Continuous and Rapid Synthesis of UiO-67 by Electrochemical Methods for the Electrochemical Detection of Hydroquinone.

Continuous and rapid synthesis of UiO-67 under mild conditions has been achieved by electrochemical methods for the first time. In the reaction system, a zirconium sheet was utilized as electrodes and a metal source for the assembly of UiO-67. High-crystalline UiO-67 with a regular tetrahedral morphology of around 1 µm was obtained within 1.5 h under the optimized solvent composition, voltage, and temperature conditions. This electrochemical synthetic method of UiO-67 in our work overcomes the shortcomings of high temperature and pressure of a traditional solvothermal method, which proposes new ideas for the large-scale and rapid synthesis of UiO-67. The UiO-67 synthesized by an electrochemical method was prepared as a UiO-67-carbon paste electrode (CPE), which exhibited a linear response to hydroquinone (HQ) in the range of 5-300 µM with a detection limit of 3.6 × 10-9 M (S/N = 3), for the electrochemical detection of HQ. It was confirmed that UiO-67-CPE possessed excellent reusability and antiinterference ability for the detection of HQ, and its detection ability even did not change after standing for 3 months. We further tried to apply UiO-67-CPE to the practical determination of HQ in tap water and river water samples, and the results proved that the recovery rate is 97.9-104.7% in real samples.

Rapid and Low-Cost Electrochemical Synthesis of UiO-66-NH2 with Enhanced Fluorescence Detection Performance.

Rapid and low-cost synthesis of metal-organic frameworks (MOFs) are very meaningful for their future practical application. In the present study, a Zr-based ultrastable MOF, UiO-66-NH2, was successfully synthesized by electrochemical method using metal Zr as the metal source at room temperature and atmospheric pressure. The effects of the reaction conditions, including the ratio of solvent (electrolyte), the applied voltage and different reaction time, on the crystallinity, morphology, and synthesis rate of the product were fully investigated. The results confirm that electrochemically synthesized UiO-66-NH2 under the optimized condition possesses apparent merits such as high crystallinity, uniform morphology and high porosity. Moreover, the electrochemical synthesis method of UiO-66-NH2 is promising for the large-scale and economical synthesis of nanoscale product to gramme degree. Interestingly, the resulting UiO-66-NH2 synthesized by this electrochemical method exhibits more excellent performance for the fluorescence detection of Fe3+ ions in water (detection limit of 10-8 mol/L) than that of the material prepared by solvothermal method.

Folic Acid Functionalized Zirconium-Based Metal-Organic Frameworks as Drug Carriers for Active Tumor-Targeted Drug Delivery.

Nanoscale metal-organic frameworks (NMOFs) have proven to be a class of promising drug carriers as a result of their high porosity, crystalline nature with definite structure information, and potential for further functionality. However, MOF-based drug carriers with active tumor-targeting function have not been extensively researched until now. Here we show a strategy for constructing active tumor-targeted NMOF drug carriers by anchoring functional folic acid (FA) molecules onto the metal clusters of NMOFs. Two zirconium-based MOFs, MOF-808 and NH2 -UiO-66, were chosen as models to reduce to the nanoscale for application as drug carriers, and then the terminal carboxylates of FA molecules were coordinated to Zr6 clusters on the surfaces of the nanoparticles by substitution of the original formate or terminal -OH ligands. The successful modification with FA was confirmed by solid-state 13 C MAS NMR and UV/Vis spectroscopy and other characterization methods. Drug loading and controlled release behavior at different pH were determined by utilizing the anticancer drug 5-fluorouracil (5-FU) as the model drug. Confocal laser scanning microscopy measurements further demonstrated that 5-FU-loaded FA-NMOFs have excellent targeting ability through the efficient cellular uptake of FA-NMOFs. This work opens up a new avenue to the construction of active tumor-targeted NMOF-based drug carriers with potential for cancer therapies.

Rapid and Large-Scale Synthesis of IRMOF-3 by Electrochemistry Method with Enhanced Fluorescence Detection Performance for TNP.

Rapid and large-scale synthesis of metal-organic frameworks (MOFs) materials is of great significance for their practical applications. For the first time, we have electrochemically synthesized IRMOF-3 at room temperature by applying a voltage to a zinc electrode immersed in electrolyte containing 2-aminoterephthalic acid (NH2-H2BDC). The reaction conditions, including the ratio of solvent (electrolyte), the applied voltage, and different reaction times, were investigated and optimized. The degree of crystallinity and nanomorphology of the synthesized IRMOF-3 can be controlled by changing the reaction conditions. More importantly, we demonstrated that the electrochemical synthesis strategy can rapidly obtain nanoscale IRMOF-3 with high crystallinity on a gram scale. In addition, in comparison with the product of solvothermal synthesis, the electrochemically synthesized nanoscale IRMOF-3 exhibits improved fluorescent detection ability to 2,4,6-trinitrophenol (TNP) with a detection limit of about 0.1 ppm.

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors.

Crystalline and porous covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H2 evolution due to their long-range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two-dimensional (2D) COF with stable MOF. By covalently anchoring NH2 -UiO-66 onto the surface of TpPa-1-COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H2 evolution under visible light irradiation. Especially, NH2 -UiO-66/TpPa-1-COF (4:6) exhibits the maximum photocatalytic H2 evolution rate of 23.41 mmol g-1 h-1 (with the TOF of 402.36 h-1 ), which is approximately 20 times higher than that of the parent TpPa-1-COF and the best performance photocatalyst for H2 evolution among various MOF- and COF-based photocatalysts.

Synthesis and luminescence properties of two novel lanthanide (III) complexes of acetophenonylcarboxymethyl sulphoxide.

A novel ligand containing multiple coordinating groups (sulfinyl, carboxyl and carbonyl groups), acetophenonylcarboxymethyl sulphoxide, was synthesized. Its corresponding two lanthanide (III) binary complexes were synthesized and characterized by element analysis, molar conductivity, FT-IR, TG-DTA and UV spectroscopy. Results showed that the composition of these complexes was REL3 L(-) (ClO4)2 · 3H2O (RE = Eu (III), Tb (III); L = C6 H5 COCH2 SOCH2 COOH; L(-) = C6H5 COCH2 SOCH2 COO(-)). FT-IR results indicated that acetophenonylcarboxymethyl sulphoxide was bonded with an RE (III) ion by an oxygen atom of the sulfinyl and carboxyl groups and not by an oxygen atom of the carbonyl group due to high steric hinderance. Fluorescent spectra showed that the Tb (III) complex had excellent luminescence as a result of a transfer of energy from the ligand to the excitation state energy level ((5)D4) of Tb (III). The Eu (III) complex displayed weak luminescence, attributed to low energy transfer efficiency between the triplet state energy level of its ligand and the excited state ((5)D0 ) of Eu (III). As a result, the Tb (III) complex displayed a good antenna effect for luminescence. The fluorescence decay curves of Eu (III) and Tb (III) complexes were also measured.

Identification of a novel survival predictor, CSF2RB, for female lung cancer in never smokers (LCNS) by a bioinformatics analysis.

Lung cancer in never smokers (LCNS) has been considered as a separate disease and the 7th cause of cancer-related death worldwide. However, limited research has focused on "female" cohorts, which have presented a higher incidence rate. In this study, the microarray data of lung cancer tissues derived from 54 female lung cancer patients, consisting of 43 nonsmokers and 11 smokers, were selected from GSE2109 dataset. A total of 249 differentially expressed genes (DEGs) including 102 up- and 147 down-regulated genes were identified and further analyzed for gene ontology (GO) terms and Kyoto encyclopedia of genes and genomes (KEGG) pathway enrichment. By constructing protein-protein interaction (PPI) network and calculating key modules, 10 hub genes were screened out. The module analysis of the PPI network presented that the progression of female LCNS was significantly associated with immune response as chemokine activity and lipopolysaccharide response, and these biological processes (BP) might be mediated by chemokine signaling pathway and cytokine-cytokine receptor interaction. Then, survival analysis by Kaplan-Meier (K-M) Plotter online platform presented down-regulated gene colony stimulating factor 2 receptor beta common subunit (CSF2RB) of female LCNS might be involved in poor clinical outcome. Female LCNS with high expression of CSF2RB might be relevant with relative risk reduction of mortality, longer median survival time and higher 5-year survival rate, while female LCNS with low expression of CSF2RB might be implicated in a poor clinical outcome. In short, our results support CSF2RB to be a candidate survival predictor for female LCNS.

Parental Mediation Moderates the Association Between Social Media Exposure and Tobacco and Alcohol Use: Differences Between Elementary and Middle School Students.

OBJECTIVE: With the popularity of social media among adolescents, the relation between social media exposure (especially exposure to undesirable content) and adolescent tobacco and alcohol use has attracted much attention. This study examined the association between social media exposure and tobacco and alcohol use, as well as the moderating role of parental active mediation and restrictive mediation; differences between elementary and middle school students were also investigated. METHOD: A total of 697 elementary school students ages 9-13 and 794 middle school students ages 12-18 were recruited to complete a questionnaire survey. RESULTS: Social media exposure was positively associated with tobacco and alcohol use among both elementary and middle school students. For elementary school students, both active mediation and restrictive mediation moderated the association between social media exposure and tobacco and alcohol use; for middle school students, neither of these moderating effects was significant. CONCLUSIONS: Findings suggest that social media exposure is a risk factor for both elementary and middle school students. Both parental active and restrictive mediation are promising targets for intervention because they can mitigate the risk of social media exposure for elementary school students. However, further research should focus on factors that effectively buffer the negative effects of social media exposure on tobacco and alcohol use among middle school students.

Fluorescence emission mechanism and fluorescence properties of ternary Tb(III) complex with diphenyl sulphoxide and bipyridine.

A novel ternary complex, TbL(5) L'(ClO(4))(3) · 3H(2)O, two binary complexes, TbL(7) (ClO(4))(3) · 3H(2)O and TbL'(3.5) (ClO(4))(3) · 4H(2)O has been synthesized (using diphenyl sulphoxide as the first ligand L, bipyridine as the second ligand L'). Their composition was analysed by element analysis, coordination titration, IR spectra and (1) H-NMR, and the fluorescence emission mechanism, fluorescence intensities and phosphorescence spectra were also investigated by comparison. It was shown that the ternary rare-earth complex showed stronger fluorescence intensities than the binary rare-earth complexes in such material. The strongest characteristic fluorescence emission intensity of the ternary system was 8.23 times, 3.58 times as strong as that of the binary systems TbL(7) (ClO(4))(3) · 3H(2)O and TbL'(3.5) (ClO(4))(3) · 4H(2)O, respectively. By fluorescence analysis it was found that both diphenyl sulphoxide and bipyridine could sensitize the fluorescence intensities of rare-earth ions. In particular, in the ternary rare-earth complex, introduction of bipyridine was of benefit to the fluorescence properties of Tb(III).

Social Media Exposure, Psychological Distress, Emotion Regulation, and Depression During the COVID-19 Outbreak in Community Samples in China.

The outbreak of coronavirus disease 2019 (COVID-19) has been a global emergency, affecting millions of individuals both physically and psychologically. The present research investigated the associations between social media exposure and depression during the COVID-19 outbreak by examining the mediating role of psychological distress and the moderating role of emotion regulation among members of the general public in China. Participants (N = 485) completed a set of questionnaires online, including demographic information, self-rated physical health, and social media exposure to topics related to COVID-19. The Impact of Event Scale-Revised (IES-R), the Beck Depression Inventory-II (BDI-II), and the Emotion Regulation Questionnaire (ERQ) were utilized to measure psychological distress about COVID-19, depression, and emotion regulation strategies, respectively. Results found that older age and greater levels of social media exposure were associated with more psychological distress about the virus (r = 0.14, p = 0.003; r = 0.22, p < 0.001). Results of the moderated mediation model suggest that psychological distress mediated the relationship between social media exposure and depression (ß = 0.10; Boot 95% CI = 0.07, 0.15). Furthermore, expressive suppression moderated the relationship between psychological distress and depression (ß = 0.10, p = 0.017). The findings are discussed in terms of the need for mental health assistance for individuals at high risk of depression, including the elderly and individuals who reported greater psychological distress and those who showed preference usage of suppression, during the COVID-19 crisis.

Mobile phone addiction and psychological distress among Chinese adolescents: The mediating role of rumination and moderating role of the capacity to be alone.

BACKGROUND: With the increasing incidence of mobile phone addiction, mobile phone addiction has been considered to be related to adolescents' psychological distress. However, the underlying mechanisms of this relation were still unclear. The present study tested the mediating role of rumination and the moderating role of the capacity to be alone in the relation between mobile phone addiction and psychological distress. METHODS: 754 middle school students were recruited to complete measures of mobile phone addiction, rumination, the capacity to be alone, psychological distress and demographic variables. RESULTS: Mobile phone addiction was significantly and positively associated with psychological distress, and this link could be mediated by rumination. Moreover, the direct effect of mobile phone addiction on psychological distress and the indirect effect of rumination in this link were moderated by the capacity to be alone. Both these two effects were stronger for adolescents with lower capacity to be alone. LIMITATIONS: The present study is limited in terms of its sample selection, cross-sectional design, and self-reported instruments. CONCLUSIONS: The present study advances our understanding of how and when or for whom mobile phone addiction is related to serious psychological distress. Education professionals and parents should pay special attention to the psychological distress of adolescents suffering from mobile phone addiction, particularly for those with lower capacity to be alone.

In situ C-C coupling and formation of a heptanuclear copper(II) cluster.

The reaction of CuCl(2) with H(2)Meppz and a base under low temperature gave rise to a heptanuclear copper compound, in which a novel ligand 2,2'-bis(H(2)Meppz) (H(4)L') was obtained through in situ C-C coupling.

The studies of enhanced fluorescence in the two novel ternary rare-earth complex systems.

Two novel ternary rare-earth complexes SmL(5).L'.(ClO(4))(2).7H(2)O and EuL(5).L'.(ClO(4))(2).6H(2)O (the first ligand L = C(6)H(5)COCH(2)SOCH(2)COC(6)H(5), the second ligand L' = C(6)H(4)OHCOO(-)) were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, (1)HNMR and UV spectra. The detailed luminescence studies on the rare-earth complexes showed that the ternary rare-earth complexes presented stronger fluorescence intensities, longer lifetimes, and higher fluorescence quantum efficiencies than the binary rare-earth materials. After the introduction of the second ligand salicylic acid group, the relative emission intensities and fluorescence lifetimes of the ternary complexes LnL(5).L'.(ClO(4))(2).nH(2)O (Ln = Sm, Eu; n=7, 6) enhanced more obviously than the binary complexes LnL(5).(ClO(4))(3).2H(2)O. This indicated that the presence of both organic ligand bis(benzoylmethyl) sulfoxide and the second ligand salicylic acid could sensitize fluorescence intensities of rare-earth ions, and the introduction of salicylic acid group was a benefit for the fluorescence properties of the ternary rare-earth complexes. The fluorescence spectra, fluorescence lifetime and phosphorescence spectra were also discussed.

Synthesis and luminescence properties of two novel lanthanide (III) perchlorate complexes with bis(benzoylmethyl) sulfoxide and benzoic acid.

Two novel ternary rare earth complexes of Tb(III) and Dy(III) perchlorates with bis(benzoylmethyl) sulfoxide (L) and benzoic acid (L') had been synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC, (1)HNMR and UV spectra. The results indicated that the composition of these complexes was REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III); L = C(6)H(5)COCH(2)SOCH(2)COC(6)H(5), L' = C(6)H(5)COO; n = 6,8). The fluorescence spectra illustrated that the ternary rare earth complexes presented stronger fluorescence intensities, longer lifetimes and higher fluorescence quantum efficiencies than the binary rare earth complexes REL(5) x (ClO(4))(3) x 2 H(2)O. After the introduction of the second ligand benzoic acid group, the relative fluorescence emission intensities and fluorescence lifetimes of the ternary complexes REL(5)L'(ClO(4))(2) x nH(2)O (RE = Tb(III), Dy(III)) enhanced more obviously than the binary complexes. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand benzoic acid could sensitize fluorescence intensities of rare earth ions, and the introduction of benzoic acid group was resulted in the enhancement of the fluorescence properties of the ternary rare earth complexes. The phosphorescence spectra were also discussed.

Synthesis and fluorescence properties of lanthanide (III) perchlorate complexes with naphthyl-naphthalinesulphonylpropyl sulfoxide.

A ligand with double sulfinyl groups, naphthyl-naphthalinesulphonylpropyl sulfoxide(dinaphthyl disulfoxide, L), was synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DTA, (1)HNMR and UV spectra. The composition of these complexes, were RE(2)(ClO(4))(6).(L)(5).nH(2)O (RE = La, Nd, Eu, Tb, Yb, n = 2 approximately 6, L = C(10)H(7)SOC(3)H(6)SOC(10)H(7)). The fluorescent spectra illustrated that the Eu (III) complex had an excellent luminescence. It was supposed that the ligand was benefited for transferring the energy from ligand to the excitation state energy level ((5)D(0)) of Eu (III). The Tb (III) complex displayed weak luminescence, which attributed to low energy transferring efficiency between the average triplet state energy level of ligand and the excited state ((5)D(4)) of Tb (III). So the Eu (III) complex displayed a good antenna effect for luminescence. The phosphorescence spectra and the relationship between fluorescence lifetime and fluorescence intensity were also discussed.

Development of MOF-based heterostructures for photocatalytic hydrogen evolution.

The construction of metal-organic framework (MOF) based heterostructures are a promising strategy to improve the photocatalytic hydrogen evolution activities of MOFs. For the intrinsic porosity, inorganic-organic hybrid nature and structural tunability of MOFs, a wide variety of MOF-based heterostructured photocatalysts with improved hydrogen evolution activities have been fabricated. In this frontier article, we present the latest advances in MOF-based heterostructures for photocatalytic hydrogen evolution. The opportunities and challenges related to MOF-based heterostructured photocatalysts are also presented.

2-(4-Chloro-phen-yl)-3-p-tolyl-1,3-thia-zolidin-4-one.

The title compound, C(16)H(14)ClNOS, a potent anti-bacterial chemical, features a dihedral angle of 49.4 (1)° between the 4-tolyl and thia-zolidinone rings, and a dihedral angle of 87.2 (5)° between the thia-zolidinone and 4-chloro-phenyl rings.

Diminished Anticipatory and Consummatory Pleasure in Dysphoria: Evidence From an Experience Sampling Study.

Anhedonia, the experience of diminished pleasure, is a core feature of major depressive disorder and is often present long before the diagnosis of depression. Most previous studies have investigated anhedonia with self-report measures of trait anhedonia or with behavioral paradigms using laboratory stimuli, and the real-time characteristics of hedonic processing in subclinical depression remain under-investigated. We used the experience sampling method to evaluate momentary experience of hedonic feelings in the context of daily life. Dysphoric (n = 49) and non-dysphoric (n = 51) college students completed assessments of their current positive affect (PA), as well as state anticipatory and consummatory pleasure, 3 or 4 times a day every day for 2 weeks. The results showed that dysphoric individuals reported less state anticipatory and consummatory pleasure compared with non-dysphoric individuals. Moreover, significant time-lagged associations between anticipatory pleasure and follow-up consummatory pleasure were found in the whole sample, after adjustment for current PA. The current findings thus hold considerable promise in advancing our understanding of anhedonia as well as the important role of state anticipatory pleasure in relation to depression.

Postoperative pituitary hormonal disturbances and hormone replacement therapy time and dosage in children with craniopharyngiomas.

BACKGROUND: The proliferative activity and penetration into the hypothalamic structures in children craniopharyngiomas (CP) often make radical resection difficult. Therefore, complete resection of CP often results in permanent multiple pituitary hormone deficiency (MPHD). This study aimed to elucidate the postoperative pituitary hormonal disturbances, and hormone replacement therapy (HRT) time and dosage in children with CP. METHODS: Twenty patients with growth retardation and CP after resection, comprising 14 boys and 6 girls, with a mean age of (10.63 +/- 3.18) years (Group A) and 10 male patients of group A aged > 10 years (Group B) were entolled. Thirty age-, sex- and Tanner stage-matched normal children (control Group A), and 44 male older children > 10 years (control Group B) served as controls. The serum concentrations of insulin-like growth factor-1 (IGF-1), growth hormone (GH), free thyroxine (FT4), thyroid-stimulating hormone (TSH), adrenocorticortropic hormone (ACTH), cortisol (COR), follicle stimulating hormone (FSH), luteinizing hormone (LH), prolactin (PRL), testosterone (T) and estradiol (E2) were measured in the CP patients after resection and in controls. The appropriate time and dosage of HRT were investigated. Linear correlation analysis was made between levothyroxine (L-T4) dosage and primary FT4 in CP patients after resection. RESULTS: All cases had MPHD. The serum peak GH, IGF-1, FT4 and COR levels of Group A were significantly lower than that of the control Group A. The serum IGF-1 concentration increased to the normal level after 3 months of rhGH therapy; the serum FSH, LH, and T levels were significantly decreased (P < 0.001); however, E2 and PRL were significantly increased (P < 0.001) in Group B compared with the control Group B; 18 cases were found to have central diabetes insipidus (DI) by water deprivation test and MRI. There was a significant negative linear regression (r = -0.8, P < 0.001) between L-T4 and primary FT4 in Group A patients with CP after resection, giving a regression equation of L-T4 dosage (microg.kg(-1).d(-1)) = 3.5-0.2 x FT4 (microg.kg(-1).d(-1)). The time and corresponding dosage of HRT for CP after resection were: rhGH started 1 year after resection and no recurrence of CP on MRI, when IGF-1 reached the normal range, the rhGH dosage was (0.13 +/- 0.04) U.kg(-1).d(-1); hydrocortisone (H-C) was started as soon as possible, and was kept in the lower normal range, at a dosage of (12.6 +/- 4.8) mg/m2; levothyroxine started after H-C or at the same time to maintain FT4 in the higher normal range, at a dosage of (1.65 +/- 0.70) microg.kg(-1).d(-1); Minirin (DDAVP) was started as soon as possible, elicited no symptoms, and maintained normal electrolyte levels; the dosage was (0.16 +/- 0.04) mg/m2. CONCLUSION: Patients with CP after resection often displayed MPHD, and needed total HRT at appropriate time and dosage to improve the quality of life and normal growth.

[Levels of interleukin-1beta and tumor necrosis factor-alpha in patients with aggressive periodontitis].

OBJECTIVE: To compare the levels of plasma IL-1beta,TNFalpha in aggressive periodontitis (AgP) patients and periodontally healthy subjects. METHODS: Venous blood samples were collected from 56 AgP patients and 39 periodontally healthy controls. Clinical examination consisted of bleeding index (BI), probing depth(PD)attachment loss measurements (AL) and percentage of severe sites. Plasma levels of IL-1beta and TNF-alpha were determined using a high-sensitivity ELISA assay. RESULTS: The concentrations of IL-1beta in AgP patients were significantly higher than those in healthy controls (7.23 ng/L vs 3.52 ng/L, P=0.003), which were positively correlated with BI, PD, AL and the percentage of severe sites (r=0.170, P=0.038; r=0.175, P=0.033; r=0.168, P=0.040; r=0.236, P=0.004). The difference between the levels of TNF-alpha in AgP patients and healthy controls was not observed (1.07 ng/L vs 1.06 ng/L, P=0.437). No correlations between the plasma level of TNF-alpha and the periodontal parameters were detected (r=0.023, P=0.808; r=0.025, P=0.782; r=0.075, P=0.407; r=0.049, P=0.586). CONCLUSION: AgP may have impact on the elevation of plasma level of IL-1beta, while no association between AgP and plasma level of TNF-alpha was found.