Search

Early/late heterobimetallic complexes are widely recognized as one of the most effective catalysts for activating coupling reactions. Herein, DFT calculations were used to investigate the specific mechanisms of terminal alkyne dimerization facilitated by two types of Zr/Co complexes: the bis (phosphinoamide) complex B and the mono (phosphinoamide) complex C. In addition, their reaction activities were compared with that of three ligand‐bridged Zr/Co complex A. The results show that the activated mechanisms of the three reactions are similar, all of them contain inner‐ and outer‐sphere mechanisms, and the inner one is the optimal process. Compared to A, the terminal alkyne dimerizations activated by B and C have the lower energy barriers and better selectivity for the E‐isomer; thus, the mono‐ and bis‐(phosphinoamide) Zr/Co complexes are expected to show better activity and selectivity than tris (phosphinoamide) complexes. The stereoselectivity of E‐, Z‐, and gem‐isomers is controlled by the reductive elimination process. The IRI analysis reveals that the selectivity for E‐ and Z‐isomers is influenced due to the notable repulsion and vdW interaction between the second alkyne and the MeNPMe2 ligand. Our work provides a theoretical basis for experimental applications and offers inspiration for the design of high selectivity heterobimetallic complexes. [ABSTRACT FROM AUTHOR]

The nature of π-hole spodium bonds in the HgLCl2⋯ZH3/CH2Y complexes (L = pyrrole 1, pyrazole 2, imidazole 3, pyridine 4, pyridazine 5, and pyrimidine 6; Z = N, P, As, and Sb; Y = O, S, Se, and Te) has been studied using theoretical calculations. The electrophilicity of the π-hole in the tri-coordinated HgII complexes varies with the type of N-heterocyclic ligand. The strength and nature of the π-hole spodium bond is closely related to the properties of the Lewis bases. In the case of HgLCl2⋯ZH3, the strength of the π-hole spodium bond weakens as the nucleophilicity of the base decreases, following the sequence HgLCl2⋯NH3 > HgLCl2⋯PH3 > HgLCl2⋯AsH3 > HgLCl2⋯SbH3. The Hg⋯Z spodium bonds change from a partially covalent interaction to a close-shelled noncovalent interaction. The nucleophilic ability of CH2Y decreases in the order CH2O > CH2S > CH2Se > CH2Te, while the strength of the π-hole spodium bond follows the order HgLCl2⋯OCH2 < HgLCl2⋯SCH2 < HgLCl2⋯SeCH2 < HgLCl2⋯TeCH2. The Hg⋯Y spodium bond undergoes a transition from a close-shelled noncovalent to a partially covalent interaction, resulting in an incremental increase in the degree of covalence. The Hg⋯Te spodium bond exhibits certain characteristics resembling those of a coordinate covalent bond. The inter-orbital interactions observed in the formation of the HgLCl2⋯YCH2 complexes appear to be significantly stronger compared to those observed in the HgLCl2⋯ZH3 complexation. [ABSTRACT FROM AUTHOR]

Our study aims to investigate the serum levels of anti-nucleosome antibody (ANuA) isotypes in patients with systemic lupus erythematosus (SLE) and clarify ANuA isotypes that may diagnose and predict SLE. We detected anti-nucleosome antibodies (ANuA) in the serum from 120 patients with SLE, 99 patients suffering from other autoimmune diseases (OAD), and 50 healthy controls by performing IgG-, IgA-, and IgM-specific ELISAs. The serum levels of total anti-nuclear antibodies (ANA IgG), ANuA IgG subclasses (IgG1, IgG2, IgG3, and IgG4), anti-dsDNA antibodies, and the avidities of ANA IgG were also analysed using ELISAs. The levels of three ANuA isotypes (IgG, IgA, and IgM) were significantly higher in patients with SLE than in patients with OAD and healthy controls (p < 0.05). Moreover, the concentrations of ANuA isotypes increased in the active SLE and lupus nephritis (LN) groups and in patients with SLE presenting high-avidity IgG ANA (p < 0.05). Furthermore, ANuA isotype levels decreased significantly with drug therapy, while anti-dsDNA IgG levels decreased with the same trend. Additionally, ANuA isotypes were positively related to the SLEDAI (SLE Disease Activity Index) score, RAI (relative avidity index) of high-avidity IgG ANAs, and serum anti-dsDNA IgG levels. Last, the sensitivity and specificity values for SLE were 83.33 and 96.67% for ANuA IgG, 85.83 and 93.33% for ANuA IgA, and83.33 and 86.67% for ANuA IgM, respectively. The sensitivity and specificity values for LN were 61.67 and 96.67% for ANuA IgG, 49.17 and 96.67% for ANuA IgA, and 52.50 and 96.67% for ANuA IgM, respectively. In conclusion, we evaluated whether ANuA isotypes represent a diagnostic tool to predict SLE activity and define subsets of patients with LN. [ABSTRACT FROM AUTHOR]

A theoretical study has been carried out on the intermolecular interactions between tetrafluoro-benzochalcogenadiazoles (chalcogen = S, Se, Te) and a series of nitrogen bases (FCN, ClCN, NP, trans-N2H2, pyridine, pyrazole, imidazole) at the B97-D3/def2-TZVP level, to obtain a better insight into the nature and strength of Ch···N chalcogen bond and secondary interaction in the binary and 1:2 ternary complexes. The dispersion force plays a prominent role on the stability of the sulfur complexes, and the electrostatic effect enhanced for the heavier chalcogen complexes. Most of intermolecular bonds display the characters of closed-shell and noncovalent interaction. For the complexes involving pyridine and imidazole, chalcogen bond is stronger than hydrogen bond, while the strength of chalcogen bond is equivalent to the secondary interaction for other complexes. With the addition of nitrogen base in the 1:2 complexes, chalcogen bond is weakened, while the secondary interaction remains unchanged. In the 1:2 complexes formed by pyridine and imidazole, stronger chalcogen bond results in larger negative cooperativity than that of other complexes. [ABSTRACT FROM AUTHOR]

Objectives: The chemokine CXCL1, known as growth-related oncogene α (GRO-α), is a potent chemoattractant and regulator of neutrophils. The purpose of our study was to evaluate the regulatory response of CXCL1 in the serum of patients with systemic lupus erythematosus (SLE) in the active stage of disease and to assess whether it was implicated in the pathogenesis/inflammatory process in lupus. Methods: CXCL1 serum concentrations were examined in 90 SLE patients, 56 other autoimmune diseases (OADs) patients and 100 healthy controls using enzyme-linked immunosorbent methodology. Results: SLE patients exhibited significant increases in serum CXCL1 concentrations [1492.86 (735.47–2887.34) pg/ml] compared with OADs patients [155.88 (10.77–366.78) pg/ml] and healthy controls [13.58 (8.46–37.22) pg/ml] (p < 0.001). Moreover, the level of CXCL1 decreased as the level of anti-dsDNA IgG decreased after treatment between the anti-dsDNA-positive SLE patients and the anti-dsDNA-negative SLE patients. Additionly, serum CXCL1 concentrations were related to different disease activity levels in SLE and lupus nephritis (LN) and high avidity of IgG ANAs (HA IgG ANAs) (p < 0.05). Furthermore, CXCL1 serum concentrations were significantly correlated with the SLE Disease Activity Index(SLEDAI) score, relative avidity index (RAI) of HA IgG ANAs and the levels of anti-dsDNA IgG, CRP, ESR, albumin, C3 and C4.Additionally, Statistical analysis revealed that positivity for IgG ANA (p < 0.001), the presence of HA IgG ANAs (p = 0.001) and the logarithmic level of anti-dsDNA IgG (p = 0.021) were significantly associated with the logarithmic level of CXCL1 with standard partial regression coefficients (95% CI) of 2.371 (1.734–3.009), 1.231 (0.52–1.937) and 0.409 (0.062–0.755), respectively. Finally, using cutoff points of 1182.17 pg/mL and 1500.31 pg/mL, serum CXCL1 levels had a similar sensitivity of 76% and specificity of 100% and 75% for the diagnosis of active SLE and LN, respectively. Conclusions: Serum CXCL13 concentrations might represent a potential marker of disease activity in systemic lupus erythematosus. [ABSTRACT FROM AUTHOR]

Background: Studies have discussed long noncoding RNA DDX11-AS1 (DDX11-AS1)-mediated downstream mechanism in hepatocellular carcinoma (HCC). The goal of this study was to investigate the regulatory mechanism of DDX11-AS1-mediated microRNA-34a-3p (miR-34a-3p)/tumor necrosis factor receptor-associated factor 5 (TRAF5) axis on HCC cells. Methods: DDX11-AS1, miR-34a-3p and TRAF5 expression levels in HCC were detected. The correlation of DDX11-AS1, miR-34a-3p and TRAF5 in HCC patients was analyzed by Pearson test. HCC cells were transfected with corresponding plasmid/oligonucleotide, and cell proliferation, migration, invasion, apoptosis and tumor formation ability were detected. Bioinformatics software, dual luciferase report experiment and RNA-pull down experiment analysis were applied to verify the targeting relationship between DDX11-AS1, miR-34a-3p and TRAF5. Results: Elevated DDX11-AS1 and TRAF5 and reduced miR-34a-3p exhibited in HCC. Silenced DDX11-AS1 or up-regulated miR-34a-3p inhibited the proliferation, migration, invasion, promoted apoptosis of HCC cells and repressed the tumor growth in nude mice. In addition, DDX11-AS1 bound to miR-34a-3p to target TRAF5. Silencing TRAF5 or elevating miR-34a-3p expression mitigated up-regulated DDX11-AS1-mediated promotion of tumor growth. Conclusion: Silenced DDX11-AS1 or up-regulated miR-34a-3p inhibits HCC cell growth via elevation of TRAF5, which could be of great benefit to find early diagnostic markers for HCC patients. [ABSTRACT FROM AUTHOR]

The aim of our study was to assess the regulatory response of the chemokine CXCL13 in the serum of systemic lupus erythematosus (SLE) patients with disease activity and to evaluate its influence on the inflammatory process in SLE. Serum samples from 97 SLE patients, 49 non-SLE patients (23 patients with other autoimmune diseases and 26 patients with rheumatoid arthritis) and 50 healthy controls were analyzed for the concentration of CXCL13 using ELISA. The results indicated that the serum levels of CXCL13 were significantly higher in SLE patients than in non-SLE patients and healthy controls (p < 0.001). Moreover, the level of CXCL13 decreased as the level of anti-dsDNA IgG decreased after treatment between the anti-dsDNA-positive SLE patients and the anti-dsDNA-negative SLE patients. In addition, serum CXCL13 levels were correlated with SLEDAI in different activities of SLE, renal involvement and active LN. Furthermore, the level of CXCL13 was positively related to the SLEDAI, level of anti-dsDNA IgG, level of ESR and RAI of high-avidity IgG ANAs (HA IgG ANAs). Additionally, statically analysis revealed that CXCL13 would be a best diagnostic value for determining the disease activity of SLE due to its moderate sensitivity (93.5%), specificity (95%), PPV (98.6%), NPV (79.2%) and OR(95%CI,250(30.303–1000)), at a cut-off level of 15.27 pg/mL. First, we indicated that CXCL13 was elevated in SLE patients regardless of the presence or absence of anti-dsDNA IgG ANAs. Furthermore, HA IgG ANAs might affect the circulation of CXCL13. Therefore, the chemokine CXCL13 might be a risk factor influencing the inflammatory process in SLE. [ABSTRACT FROM AUTHOR]

Objectives: Our study purpose was to detect the distribution of anti-nuclear antibody (ANA) IgG subclasses in patients with systemic lupus erythematosus (SLE) and to evaluate their influence on the inflammatory process in SLE. Methods: We determined the serum levels of ANA IgG subclasses from 70 SLE patients, 25 patients with other autoimmune diseases (OAD), and 25 healthy controls using ELISA. The serum level of total ANA IgG and the avidity of ANA IgG, dsDNA IgG, and dsDNA IgG subclasses were analysed by ELISA. Results: The results indicated that levels of four ANA IgG subclasses (IgG1, IgG2, IgG3 and IgG4) and total IgG were significantly higher in SLE patients than in OAD patients and healthy controls (p < 0.001). Moreover, the level of each ANA IgG subclass and the prevalence of high-avidity IgG ANAs (HA IgG ANAs) were significantly higher in the active cases than in the inactive cases of SLE and LN. Furthermore, level of ANA IgG subclasses decreased as level of dsDNA IgG subclasses decreased in 30 patients with SLE. In comparison, ANA IgG3 was significantly effective in high-dose prednisone combined with hydroxychloroquine (p = 0.025). Additionally, it revealed that level of dsDNA IgG had a significant influence on four ANA IgG subclasses, especially on ANA IgG3 (β coefficient = 0.649, p < 0.001). Level of ANA IgG3 was also positively related to the serum level of dsDNA IgG (r = 0.729, p < 0.001) and RAI of HA IgG ANAs (r = 0.504, p < 0.001). However, the level of ANA IgG4 was positively related to the serum level of albumin (r = 0.572, p < 0.001) and RAI of HA IgG ANAs (r = 0.549, p < 0.001). Moreover, the results revealed that cutaneous and renal involvement were mainly associated with the ANA IgG1 and IgG4 subclasses. Although, arthritic involvement was mainly associated with ANA IgG3. Conclusions: First, we demonstrated that the ANA IgG subclasses were diagnostic tools in SLE patients. Furthermore, HA IgG ANAs might affect the distribution of ANA IgG3 and IgG4. Moreover, ANA IgG3 might play a particular role in the activity of SLE disease and therapy. Therefore, an altered ANA IgG subclass distribution might be a risk factor influencing the inflammatory process in SLE. [ABSTRACT FROM AUTHOR]

Background: Studies have discussed long noncoding RNA DDX11-AS1 (DDX11-AS1)-mediated downstream mechanism in hepatocellular carcinoma (HCC). The goal of this study was to investigate the regulatory mechanism of DDX11-AS1-mediated microRNA-34a-3p (miR-34a-3p)/tumor necrosis factor receptor-associated factor 5 (TRAF5) axis on HCC cells. Methods: DDX11-AS1, miR-34a-3p and TRAF5 expression levels in HCC were detected. The correlation of DDX11-AS1, miR-34a-3p and TRAF5 in HCC patients was analyzed by Pearson test. HCC cells were transfected with corresponding plasmid/oligonucleotide, and cell proliferation, migration, invasion, apoptosis and tumor formation ability were detected. Bioinformatics software, dual luciferase report experiment and RNA-pull down experiment analysis were applied to verify the targeting relationship between DDX11-AS1, miR-34a-3p and TRAF5. Results: Elevated DDX11-AS1 and TRAF5 and reduced miR-34a-3p exhibited in HCC. Silenced DDX11-AS1 or up-regulated miR-34a-3p inhibited the proliferation, migration, invasion, promoted apoptosis of HCC cells and repressed the tumor growth in nude mice. In addition, DDX11-AS1 bound to miR-34a-3p to target TRAF5. Silencing TRAF5 or elevating miR-34a-3p expression mitigated up-regulated DDX11-AS1-mediated promotion of tumor growth. Conclusion: Silenced DDX11-AS1 or up-regulated miR-34a-3p inhibits HCC cell growth via elevation of TRAF5, which could be of great benefit to find early diagnostic markers for HCC patients. [ABSTRACT FROM AUTHOR]

Objectives: Our aim was to investigate the prevalence value of a high-avidity antinuclear antibody (ANA) of the IgG isotype (HA IgG ANA) compared with that of ANAs of other isotypes in patients with systemic lupus erythematosus (SLE) and to assess the associations of HA IgG ANA with the activity of SLE and lupus nephritis. Methods: We retrospectively analyzed clinical and laboratory data from subjects. Blood samples were acquired from 101 SLE patients, 67 patients with other autoimmune diseases, and 65 healthy donors. The levels of HA IgG ANA and other isotype ANAs were measured by indirect immunofluorescence (IIF). The prevalence and diagnosis value of HA IgG ANA and other antibodies in SLE patient were tested. The advantage of HA IgG ANA compared with HA anti-dsDNA antibodies IgG (HA dsDNA IgG) was verified by ELISA. We monitored the relative avidity indexes (RAIs) of HA IgG ANA and HA dsDNA IgG at 3 time points after the start of treatment in the same individuals with SLE. Results: The prevalence of HA IgG ANA was significantly higher in active cases than in inactive cases of SLE and LN, which is consistent with data for IgG ANAs, anti-dsDNA IgG antibodies, low C3 levels, low C4 levels, and anti-C1q antibodies. HA IgG ANA showed moderate sensitivity and specificity (80% and 81.3%) for discriminating active and inactive SLE cases. However, HA IgG ANA showed no significant differences among the different clinical manifestations of SLE. Compared with that of HA dsDNA IgG, the RAI of HA IgG ANA was positively related to SLEDAI scores after treatment at 0, 1, and 3 months (r = 0.6813, p = 0.0026; r = 0.5972, p = 0.0114; r = 0.4817, p = 0.0474). Conclusions: First, we demonstrated that HA IgG ANA was a reliable diagnostic tool in SLE patients. Furthermore, HA IgG ANA was supposed to be more appropriate for identifying the activity of SLE compared with HA dsDNA IgG. In summary, HA IgG ANA may be a new biomarker for diagnosing SLE and identifying SLE activity. Key Points • We first introduced the concept of a "high-avidity IgG ANA (HA IgG ANA)" that could distinguish between the early stage of SLE and SLE that had been active for some time. • The relative avidity indexes (RAIs) of HA IgG ANA and HA dsDNAIgG were presented and applied here to evaluate the avidities of antibodies involved in SLE. • In our study, we confirmed the value of HA IgG ANA in diagnosing SLE. In addition, HA IgG ANA was more appropriate for identifying the activity of SLE than was HA dsDNA IgG. • In conclusion, HA IgG ANA could be a potential biomarker for the assessment of the prognosis of SLE activity. [ABSTRACT FROM AUTHOR]

Summary: The power conversion efficiency of organic‐inorganic hybrid perovskite solar cells (PSCs) has exceeded 25%, but the instability limited their practical applications. In this paper, we report a comprehensive study on a Sn‐ and Sr‐mixed lead‐free perovskites, MASn1−xSrxI3(x = 0, 0.25, 0.5, 0.75, 1), by using the first‐principles calculations based on the density functional theory. The crystal structures, band gaps, surface properties, and the adsorptions of oxygen and water molecules on the surfaces of the materials were analyzed and discussed. Our results show that the lattice constants and band gaps of MASn1−xSrxI3 become larger with the increase of Sr components. The band gap of MASrI3 is 4.16 eV, which is too large to be suitable as an efficient photo absorber in the solar cell, but one of the half substituted compounds, MASn0.5Sr0.5I3, has an adequate band gap of 1.37 eV. Both oxygen and water molecules prefer to adsorb on the metal sites (Sn and Sr), and Sr atom has larger attractive ability to oxygen and water molecules than Sn atom. The adsorptions of water on metal atoms are stronger than that of oxygen molecule. The charge transfer from Sn atom to O2/H2O molecule is larger than that from Sr to the adsorbate in the adsorption process, meaning that Sn atom is easier to be oxidized than Sr atom in the air condition. The adsorption energies for O2/H2O adsorbed on clean, and H2O/O2 preadsorbed surfaces are comparable, indicating that the already adsorbed molecule does not exclude the upcoming molecule. So, we predict that a stable Sn‐ and Sr‐mixed PSC material with a suitable band gap can be obtained through the substitution of Sn atom in MASnI3 by Sr atom, and the addition of Sr atom would protect Sn atom from the oxidation to a certain extent. This study is expected to be helpful for further experiments to find new kinds of possible lead‐free perovskite materials. [ABSTRACT FROM AUTHOR]

Nursing students from vocational college programs contribute to over 60% of the nursing student population in China. However, there remains a lack of systematic, quantitative studies examining the prevalence of mental health problems in this population. The purpose of this study was to explore the prevalence of depression, anxiety and stress symptoms and associated factors in vocational college nursing students in Sichuan, China. A total of 554 nursing students from vocational colleges participated in this cross-sectional study. Outcomes were measured with the Depression, Anxiety and Stress Scale 21 (DASS 21). Logistic regressions analysis was performed to examine correlates of mental health problems. The prevalence rates of depression, anxiety and stress symptoms among vocational college nursing students in China were 28.7% (95% CI 24.9%–32.5%), 41.7% (95% CI 37.6%–45.9%) and 20.2% (95% CI 16.8%–23.6%). Mental health problems were elevated as compared to a reference population of Chinese college students of all majors. However, only two percent indicated to seek treatment. The most consistent correlates of mental health problems were reduced engagement in physical and other leisure activities, poor sleep quality, experience of negative life events and poor self-perceived mental health. [ABSTRACT FROM AUTHOR]

• The UV-induced C-H activation mechanism is a good alternative catalytic cycle. • The re-coordination of CO to the Fe occurs before the releasing of H 2. • Benzene with strong electron-withdrawing group is favorable to the para -product. The heterobimetallic complex [(NHC)Cu-FeCp(CO) 2 ] ([LCu-Fp]) is an efficient and sustainable catalyst for C-H borylation under UV light irradiation, whereas the catalytic mechanism is still debating. One opinion is the thermal induced mechanism, in which Cu-Fe bond in [LCu-Fp] firstly dissociated by B-H activation, and then induced the decarbonylation of FpBpin by UV irradiation. The other is the UV-induced mechanism, the decarbonylation of [LCu-Fp] occurred before the Cu-Fe broken. In this work, detailed mechanism of UV-induced has been investigated by DFT calculations and compared with the thermal induced mechanism. Our calculated results show that both of them can occur under UV light irradiation at room temperature. The UV-induced mechanism contains four steps: CO dissociation, Cu-Fe bond breakage by B-H activation, C-H borylation, and H-H reductive elimination. In the last step, it is the re-coordination of CO to the Fe occurs before the releasing of H 2. The strong election-withdrawing substituent of benzene would increase the yield of para -product, whereas the election-donating substituent has little influence on the regioselectivity. Our calculation determines the detail mechanism of the title reaction and provides reasonable explanation for the regioselectivity of C-H borylation of substituted benzene, which would help for the widely usages of the heterobimetallic catalysts. The detailed mechanism of UV-induced decarbonylation of [LCu-Fp] in B-H activation process in C-H Borylation was investigated by DFT calculations and compared with the thermal-induced B-H activation process. Both of the two cases can occur under UV light irradiation at room temperature. The strong election-withdrawing substituent of benzene would increase the yield of para -product, whereas the election-donating substituent has little influence on the regioselectivity. [Display omitted] [ABSTRACT FROM AUTHOR]

The "windmill" pattern cyclic halogen polymers (XBr)3 (X = Cl, Br, I) and (BrY)n (n = 3–6, Y = Cl, Br, I) have been investigated using the density functional theory. Due to the anisotropic distribution of its electron density, the halogen atom can form halogen‐bonded interactions by functioning as both electron donor sites and electron acceptor sites. For (XBr)3 (X = Cl, Br, I) trimers, the Cl···Cl interaction is the weakest, and the I···I interaction is the strongest. For (BrY)n (n = 3–6, Y = Cl, Br, I), the Br···Br halogen bonds are the strongest in (BrY)4 tetramers. We predict that the iodine‐4 synthon may allow creation of a self‐assembled island during crystal growth. The angle formed by the electron‐depleted sigma‐hole, the halogen atom and the electron‐rich equatorial belt perpendicular to the bond direction, together with the halogen‐bond angle, can be used to explain the geometries and strength of the halogen‐bond interactions. © 2018 Wiley Periodicals, Inc. M06‐2X calculations with def2‐TZVPD basis set was used to investigate the halogen‐n (n = 3–6) synthons to form the "windmill" pattern bonding. [ABSTRACT FROM AUTHOR]

Highlights • TGF-β1 up-regulated LOXL1 expression in LX2 cells. • Knockdown of LOXL1 inhibited TGF-β1-induced proliferation of LX2 cells. • Knockdown of LOXL1 suppressed TGF-β1-induced fibrogenic response. • Knockdown of LOXL1 repressed TGF-β1-induced Smad2/3 phosphorylation. Abstract Liver fibrosis is pathological condition that seriously threatens human health. The lysyl oxidase (LOX) family has been reported to promote liver fibrosis. However, the effect of LOX-like 1 (LOXL1), a member of LOX family, on fibrogenesis of hepatic stellate cells (HSCs) remains unknown. The current study aimed to investigate the role of LOXL1 in liver fibrosis and the potential mechanism. We found that the mRNA and protein levels of LOXL1 were increased in transforming growth factor-beta 1 (TGF-β1)-stimulated human hepatic stellate cell line LX-2. Knockdown of LOXL1 inhibited the proliferation of TGF-β1-stimulated LX-2 cells. Knockdown of LOXL1 suppressed TGF-β1-induced expression of metalloproteinase type 1 (TIMP1), α-smooth muscle actin (α-SMA), and collagen type I (Col-I), as well as phosphorylation of Smad2 and Smad3 in LX-2 cells. In addition, the cell proliferation and fibrogenesis mediated by TGF-β1 stimulation and LOXL1 overexpression were abolished by knockdown of Smad2 and Smad3. Collectively, knockdown of LOXL1 suppressed cell proliferation and fibrogenesis in TGF-β1-stimulated HSCs via regulating the phosphorylation of Smad2/3. [ABSTRACT FROM AUTHOR]

Cervical cancer is one of the leading causes of cancer-related deaths among women and it is caused by the human papillomavirus (HPV). High variation has been reported in the attribution of specific HPV genotypes to cervical neoplasia among various geographic regions. For effective control of cervical cancer through HPV vaccination, it is essential to estimate the cost-effectiveness of vaccination, to monitor the potential transition into other HPV genotypes, and to understand the distribution of specific HPV genotypes across a specific geographic region. In this study, the distribution of HPV genotypes was investigated in southeast China, from 2011 to 2016. The 12,816 cervical swabs collected from women (age 18–78 years, median 43.6 years) outpatients were analyzed. HPV prevalence among 12,816 cervical swabs analyzed was 22.3% (2,856/12,816). Among these positive cases, 2,216 had only one HPV genotype while 640 had multiple HPV genotypes. The cases with multiple types revealed 23 different HPV genotypes with the five most prevalent being HPV18 (18.2%), HPV52 (14.1%), HPV16 (11.9%), HPV58 (10.6%), and HPV33 (5.5%). The rates of HPV infection in patients with cervical inflammation, CIN-1, CIN-2, CIN-3, squamous carcinoma, and adenocarcinoma were 38.4%, 80.5%, 82.6%, 92.3%, 97.5%, and 93.4%, respectively. Four HPV genotypes, HPV18, HPV16, HPV52, and HPV58, were more prevalent in patients with CIN-2-CIN-3 and invasive cervical cancer. A comparison of HPV genotypes attribution to cervical cancer between southeast China and global incidences revealed distinct differences. Due to this unique prevalence, it is essential to streamline the vaccination development protocol prior to administering vaccines based on global data. [ABSTRACT FROM AUTHOR]

Objectives To investigate the prevalence and associated factors of sarcopenia defined by different criteria in nursing home residents. Design A cross-sectional study. Setting Four nursing homes in Chengdu, China. Participants Elderly adults aged 65 years or older. Measurements We applied 4 diagnostic criteria [European Working Group on Sarcopenia in Older People (EWGSOP), Asia Working Group for Sarcopenia (AWGS), International Working Group on Sarcopenia (IWGS), and Foundation for the National Institutes of Health (FNIH)] to define sarcopenia. Muscle mass, strength, and function were measured based on bioimpedance analysis, handgrip strength, and walking speed, respectively. Nutrition status, activities of daily living, calf circumference (CC), and other covariates were evaluated. Results We included 277 participants. The prevalence of sarcopenia was 32.5%, 34.3%, 38.3%, and 31.4% according to the EWGSOP, AWGS, IWGS, and FNIH criteria, respectively. Fifty-eight participants (20.9%) were sarcopenic by all the 4 criteria. Regardless of the diagnostic criteria of sarcopenia, malnutrition was independently associated with sarcopenia [EWGSOP: odds ratio (OR) 4.02, 95% confidence interval (CI) 1.05-15.39; IWGS: OR 2.46, 95% CI 1.23-4.90; AWGS: OR 3.29, 95% CI 1.49-7.28; FNIH: OR 4.52, 95% CI 1.28-16.00], whereas CC was negatively associated with sarcopenia [EWGSOP: OR per standard deviation (SD) 0.32, 95% CI 0.20-0.52; IWGS: OR per SD 0.26, 95% CI 0.15-0.43; AWGS: OR per SD 0.32, 95% CI 0.19-0.52; FNIH: OR per SD 0.39, 95% CI 0.25-0.60]. Furthermore, falls ≥1 time in the past year were associated with AWGS-defined sarcopenia (OR 2.92, 95% CI 1.04-8.22). Conclusion/Implications Sarcopenia is highly prevalent in elderly Chinese nursing home residents regardless of the diagnostic criteria. Malnutrition and CC are associated with sarcopenia defined by different criteria. Therefore, it is important to assess sarcopenia and malnutrition in the management of nursing home residents. Prospective studies addressing the outcomes of sarcopenia in nursing home residents are warranted. [ABSTRACT FROM AUTHOR]

Compressed sensing (CS) is a popular data compression theory for many computer vision tasks, but the high reconstruction complexity for images prevents it from being used in many real-world applications. Existing end-to-end learning methods achieved real time sensing but lack theory guarantee for robust reconstruction results. This paper proposes a neural network called RootsNet, which integrates the CS mechanism into the network to prevent error propagation. So, RootsNet knows what will happen if some modules in the network go wrong. It also implements real-time and successfully reconstructed extremely low measurement rates that are impossible for traditional optimization-theory-based methods. For qualitative validation, RootsNet is implemented in two real-world measurement applications, i.e., a near-field microwave imaging system and a pipeline inspection system, where RootsNet easily saves 60% more measurement time and 95% more data compared with the state-of-the-art optimization-theory-based reconstruction methods. Without losing generality, comprehensive experiments are performed on general datasets, including evaluating the key components in RootsNet, the reconstruction uncertainty, quality, and efficiency. RootsNet has the best uncertainty performance and efficiency, and achieves the best reconstruction quality under super low-measurement rates. [ABSTRACT FROM AUTHOR]

Abstract: The intermolecular π‐hole···π‐electrons interactions between F2ZO (Z = C, Si, Ge) molecules and unsaturated hydrocarbons including acetylene, ethylene, 1,3‐butadiene and benzene were constructed to reveal the differences of tetrel bonds forming by carbon and heavier tetrel atoms. The ab initio computation in association with topological analysis of electron density, natural bond orbital, and energy decomposition analysis demonstrate that the strength of Si···π and Ge···π tetrel bonds is much stronger than that of C···π tetrel bonds. The Si···π and Ge···π tetrel bonds exhibit covalent or partially covalent interaction nature, while the weak C···π tetrel bonds display the hallmarks of noncovalent interaction, the electrostatic interaction is the primary influencing factor. The Si···π and Ge···π interactions are determined by both the σ‐ and π‐electron densities, while the C···π interactions are dominated mainly by the π‐electron densities. The π‐hole···π‐electrons tetrel bonds are dominated by electrostatic interaction, and polarization has a comparable contribution in the Si···π and Ge···π tetrel bonds. [ABSTRACT FROM AUTHOR]

The high-level theoretical study on the reactions of methacrolein and methyl vinyl ketone with hydroperoxyl radical was carried out using the M06-2X method in conjunction with the 6-311+G(2df,2pd) basis sets. For the two reactions, all possible addition and abstraction channels initiate from the reactant complexes. The most favorable reaction channel is the concerted addition of the terminal O atom of HO2 radical to the aldehyde-C (or carbonyl-C) and H-transfer from HO2 to the aldehyde-O (or carbonyl-O) forming the α-hydroxyalkenylperoxy radical. For the methacrolein + HO2 and methyl vinyl ketone + HO2 reactions, the calculated rate constants decrease as the temperature increases from 200 K to 500 K, and at 298 K, they are 1.34 × 10−14 and 2.56 × 10−14 cm3 molecule−1 s−1, respectively. The calculated results are close to the previous theoretical and experimental observations for the reactions of HO2 radical with formaldehyde, acetaldehyde, and acetone. [ABSTRACT FROM AUTHOR]

• Cu-carbene and Mn-carbonyl are good synergistic catalysts for C-C coupling. • The reaction catalyzed by [Mn(CO) 5 ]− belongs the S N 2 mechanism. • Metal carboxyl anions with low nucleophilicity are suitable catalysts. Carbonylative Suzuki-Miyura coupling reaction is one of the most efficient methods to synthetize ketones. In this work, the reaction mechanism of arylboronic esters with alkyl halides catalyzed by Cu/Mn synergistic catalysts has been studied by DFT calculation. The calculated results show that the whole reaction contains two cycles, one is the Cu-catalyzed transformation of Ar-Bneop to RO-Bneop, and the other is Mn-catalyzed Heck–Breslow cycle for alkyl halide carbonylation. At the last step, the final product aryl ketone is produced through the C-C cross-coupling between the two intermediates, which form from the above separate two cycles. For the title reaction, the [Mn(CO) 5 ]− catalyzed the Heck–Breslow cycle belongs to SN 2 mechanism, and Mn 2 (CO) 10 catalyzed cycle is SET mechanism. In addition to [Mn(CO) 5 ]−, the metal carbonyl anions with moderate even low nucleophilicity are suitable to co-catalyze the carbonylative Suzuki-Miyaura coupling with the Cu-carbene catalyst. Our calculation results are consistent with and provide explanations the experimental observations, as well as shed lights on further advancement of new bimetallic catalysts. Reaction mechanism of arylboronic esters with alkyl halides catalyzed by Cu/Mn synergistic catalysts are investigated and metal carbony anions matched Cu-carbene catalyst for C-C coupling are screened. [Display omitted] [ABSTRACT FROM AUTHOR]

The enhancing effects of molecule X (X = PH2Cl, SHCl, ClCl) on S···S and Se···Se chalcogen-chalcogen bonds in the cyclic trimers SHCl···SHCl···X and SeHCl···SeHCl···X were investigated by calculations at the MP2/aug-cc-pVTZ level. When molecule X is added to the dimer SHCl···SHCl (SeHCl···SeHCl), cyclic trimers are formed. Compared with the dimer, all the cyclic trimers have shorter S···S (Se···Se) lengths, greater electron densities, negative three-body interaction energies, and larger second-order perturbation energies. These results indicate that the addition of molecule X strengthens the original S···S (Se···Se) bond. For the SHCl···SHCl···X cyclic trimers, the S···S bond is strongest in SHCl···SHCl···PH2Cl, weaker in SHCl···SHCl···SHCl, and weakest in SHCl···SHCl···ClCl. This same trend is observed for the Se···Se bond in SeHCl···SeHCl···X. This means that PH2Cl provides the greatest enhancement to the S···S (Se···Se) interaction. [ABSTRACT FROM AUTHOR]

The bimolecular and termolecular complexes involving POCl and XCN/CH (X = F, Cl, Br) were designed to form the π-hole pnicogen bonds and σ-hole halogen bonds, to compare the two types of interactions and investigate the mutual influences between them. POCl was used as simultaneous π-hole and σ-hole donor; it can interact with electron donor to form π-hole pnicogen bond and σ-hole halogen bond. The π-hole interactions are stronger than the σ-hole interactions, in both the bimolecular and the termolecular complexes. Comparing the mutual effects of the π-hole interactions and σ-hole interactions, the π-hole interaction has a greater influence on the σ-hole interaction than vice versa. With the addition of σ-hole halogen bond, the V value outside the π-hole region of POCl becomes decreasingly positive, resulting in a weaker π-hole interaction. With the addition of π-hole pnicogen bond, the V value outside the σ-hole region of POCl becomes small, also resulting in a weaker σ-hole interaction. The π-hole pnicogen bond and σ-hole halogen bond weaken each other, i.e., there is a negative cooperative effect in the termolecular complexes. [ABSTRACT FROM AUTHOR]

The σ-hole of M2H6 (M = Al, Ga, In) and π-hole of MH3 (M = Al, Ga, In) were discovered and analyzed, the bimolecular complexes M2H6···NH3 and MH3···N2P2F4 (M = Al, Ga, In) were constructed to carry out comparative studies on the group III σ-hole interactions and π-hole interactions. The two types of interactions are all partial-covalent interactions; the π-hole interactions are stronger than σ-hole interactions. The electrostatic energy is the largest contribution for forming the σ-hole and π-hole interaction, the polarization energy is also an important factor to form the M···N interaction. The electrostatic energy contributions to the interaction energy of the σ-hole interactions are somewhat greater than those of the π-hole interactions. However, the polarization contributions for the π-hole interactions are somewhat greater than those for the σ-hole interactions. © 2016 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Apolipoprotein B mRNA-editing enzyme catalytic polypeptide-like 3G (APOBEC3G, A3G) exert antiviral defense as an important factor of innate immunity. A variety of cytokines such as IFN-γ、IL2、IL15、IL7 could induce the transcription of A3G. However, the regulation of other nuclear factor on the transcription of A3G have not been reported at the present. To gain new insights into the transcriptional regulation of this restriction factor, we cloned and characterized the promoter region of A3G and investigate the modulation of USF1 gene on the transcription of A3G. We identified a 232 bp region that was sufficient to regulate the activity of full promoter. Transcriptional start sites (TSS) were identified by the luciferase reporter assays of plasmids containing full or shorter fragments of the A3G promoter. The results demonstrated that the core promoter of A3G is located within the region -159/-84 relative to the TSS. Transcriptional activity of A3G core promoter regulated by USF1 was dependent on an E-box (located at position -91/-86 relative to the major TSS) and was abolished after mutation of this DNA element. USF1 gene can take part in basal transcription regulation of the human A3G gene in hepatocyte, and the identified E-box represented a binding site for the USF1. [ABSTRACT FROM AUTHOR]

The positive electrostatic potentials (ESP) outside the σ-hole along the extension of OP bond in OPH3 and the negative ESP outside the nitrogen atom along the extension of the CN bond in NCX could form the Group V σ-hole interaction OPH3⋯NCX. In this work, the complexes NCY⋯OPH3⋯NCX and OPH3⋯NCX⋯NCY (X, YF, Cl, Br) were designed to investigate the enhancing effects of Y⋯O and X⋯N halogen bonds on the P⋯N Group V σ-hole interaction. With the addition of Y⋯O halogen bond, the VS, max values outside the σ-hole region of OPH3 becomes increasingly positive resulting in a stronger and more polarizable P⋯N interaction. With the addition of X⋯N halogen bond, the VS, min values outside the nitrogen atom of NCX becomes increasingly negative, also resulting in a stronger and more polarizable P⋯N interaction. The Y⋯O halogen bonds affect the σ-hole region (decreased density region) outside the phosphorus atom more than the P⋯N internuclear region (increased density region outside the nitrogen atom), while it is contrary for the X⋯N halogen bonds. © 2015 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

The cation··· π interactions of alkali metal cations (Li, Na, and K) with five-membered heteroaromatic rings [furan(CHO), thiophene(CHS), pyrrole(CHN)] were examined by high level ab initio calculations, to investigate the different roles of CHO, CHS, and CHN as the electron donor, the influential factors that affect these interactions, the nature of this kind of cation··· π interaction, and to determine topological and energetical properties to characterize these interactions. The sulfur atom in CHS plays a certain role in the cation··· π interactions except the C-C π bond, which is different from CHO and CHN. The size of cation and the character of heteroaromatic ring are two influential factors that affect the cation··· π interactions. The studied cation··· π interactions can be classified as 'closed-shell' and noncovalent interactions. The electron density and its Laplacian at the bond critical points and ring critical points generated upon complexation are useful measurements for the strength of cation··· π interactions. [ABSTRACT FROM AUTHOR]

Halogen-bonding interactions arehighly directional intermolecular interactions that are often importantin crystal engineering. In this work, the second-order Møller–Plessetperturbation theory (MP2) calculations and the quantum theory of “atomsin molecules” (QTAIM) and noncovalent interaction (NCI) studieswere carried out on a series of X···N halogen bondsbetween substituted haloperfluoroarenes C6F4XY (X = Cl, Br, I; Y = F, CN, NO2) as bond donors and1,2-diaminoethane as bond acceptor. Our research supports earlierwork that electron-withdrawing substituents produce an enhancementeffect on the size of the σ-hole and the maximum positive electrostaticpotentials (VS,max), which further strengthensthe halogen bonding. The metallic ion M+(M+= Li+, Na+) has the ability to enhance thesize of both the σ-hole and VS,maxvalue with the formation of [MNCC6F4X]+, resulting in more electronic charge transfer away from thehalogen atom X and an increase in the strength of the halogen bond.It is found that the values of VS,maxatthe σ-holes are linear in relation to the halogen-bonded interactionenergies and the halogen-bonding interaction distance, indicatingthat the electrostatic interaction plays a key role in the halogen-bondinginteractions. The values of VS,maxatthe σ-holes are also linear in relation to the electron densityρb,its Laplacian ∇2ρb, and −Gb/Vbof XB, indicating that the topological properties (ρb, ∇2ρb) and energy properties(Gb, Vb) atthe BCPs are correlated with the electrostatic potentials. [ABSTRACT FROM AUTHOR]

The positive electrostatic potentials (σ-hole) have been found in ylides CHXH (X = P, As, Sb) and CHYH (Y = S, Se, Te), on the outer surfaces of group VA and VIA atoms, approximately along the extensions of the C-X and C-Y bonds, respectively. These electrostatic potentials suggest that the above ylides can interact with nucleophiles to form weak, directional noncovalent interactions similar to halogen bonding interactions. MP2 calculations have confirmed the formation of CHXH···HM complexes (X = P, As, Sb; M = BeH, ZnH, MgH, Li, Na). The interaction energies, interaction distances, topological properties (electron density and its Laplacian), and energy properties (kinetic electron energy density and potential electron energy density) at the X(1)···H(10) bond critical points are all correlated with the most negative electrostatic potential value of HM, indicating that electrostatic interactions play an important role in these weak X···H interactions. Similar to the halogen bonding interactions, weak interactions involving ylides may be significant in several areas such as organic synthesis, crystal engineering, and design of new materials. [ABSTRACT FROM AUTHOR]

The effect of DDX11-AS1/miR-34a-3p/TRAF5 on the malignant phenotype of xenografts. Reference 1 Ding G, Zeng Y, Yang D. Silenced lncRNA DDX11-AS1 or up-regulated microRNA-34a-3p inhibits malignant phenotypes of hepatocellular carcinoma cells via suppression of TRAF5. [Extracted from the article]

The character of the cooperativity between the HOX···OH/SH halogen bond (XB) and the Y-H···(H)OX hydrogen bond (HB) in OH/SH···HOX···HY (X = Cl, Br; Y = F, Cl, Br) complexes has been investigated by means of second-order Møller−Plesset perturbation theory (MP2) calculations and 'quantum theory of atoms in molecules' (QTAIM) studies. The geometries of the complexes have been determined from the most negative electrostatic potentials ( V) and the most positive electrostatic potentials ( V) on the electron density contours of the individual species. The greater the V values of HY, the larger the interaction energies of halogen-bonded HOX···OH/SH in the termolecular complexes, indicating that the ability of cooperative effect of hydrogen bond on halogen bond are determined by V of HY. The interaction energies, binding distances, infrared vibrational frequencies, and electron densities ρ at the BCPs of the hydrogen bonds and halogen bonds prove that there is positive cooperativity between these bonds. The potentiation of hydrogen bonds on halogen bonds is greater than that of halogen bonds on hydrogen bonds. QTAIM studies have shown that the halogen bonds and hydrogen bonds are closed-shell noncovalent interactions, and both have greater electrostatic character in the termolecular species compared with the bimolecular species. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Evidence has shown that the p7, NS2 and NS3 genes affect the outcome of pegylated-IFN-α/ribavirin (PEG-IFN/RBV) combination therapy in different populations with HCV infections. Here, we test the hypothesis that diversity in the p7, NS2 and NS3 genes influences the probability of obtaining either a sustained (SVR) or non-sustained (non-SVR) viral response in Chinese patients with genotype 1b chronic hepatitis C. There were significantly more unique variations in the p7, NS2 and NS3 genes in the sequences from SVR than non-SVR patients. Inter-patient variations related to treatment outcome in NS3 were concentrated in the protease domain. There were no significant differences in the frequency of variations in the core, E1 and E2 proteins between the groups. In conclusion, increased amino acid sequence diversity in the p7, NS2 and NS3 genes is associated with an SVR to PEG-IFN/RBV therapy in Chinese patients with genotype 1b chronic hepatitis C. [ABSTRACT FROM AUTHOR]

The intermolecular interactions existing at three different sites between phenylacetylene and LiX (X = OH, NH2, F, Cl, Br, CN, NC) have been investigated by means of second-order Møller−Plesset perturbation theory (MP2) calculations and quantum theory of 'atoms in molecules' (QTAIM) studies. At each site, the lithium-bonding interactions with electron-withdrawing groups (F, Cl, Br, CN, NC) were found to be stronger than those with electron-donating groups (OH and NH2). Molecular graphs of C6H5CCH···LiF and πC6H5CCH···LiF show the same connectional positions, and the electron densities at the lithium bond critical points (BCPs) of the πC6H5CCH···LiF complexes are distinctly higher than those of the σC6H5CCH···LiF complexes, indicating that the intermolecular interactions in the C6H5CCH···LiX complexes can be mainly attributed to the π-type interaction. QTAIM studies have shown that these lithium-bond interactions display the characteristics of 'closed-shell' noncovalent interactions, and the molecular formation density difference indicates that electron transfer plays an important role in the formation of the lithium bond. For each site, linear relationships have been found between the topological properties at the BCP (the electron density ρb, its Laplacian ∇2ρb, and the eigenvalue λ3 of the Hessian matrix) and the lithium bond length d(Li-bond). The shorter the lithium bond length d(Li-bond), the larger ρb, and the stronger the π···Li bond. The shorter d(Li-bond), the larger ∇2ρb, and the greater the electrostatic character of the π···Li bond. © 2012 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Series of typical π-type and pseudo-π-type halogen-bonded complexes B ···ClY and B ···BrY and hydrogen-bonded complex B ···HY (B = C2H4, C2H2, and C3H6; Y = F, Cl, and Br) have been investigated using the MP2/aug-cc-pVDZ method. A striking parallelism was found in the geometries, vibrational frequencies, binding energies, and topological properties between B ···XY and B ···HY (X = Cl and Br). It has been found that the lengths of the weak bond d(X ···π)/ d(H ···π), the frequencies of the weak bond ν(X ···π)/ν(H ···π), the frequency shifts Δν(XY)/Δν(HY), the electron densities at the bond critical point of the weak bonds ρc(X ···π)/ρc(H ···π), and the electron density changes Δρc(XY)/Δρc(HY) could be used as measures of the strengths of typical π-type and pseudo-π-type halogen/hydrogen bonds. The typical π-type and pseudo-π-type halogen bond and hydrogen bond are noncovalent interactions. For the same Y, the halogen bond strengths are in the order B ···ClY < B ···BrY. For the same X, the halogen bond strength decreases according to the sequence F > Cl > Br that is in agreement with the hydrogen bond strengths B ···HF > B ···HCl > B ···HBr. All of these typical π-type and pseudo-π-type hydrogen-bonded and halogen-bonded complexes have the 'conflict-type' structure. Contour maps of the Laplacian of π electron density indicate that the formation of B ···XY halogen-bonded complex and B ···HY hydrogen-bonded complex is very similar. Charge transfer is observed from B to XY/HY and both the dipolar polarization and the volume of the halogen atom or hydrogen atom decrease on B ···XY/B ···HY complex formation. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 [ABSTRACT FROM AUTHOR]

The nature of the interactions of furan and thiophene with hydrogen halides and lithium halides has been investigated using ab initio calculations and QTAIM analysis. The concept of molecule formation density difference (MFDD) is introduced to study weak hydrogen bond (HB) and lithium bond (LB) interactions. The results have shown the molecular electrostatic potentials of furan and thiophene, as well as of the hydrogen halides and lithium halides, determine the geometries of the complexes. Both the studied HB and LB interactions can be classified as 'closed-shell' weak interactions. The topological properties and energy properties at the bond critical points of HB and LB have been shown to be exponentially dependent on intermolecular distances d(H-bond) and d(Li-bond), which enables interpretation of the strength of the HB and LB interactions in terms of these ρ(r) properties. Electron transfer plays a more important role in the formation of HB than in that of LB, while electrostatic interaction in LB is more dominant than that in HB. Table of Contents (TOC) Image [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Abstract: The structures and properties of hydrogen storage alloy Mg2Ni, of aluminum and silver substituted alloys Mg2−x M x Ni (M = Al and Ag, x = 0.16667), and of their hydrides Mg2NiH4, Mg2−x M x NiH4 (M = Al and Ag, x = 0.125) have been calculated from first-principles. Results show that the primitive cell sizes of the intermetallic alloys and hydrides were reduced by substitution of Mg with Al or Ag. Also, the interaction of Ni–Ni was weakened by the substitution. A strong covalent interaction between H and Ni atoms forms tetrahedral NiH4 units in Mg2NiH4. The NiH4 unit near the Al/Ag atom became tripod-like NiH3 in Mg2−x M x NiH4 (M = Al, Ag), indicating that the hydrogen storage capacity was decreased by the substitution. The calculated enthalpies of hydrogenation for Mg2Ni, Mg2−x Al x Ni and Mg2−x Ag x Ni are −65.14, −51.56 and −53.63 kJ/mol H2, respectively, implying that the substitution destabilizes the hydrides. Therefore, the substitution is an effective technique for improving the thermodynamic behavior of hydrogenation/dehydrogenation in magnesium-based hydrogen storage materials. [ABSTRACT FROM AUTHOR]

Abstract: Ab initio and “Atoms in Molecules” studies have been carried on the intermolecular interactions between oxygen-containing σ-electron donors B (B=H2O, H2CO, (CH2)2O) and hydrogen halide HY and dihalogen molecules XY (X, Y=F, Cl, Br). The geometries, energies and topological characteristics of hydrogen-bonded systems have been compared with those of halogen-bonded systems. In general, many properties of the halogen bond are analogous to those of the hydrogen bond. For the same electron acceptor H or X atom, the properties such as bond distance, binding energy, electron density and charge transfer decrease in the sequence of B···HF>B···HCl>B···HBr, B···ClF>B···Cl2, B···BrF>B···BrCl>B···Br2. The bond distance, frequency shift and electron density may be applied as the measure of strength of hydrogen and halogen bond. The decrease in the atomic dipolar polarization and the atomic volume are dependent of the strength of halogen-bonded interaction, while they are independent of the strength of hydrogen-bonded interaction. [Copyright &y& Elsevier]

Abstract: The reactions of dimethyl sulfoxide (DMSO) with XO (X=NO2, Cl, Br, I) have been studied at CCSD/6-311G(d,p)//B3LYP/6-311G(d,p) level. Two reaction channels have been considered: (1) the oxygen-atom transfer (OAT) from XO (X=NO2, Cl, Br, I) to DMSO and (2) the hydrogen-abstraction by XO (X=NO2, Cl, Br, I). The reaction mechanisms of DMSO with NO3, ClO and BrO are similar: the OAT channel is the dominant channel and DMSO2 is the primary product; the hydrogen-abstraction channel is not likely to be competitive with the OAT channel. The DMSO+IO reaction, because two reaction channels have the overall negative reaction activation energies and Gibbs free energies, the reaction could occur on both reaction channels. Furthermore, the formation of the stable complex may vary the yield rate of DMSO2. [Copyright &y& Elsevier]

Abstract: The reactions of SSHX to HSSX (X=F, Cl, Br and I) have been studied at the MP2/6-311++G(2df,pd)//B3LYP/6-311++G(2df,pd) level. The Sh name="sbnd" />H and Sh name="sbnd" />X ring structure transition region (STR) and respective structure transition state (STS) have been studied in the framework of the “Atoms in Molecules” theory. The following conclusions are drawn: (a) For the Sh name="sbnd" />H and Sh name="sbnd" />X ring structures, according to the sequence of X=F, Cl, Br and I, the STR becomes broader and the STS appears later. (b) For the H atom transfer pathway and X atom transfer pathway, the lower the energy barrier is, the broader the ring STR (Sh name="sbnd" />H ring STR or Sh name="sbnd" />X ring STR) is and the later the STS appears. [Copyright &y& Elsevier]

Abstract: The new reactions for preparing IONO2 and IONO have been found. IONO2 and IONO can be easily prepared in vacuum by the heterogeneous reactions of gaseous ICl over the solid powders AgNO3(s) at the room temperature and AgNO2(s) at 0(±1)°C which were loosely filled into the quartz inlet tube (about 1.5cm inside diameter and 5cm long) and supported on the quartz wool, respectively, and then are characterized well by the PES experiment and the ROVGF calculations. [Copyright &y& Elsevier]

Abstract: A cluster DFT (B3LYP) calculation study of ClN3 and BrN3 dissociation pathways catalyzed by molecular sieve is reported. A three-tetrahedral molecular sieve cluster (Al(OHSiH3)(OSiH3)(OH)2, called T3) has been chosen in this study. Triplet-state products ClN and BrN are more easily produced with T3 molecular sieve cluster. Although the potential energy surfaces with T3 molecular sieve cluster are similar with those without T3 molecular sieve cluster, the dissociation process of ClN3 and BrN3 with T3 molecular sieve cluster becomes easier, which can be attributed to smaller energy gaps from the ground state reactant to the intersystem crossing point. [Copyright &y& Elsevier]

The reactions of BrNCO to BrOCN, BrNCS to BrSCN and BrNCSe to BrSeCN have been studied at MP2/6-311++G(2df)//B3LYP/6-311++G(2df) level. Geometries of the reactants, transition states and products have been optimized and geometries of the transition states are found for the first time. The reasons of why BrNCO, BrSCN and BrSeCN are easily detected instead of BrOCN, BrNCS and BrNCSe have been explained successfully. The breakage and formation of the chemical bonds in the reactions have been discussed by the topological analysis method of electronic density. The calculated results show that there are two kinds of structure transition states in topic reactions. [Copyright &y& Elsevier]

Mechanisms of RN3 (R=CH3, CH3CH2, (CH3)2CH, (CH3)3C) dissociations are proposed based on CAS, MP2 and B3LYP methods. The energy gaps between the ground-state reactants RN3 and the intersystem crossing (ISC) points are only a little lower than respective potential energy barriers of the spin-allowed reactions, 1RN3 → 1RN + 1N2. The ISC point, therefore, is considered as a transition state of the spin-forbidden reactions, 1RN3 → 3RN + 1N2. The methods of IRC and topological analysis of electron density are used to explain and predict the thermal dissociation pathways of the reactions studied. [Copyright &y& Elsevier]

Mechanisms of XN3 (X: F, Cl, Br, I) dissociations are proposed based on B3LYP calculated potential energy surfaces. The energy gaps between the ground-state reactants XN3(x˜ 1A′) and the intersystem crossing (ISC) points are only a little lower than respective potential energy barriers of the spin-allowed reactions, XN3(x˜ 1A′)→XN(a 1Δ)+N2(x˜ 1Σg+). The ISC point, therefore, is considered as a ‘transition state’ of the spin-forbidden reactions, XN3(x˜ 1A′)→XN(x˜ 3Σ−)+N2(x˜ 1Σg+). The methods of IRC and topological analysis of electron density are used to predict the thermal dissociation pathway of the reactions studied. [Copyright &y& Elsevier]

Carbon fiber-reinforced polymer (CFRP) is a widely-used composite material that is vulnerable to impact damage. Light impact damages destroy the inner structure but barely show obvious change on the surface. As a non-contact and high-resolution method to detect subsurface and inner defect, near-field radiofrequency imaging (NRI) suffers from high imaging times. Although some existing works use compressed sensing (CS) for a faster measurement, the corresponding CS reconstruction time remains high. This paper proposes a deep learning-based CS method for fast NRI, this plugin method decreases the measurement time by one order of magnitude without hardware modification and achieves real-time imaging during CS reconstruction. A special 0/1-Bernoulli measurement matrix is designed for sensor scanning firstly, and an interpretable neural network-based CS reconstruction method is proposed. Besides real-time reconstruction, the proposed learning-based reconstruction method can further reduce the required data thus reducing measurement time more than existing CS methods. Under the same imaging quality, experimental results in an NRI system show the proposed method is 20 times faster than traditional raster scan and existing CS reconstruction methods, and the required data is reduced by more than 90% than existing CS reconstruction methods. [ABSTRACT FROM AUTHOR]

Objectives: This systematic review and meta‐analysis aimed to determine the prevalence of loneliness and social isolation among informal carers of individuals with dementia and to identify potential influencing factors. Methods: We conducted a comprehensive search across 10 electronic databases, including PubMed, Cochrane, Embase, Web of Science, PsycINFO, CINAHL, Scopus, Chinese Biomedical, China National Knowledge Internet, and WANFANG. Our search strategy covered the inception of the databases up to September 16, 2023, with an updated search conducted on March 8, 2024. Prevalence estimates of loneliness and social isolation, presented with 95% confidence intervals, were synthesized through meta‐analysis. Subgroup analyses and meta‐regression were employed to explore potential moderating variables and heterogeneity. Results: The study encompassed 27 research papers involving 11,134 informal carers from 17 different countries. The pooled prevalence of loneliness among informal carers of individuals with dementia was 50.8% (95% CI: 41.8%–59.8%), while the pooled prevalence of social isolation was 37.1% (95% CI: 26.7%–47.6%). Subgroup analyses and meta‐regression indicated that various factors significantly influenced the prevalence of loneliness and social isolation. These factors included the caregiving setting, study design, the intensity of loneliness, geographical location (continent), data collection time, and the choice of assessment tools. Conclusions: This study underscores the substantial prevalence of loneliness and social isolation among informal carers of individuals with dementia. It suggests that policymakers and healthcare providers should prioritize the development of targeted interventions and support systems to alleviate loneliness and social isolation within this vulnerable population. Key points: Informal carers of people with dementia contend with unique circumstances that render them susceptible to both loneliness and social isolation.There is a significant prevalence of loneliness and social isolation in informal carers of individuals with dementia.Several significant moderators influence the prevalence of loneliness and social isolation among informal carers of individuals with dementia.Moderator analysis can guide targeted interventions and support systems for at‐risk informal carers of people with dementia to alleviate loneliness and social isolation. [ABSTRACT FROM AUTHOR]

The nature of coinage–metal bonds between AuX (X = F, Cl, Br, CN, NO2, CH3) and aromatic moieties with different electronic properties (benzene, 1,3,5-trifluorobenzene and hexafluorobenzene) has been characterized within the framework of energy decomposition analysis, natural bond orbital analysis, quantum theory of atoms in molecules, and the electron localization function method. The strength and covalency of π⋯AuX interactions depend on the nature of the aromatic moiety and coin metal substituents. The binding energy varies from −6.6 to −34.8 kcal mol−1, and becomes more negative in the order of π = C6F6 < C6H3F3 < C6H6 and X = CH3 < NO2 < CN < Br < Cl < F. Most of the coinage–metal bonds have partially covalent characters, and the degree of covalency is larger in electron-deficient π-systems than in electron-rich π-systems. For the same aromatic moiety, the coinage–metal bond is more covalent when the substituent is a halogen, and the degree of covalency increases with the sequence of CH3 < CN < NO2 < Br < Cl < F. Appreciable tuning of the coinage–metal bond would be possible by varying the substituents on the coinage–metal and aromatic ring. The polarization effect plays an important role in the π⋯AuX interactions, and there is significant charge transfer from the occupied π(C–C) orbital to the empty Au orbital or antibonding Au–X orbital in the formation of coinage–metal bonds. [ABSTRACT FROM AUTHOR]

Abstract: Recent studies showed that two single nucleotide polymorphisms (SNPs) (rs12979860 and rs8099917) near the gene IL28B coding for IFNλ3 were associated with the antiviral treatment response of the combination therapy of pegIFN plus RBV. We established the use of tetra-primer amplification refractory mutation system polymerase chain reaction (ARMS-PCR) for detecting IL28B rs8099917 genotype (T>G) in 56 Chinese chronic hepatitis C patients infected with Hepatitis C Virus (HCV) genotype 1. The new assay showed 98.2% specificity, and was confirmed by direct sequencing. Among the 56 samples, TT genotype and TG genotype accounted for 80.4% (45/56) and 19.6% (11/56), respectively. GG genotype was not found. The proportion of responders in TT group was higher than that in TG group (68.9% vs. 27.3%, p =0.029). For HCV clinical decision-making, using the new assay, rs8099917 genotyping could provide similar information to rs12979860 genotyping due to a strong association between the two SNPs in Chinese patients. The assay system in this study can be implemented using basic laboratory equipments, making it convenient for clinical and research purposes. [Copyright &y& Elsevier]

Chalcogen bond catalysis, particularly cationic hypervalent chalcogen bond catalysis, is considered to be an effective strategy for organocatalysis. In this work, the cationic hypervalent chalcogen bond catalysis for the Povarov reaction between N‐benzylideneaniline and ethyl vinyl ether was investigated by density functional theory (DFT). The catalytic reaction involves the cycloaddition process and the proton transfer process, and the rate‐determining step is the cycloaddition process. Cationic hypervalent tellurium derivatives bearing CF3 and F groups exhibit superior catalytic activity. For the rate‐determining step, the Gibbs free energy barrier decreases as the positive electrostatic potential of the chalcogen bond catalysts increases. More importantly, the Gibbs free energy barrier has a strong linear correlation with the electrostatic energy of the chalcogen bond in the catalyst‐substrate complex. Furthermore, the catalytic reactions include the endo pathway and exo pathway. The C−H⋅⋅⋅π interaction between the substituent of the ethyl vinyl ether and the aryl ring of the N‐benzylideneaniline contributes to the endo‐selectivity of the reaction. This research contributes to a deeper understanding of chalcogen bond catalysis, providing insights for designing chalcogen bond catalysts with high performance. [ABSTRACT FROM AUTHOR]