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Phosphoroselenoates are important organic molecules because they have found widespread applications in many fields. Herein, an efficient electrochemical dehydrogenative approach to prepare phosphoroselenoates from (hetero)arenes and phosphonates using elemental selenium as the selenium source is reported. This approach is compatible with various functional groups and can be easily scaled up. Our control experiments revealed that electricity plays an important role in this transformation.

Herein, we report an efficient electrochemical activation of the C-C bond of aryl ketones for the preparation of amides under catalyst- and external-oxidant-free conditions using aliphatic amines as the N source. Under environmentally benign electrolysis conditions, a series of amides were synthesized in good yield. Our control experiments revealed that electricity plays an important role in this transformation.

Purpose The upregulation of spinal NMDA receptor is a crucial mechanism in remifentanil -induced hyperalgesia (RIH). Wnt3a/β-catenin pathway plays an important role in neuropathic pain. We hypothesized that wnt3a inhibitor (iwp-2) could downregulate the expression of NR2B subunit in NMDA receptor, in order to relieve RIH. Materials and Methods The study has 2 phases. The phase 1 study is designed by different doses of iwp-2 groups to create an appropriate iwp-2 dose used in RIH alleviation. The phase 2 study is designed to prove that the wnt3a inhibitor could downregulate the activation of the NR2B to inhibit RIH in rats. Thermal hyperalgesia (PWTL) and mechanical allodynia (PWMT) were evaluated after RIH. The area under the PWTL and PWMT curves (AUC) were calculated. The amount of activated NR2B subunit, c-fos, NF-κB, β-catenin, wnt3a and p-GSK-3β (Ser9) were detected in the lumbar spinal cord. Results Remifentanil infusion could induce overexpression of β-catenin and wnt3a in rats. Iwp-2 (60μM, 120μM, 180μM) could dose-dependently inhibit thermal hyperalgesia and mechanical allodynia in rats. In phase 2 study, both NR2B subunit antagonist Ro25-6981 and iwp-2 decreased the amount of activated NR2B, enhanced p-GSK-3β (Ser9), reduced β-catenin, c-fos and NF-κB in the lumbar spinal cord (p < 0.001). In comparison with the group iwp-2, the group of Ro25-6981 had more benefit in reversing hyperalgesia, including higher AUC value of PWTL (p = 0.022) and PWMT (p = 0.035). Conclusion Remifentanil exposure could induce overexpression of wnt3a and enhance the production of β-catenin in the spinal dorsal horn. Inhibition of wnt3a response was capable of attenuating RIH in alleviating hyperalgesia -related behavioral parameters, as well as reducing overexpression of c-fos, NF-κB, NR2B in spinal dorsal horn.

An electrochemical dehydrogenative [2 + 2 + 1] annulation used for the synthesis of imidazoles has been developed under undivided electrolytic conditions. In an undivided cell, aryl ketones and amines can smoothly participate in this transformation to furnish a variety of substituted imidazoles. The reaction avoids the use of both transition-metal catalysts and peroxide reagents, which makes it more sustainable and renewable.

This retrospective study analyzed the clinical characteristics of autoimmune encephalitis (AE) patients to explore the predictors of poor prognosis. According to the modified Rankin scale score at the last follow-up, the functional prognosis of the patients was reflected. And the prognosis of the patients was comprehensively evaluated by the functional prognosis and the relapse of the patients. The results showed that disturbance of consciousness and delayed first-line immunotherapy were independent risk factors for the poor functional prognosis of AE. In addition, patients with psychiatric symptoms, should be alert for relapse.

CO2/photoredox-cocatalyzed tandem oxidative cyclization of α-bromo ketones and amines for the preparation of substituted oxazoles has been achieved. The avoidance of using both transition-metal catalysts and peroxides makes this method more sustainable and renewable.

Urban and transportation development largely depends on innovative information technologies for decision making support in its planning and management processes to achieve beneficial economic, social and environmental outcomes. Among these technologies, techniques and tools for collaborative visualization, manipulation, and exploration of spatial information are particularly useful. Existing Geographic Information Systems (GISs), however, lack of the capability to support collaborative spatial decision making (CSDM). This thesis presents a research effort in the development of GIS software tools that support synchronized collaborations between multiple participants via the Internet, to explore urban and transportation development scenarios for collective decision making. While the design and development focused on integrating decision making tools with commercial GIS development Toolkits (e.g., Map Objects Java Edition) using collaborative Java APIs, the approach and insights gained should be of general interest. The initial usefulness testing indicates that an Internet-based synchronous GIS can help improve decision making processes of urban corridor planning and ease participation in such decision making activities.

Purpose The upregulation of spinal NMDA receptor is a crucial mechanism in remifentanil -induced hyperalgesia (RIH). Wnt3a/β-catenin pathway plays an important role in neuropathic pain. We hypothesized that wnt3a inhibitor (iwp-2) could downregulate the expression of NR2B subunit in NMDA receptor, in order to relieve RIH. Materials and Methods The study has 2 phases. The phase 1 study is designed by different doses of iwp-2 groups to create an appropriate iwp-2 dose used in RIH alleviation. The phase 2 study is designed to prove that the wnt3a inhibitor could downregulate the activation of the NR2B to inhibit RIH in rats. Thermal hyperalgesia (PWTL) and mechanical allodynia (PWMT) were evaluated after RIH. The area under the PWTL and PWMT curves (AUC) were calculated. The amount of activated NR2B subunit, c-fos, NF-κB, β-catenin, wnt3a and p-GSK-3β (Ser9) were detected in the lumbar spinal cord. Results Remifentanil infusion could induce overexpression of β-catenin and wnt3a in rats. Iwp-2 (60μM, 120μM, 180μM) could dose-dependently inhibit thermal hyperalgesia and mechanical allodynia in rats. In phase 2 study, both NR2B subunit antagonist Ro25-6981 and iwp-2 decreased the amount of activated NR2B, enhanced p-GSK-3β (Ser9), reduced β-catenin, c-fos and NF-κB in the lumbar spinal cord (p < 0.001). In comparison with the group iwp-2, the group of Ro25-6981 had more benefit in reversing hyperalgesia, including higher AUC value of PWTL (p = 0.022) and PWMT (p = 0.035). Conclusion Remifentanil exposure could induce overexpression of wnt3a and enhance the production of β-catenin in the spinal dorsal horn. Inhibition of wnt3a response was capable of attenuating RIH in alleviating hyperalgesia -related behavioral parameters, as well as reducing overexpression of c-fos, NF-κB, NR2B in spinal dorsal horn.

Absolute adsorption has been found being more accurate than directly measured excess adsorption value for estimating the in-situ shale gas-in-place storage. To obtain accurate absolute adsorption, traditional methods determined the adsorbed gas density using complicated molecular simulation methods, which is employed to correct the measured excess value. In this work, excess adsorption, which is deemed to be inaccurate in previous work, of CH4 and C3H8 is first measured on three typical shale rocks. The adsorbed-layer density is then reasonably calculated using the simplified local density theory (SLD) to obtain corresponding absolute adsorption of CH4 and C3H8. It is found that the adsorbed layer density calculated from SLD theory is comparable to that obtained from molecular simulation methods, while it is more efficient for the density computation. Compared to CH4, C3H8 presents stronger adsorption capacity on shale rocks, suggesting that C3H8 is more affinity to organic shale. The CH4′s absolute adsorption is stronger than its excess value and their deviation enlarges as pressure increases, while absolute adsorption for C3H8 is found to be more or less the same with the measured excess value. The importance of this work lies in that we propose a new method for efficiently obtaining the adsorbed-layer density, which is crucial for accurately determining gas and oil storage in shale reservoirs.

Nuclear factor kappa B (NF-κB), a key nuclear transcription factor, is associated with prognosis in a variety of human cancers. However, the clinical value of NF-κB in non-small cell lung cancer (NSCLC) is still controversial. Therefore, the aim of this meta-analysis was to obtain an accurate evaluation of the relationship between NF-κB expression and survival prognosis of NSCLC patients based on published articles. PubMed, EMBASE and Web of Science databases were systematically searched for potential articles. A total of 1159 patients from 7 eligible studies comparing prognostic significance of NF-κB expression levels in NSCLC were included in our meta-analysis. I2 statistic and P value were performed to evaluate heterogeneity using Review Manager version 5.3. The results of analysis were presented as hazard ratio (HR) or odds ratios with 95% confidence interval (95% CI). Subgroup analysis based on ethnicity of NSCLC patients was conducted to illustrate the potential discrepancy. Significant heterogeneity was considered at I2 > 50% and P < 0.05, and random-effects model was used. The combined results indicated that higher NF-κB expression was associated with shorter overall survival of NSCLC patients (HR = 2.78, 95% CI = 1.51–5.12, P = 0.001). Moreover, NF-κB expression was closely associated with tumor stage (HR = 0.32, 95% CI = 0.18–0.57, P < 0.0001) and lymph node metastasis (HR = 0.56, 95% CI = 0.38–0.83, P = 0.004). We conclude that NF-κB expression may be a potential unfavorable prognostic marker for NSCLC patients.

BACKGROUND. Data are limited on the impact of neuraminidase inhibitor (NAI) treatment on avian influenza A(H7N9) virus RNA shedding. METHODS. In this multicenter, retrospective study, data were collected from adults hospitalized with A(H7N9) infection during 2013–2017 in China. We compared clinical features and A(H7N9) shedding among patients with different NAI doses and combination therapies and evaluated factors associated with A(H7N9) shedding, using Cox proportional hazards regression. RESULTS. Among 478 patients, the median age was 56 years, 71% were male, and 37% died. The median time from illness onset to NAI treatment initiation was 8 days (interquartile range [IQR], 6–10 days), and the median duration of A(H7N9) RNA detection from onset was 15.5 days (IQR, 12–20 days). A(H7N9) RNA shedding was shorter in survivors than in patients who died (P < .001). Corticosteroid administration (hazard ratio [HR], 0.62 [95% confidence interval {CI}, .50-.77]) and delayed NAI treatment (HR, 0.90 [95% CI, .91-.96]) were independent risk factors for prolonged A(H7N9) shedding. There was no significant difference in A(H7N9) shedding duration between NAI combination treatment and monotherapy (P = .65) or between standard-dose and double-dose oseltamivir treatment (P = .70). CONCLUSIONS. Corticosteroid therapy and delayed NAI treatment were associated with prolonged A(H7N9) RNA shedding. NAI combination therapy and double-dose oseltamivir treatment were not associated with a reduced A(H7N9) shedding duration as compared to standard-dose oseltamivir.

Synthesis of aziridines by electrochemical oxidative annulation of chalcone 1,3-diphenyl-2-propen-1-one with primary amines has been developed under external oxidant - and base-free conditions. The reaction constitutes a new transformation of chalcones with primary amines to aziridines, providing a complementary, simple, and environmentally friendly approach to the currently available methods. A reaction mechanism for this transformation has been proposed based on the cyclic voltammetry.

The direct alkylheteroarylation of alkenes with cyclic and acyclic ethers via distal heteroaryl ipso-migration has been accomplished through the design of a photoredox-mediated C-H functionalization pathway. The use of inexpensive ethers as radical precursors combined with a straightforward method makes this a practical approach.

CO

An electrochemical multicomponent [3 + 1 + 1] annulation used for the synthesis of 1,3,5-trisubstituted 1,2,4-triazoles has been developed under transition-metal-, acid-, base- and external-oxidant-free conditions. In an undivided cell, a variety of hydrazones and aldehydes smoothly participate in this transformation to furnish a range of substituted 1,2,4-triazoles. The reaction constitutes a new transformation from hydrazones, aldehydes and NH4OAc into 1,2,4-triazoles, providing a unifying, simple and environmentally friendly approach to the currently available methods.

A new Pd-catalyzed carbonylation of indoles for the synthesis of indol-3-yl aryl ketones under CO-free conditions was developed. The reaction showed a broad substrate scope with moderate to excellent yields.

A visible-light-catalyzed synthesis of indol-3-yl aryl ketones from aryldiazonium salts, CO and indoles at room temperature was developed. This process provides a useful method for the preparation of diverse indol-3-yl aryl ketones from readily accessible reactants under base-free, acid-free and transition-metal-free conditions.

A visible-light-induced synthesis of 3-acylindoles from simple indoles and α-oxo acids at room temperature has been discovered. The reaction tolerates a wide range of functional groups and gives a variety of valuable 3-acylindoles in moderate to high yields under mild conditions.

A [bmIm]OH-catalyzed amidation of azides and aldehydes is reported. This reaction is easily handled and proceeds under mild conditions. The overall transformation involves azide–enolate cycloaddition, which subsequently undergoes rearrangement to give amides. Importantly, the employment of ionic liquid makes this transformation green and practical.

A new direct alkylheteroarylation of alkenes with simple alkylnitriles via distal heteroaryl ipso-migration has been accomplished under metal-free conditions, in which inexpensive alkylnitriles served as radical precursors, which together with ease of operation makes this process a very practical protocol.

A novel nickel N-heterocyclic carbene catalyzed cross-coupling reaction of aryl aldehydes with boronic esters for the synthesis of aryl ketones was developed. This reaction provides a mild, practical method toward aryl ketones, which are versatile intermediates and building blocks in organic synthesis.

It was found for the first time that Cs2CO3 serves as highly efficient catalyst for the direct hydroxylation reactions of phosphonates under mild conditions. This reaction provides an efficient approach to quaternary α-hydroxy phosphonates, which possess intriguing biological activities and are widely used in many areas.

Background Distribution of HIV-1 subtypes, transmitted drug resistance (TDR)/drug resistance mutation (DRM), and their impact on response to combination antiretroviral therapy remain poorly understood in China. Methods We analyzed data from our multicenter cohort study with 444 antiretroviral-naive participants recruited between 2008 and 2010. HIV-1 subtype and tropism were determined by V3 sequencing, and TDR/DRM was determined by Pol sequencing. Virologic and immunologic responses were monitored over 96 weeks of follow-up. The initial combination antiretroviral therapy regimen for all patients was nevirapine + lamivudine + zidovudine or stavudine. Analysis 1 included patients who finished 96 weeks of follow-up (n = 379), and analysis 2 included all 444 patients. Results Subtype B/B' was associated with higher prevalence of TDR/DRM to nucleoside reverse transcriptase inhibitors and nonnucleoside reverse transcriptase inhibitors. Median time to HIV-1 suppression was 18 weeks in all 3 subtype groups. In Cox proportional models for viral suppression, neither viral tropism nor HIV-1 subtypes had any impact on viral suppression; however, subtypes CRF01_AE and C/CRF07_BC/CRF08_BC were associated with lower risk of virologic failure compared with subtype B/B', with adjusted hazard ratio of 0.11 (P = 0.032) and 0.06 (P = 0.036), respectively in analysis 1, 0.42 (P = 0.047) and 0.22 (P = 0.008), respectively in analysis 2. This association was attenuated by adding DRM profiles to multivariate regression models. Neither subtype nor HIV-1 tropism affected immunologic response. Conclusions HIV-1 subtype tended to be associated with virologic but not immunologic response; this effect could be ascribed to baseline DRM.

An efficient copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkynes via C–C triple bonds cleavage has been demonstrated. The aniline compounds were found to be crucial in our conditions and a plausible mechanism was put forward. This reaction constitutes a new transformation from 1,2-diarylalkynes into bisaryl ketones with a practical, neutral, and mild synthetic approach.

A novel copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkynes via the cleavage of C–C triple bonds is reported. This reaction is a new transformation of 1,2-diarylalkynes into bisaryl ketones.

A visible-light-catalyzed synthesis of aryl ketones from aryldiazonium salts, CO and (hetero)arenes at room temperature is discovered. This transformation represents an efficient and attractive synthetic utilization of aryl diazonium salts.

A highly efficient Cu-catalyzed direct hydroxylation of phosphonate compounds has been developed. This transformation provides a powerful method for the synthesis of quaternary α-hydroxy phosphonates in good yields. The direct transformation process, regiospecific selectivity, and good tolerance to a variety of substituents make it an alternative approach to the reported protocols.

A visible-light-catalyzed synthesis of unsymmetrical 2,3-diaryl-substituted indoles from arylsulfonyl chlorides and o-azidoarylalkynes at room temperature has been discovered. This transformation exhibits excellent substrate scope and functional group tolerance. The use of inexpensive eosin Y as the catalyst with easy operation makes this protocol very practical.

A novel palladium/copper-catalyzed aerobic synthesis of bisaryl ketones from 1,2-diarylalkenes via C-C double bonds cleavage has been described. This reaction constitutes a new transformation from 1,2-diarylalkenes into bisaryl ketones, providing a unifying, simple and environmentally friendly complement to the available methods.

The Book of Job is often viewed as a story of unnecessary and undeserved suffering. A man who is “blameless” in the eyes of God is put through senseless anguish and misery simply because God and the Adversary have a wager. It is a story of a whimsical God who does not understand or care about human beings and their sufferings, and of an insignificant and yet defiant being who epitomizes human dignity and fortitude. This and other similar accounts make God villainous and human sufferings mysterious and incomprehensible. This article seeks to cast these issues in a different light by exploring some of the key terms in the Prologue and the speeches of God in the Theophany. The exploration ends with some reflections on Job in the Epilogue of the Book.

A practical and simple synthesis of benzoxazoles from easily available substrates was developed. The protocol is triggered by an iron-catalyzed tandem oxidative process from simple ether derivatives.

Elevated polycyclic aromatic hydrocarbon (PAH) concentrations were determined in different Chinese coals, with the highest concentrations in bituminous coals. Phenanthrene (Phen) was chosen as the probe compound for PAHs to study the sorption behavior of coal. No native Phen was detected in desorption experiments indicating irreversible sorption–desorption behavior of PAHs in raw coal samples. Sorption mechanism was further studied under varying conditions of pH value and ionic strength. Different ranks of coal showed different sorption behavior under acidic, neutral, and alkaline conditions. Batch experiments were further processed for the selected coals at pH values from 3 to 11 at a constant aqueous concentration. Sorption capacities of all coals decreased with increased pH except for YJ coal. Furthermore, although DOC-associated Phen mass contributed little to the total Phen mass under different pH values, the significant negative correlations between M DOC and log K OC values were observed for all coal samples, indicating a significant role played by DOC in the coal sorption. In addition, sorption experiments under varying ionic strength showed that the ionic strength influence was more obvious in sorption isotherms for higher rank coals with increasing ionic strength, and this effect was most significant when ionic strength increased from 0 to 0.15 M, especially at relatively low aqueous concentrations.

The occurrence and distribution of five groups of antibiotics were investigated in the surface water of Yangtze Estuary over four seasons. Of the 20 antibiotics, only sulfamerazine was not detected at all sampling sites, indicating widespread occurrence of antibiotic residues in the study area. Detection frequencies and concentrations of antibiotics were generally higher in January, indicating that low flow conditions and low temperature might enhance the persistence of antibiotics in water. Antibiotic levels varied with location, with the highest concentrations being observed around river discharge and sewage outfall. Furthermore, a positive correlation between total antibiotic and DOC concentrations revealed the significant role played by DOC. Risk assessment based on single compound exposure showed that sulfapyridine and sulfamethoxazole could cause medium risk to daphnid in the Yangtze Estuary. © 2012 Elsevier Ltd. All rights reserved.

A novel series of ethyl 1,3-disubstituted-1,6-dihydropyrrolo[2,3-c]pyrazole-5-carboxylates can be rapidly and efficiently synthesized in excellent yields by condensing a variety of 1,3-substituted-4-formyl-5-chloropyrazole with ethyl isocyanoacetate in the presence of 1-methyl-3-butylimidazolium hydroxide under microwave irradiation. The simple experimental procedure, DMSO-free condition, short period of conversion, and excellent yields are the advantages of the present method. The structures of the novel compounds are confirmed by IR, 1H NMR, 13C NMR, MALDI-TOF MS, and elemental analysis.

A Cu-mediated cyanation of aryl methyl ketones using cyanide anions as the nitrogen source was achieved to provide aromatic nitriles in moderate to good yields. The reaction tolerates a variety of synthetically important functional groups.

A new Pd-catalyzed carbonylation of indoles for the synthesis of indol-3-yl aryl ketones under CO-free conditions was developed. The reaction showed a broad substrate scope with moderate to excellent yields.

A [bmIm]OH-catalyzed amidation of azides and aldehydes is reported. This reaction is easily handled and proceeds under mild conditions. The overall transformation involves azide–enolate cycloaddition, which subsequently undergoes rearrangement to give amides. Importantly, the employment of ionic liquid makes this transformation green and practical.

A Cu-mediated cyanation of aryl methyl ketones using cyanide anions as the nitrogen source was achieved to provide aromatic nitriles in moderate to good yields. The reaction tolerates a variety of synthetically important functional groups.

A visible-light-induced synthesis of 3-acylindoles from simple indoles and α-oxo acids at room temperature has been discovered. The reaction tolerates a wide range of functional groups and gives a variety of valuable 3-acylindoles in moderate to high yields under mild conditions.

A visible-light-catalyzed synthesis of indol-3-yl aryl ketones from aryldiazonium salts, CO and indoles at room temperature was developed. This process provides a useful method for the preparation of diverse indol-3-yl aryl ketones from readily accessible reactants under base-free, acid-free and transition-metal-free conditions.

An improved procedure for the synthesis of indole-2-carboxylic acid esters in excellent yields has been achieved by the condensation of 2-halo aryl aldehydes or ketones and ethyl isocyanoacetate using ionic liquid under controlled microwave irradiation (100 W) at 50 °C. This method offers a number of advantages in terms of methodology, high-product yield, short period of conversion, mild reaction conditions and easy workup. Um procedimento melhorado para a síntese de ésteres ácido indol-2-acético em rendimentos excelentes foi obtido pela condensação de 2-halo aril aldeídos ou cetonas e isocianoacetato de etila usando líquido iônico sob irradiação de microondas controlada (100 W) a 50 ºC. Este método oferece um número de vantagens em termos de metodologia simples, com rendimento elevado num tempo de reação curto e em condições de reação amenas.

6-Aryl substituted phenanthridines were synthesized via a visible-light-catalyzed cyclization of 2-isocyanobiphenyls with arylsulfonyl chlorides under oxidant-free and transition-metal-free conditions. This transformation represents an efficient and attractive synthetic utilization of arylsulfonyl chlorides.

Nuclear factor kappa B (NF-κB), a key nuclear transcription factor, is associated with prognosis in a variety of human cancers. However, the clinical value of NF-κB in non-small cell lung cancer (NSCLC) is still controversial. Therefore, the aim of this meta-analysis was to obtain an accurate evaluation of the relationship between NF-κB expression and survival prognosis of NSCLC patients based on published articles. PubMed, EMBASE and Web of Science databases were systematically searched for potential articles. A total of 1159 patients from 7 eligible studies comparing prognostic significance of NF-κB expression levels in NSCLC were included in our meta-analysis. I2 statistic and P value were performed to evaluate heterogeneity. The results of analysis were presented as hazard ratio (HR) or odds ratios (OR) with 95% confidence interval (95% CI). Subgroup analysis based on ethnicity of NSCLC patients and NF-kB cellular localization within cancer cells were conducted to illustrate the potential discrepancy. Significant heterogeneity was considered at I2>50% and P

In a search for a new inhibitor of aspartyl protease, the ferrocenyl group was introduced from the C-terminus of statine to create a novel bis-statine-based peptide containing ferrocenyl moiety in solution. The target compound was characterized by infrared, 1H NMR spectroscopy, mass spectrometry, and elemental analysis.

A facile method has been developed for the fabrication of porous silicon carbide (SiC) by means of sintering a mixture of SiC powder and carbon pellets at a relatively lower temperature, that is, 1450 degrees C, in air. The pore density and the total pore volume of the resulting porous SiC could be tuned by changing the initial SiC/C weight ratio. The structure evolution and the associated property changes during the preparation were examined through X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, (29)Si magic-angle spinning (MAS) NMR spectroscopy, and mercury-intrusion porosimetry analyses. Silica and SiO(x)C(y) ceramics formed in situ during the calcination process acted as binders of the porous SiC grains. The porous SiC can be used as a host for the growth of ZSM-5 zeolite crystals to form the ZSM-5/porous-SiC composite material. After loading another catalytic active component of molybdenum, a novel catalytic material, Mo-ZSM-5/porous-SiC, was obtained, which exhibited improved catalytic activity in the methane dehydroaromatization reaction.