Tetrel-hydride interaction between XH3F (X = C, Si, Ge, Sn) and HM (M = Li, Na, BeH, MgH).

A tetrel-hydride interaction was predicted and characterized in the complexes of XH3F···HM (X = C, Si, Ge, Sn; M = Li, Na, BeH, MgH) at the MP2/aug-cc-pVTZ level, where XH3F and HM are treated as the Lewis acid and base, respectively. This new interaction was analyzed in terms of geometrical parameters, interaction energies, and spectroscopic characteristics of the complexes. The strength of the interaction is essentially related to the nature of X and M groups, with both the larger atomic number of X and the increased reactivity of M giving rise to a stronger tetrel-hydride interaction. The tetrel-hydride interaction exhibits similar substituent effects to that of dihydrogen bonds, where the electron-donating CH3 and Li groups in the metal hydride strengthen the binding interactions. NBO analyses demonstrate that both BD(H-M) → BD*(X-F) and BD(H-M) → BD*(X-H) orbital interactions play the stabilizing role in the formation of the complex XH3F···HM (X = C, Si, Ge, and Sn; M = Li, Na, BeH, and MgH). The major contribution to the total interaction energy is electrostatic energy for all of the complexes, even though the dispersion/polarization parts are nonnegligible for the weak/strong tetrel-hydride interaction, respectively.

Design of highly sensitive phosphorescence sensor for determination of procaterol hydrochloride based on inhibition of KClO3 oxidation fluorescein isothiocyanate.

Procaterol hydrochloride (Prh) can inhibit KClO3 oxidation of fluorescein isothiocyanate (FITC) to form a non-phosphorescent compound, which causes room temperature phosphorescence (RTP) of FITC in the system to enhance sharply the linear relationship between ∆Ip and the Prh content. Thus, a rapid response and highly sensitive phosphorescence sensor for the determination of Prh has been developed based on the inhibiting effect of Prh on KClO3 oxidation of FITC. This simple, high sensitivity (detection limit (LD) calculated by 3Sb /k was 0.019 fg/spot, sample volume 0.40 µl, corresponding concentration 4.8 × 10(-14) g ml(-1) ) and selective sensor with a wide linear range (0.080-11.20 g/spot) has been applied to detect Prh in blood samples, and the results were consistent with those obtained by high-performance liquid chromatography (HPLC). Simultaneously, the mechanism of the phosphorescence sensor for the detection of Prh was also investigated using infrared spectroscopy.

Highly sensitive fluorescent probe for clenbuterol hydrochloride detection based on its catalytic oxidation of eosine Y by NaIO4.

A highly sensitive fluorescent probe for clenbuterol hydrochloride (CLB) detection has been first designed based on its catalytic effect on NaIO4 oxidating eosine Y (R). And this environment-friendly, simple, rapid, selective and sensitive fluorescent probe has been utilized to detect CLB in the practical samples with the results consisting with those obtained by GC/MS. The structures of R and CLB were characterized by infrared spectra. The mechanism of the proposed assay for the detection of CLB was also discussed.

A highly sensitive solid substrate room temperature phosphorimetry for carbaryl detection based on its activating effect on NaIO4 oxidizing fluorescein.

Fluorescein (HFin) could emit strong and stable room temperature phosphorescence (RTP) signal on polyamide membrane (PAM) using Pb(2+) as the ion perturber. Carbaryl could activate effect on NaIO4 oxidating HFin, which caused the RTP signal of the system to quench sharply. The phosphorescence intensity (ΔI p) of activating system higher 3.3 times (119.4/36.0) than that of non-activating system, and is directly proportional to the content of carbaryl. Thus, an activating solid substrate room temperature phosphorimetry (SSRTP) for carbaryl detection has been established. This sensitive (the limit of quantification (LOQ) was 2.0 × 10(-13) g mL(-1)), selective, simple and rapid method has been applied to determine trace carbaryl in water samples with the results consisting with those obtained by fluorimetry, showing its high accuracy. The apparent activation energy (E) and rate constant (k) of this activating reaction were 20.77 kJ mol(-1) and 1.85 × 10(-4) s(-1), respectively. Meanwhile, the mechanism of activating SSRTP for carbaryl detection was also discussed using infrared spectra (IR).

Effects of the cage unit size and number of cage units as well as bridge unit on the second order nonlinear optical response in multicage electride molecules.

Interesting effects of the cage unit size and number of cage units as well as bridge unit on the static first hyperpolarizabilities (ß0) for novel multicage electrides are revealed. (1) The small cage unit C8 systems have larger ß0 for cage unit size effect. (2) The ß0 increases with increasing cage unit number. (3) The effect of the bridge between cage units on ß0 is O > NH > CH2. Specially, a novel relationship between the excess electron cloud and ß0 is revealed. Assembling the three effects, the constructed multicage electride structure with three small C8 cage units connected by the O-bridge (K···3C8(O)) is a electride salt K(+)[e@3C8(O)](-) and has the considerable ß0 value of 7.1 × 10(5) au, which is about 55 times larger than the 13 000 au of the single-cage electride molecule Na3O(+)(e@C20F20)(-). The novel multicage strategy is effective to enhance nonlinear optical (NLO) response.

[Effect of protein on the detection of antipsychotic drug residues in human serum and its elimination].

Using pure human serum albumin (HSA) as the model protein, the effects of protein on the extraction of antipsychotic drugs (APDs: diazepam, chlorpromazine hydrochloride, and perphenazine) in human serum sample were studied. The present paper investigated the interaction between APDs and HSA by fluorescence spectrometry in detail The influences of different ethanol concentration solution on protein denaturation were studied by Rayleigh scattering. The results showed that APDs strongly bound with HSA. In the phi (ethanol) 80% extracting solution, a slow but full protein denaturation takes place, which causes the unfolding of protein and the dissociation of drugs. Then K2 HPO4 was added into the extracting solution to form aqueous two-phase system, and meanwhile the drug residues were extracted into upper phase with high extraction efficiencies. After filtration, the upper phase was ready for analysis of drug residues by HPLC system. The detection limits were in the range of 18.8-38.4 ng x mL(-1), and the spiked recovery was 94.2%-98.7% for determination of antipsychotic drugs in human serum. The method is efficient, solvent-saving, environment-friendly, and accurate.

A promising CdSe@CdS-quantum dots-cysteine for the determination of trace IgE by solid substrate room temperature phosphorescence immunoassay.

The labelling reagent CdSe@CdS-QDs-Cys (QDs-Cys) with the grain diameter of 4.5 nm was synthesized by modifying CdSe@CdS quantum dots (QDs) with cysteine (Cys). At the same time, QDs-Cys-Ab(IgE), a phosphorescent quantum dot probe, was developed based on the labelling reaction between -COOH of QDs-Cys and -NH(2) of goat anti human IgE antibody (Ab(IgE)). This probe with excellent biocompatibility and high specificity could not only emit strong and stable room temperature phosphorescence (RTP), but also could carry out specific immunoassay (IA) with immunoglobulin E (IgE), causing the RTP of the system to sharply enhance. Thus, a new solid substrate room temperature phosphorescence immunoassay (SSRTPIA) for the determination of IgE was established. The limit of quantification (LOQ) of the method was 0.12 fg spot(-1), corresponding concentration was 3.0 × 10(-13) g mL(-1) and sampling quantity was 0.40 µL spot(-1). This highly selective, sensitive and accurate SSRTPIA has been applied to determine IgE in biological samples and diagnose diseases, and the results agreed well with those obtained by enzyme-link immunoassay (ELISA). Meanwhile, the mechanisms of QDs-Cys labelling Ab(IgE) and the determination of IgE by SSRTPIA were also discussed.

Exceptionally large second-order nonlinear optical response in donor-graphene nanoribbon-acceptor systems.

Graphene nanoribbon (GNR) has been used, for the first time, as an excellent conjugated bridge in a donor-conjugated bridge-acceptor (D-B-A) framework to design high-performance second-order nonlinear optical materials. Owing to the unique diradical planar conjugated bridge of GNR, D(NH(2))-GNR-A(NO(2)) exhibits exceptionally large static first hyperpolarizability (ß(0)) up to 2.5×10(6) a.u. (22000×10(-30) esu) for H(2)N-(7,3)ZGNR-NO(2) (ZGNR=zigzag-edged GNR), which is about 15 times larger than the recorded value of ß(0) (1470×10(-30) esu) for the D-A polyene reported by Blanchard-Desce et al. [Chem. Eur. J. 1997, 3, 1091]. Interestingly, we have found that the size effect of GNR plays a key role in increasing ß(0) for the H(2)N-GNR-NO(2) system, in which the width effect of GNR perpendicular to the D-A direction is superior to the length effect along the D-A direction.

Determination of trace deoxyribonucleic acid by using fluorescein isothiocyanate-phenosafranine as a double-luminescent phosphorescence probe.

Using Pb(2+) as ion perturber, phenosafranine (PF) and fluorescein isothiocyanate (FITC) could emit strong and stable room temperature phosphorescence (RTP) signal on the filter paper, respectively. When they were mixed, the phenomenon that the RTP signal of PF and FITC enhanced significantly was found. And 1.12 ag DNA spot(-1) (sample volume was 0.40 µL, corresponding concentration was 2.8 × 10(-15) g mL(-1)) could cause the RTP signal of both PF and FITC to enhance sharply. The content of DNA was proportional to the ΔI(p) of PF and FITC in the system at 634 and 659 nm. Thus, a new solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace DNA was established by using FITC-PF as double-luminescent phosphorescence probe. The detection limit (LD) of this method calculated by 3S(b)/k was 14 zg DNA spot(-1) for PF and 18 zg DNA spot(-1) for FITC, respectively, showing high sensitivity. It has been applied to the determination of trace DNA in practical samples and the analysis results were in accordance with those of fluorescence probe. The reaction mechanism of SSRTP for the determination of trace DNA was also discussed.

Some measures for making halogen bonds stronger than hydrogen bonds in H2CS-HOX (X = F, Cl, and Br) complexes.

The properties and applications of halogen bonds are dependent greatly on their strength. In this paper, we suggested some measures for enhancing the strength of the halogen bond relative to the hydrogen bond in the H(2)CS-HOX (X = F, Cl, and Br) system by means of quantum chemical calculations. It has been shown that with comparison to H(2)CO, the S electron donor in H(2)CS results in a smaller difference in strength for the Cl halogen bond and the corresponding hydrogen bond, and the Br halogen bond is even stronger than the hydrogen bond. The Li atom in LiHCS and methyl group in MeHCS cause an increase in the strength of halogen bonding and hydrogen bonding, but the former makes the halogen bond stronger and the latter makes the hydrogen bond stronger. In solvents, the halogen bond in the Br system is strong enough to compete with the hydrogen bond. The interaction nature and properties in these complexes have been analyzed with the natural bond orbital theory.

Electric field-driven acid-base chemistry: proton transfer from acid (HCl) to base (NH3/H2O).

It is well-known that single H3N-HCl and H2O-HCl acid-base pairs do not react to form the ion pairs, H4N(+)Cl(-) and H3O(+)Cl(-), in isolation. On the basis of ab initio method, we propose a physical method of external electric field (Eext) to drive the proton transfer from acid (HCl) to base (NH3/H2O). Our results show that when Eext along the proton-transfer direction achieves or exceeds the critical electric field (Ec), the proton transfer occurs, such as, the Ec values of proton transfer for H3N-HCl and H2O-HCl are 54 × 10(-4) and 210 × 10(-4) au, respectively. And the degree of the proton transfer can be controlled by modulating the strength of Eext. Furthermore, we estimate the inductive strength of an excess electron (Ee) equivalent to the Eext = 125 × 10(-4) au, which is greater than the Ec (54 × 10(-4) au) of NH3-HCl but less than the Ec (210 × 10(-4) au) of H2O-HCl. This explains well the anion photoelectron spectroscopy [Eustis et al. Science 2008, 319, 936] that an excess electron can trigger the proton transfer for H3N-HCl but not for H2O-HCl. On the basis of the above estimation, we also predict that two excess electrons can induce H2O-HCl to undergo the proton transfer and form the ion pair H3O(+)Cl(-).

Increased blood pressure variability predicts poor outcomes from endovascular treatment for aneurysmal subarachnoid hemorrhage.

BACKGROUND: Predictors of outcomes following endovascular treatment (ET) for aneurysmal subarachnoid hemorrhage (aSAH) are not well-defined. Identifying them would be beneficial in determining which patients might benefit from ET. OBJECTIVE: To identify the predictive factors for poor outcomes following ET for aSAH. METHODS: 120 patients with ruptured cerebral aneurysms underwent endovascular embolization between January 2017 and December 2018. Blood pressure variability was examined using the standard deviation of the 24-hour systolic blood pressure (24hSSD) and 24-hour diastolic blood pressure (24hDSD). Predictors were identified through univariate and multivariate regression analysis. All patients were followed up for three months. RESULTS: At follow-up, 86 patients (71.7%) had good outcomes and 34 (28.3%) had poor outcomes. Patients with poor outcomes had significantly higher 24hSSD than those with good outcomes (19.3 ± 5.5 vs 14.1 ± 4.8 mmHg; P < 0.001). The 24hDSD did not differ significantly between patients with good outcomes and those with poor outcomes (9.5 ± 2.3 vs 9.9 ± 3.5 mmHg; P = 0.464). The following were significant risk factors for poor outcomes after endovascular embolization: age ≥ 65 years (odds ratio [OR] = 23.0; 95% confidence interval [CI]: 3.0-175.9; P = 0.002); Hunt-Hess grade 3-4 (OR = 6.8; 95% CI: 1.1-33.7; P = 0.039); Fisher grade 3-4 (OR = 47.1; 95% CI: 3.8-586.5; P = 0.003); postoperative complications (OR = 6.1; 95% CI: 1.1-34.8; P = 0.042); and 24hSSD ≥ 15 mmHg (OR = 14.9; 95% CI: 4.0-55.2; P < 0.001). CONCLUSION: Elevated 24hSSD is a possibly treatable predictive factor for poor outcomes after ET for aSAH.

Efficacy and safety of massage therapy for autism spectrum disorders: A protocol for systematic review and meta-analysis.

BACKGROUND: Autism spectrum disorder is a neurodevelopmental disorder with increasing incidence. At present, the global incidence of the disease is on the rise, and the cause is unknown. There is no specific treatment for this disease at present, mainly education and training. Traditional Chinese medicine treatment has a certain effect on the improvement of the symptoms of the disease. The treatment methods are mainly oral Chinese medicine and acupuncture, but children are often not easy to cooperate. As a safe and effective green therapy, massage is easy to be accepted by children. METHODS: We will search the following electronic databases for randomized controlled trials to evaluate the effectiveness and safety of massage therapy in treating autism spectrum disorders: Wanfang and PubMed Database, China National Knowledge Infrastructure Database, Cochrane Central Register of Controlled Trials, Cumulative Index of Nursing and Allied Health Literature, and Excerpta Medica database. Each database will be searched from inception to March 2021. The entire process will include study selection, data extraction, risk of bias assessment, and meta-analyses. RESULTS: This proposed study will evaluate the effectiveness and safety of massage therapy for patients with autism spectrum disorders. The outcomes will include changes in autism spectrum disorder relief and adverse effect. CONCLUSION: This proposed systematic review will evaluate the existing evidence on the effectiveness and safety of massage therapy for patients with autism spectrum disorders. DISSEMINATION AND ETHICS: The results of this review will be disseminated through peer-reviewed publication. Because all of the data used in this systematic review and meta-analysis have been published, this review does not require ethical approval. Furthermore, all data will be analyzed anonymously during the review process.

Analysis of Gene Expression Profiles, Cytokines, and Bacterial Loads Relevant to Alcoholic Liver Disease Mice Infected With V. vulnificus.

Patients with liver disease are susceptible to infection with Vibrio vulnificus (V. vulnificus), but the specific reasons remain elusive. Through RNA-seq, we found that when mice with alcoholic liver disease (ALD) were infected with V. vulnificus by gavage, compared with the Pair group, the small intestinal genes affecting intestinal permeability were upregulated; and the number of differentially expressed genes related to immune functions (e.g., such as cell chemotaxis, leukocyte differentiation, and neutrophil degranulation) decreased in the liver, spleen, and blood. Further analysis showed that the number of white blood cells decreased in the Pair group, whereas those in the ALD mice did not change significantly. Interestingly, the blood bacterial load in the ALD mice was about 100 times higher than that of the Pair group. After the ALD mice were infected with V. vulnificus, the concentrations of T cell proliferation-promoting cytokines (IL-2, IL-23) decreased. Therefore, unlike the Pair group, ALD mice had weaker immune responses, lower T cell proliferation-promoting cytokines, and higher bacterial loads post-infection, possibly increasing their susceptibility to V. vulnificus infection. These new findings we presented here may help to advance the current understanding of the reasons why patients with liver disease are susceptible to V. vulnificus infection and provides potential targets for further investigation in the context of treatment options for V. vulnificus sepsis in liver disease patient.

Push-pull electron effects of the complexant in a Li atom doped molecule with electride character: a new strategy to enhance the first hyperpolarizability.

Differing from the reported strategy of push or pull electron effects of the complexant, a new strategy of the combination effects of both push and pull electrons of the complexant to enhance the first hyperpolarizability is performed with two Li atom doped complexants with a pair of difluorophenyl subunit rings. Large variance of the static first hyperpolarizabilities (beta(0)) are exhibited at the MP2/6-311++G(d,p) level. The order of the beta(0) values is 2.9 x10(2) (complexant UD) << 5.9 x 10(3) (LL) < 1.9 x 10(4) (H-L) < 2.3 x 10(4) (H(F)-L) < 3.2 x 10(4) (L-L) < 7.8 x 10(5) a.u. (H(F)-L(F)). It is found that H(F)-L(F) with the edge-type push-pull electronic effect of the complexant has the largest beta(0). The edge-type push-pull electronic effect brings a 2700 times increase in the beta(0) from the UD to H(F)-L(F) structure. It shows that the push-pull electronic effect is a highly effective strategy to enhance the beta(0) value. The beta(0) (7.8 x 10(5) a.u.) of the H(F)-L(F) is considerable, due to the small DeltaE and the very large Delta mu (18.085 a.u.), which comes from the corresponding long-range charge transfer transition. It is interesting that a pair of subunit rings of the complexant may have different electronic effects. In H-L and H(F)-L(F), the left ring with a longer distance between Li and the subunit ring exhibits a push electronic effect, while the right ring with the shorter distance exhibits a pull electronic effect. This work may contribute to the development of potential high-performance nonlinear optical materials.

Thioredoxin reductase 1 upregulates MCP-1 release in human endothelial cells.

To know if thioredoxin reductase 1 (TrxR1) plays a role in antioxidant defense mechanisms against atherosclerosis, effect of TrxR1 on expression/release of monocyte chemoattractant protein (MCP-1) was investigated in activated human endothelial-like EAhy926 cells. The MCP-1 release and expression, cellular generation of reactive oxygen species (ROS), nuclear translocation and DNA-binding activity of NF-kappaB subunit p65 were assayed in cells either overexpressing recombinant TrxR1 or having their endogenous TrxR1 knocked down. It was found that overexpression of TrxR1 enhanced, while knockdown of TrxR1 reduced MCP-1 release and expression. Upregulation of MCP-1 by TrxR1 was associated with increasing generation of intracellular ROS generation, enhanced nuclear translocation and DNA-binding activity of NF-kappaB. Assay using NF-kappaB reporter revealed that TrxR1 upregulated transcriptional activity of NF-kappaB. This study suggests that TrxR1 enhances ROS generation, NF-kappaB activity and subsequent MCP-1 expression in endothelial cells, and may promote rather than prevent vascular endothelium from forming atherosclerotic plaque.

Rare gas atomic number dependence of the hyperpolarizability for rare gas inserted fluorohydrides, HRgF (Rg = He, Ar, and Kr).

The three structures of rare gas inserted fluorohydrides HRgF (Rg = He, Ar, and Kr) with all real frequencies are obtained at the QCISD(T)/aug-cc-pVTZ level. The static first hyperpolarizabilities (beta(0)) at the QCISD/aug-cc-pVQZ level are 8 a.u. (HF), 384 a.u. (HHeF), 737 a.u. (HArF), and 465 a.u. (HKrF). The beta(0) value remarkably increases by about 50-90 times from 8 a.u. (HF) to 384-737 a.u. (HRgF) due to the inserted rare gas (Rg). The Rg atomic number dependence of beta(0) for HRgF (Rg = He, Ar, and Kr) is found at the first time. The order of beta(0) is unmonotonic to be HHeFHKrF, but not monotonic (HHeF

Determination of trace alpha-fetoprotein variant by affinity adsorption solid substrate-room temperature phosphorimetry.

The 3.5-generation dendrimers (3.5G-D)-porphyrin (P) dual luminescent molecule (3.5G-D-P) was used to label concanavalin agglutinin (Con A); the product of the reaction is 3.5G-D-P-Con A. A new method for the determination of trace AFP-V by affinity adsorption solid substrate-room temperature phosphorimetry (AA-SS-RTP) was established, based on the room temperature phosphorescence (RTP) property of the product on polyamide membrane (PAM) substrate and the specific affinity adsorption (AA) reaction between 3.5G-D-P-Con A and alpha-fetoprotein variant (AFP-V), which caused the RTP of the system to be sharply enhanced, the DeltaIp was linearly correlated to the content of AFP-V. The sensitivity of the method was obviously high. It could accurately detect the content of AFP-V in serum. The results were tallied well with those obtained by the ELISA method.

Theoretical Design of Near-Infrared Fluorescent Sensor for F Anion Detection Based on 10-Hydroxybenzo[h]quinoline Backbone.

Proper design and development of near-infrared (NIR) fluorescent sensors is very important for applications in vivo. In this work, we theoretically designed a ratiometric and NIR fluorescent sensor based on the 10-hydroxybenzo[h]quinoline (HBQ) backbone via systematically investigating the substituent effects of electron-donating groups (-NH2, -CH3, -C(CH3)3) and electron-withdrawing groups (-NO2, -CN, -F, -Cl, -CF3) at the proton donor site on the proton transfer process in HBQ in both the S0 and the S1 states. According to the calculated potential energy profiles along the proton transfer as well as the photophysical properties among all the derivatives, we successfully screened out that 7NH2-HBQ is a promising fluorescent sensor exhibiting the near IR emission spectra accompanied by the large Stokes shift. The potential use of 7NH2-HBQ for F- detection among anions (F-, Cl-, and Br-) was further studied, and the results showed that 7NH2-HBQ is very sensitive and selective toward F- based on the intermolecular hydrogen bonding interaction between F- and OH bond, forming a new complex FACS0 . The ratiometric change in the fluorescence intensity could be induced by the H-F bond transfer from the O atom to the N atom in the S1 state.

Nonlinear optical properties of aluminum nitride nanotubes doped by excess electron: a first principle study.

Aluminum nitride nanotubes (AlNNTs) doped by the excess electron, e@AlNNT and M@N-AlNNT (M = Li, Na, K), have been designed and their geometrical, electronic, and nonlinear optical (NLO) properties have been explored theoretically. The results showed that the excess electron narrows the energy gap between HOMO and LUMO values (EH-L) of the doped systems in the range of 3.42-5.37 eV, which is due to a new energy level HOMO formed for the doped excess electron, with higher energy than the original HOMO of AlNNT. Importantly, the doped excess electron considerably increases the first hyperpolarizability (ß0) from 130 a.u. of the undoped AlNNT to 646 a.u. for e@AlNNT, 2606 a.u. for Li@N-AlNNT, while 1.14 × 105 a.u. for Na@N-AlNNT, and 1.37 × 106 a.u. for K@N-AlNNT. The enormous ß0 values for Na@N-AlNNT and K@N-AlNNT are attributed to the low transition energy. These results demonstrate that AlNNTs are a promising material in high-performance NLO nanomaterials for electronic devices.