Iso- and hetero-polyoxovanadium glycolates [VIV6O6(glyc)6MIII(OH)6]3- (M = V, Cr, Fe, and Al) encapsulating metal hydroxides.

Polyoxovanadium glycolates (NH4)3[V6O6(glyc)6V(µ-OH)6]·10H2O (1-V7) (H2glyc = glycolic acid) and its derivatives added with ammonium sulfates (NH4)3[V6O6(glyc)6M(µ-OH)6][(NH4)2SO4]2·xH2O (M = Cr, x = 6, 2-CrV6; M = Fe, x = 7, 3-FeV6; M = Al, x = 6, 4-AlV6) were obtained through self-assembly and fully characterized. Compounds 1-4 are composed of the same fully reduced cyclic {VIV6O6} unit bridged by six glycolate ligands. The framework encapsulated an octahedral metal(III) hydroxide {M(OH)6} (M = V3+, Cr3+, Fe3+, and Al3+) in the center, forming an iso- or hetero-heptanuclear Anderson-type structure. Moreover, two sulfate anions capped the two sides of cyclic {V6O6} units in compounds 2-4. Each sulfate formed a strong triple hydrogen bond (2.657-2.829 Å) with the µ3-OH group of the hydroxide. The sulfate anions played important roles in the formation of layered structures in 2-4, while the clusters were stacked compactly through strong hydrogen bonds in 1-V7. Because of the different central metals, these heptanuclear clusters exhibited distinct electronic structures as well as redox and magnetic properties. Magnetic studies showed that compounds 1-3 exhibited weak antiferromagnetic interactions in decreasing order with Fe3+, V3+ and Cr3+, while 4-AlV6 displayed weak ferromagnetic interactions. Their relationships with the local environment of the FeV-cofactor in V-nitrogenase are also discussed.

Formation of atmospheric molecular clusters containing nitric acid with ammonia, methylamine, and dimethylamine.

This study investigates the formation of atmospheric molecular clusters containing ammonia (NH3, A), methylamine (CH3NH2, MA), or dimethylamine (CH3NHCH3, DMA) with nitric acid (HNO3, NA) using quantum mechanics. The Atmospheric Cluster Dynamic Code (ACDC) was employed to simulate the total evaporation rate, formation rate, and growth pathways of three types of clusters under dry and hydrated conditions. This study evaluates the enhancing potential of A/MA/DMA for NA-based new particle formation (NPF) at parts per trillion (ppt) levels. The results indicate that A/MA/DMA can enhance NA-based NPF at high nitric acid concentrations and low temperatures in the atmosphere. The enhancing potential of MA is weaker than that of DMA but stronger than that of A. Cluster growth predominantly follows the lowest free energy pathways on the acid-base grid, with the formation of initial acid-base dimers (NA)(A), (NA)(MA), and (NA)(DMA) being crucial. Hydration influences the evaporation rate and formation rate of clusters, especially for initial clusters. When the humidity is at 100%, the formation rate for NA-A, NA-MA, and NA-DMA clusters can increase by approximately 109, 107, and 104-fold compared to the corresponding unhydrated clusters, respectively. These results highlight the significance of nitric acid nucleation in NPF events in low-temperature, high-humidity atmospheres, particularly in regions like China with significant automobile exhaust pollution.

Data for developing computerized adaptive testing of problematic mobile phone use.

With the popularity of smart terminals and mobile Internet, mobile phone had been a necessity in everyone's daily life. Problematic mobile phone use (PMPU) also needs attention. Although there were multiple measurements to assess the PMPU, most of the tools were in traditional forms with fixed items. Therefore, the current study aimed to develop a computerized adaptive testing for problematic mobile phone use (CAT-PMPU) based on the Item Response Theory, which might help to provide an optimal solution to psychological assessments with long-scale and heterogeneous samples. The data in this article provided results of PMPU with different measurements. The dataset provided in this article includes 1619 participants, encompassing middle school students, undergraduate students, and graduate students recruited from various grades in China. The sample consists of 628 males and 991 females. Self-report measures were administrated including the Chinese version of the Nomophobia Questionnaire, Smartphone Addiction Proneness Scale, Smartphone Addiction Inventory, Mobile Phone Addiction Scale, Mobile Phone Addiction Tendency Scale, Smartphone Addiction Scale for College Students, and the Smartphone Addiction Scale for Chinese Adults. All the measurements were in the Chinese version. A .csv file consists of major variables we used was included as supplementary material on the Zenodo Repository. The discussion of the findings based on the dataset could be found in two articles: Development of a Computerized Adaptive Test for Problematic Mobile Phone Use & Generalizing computerized adaptive testing for problematic mobile phone use from Chinese adults to adolescents.

Fluoride-Mediated Aryne 1,2-Difunctionalization Involving C═S Bond Heterolysis.

We have successfully synthesized a series of bidentate ligands by utilizing 2-(trimethylsilyl)phenyl trifluorosulfonate as a precursor for the benzyl group. This method proceeded by inserting a polythiourea into the C═S π-bond, intramolecular ring proton migration, and ring opening. Salient features of this strategy are mild reaction conditions, a novel product structure, excellent stereochemistry, and a good functional group tolerance. Furthermore, a series of density functional theory calculations were performed to gain insights into the transfer mechanism.

The "Hypointense Focal Brain" on susceptibility-weighted imaging as a sign of venous congestion in cranial dural arteriovenous fistulas.

BACKGROUND: Cranial dural arteriovenous fistulas (dAVFs) are complex neurovascular malformations accounting for approximately 10%-15% of all intracranial arteriovenous malformations. The objective is to investigate the utility of susceptibility-weighted imaging (SWI) in identifying "hypointense focal brain" as an additional helpful sign of venous congestion in cranial dAVFs. MATERIALS AND METHODS: A retrospective review of patients diagnosed with cranial dAVFs between January 2015 and June 2023 was conducted, and SWI was used to identify the "hypointense focal brain" sign within the venous drainage region of the dAVF. The "hypointense focal brain" on SWI was identified as a low-intensity signal within the venous drainage region, indicative of venous congestion. The presence of this imaging sign was assessed by two neuroradiologists and signal intensity measurements were performed to support the presence of the sign. RESULTS: The study included six patients with cranial dAVFs exhibiting cortical venous retrograde drainage and the "hypointense focal brain" on SWI. Follow-up imaging post-treatment revealed resolution or improvement of the hypointense signal, confirming its association with venous congestion. Signal intensity measurements further supported the presence of this imaging sign in pre-treatment scans. CONCLUSION: The study's findings demonstrate the presence of a reversible "hypointense focal brain" sign on SWI in patients with cranial dAVFs and CVR, which can be useful as an additional imaging sign for venous congestion.

Radiological insights into rheumatoid meningitis - a rare central nervous system manifestation of rheumatoid arthritis: a retrospective review of six cases.

BACKGROUND: The objective is to analyze and review the clinical, laboratory, and neuroimaging characteristics of rheumatoid meningitis (RM) in six patients with known rheumatoid arthritis (RA). METHODS: We performed a retrospective review of patients diagnosed with RM from August 2012 to June 2023. To identify the cases, we used medical term search engines and the hospital´s radiology case database. Clinical information and laboratory findings were gathered from the medical records. A neuroradiologist with five years of experience reviewed and analyzed the RM to determine the characteristics findings of RM. RESULTS: Six patients with RM are included. Seizures along with headaches were among the clinical signs that were documented. All the patients had high levels of rheumatoid factor (RF) and anti-cyclic citrullinated peptides (ACPA) in the peripheral blood. Biopsy in two cases confirmed typical rheumatoid nodules. Leptomeningeal enhancement was found bilaterally in all cases and was predominantly found in the frontoparietal region. "Mismatch DWI/FLAIR" was found in five patients. Bilateral subdural collections could be found in two patients. Brain PET scan revealed increased metabolism in two cases. CONCLUSION: Rheumatoid meningitis is a rare complication of rheumatoid arthritis (RA) with challenging clinical diagnosis due to non-specific symptoms. This study highlights the importance of MR in detecting characteristic neuroimaging patterns, including "mismatch DWI/FLAIR", to aid in early diagnosis. Increased awareness of this condition may facilitate timely intervention and improve prognosis. These results still need to be verified by large studies.

Crown ether-like octanuclear molybdenum(V) clusters for cation binding and gas adsorption.

Octanuclear polyoxomolybdenum-based porous materials, Na8[Mo8O8(µ2-O)8(µ2-OH)8(3-apz)4]2·26H2O (1, 3-Hapz = 3-aminopyrazole), K8[Mo8O8(µ2-O)8(µ2-OH)8(3-apz)4]2·7H2O (2) and (NH4)4[Mo8O8(µ2-O)8(µ2-OH)4(3-apz)8]·20.5H2O (3), have been successfully synthesized by a hydrothermal method and fully characterized. X-ray structural analyses show that microporous materials 1-3 contain round pores formed by octanuclear molybdenum-oxygen groups connected sequentially with pore sizes of 4.0, 4.0, and 4.8 Å, respectively. Both 1 and 2 are composed of two {Mo8} rings, which are connected by strong intramolecular hydrogen bonds between bridging hydroxy groups and oxygen atoms to form dimeric structures. The central pores in 1 and 2 are occupied by Na+ and K+, respectively, while they are empty in 3. This reflects the structural expansion and contraction effects induced by different cations. Through intermolecular stacking, 1-3 also exhibit channels with sizes of 14.0 × 6.4, 4.6 × 2.6, and 5.4 × 5.4 Å, respectively, which were used for the studies of gas adsorption. The results show that 1-3 can selectively adsorb CO2 and O2, including the empty hole in 3, while they show little or no affinity for gases H2, N2, and CH4. Moreover, an additional polyoxomolybdenum-based species (Mo8O26)n·4n(3-H2apz) (4) has been obtained with protonated 3-aminopyrazole in the absence of a reducing agent, which can serve as an intermediate for the polyoxomolybdenum-based porous products.

The relationship between nomophobia and latent classes of personality.

The phenomenon of nomophobia, defined as the anxiety experienced when a person is without their mobile phone or is unable to use it, has been identified as having serious negative effects on individuals, particularly students. Previous research has explored the relationship between personality traits and nomophobia, but the findings have been inconclusive. The main objective of this study was to classify personality types through latent class analysis and explore the relationship between these personality types and nomophobia. The Chinese version of the Nomophobia Scale and the Chinese brief version of the Big Five Personality Inventory were used in this study to survey 1906 Chinese college students. The results indicated that (1) a four-class model provided the best fit and categorized the personality traits as the overcontrolled class, resilient class, moderate class, and vulnerable class; (2) significant differences were observed between the four personality types and nomophobia, with overcontrolled and resilient personality types consistently scoring significantly lower than moderate and vulnerable personality types. Our finding highlights the key feature of the study.

Multi-omics panoramic analysis of HBV integration, transcriptional regulation, and epigenetic modifications in PLC/PRF/5 cell line.

The clearance or transcriptional silencing of integrated HBV DNA is crucial for achieving a functional cure in patients with chronic hepatitis B and reducing the risk of hepatocellular carcinoma development. The PLC/PRF/5 cell line is commonly used as an in vitro model for studying HBV integration. In this study, we employed a range of multi-omics techniques to gain a panoramic understanding of the characteristics of HBV integration in PLC/PRF/5 cells and to reveal the transcriptional regulatory mechanisms of integrated HBV DNA. Transcriptome long-read sequencing (ONT) was conducted to analyze and characterize the transcriptional activity of different HBV DNA integration sites in PLC/PRF/5 cells. Additionally, we collected data related to epigenetic regulation, including whole-genome bisulfite sequencing (WGBS), histone chromatin immunoprecipitation sequencing (ChIP-seq), and assays for transposase-accessible chromatin using sequencing (ATAC-seq), to explore the potential mechanisms involved in the transcriptional regulation of integrated HBV DNA. Long-read RNA sequencing analysis revealed significant transcriptional differences at various integration sites in the PLC/PRF/5 cell line, with higher HBV DNA transcription levels at integration sites on chr11, chr13, and the chr13/chr5 fusion chromosome t (13:5). Combining long-read DNA and RNA sequencing results, we found that transcription of integrated HBV DNA generally starts downstream of the SP1, SP2, or XP promoters. ATAC-seq data confirmed that chromatin accessibility has limited influence on the transcription of integrated HBV DNA in the PLC/PRF/5 cell line. Analysis of WGBS data showed that the methylation intensity of integrated HBV DNA was highly negatively correlated with its transcription level (r = -0.8929, p = 0.0123). After AzaD treatment, the transcription level of integrated HBV DNA significantly increased, especially for the integration chr17, which had the highest level of methylation. Through ChIP-seq data, we observed the association between histone modification of H3K4me3 and H3K9me3 with the transcription of integrated HBV DNA. Our findings suggest that the SP1, SP2 and XP in integrated HBV DNA, methylation level of surrounding host chromosome, and histone modifications affect the transcription of integrated HBV DNA in PLC/PRF/5 cells. This provides important clues for future studies on the expression and regulatory mechanisms of integrated HBV.

Interaction between hydroxymethanesulfonic acid and several organic compounds and its atmospheric significance.

The interactions of the micro-mechanism of hydroxymethanesulfonic acid (HMSA) with the typical small organic molecule in atmospheric (X = methanol, formaldehyde, formic acid, methyl formate, dimethyl ether, acetone) has been investigated by density functional theory (DFT), quantum theory of atoms in molecules (QTAIM), Generalized Kohn-Sham Enery Decomposition Analysis (GKS-EDA) and the atmospheric clusters dynamic code (ACDC). The results of DFT show that the stable six- to eight-membered ring structures are easily formed in HMSA-X clusters. According to the topological analysis results of the AIM theory and the IRI method, a strong hydrogen bonding interaction is present in the complex. GKS-EDA results show that electrostatic energy is the main contributor to the interaction energy as it accounts for 51 %-55 % of the total attraction energy. The evaporation rates of HMSA-HMSA and HMSA-HCOOH clusters were much lower than those of the other HMSA complexes. In addition, the Gibbs energy of formation (ΔG) of HMSA-X dimers is investigated under atmosphere temperature T = 217-298 K and p = 0.19-1.0 atm, the ΔG decreased with decreasing of the atmosphere temperature and increased with the decrease of atmospheric pressure, indicating that the low temperature and high pressure may significantly facilitate to the formation of dimers.

A randomized double-blinded trial to assess recurrence of systemic allergic reactions following COVID-19 mRNA vaccination.

BACKGROUND: Systemic allergic reactions (sARs) following coronavirus disease 2019 (COVID-19) mRNA vaccines were initially reported at a higher rate than after traditional vaccines. OBJECTIVE: We aimed to evaluate the safety of revaccination in these individuals and to interrogate mechanisms underlying these reactions. METHODS: In this randomized, double-blinded, phase 2 trial, participants aged 16 to 69 years who previously reported a convincing sAR to their first dose of COVID-19 mRNA vaccine were randomly assigned to receive a second dose of BNT162b2 (Comirnaty) vaccine and placebo on consecutive days in a blinded, 1:1 crossover fashion at the National Institutes of Health. An open-label BNT162b2 booster was offered 5 months later if the second dose did not result in severe sAR. None of the participants received the mRNA-1273 (Spikevax) vaccine during the study. The primary end point was recurrence of sAR following second dose and booster vaccination; exploratory end points included biomarker measurements. RESULTS: Of 111 screened participants, 18 were randomly assigned to receive study interventions. Eight received BNT162b2 second dose followed by placebo; 8 received placebo followed by BNT162b2 second dose; 2 withdrew before receiving any study intervention. All 16 participants received the booster dose. Following second dose and booster vaccination, sARs recurred in 2 participants (12.5%; 95% CI, 1.6 to 38.3). No sAR occurred after placebo. An anaphylaxis mimic, immunization stress-related response (ISRR), occurred more commonly than sARs following both vaccine and placebo and was associated with higher predose anxiety scores, paresthesias, and distinct vital sign and biomarker changes. CONCLUSIONS: Our findings support revaccination of individuals who report sARs to COVID-19 mRNA vaccines. Distinct clinical and laboratory features may distinguish sARs from ISRRs.

Metabolism-dependent mutagenicity of two structurally similar tobacco-specific nitrosamines (N-nitrosonornicotine and N-nitrosoanabasine) in human cells, partially different CYPs being activating enzymes.

N-nitrosonornicotine (NNN) and N-nitrosoanabasine (NAB) are both tobacco-specific nitrosamines bearing two heterocyclic amino groups, NAB bearing an extra -CH2- group (conferring a hexa- rather than penta-membered cycle) but with significantly decreased carcinogenicity. However, their activating enzymes and related mutagenicity remain unclear. In this study, the chemical-CYP interaction was analyzed by molecular docking, thus the binding energies and conformations of NNN for human CYP2A6, 2A13, 2B6, 2E1 and 3A4 appeared appropriate as a substrate, so did NAB for human CYP1B1, 2A6, 2A13 and 2E1. The micronucleus test in human hepatoma (HepG2) cells with each compound (62.5-1000 µM) exposing for 48 h (two-cell cycle) was negative, however, pretreatment with bisphenol AF (0.1-100 nM, CYPs inducer) and ethanol (0.2% v:v, CYP2E1 inducer) potentiated micronucleus formation by both compounds, while CITCO (1 µM, CYP2B6 inducer) selectively potentiated that by NNN. In C3A cells (endogenous CYPs enhanced over HepG2) both compounds induced micronucleus, which was abolished by 1-aminobenzotriazole (60 µM, CYPs inhibitor) while unaffected by 8-methoxypsoralen (1 µM, CYP2A inhibitor). Consistently, NNN and NAB induced micronucleus in V79-derived recombinant cell lines expressing human CYP2B6/2E1 and CYP1B1/2E1, respectively, while negative in those expressing other CYPs. By immunofluorescent assay both compounds selectively induced centromere-free micronucleus in C3A cells. In PIG-A assays in HepG2 cells NNN and NAB were weakly positive and simply negative, respectively; however, in C3A cells both compounds significantly induced gene mutations, NNN being slight more potent. Conclusively, both NNN and NAB are mutagenic and clastogenic, depending on metabolic activation by partially different CYP enzymes.

Analyses of the electronic structures of FeFe-cofactors compared with those of FeMo- and FeV-cofactors and their P-clusters.

The electronic structures of FeFe-cofactors (FeFe-cos) in resting and turnover states, together with their PN clusters from iron-only nitrogenases, have been calculated using the bond valence method, and their crystallographic data were reported recently and deposited in the Protein Data Bank (PDB codes: 8BOQ and 8OIE). The calculated results have also been compared with those of their homologous Mo- and V-nitrogenases. For FeFe-cos in the resting state, Fe1/2/4/5/6/7/8 atoms are prone to Fe3+, while the Fe3 atom shows different degrees of mixed valences. The results support that the Fe8 atom at the terminal positions of FeFe-cos possesses the same oxidation states as the Mo3+/V3+ atoms of FeMo-/FeV-cos. In the turnover state, the overall oxidation state of FeFe-co is slightly reduced than those in the resting species, and its electronic configuration is rearranged after the substitution of S2B with OH, compatible with those found in CO-bound FeV-co. Moreover, the calculations give the formal oxidation states of 6Fe2+-2Fe3+ for the electronic structures of PN clusters in Fe-nitrogenases. By the comparison of Mo-, V- and Fe-nitrogenases, the overall oxidation levels of 7Fe atoms (Fe1-Fe7) for both FeFe- and FeMo-cos in resting states are found to be higher than that of FeV-co. For the PN clusters in MoFe-, VFe- and FeFe-proteins, they all exhibit a strong reductive character.

Solution-Induced Degradation of the Silicon Nanobelt Field-Effect Transistor Biosensors.

Field-effect transistor (FET)-based biosensors are powerful analytical tools for detecting trace-specific biomolecules in diverse sample matrices, especially in the realms of pandemics and infectious diseases. The primary concern in applying these biosensors is their stability, a factor directly impacting the accuracy and reliability of sensing over extended durations. The risk of biosensor degradation is substantial, potentially jeopardizing the sensitivity and selectivity and leading to inaccurate readings, including the possibility of false positives or negatives. This paper delves into the documented degradation of silicon nanobelt FET (NBFET) biosensors induced by buffer solutions. The results highlight a positive correlation between immersion time and the threshold voltage of NBFET devices. Secondary ion mass spectrometry analysis demonstrates a gradual increase in sodium and potassium ion concentrations within the silicon as immersion days progress. This outcome is ascribed to the nanobelt's exposure to the buffer solution during the biosensing period, enabling ion penetration from the buffer into the silicon. This study emphasizes the critical need to address buffer-solution-induced degradation to ensure the long-term stability and performance of FET-based biosensors in practical applications.

Towards promoting wound healing: A near-infrared light-triggered persistently antibacterial, synergistically hemostatic nanoarchitecture-integrated chitosan hydrogel.

The skin, the primary barrier of the body, is inevitably broken. However, the development of materials that facilitate wound healing with sustained antimicrobial, hemostatic, and biocompatible properties remains a formidable challenge. In this article, we prepared a photopolymerizable composite hydrogel consisting of a hydrogel matrix, a hemostatic/antibacterial agent, and a photothermal therapy agent. The photopolymerizable hydrogel matrix was prepared by grafting the photoinitiator and polymerizable active monomer onto the chitosan chain segment, which exhibits excellent biocompatibility. Furthermore, linalool is adsorbed on the surface of halloysite nanotubes (HNTs) to form a hemostatic and antibacterial. Meanwhile, dopamine is employed as a coating material for hollow glass microsphere (HGM), which enables them to function as photothermal therapy agents. Upon exposure to near-infrared radiation, the PHA hydrogel releases linalool molecules from the surface of the HNTs, which diffuse into the hydrogel matrix, resulting in a sustained antimicrobial effect. At the same time, rapid curing of the photopolymerizable hydrogel under UV light forms a physical barrier that synergistically enhances the hemostatic properties of the HNTs. From the above, the results pave the way to develop a potential hemostatic antimicrobial dressing for clinical use in wound healing.

Genome Mining of Cinnamoyl-Containing Nonribosomal Peptide Gene Clusters Directs the Production of Malacinnamycin.

Cinnamoyl-containing nonribosomal peptides (CCNPs) constitute a unique family of actinobacterial secondary metabolites that display a broad spectrum of biological activities. Here, we present a genome mining approach targeting cyclase and is isomerase to discover new CCNPs, which led to the identification of 207 putative CCNP gene clusters from public bacterial genome databases. After strain prioritization, a novel class of CCNP-type glycopeptides named malacinnamycin was identified. A plausible biosynthetic pathway for malacinnamycin was deduced by bioinformatics analysis.

Type 2 cytokine signaling in macrophages protects from cellular senescence and organismal aging.

Accumulation of senescent cells in organs and tissues is a hallmark of aging and known to contribute to age-related diseases. Although aging-associated immune dysfunction, or immunosenescence, is known to contribute to this process, the underlying mechanism remains elusive. Here, we report that type 2 cytokine signaling deficiency accelerated aging and, conversely, that the interleukin-4 (IL-4)-STAT6 pathway protected macrophages from senescence. Mechanistically, activated STAT6 promoted the expression of genes involved in DNA repair both via homologous recombination and Fanconi anemia pathways. Conversely, STAT6 deficiency induced release of nuclear DNA into the cytoplasm to promote tissue inflammation and organismal aging. Importantly, we demonstrate that IL-4 treatment prevented macrophage senescence and improved the health span of aged mice to an extent comparable to senolytic treatment, with further additive effects when combined. Together, our findings support that type 2 cytokine signaling protects macrophages from immunosenescence and thus hold therapeutic potential for improving healthy aging.