl4/o‐AT‐2Cl having the largest interfacial charge separation rate. The results suggested that BHJs composed of bacteriochlorin and NFAs can improve OSCs’ photovoltaic performance, providing a feasible scheme for designing efficient OSCs.
Thieno[3,2‐b]thiophene Incorporated Redox Active 22π and 34π Core‐Modified Expanded Isophlorinoids
Authors: Udaya Hosahalli S. , Anand Venkataramanarao G.
Published: October 2024

Incorporation of a thieno[3,2‐b]thiophene into an isophlorinoid‐like framework alters the aromaticity by extending the macrocyclic π‐circuit. Their opto‐electronic and aromatic properties significantly differ from other 22π and 34π porphyrinoids. Among the three different 34π hexaphyrins, furan based hexaphyrin adopts a non‐aromatic ‘figure‐of‐eight’ conformation. Replacing all the furans either by thiophene or selenophene induces a planar conformation with aromatic characteristics. Spectro‐electrochemical studies revealed reversible two‐electron ring oxidation to yield their 4nπ dicationic species respectively.
Triscyanocorrole, the Newest and Most Intriguing Member of the C1‐Substituted Corrole Family
Authors: Saini Azad , Sharma Vinay K. , Fridman Natalia , Mahammed Atif , Gross Zeev
Published: October 2024

Considering the potential advantages of minimally sized corroles for diverse applications, this study reports a facile access to cyano‐substituted derivatives via a rare CF3/CN conversion. Investigation of the fully characterized gallium, phosphorus, and cobalt complexes discloses multiple effects of the meso‐nitrile groups attached to the macrocycle. This corrole appears to be the most electron poor derivative which comes into play in the redox potentials of the corresponding complexes. Compared to its precursor, both the absorption and emission are strongly red shifted and the fluorescence lifetime and quantum yield are much larger. The coordination chemistry is affected as well, by virtue of axial ligands being perpendicular rather than parallel relative to each other.
Association Between Overweight/Obesity Metabolic Phenotypes Defined by Two Criteria of Metabolic Abnormality and Cardiovascular Diseases: A Cross‐Sectional Analysis in a Chinese Population
Authors: Qiu Yue , Fan Shujin , Liu Jing , He Xiaodan , Zhu Tianxin , Yan Li , Ren Meng
Published: October 2024

Objectives

Obesity/overweight and metabolic anomalies are known to be associated with elevated cardiovascular disease (CVD) risk. However, there is a paucity of research exploring the association between different body weights, varying metabolic statuses, and the occurrence of CVD in the Chinese population. Thus, we performed this study to explore the relation between different metabolic overweight/obesity phenotypes and the prevalence of CVD.

Methods

We analyzed data from 9075 participants in the Risk Evaluation of cAncers in Chinese diabeTic Individuals: A lONgitudinal (REACTION) study. Participants were classified into four metabolic phenotypes based on their metabolic status and obesity/overweight status. Regression analysis was used to evaluate the relationship between CVD and different groups. Additionally, we conducted a subgroup analysis to further explore the relationship between CVD and different metabolic abnormalities.

Results

Compared to metabolically healthy non‐overweight/obesity (MHNO) individuals, both overweight/obesity and metabolic anomalies were positively associated with CVD prevalence. Among other metabolically unhealthy and overweight/obesity phenotypes, metabolically healthy overweight/obesity (MHO) generally exhibited a comparatively lower association with CVD. In the elderly, high waist circumference was significantly associated with CVD, rather than body weight. Further analysis revealed that hypertension had the strongest association with CVD.

Conclusion

Elderly individuals should place more emphasis on managing their waist circumference rather than only on BMI. CVD prevention should focus on both body weight management and treatment of metabolic diseases, with particular emphasis on antihypertensive therapy.
Insights Into the Gas‐Phase Structure and Internal Dynamics of Diphenylsilane: A Broadband Rotational Spectroscopy Study
Authors: Batra Gayatri , Schnell Melanie
Published: October 2024

The rotational spectrum of diphenylsilane was investigated using chirped‐pulse Fourier transform microwave spectroscopy in the frequency range of 2–8 GHz. The lowest energy structure of diphenylsilane has C
point group symmetry with the C
symmetry axis coinciding with the
‐inertial axis of the molecule. Through the assignment of the main isotopologue as well as singly substituted heavy‐atom isotopologues, including
C,
Si, and
Si, we were able to obtain a comprehensive gas‐phase structure of diphenylsilane. The structure of diphenylsilane was compared with its oxygen analogue, diphenylether, including a discussion of the barrier height to the large‐amplitude motion of the phenyl rings. Furthermore, the structural comparison was extended to include a range of C−Si bond lengths and bond angles from other organosilicon molecules where the silicon atom is bonded to aliphatic and/or aromatic moieties.
A Low‐Cost and Green Zinc‐Iron Battery Achieved by Ethaline Deep Eutectic Solvent
Authors: Cao Xiaozhou , Wang Xiwen , Xue Xiangxin
Published: October 2024

Deep eutectic solvents (DESs) were considered as a potential electrolyte because of their low price, harmless to environment and wider electrochemical window potential compared to water. In this work, Fe(III)/Fe(II) and Zn(II)/Zn redox couples were used as the positive and negative active materials, respectively, in a DES system using choline chloride and ethylene glycol in a molar ratio of 1 : 2 (ethaline). The possible working mechanism of the battery was studied by cyclic voltammetry, spectroscopic and simulation methods. The effects of different temperatures, concentrations of zinc ions in the anolyte and current densities on battery performance were evaluated. The results showed that the designed zinc‐iron battery should preferably be operated at a current density of 0.5 mA cm−2 and the temperature of 313~323 K, which will improve the energy efficiency and maintain a high coulombic efficiency. The variation of cycle performance test presents a different pattern from the usual batteries, which is due to the effect of RO− group. At 313 K and 0.5 mA cm−2, the coulombic efficiency increases from 14.1 % to 100.2 % after 46 cycles, and then remains at about 100 % during the rest 54 cycles, which demonstrates a good cycle stability of DES‐based zinc‐iron battery.
Inhibitory effect of hydroxychloroquine on glucocorticoid‐induced osteoporosis in lupus therapy
Authors: Qiu Wenlin , Han Xiaoxiao , Yu Tong , Jiang Lijuan , Wang Xuefei , Feng Ruizhi , Duan Xiaoru , Teng Yao , Yin Haifeng , Bokarewa Maria I , Deng Guo‐Min
Published: October 2024

Objectives

Systemic lupus erythematosus (SLE) is a chronic and severe autoimmune disease characterised by persistent inflammation. Hydroxychloroquine (HCQ) and glucocorticoids (GCs) are the primary agents commonly used in combination as the first‐line treatment for SLE. Nevertheless, the specific mechanisms responsible for the effectiveness of this combined therapy with HCQ and GCs have not been fully elucidated. This study aimed to reveal the mechanism behind combined HCQ and GC treatment in lupus.

Methods

An SLE IgG‐induced inflammation model was used to investigate the anti‐inflammatory effects of HCQ and dexamethasone (DXM). A glucocorticoid‐induced osteoporosis (GIOP) model was used to investigate the inhibitory effect of HCQ on osteoclastogenesis. Inflammation was assessed by haematoxylin and eosin staining. Bone metabolism was determined structurally via microcomputer tomography and in bone marrow‐derived osteoclast cultures.

Results

An SLE IgG‐induced inflammation model demonstrated that HCQ could not ameliorate inflammation alone but could enhance the anti‐inflammatory effect of GCs by decreasing the expression of FcγRI on macrophages. HCQ inhibited osteoclastogenesis induced by GCs and RANKL by upregulating nuclear factor erythroid 2‐related factor 2 and limiting reactive oxygen species formation, which mitigated GC‐induced bone loss.

Conclusion

The results indicate that HCQ improved the anti‐inflammatory effects of GCs and inhibits the osteoclastogenesis in experimental lupus. This study offers valuable insights into the mechanisms underlying the combined treatment of lupus with HCQ and GCs.
Bridging the gap: Insights in the immunopathology of Lyme borreliosis
Authors: Snik Marijn E. , Stouthamer Noor E.I.M. , Hovius Joppe W. , van Gool Melissa M.J.
Published: October 2024

Lyme borreliosis (LB), caused by Borrelia burgdorferi sensu lato (Bbsl) genospecies transmitted by Ixodes spp. ticks, is a significant public health concern in the Northern Hemisphere. This review highlights the complex interplay between Bbsl infection and host–immune responses, impacting clinical manifestations and long‐term immunity. Early localized disease is characterized by erythema migrans (EM), driven by T‐helper 1 (Th1) responses and proinflammatory cytokines. Dissemination to the heart and CNS can lead to Lyme carditis and neuroborreliosis respectively, orchestrated by immune cell infiltration and chemokine dysregulation. More chronic manifestations, including acrodermatitis chronica atrophicans and Lyme arthritis, involve prolonged inflammation as well as the development of autoimmunity. In addition, dysregulated immune responses impair long‐term immunity, with compromised B‐cell memory and antibody responses. Experimental models and clinical studies underscore the role of Th1/Th2 balance, B‐cell dysfunction, and autoimmunity in LB pathogenesis. Moreover, LB‐associated autoimmunity parallels mechanisms observed in other infectious and autoimmune diseases. Understanding immune dysregulation in LB provides insights into disease heterogeneity and could provide new strategies for diagnosis and treatment.
Blood transcriptome profiling reveals distinct gene networks induced by mRNA vaccination against COVID‐19
Authors: Riemann Lennart , Weskamm Leonie M. , Mayer Leonie , Odak Ivan , Hammerschmidt Swantje , Sandrock Inga , Friedrichsen Michaela , Ravens Inga , Fuss Janina , Hansen Gesine , Addo Marylyn M. , Förster Reinhold
Published: October 2024

Messenger RNA (mRNA) vaccines represent a new class of vaccines that has been shown to be highly effective during the COVID‐19 pandemic and that holds great potential for other preventative and therapeutic applications. While it is known that the transcriptional activity of various genes is altered following mRNA vaccination, identifying and studying gene networks could reveal important scientific insights that might inform future vaccine designs. In this study, we conducted an in‐depth weighted gene correlation network analysis of the blood transcriptome before and 24 h after the second and third vaccination with licensed mRNA vaccines against COVID‐19 in humans, following a prime vaccination with either mRNA or ChAdOx1 vaccines. Utilizing this unsupervised gene network analysis approach, we identified distinct modular networks of co‐varying genes characterized by either an expressional up‐ or downregulation in response to vaccination. Downregulated networks were associated with cell metabolic processes and regulation of transcription factors, while upregulated networks were associated with myeloid differentiation, antigen presentation, and antiviral, interferon‐driven pathways. Within this interferon‐associated network, we identified highly connected hub genes such as STAT2 and RIGI and associated upstream transcription factors, potentially playing important regulatory roles in the vaccine‐induced immune response. The expression profile of this network significantly correlated with S1‐specific IgG levels at the follow‐up visit in vaccinated individuals. Those findings could be corroborated in a second, independent cohort of mRNA vaccine recipients. Collectively, results from this modular gene network analysis enhance the understanding of mRNA vaccines from a systems immunology perspective. Influencing specific gene networks could lead to optimized vaccines that elicit augmented vaccine responses.
Electrodeposition Decoration of Pd0 on F‐Co(OH)2 Nanoarrays with Intentionally Introduced Pd2+ Species for Efficient Electrocatalytic Hydrodechlorination of 2,4‐Dichlorophenol
Authors: Xiang Rui , Yu Yingxue , Gao Qing , Zhuang Yujuan , Wang Chengyun , Peng Lishan
Published: October 2024

Developing a Pd‐based catalyst possessing high efficiency and low mass loading remains a big obstacle for the large‐scale application of electrocatalytic hydrodechlorination (EHDC) of chlorophenols (CPs). Herein, high dispersion Pd nanoparticles imbedded in Pd2+ hydroxide species are decorated on the surface of F−Co(OH)2 nanowire arrays with a newly developed electrodeposition and hydrolysis coupled process. EHDC of 2,4‐dichlorophenol (2,4‐DCP) with the as‐obtained Pd/F−Co(OH)2/NF‐a exhibits superior performance than other control samples in this work and literature reports. A 100 % removal of 2,4‐DCP is accomplished within 120 min, featuring fast reaction kinetics (kobs=5.0×10−2 min−1) and mass activity (MA=22.2 min−1 g−1Pd). Mechanism investigation shows that the intentionally introduced Pd2+ sites play a pivotal role in the adsorption of 2,4‐DCP, while high dispersion of Pd facilitates the generation of active H*, thus promoting the catalytic performance. This work presents a valuable example for designing high‐performance Pd‐based EHDC catalysts by composition tuning.