Visible-Light-Promoted Thiolation of Benzyl Chlorides with Thiosulfonates via a Photoactive Electron Donor-Acceptor Complex.

Visible-light-promoted thiolation of benzyl chlorides with thiosulfonates is disclosed via an electron donor-acceptor complex strategy. In addition to efficiently delivering a series of arylbenzylsulfide compounds, versatile thioglycosides were also successfully constructed by applying the metal- and photocatalyst-free protocol. Preliminary mechanistic studies suggest that a radical-radical coupling process was involved in this transformation.

Comparison of outcomes for general and local anesthesia in the management of nasal bone fractures: a meta-analysis.

BACKGROUND: This meta-analysis aimed to perform a head-to-head comparison of the role of general anesthesia (GA) and local anesthesia (LA) in the management of patients with nasal bone fractures (NBFs). METHODS: PubMed, Embase, and Web of Science were comprehensively searched. Studies investigating the clinical outcomes of GA and LA in the management of NBFs were included. Pooled odds ratios (OR) with the respective 95% confidence intervals (CIs) were calculated. Heterogeneity between the included studies was evaluated. The risk of bias in the included studies was assessed. RESULTS: Eight studies were included in this meta-analysis. The pooled ORs for cosmetic results, residual septal deformity, the need for further surgery, patients' satisfaction with the anesthesia procedure, and patients' satisfaction with the surgery results were 0.70 (95% CI 0.18, 2.64; z = - 0.53, p = 0.5957), 1.11 (95% CI 0.37, 3.30; z = 0.18, p = 0.8558), 1.19 (95% CI 0.65, 2.20; z = 0.56, p = 0.5760), 1.57 (95% CI 0.92, 2.69; z = 1.65, p = 0.0982), and 1.00 (95% CI 0.55, 1.80; z = - 0.00, p = 0.9974). CONCLUSIONS: Insignificant difference on clinical outcomes was observed between GA and LA in the manipulation of patients with NBFs, and the choice of anesthetic approach should be based on the tolerability of the methods and the severity of nasal fractures.

Dual-Emissive Monoruthenium Complexes of N(CH3)-Bridged Ligand: Synthesis, Characterization, and Substituent Effect.

Three monoruthenium complexes 1(PF6)2-3(PF6)2 bearing an N(CH3)-bridged ligand have been synthesized and characterized. These complexes have a general formula of [Ru(bpy)2(L)](PF6)2, where L is a 2,5-di(N-methyl-N'-(pyrid-2-yl)amino)pyrazine (dapz) derivative with various substituents, and bpy is 2,2'-bipyridine. The photophysical and electrochemical properties of these compounds have been examined. The solid-state structure of complex 3(PF6)2 is studied by single-crystal X-ray analysis. These complexes show two well-separated emission bands centered at 451 and 646 nm (Δλmax = 195 nm) for 1(PF6)2, 465 and 627 nm (Δλmax = 162 nm) for 2(PF6)2, and 455 and 608 nm (Δλmax = 153 nm) for 3(PF6)2 in dilute acetonitrile solution, respectively. The emission maxima of the higher-energy emission bands of these complexes are similar, while the lower-energy emission bands are dependent on the electronic nature of substituents. These complexes display two consecutive redox couples owing to the stepwise oxidation of the N(CH3)-bridged ligand and ruthenium component. Moreover, these experimental observations are analyzed by computational investigation.

Serum level and clinical significance of vitamin E in pregnant women with allergic rhinitis.

BACKGROUND: Allergic rhinitis is a frequent disorder during pregnancy, while in children it is triggered by significantly lower serum vitamin E level. This research aimed to investigate whether serum vitamin E level exhibited clinical significance in pregnant women with allergic rhinitis. METHODS: In this study, 37 pregnant women with allergic rhinitis and 35 healthy pregnant women were recruited. Allergic rhinitis severity was analyzed by the Total Nasal Symptom Score (TNSS) questionnaire. Blood samples were collected to evaluate serum vitamin E, interleukin (IL), and total IgE levels. RESULTS: In pregnant women with allergic rhinitis, serum level of vitamin E was significantly lower than in healthy pregnant women. Serum vitamin E level in pregnant women with allergic rhinitis showed a negative correlation with TNSS, IL-13, IL-4, and total IgE levels. CONCLUSION: In conclusion, this research has demonstrated that pregnant women with allergic rhinitis showed significantly lower serum level of vitamin E. The decreased vitamin E showed a correlation with the pathogenesis of allergic rhinitis in pregnant women.

Atypical manifestations of acute coronary syndrome - throat discomfort: a multi-center observational study.

To present the clinical characteristics and the misdiagnosis rate of acute coronary syndrome manifested primarily as throat discomfort, we conducted a multicentric and retrospective study in the cardiology and otorhinolaryngology departments. Records of patients with primary complaint of throat discomfort, absence of chest pain at onset, and an ultimate diagnosis of acute coronary syndrome, as well as patients with pharyngitis (as controls) were collected from May 2015 to April 2016. The patients' main manifestations were compared. Logistic regression results showed that chest tightness, dyspnea, perspiring, and exertional throat symptoms were significantly associated with acute coronary syndrome, with odds ratios of 8.3 (95% CI 2.2-31.5), 10.9 (95% CI 1.8-66.9), 25.4 (95% CI 3.6-179.9), and 81.2 (95% CI 13.0-506.7). A total of 25 (56.82%) out of 44 acute coronary syndrome patients, who were first admitted to the otorhinolaryngology department, were misdiagnosed, with a 12% (3/25) mortality rate. Throat discomfort can be the principal manifestation of acute coronary syndrome. Such patients exhibit high misdiagnosis and mortality rates. Exertional throat symptoms, chest tightness, perspiring, and dyspnea were important indicators of acute coronary syndrome in patients whose main complaint was throat discomfort. The awareness of this condition will result in prompt diagnosis and reduce morbidity and mortality.

Nickel-Catalyzed Chemo- and Regioselective Benzylarylation of Unactivated Alkenes with o-Bromobenzyl Chlorides.

Chemo- and regioselectively nickel-catalyzed reductive benzylarylation of unactivated alkenes with o-bromobenzyl chlorides is disclosed herein, in which electrophiles participate through a single-component double-site approach. Moreover, its utility is underscored by the concise synthesis of bioactive Indane compounds and postreaction functionalizations leading to structurally diverse scaffolds. Preliminary mechanistic investigations suggest a radical chain reaction mechanism.

Discovery of quinazoline derivatives as novel small-molecule inhibitors targeting the programmed cell death-1/programmed cell death-ligand 1 (PD-1/PD-L1) interaction.

Development of small molecule PD-1/PD-L1 inhibitors as a novel immunotherapy strategy exhibits great promise. Herein, a novel series of quinazoline derivatives were designed, synthesized and their inhibitory activity against the PD-1/PD-L1 interaction was evaluated through a homogenous time-resolved fluorescence (HTRF) assay. Among them, the compound 39 exhibited the most potent inhibitory activity with an IC50 value of 1.57 nM. Furthermore, the cellular level assays revealed that 39 could inhibit the PD-1/PD-L1 interaction and restore T-cell function, and showed low toxicity on the PBMCs. In addition, the structure-activity relationships (SARs) of the novel quinazoline derivatives were explored and the binding mode of 39 with dimeric PD-L1 was analyzed by molecular docking. This work demonstrates that incorporation of pyrimidine group between the 2 and 3-positions of the biphenyl structure is an effective strategy for designing novel and more potent small molecule PD-1/PD-L1 inhibitors, and 39 can be regarded as a promising lead compound for further investigation.

Dual-Emissive Tris-Heteroleptic Ruthenium Complexes: Tuning the DNA-Triggered Ratiometric Emission Response by Ancillary Ligands.

Three tris-heteroleptic mononuclear Ru(II) complexes with dual fluorescence and phosphorescence-[Ru(dpma)(bpy)(phen)]2+ (12+), [Ru(dpma)(bpy)(dppz)]2+ (22+), and [Ru(dpma)(phen)(dppz)]2+ (32+)-have been designed and used as ratiometric light-response probes for DNA, where dpma is di(pyrid-2-yl)(methyl)-amine, bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline, and dppz is dipyridophenazine, respectively. Single crystals of complex 2(PF6)2 have been obtained and studied by X-ray analysis. The interactions of these complexes with different DNAs are investigated by means of spectroscopic methods, viscosity measurements, and molecular modeling. In the presence of calf thymus DNA, complexes 2(PF6)2 and 3(PF6)2 show the emergence of a new lower-energy phosphorescence emission band; meanwhile, the higher-energy fluorescence emission band is essentially unchanged, functioning as an intrinsic internal reference. These two complexes exhibit stronger preference for calf thymus DNA over single-strand DNA (d(A)16 and d(C)16). In contrast, no binding interaction between 1(PF6)2 and calf thymus DNA is observed. The intrinsic binding constants (Kb) of 2(PF6)2 and 3(PF6)2 with calf thymus DNA are determined to be (1.4 ± 0.4) × 105 and (9.5 ± 0.15) × 104 M-1, respectively. In addition, these spectroscopic results are compared with those of the prototype complex [Ru(bpy)2(dppz)]2+ (42+), and density functional theory and time-dependent density functional theory calculations are employed to elucidate these experimental findings.

The Association Between the XRCC1 Arg399Gln Polymorphism and the Risk of Head and Neck Cancer: An Updated Meta-Analysis Including 14586 Subjects.

BACKGROUND: Accumulated evidence shows that DNA repair gene X-ray repair cross complementing group 1 (XRCC1) may determine individual susceptibility to head and neck cancer (HNC) as a major DNA repair gene. However, the results from previous studies have been conflictive and inconsistent. In order to more accurately estimate and integrate the association between XRCC1 Arg399Gln polymorphism and HNC risk, we conducted a meta-analysis including 14586 subjects. METHODS: In this meta-analysis, literatures were collected up until September 15, 2020 through multifarious retrieval strategies by searching through electronic databases of PubMed, Cochrane Library, EMBASE, Medline, Web of Science and CNKI. The association between the XRCC1 Arg399Gln polymorphism and HNC was analyzed through calculating summary odds ratios (OR) and 95% confidence intervals (CI). RESULTS: Thirty-one studies consisting of 6025 cases and 8561 controls were identified and analyzed. No significant association between XRCC1 Arg399Gln polymorphisms and HNC risk was found under the allelic (OR = 0.94, 95% CI: 0.82-1.07, P = 0.35), homozygous (OR = 0.99, 95% CI: 0.81-1.21, P = 0.91), heterozygous (OR = 1.01, 95% CI: 0.90-1.13, P = 0.91), dominant (OR = 1.05, 95% CI: 0.85-1.29, P = 0.67) or recessive (OR = 0.93, 95% CI: 0.80-1.08, P = 0.35) genetic models in the overall comparison. In addition, subgroup analyses according to tumor site also displayed no significant association between XRCC1 Arg399Gln polymorphisms and HNC risk. However, subgroup analyses based on ethnicity indicated that HNC risk was significantly related to Arg399Gln genetic heterozygous model (OR = 1.21, 95%CI: 1.04-1.42, P = 0.02) and dominant model (OR = 1.27, 95%CI: 1.02-1.60, P = 0.04) in Caucasians populations. CONCLUSION: The results from this meta-analysis suggest that the XRCC1 Arg399Gln variants (Arg/Gln and Arg/Arg+Arg/Gln) may contribute to high HNC risk among Caucasians. Further well-designed studies and larger sample sizes are needed to validate our findings.

Ratiometric detection of amyloid-ß aggregation by a dual-emissive tris-heteroleptic ruthenium complex.

A dual-emissive tris-heteroleptic ruthenium complex is designed, synthesized and applied for the ratiometric photoluminescent detection of amyloid-ß (Aß) aggregation in both steady and transient states. The Aß aggregation is supported by transmission electron microscopy and confocal laser scanning microscopy analysis. In addition, molecular docking calculations have been performed to gain insights into the interaction mode between the ruthenium complex and Aß fibrils.

Nanocrystalline Sb-doped SnO2 films modified with cyclometalated ruthenium complexes for two-step electrochromism.

Sb-Doped nanocrystalline SnO2 (SnO2:Sb) thin films functionalized with cyclometalated ruthenium complexes 1 or 2 on FTO conductive glasses have been prepared and characterized. These complexes contain a redox-active amine unit separated from the ruthenium ion by a phenyl or biphenyl linker, respectively, to modify the absorption wavelengths at different redox states. Near-infrared electrochromism of both films has been examined by oxidative spectroelectrochemical measurements and double-potential-step chronoamperometry. A contrast ratio (ΔT%) of 33% at 1070 nm and 63% at 696 nm has been achieved for the SnO2:Sb/1 film in two stepwise oxidation processes, respectively. The other film with complex 2 shows two-step electrochromism at 1310 and 806 nm with ΔT% of 36% and 76%, respectively. The response time of electrochromic switching is around a few seconds. Taking advantage of the good contrast ratio, the rapid response, and the long retention time of each oxidation state, these films have been successfully used to demonstrate surface-confined flip-flop memory functions with a high ON/OFF ratio.

Tuning the dual emissions of a monoruthenium complex with a dangling coordination site by solvents, O2, and metal ions.

A polypyridyl monoruthenium complex with a dangling coordination site shows dual fluorescence/phosphorescence emissions at room temperature. The emission properties can be modulated by multiple stimuli including solvents, O2, and metal ions.

Endoscopic dacryocystorhinostomy with an otologic T-type ventilation tube in repeated revision cases.

BACKGROUND: To compare the frequency of appearance of complications, anatomical success and functional success after conventional endoscopic dacryocystorhinostomies (EN-DCRs) or EN-DCR with otologic T-Type ventilation tube combined with silicone tube intubation in repeated revision cases. METHODS: Twenty-two patients who had epiphora and recurrent dacryocystitis after at least a previous failed revision DCR as well as 22 patients receiving conventional EN-DCR only were enrolled in the study between January 2008 and December 2011. Operations were performed by using an otologic T-tube combined with silicone tube intubation. Oral antibiotics, nasal steroids, oral antihistamines, and antibiotic eyedrops were given to all cases. The ventilation tubes were removed 6 to 20 weeks after surgery. RESULTS: Of 22 cases, all cases achieved anatomical success, 19 cases were symptom free, and 3 cases had decreased continuation in complications with a functional success rate of 81.8%. The overall success rates were significantly higher than those in patients undertaking conventional EN-DCR only (P < 0.01). CONCLUSION: The revision endoscopic DCR has a high rate of failure. The usage of a T-type ventilation tube can significantly improve the success rate of surgery. TRIAL REGISTRATION NUMBER: ChiCTR-INR-17012160, retrospectively registered on July 27th, 2017.

Effect of curcumin on nasal symptoms and airflow in patients with perennial allergic rhinitis.

BACKGROUND: Allergic rhinitis (AR) is a common disorder that can significantly affect patient quality of life. Previous studies have found that curcumin had anti-inflammatory and antioxidant effects and clinical benefits in cancer and asthma. OBJECTIVE: To determine the efficacy of curcumin in the treatment of AR and to explore the molecular mechanisms involved. METHODS: In a randomized, double-blind study, 241 patients with AR received either placebo or oral curcumin for 2 months. The therapeutic effects of curcumin were evaluated by nasal symptoms and nasal airflow resistance. In addition, the production of interferon γ, interleukin (IL) 4, IL-10, and tumor necrosis factor α from mononuclear cells and IL-8, soluble intercellular adhesion molecule, polyethylene glycol 2, and leukotriene C4 from polymorphonuclear neutrophils were compared before and after curcumin treatment. RESULTS: Curcumin alleviated nasal symptoms (sneezing and rhinorrhea) and nasal congestion through reduction of nasal airflow resistance. Curcumin was found to exert diverse immunomodulatory effects, including suppression of IL-4, IL-8, and tumor necrosis factor α and increased production of IL-10 and soluble intercellular adhesion molecule. However, curcumin did not affect the release of prostaglandin E2 and leukotriene C4 from polymorphonuclear neutrophils. CONCLUSION: This pilot study provides the first evidence of the capability of curcumin of improving nasal airflow and modulating immune response in patients with AR.

Transition from a Metal-Localized Mixed-Valence Compound to a Fully Delocalized and Bridge-Biased Electrophore in a Ruthenium-Amine-Ruthenium Tricenter System.

A series of cyclometalated diruthenium complexes with a redox-active amine bridge were synthesized. Depending on the terminal ligands of the ruthenium components and the substituent on the amine unit, the one-electron-oxidized state can be either in the form of a weakly or strongly coupled mixed-valence diruthenium complex, a fully charge-delocalized three-center system, or a bridge-biased electrophore. This transition among different electronic forms was supported by electrochemistry, near-infrared absorption, electron paramagnetic resonance, and density functional theory analysis.

Knockdown of phosphodiesterase 4D inhibits nasopharyngeal carcinoma proliferation via the epidermal growth factor receptor signaling pathway.

Phosphodiesterase 4D (PDE4D) is a subtype of metallohydrolases, and it has been reported that PDE4D functions as a proliferation promoting factor in certain types of cancer, including head and neck cancer. The present study first investigated the function of PDE4D in nasopharyngeal carcinoma (NPC). Western blot analysis was applied to detect PDE4D expression in NPC samples and cells. A lentiviral infection technique was used to stabilize the knockdown of PDE4D, which was subsequently examined in vitro and in vivo. The results showed that PDE4D was overexpressed in the NPC tissues and cells. Knockdown of PDE4D inhibited the growth of CNE2 and 5-8F, inducing cell cycle arrest in the G0/G1 phase in CNE2. These effects could be reversed by epidermal growth factor (EGF) stimulation. Furthermore, knockdown of PDE4D significantly inhibited the phosphorylation of epidermal growth factor receptor (EGFR) and AKT. The results were further validated in an NPC xenograft in nude mice. In conclusion, this study demonstrated that PDE4D may function as a proliferation promoting factor in NPC, by affecting the EGFR/PI3K/AKT signaling pathway. Therefore, the targeting of PDE4D may be a rational strategy in the treatment of NPC.

[Mastoidectomy in the treatment of secretory otitis media].

OBJECTIVE: To investigate mastoidectomy efficacy in treating secretory otitis media. METHOD: Retrospective analysis of 22 cases (24 ears) with chronic secretory otitis media,20 ears were treated with intact canal wall mastoidectomy combined with facial recess opening,4 ears were treated with opened mastoid surgery,3 ears simultaneously accepted tube insertion. Ventilation tube was pulled out in 6 months. Hearing test was inspected before and after surgery. RESULT: None of the patients had hearing loss, 19 ears had varying degrees of hearing improvement. Seventeen ears were type A tympanometry curve, 7 ears were C-shaped curve. No recurrence of otitis media was observed after 6 - 36 months followed-up. CONCLUSION: Mastoidectomy may improve eustachian tube function and decrease the risk of recurrence of secretory otitis media.

[Clinical efficacy of mouse nerve growth factor in the treatment of sudden deafness].

OBJECTIVE: To study the clinical efficacy of mouse nerve growth factor (NGF) in the treatment of sudden deafness. METHOD: A retrospective analysis was performed on 115 cases of hospitalized patients who were suffered from sudden deafness. Patients were divided into two groups according to treatment medicine. Control group: patients were treated with intravenous vasodilators, energy mixture, steroid pulse therapy, and methylcobalamin neurotrophic therapy. NGF group: intramuscular NGF treatment was added on the basis of conventional therapy mentioned above. Both treatments lasted 14 days, the total efficiency were compared. Patients were further divided into sub-groups according to age, duration and the level of pre-treatment PTA, and the treatment efficiency was further compared. By SPSS 11.0 statistical analysis, a P < 0.05 was considered as statistical significant difference. RESULT: (1) The total efficiency of NGF group was significantly higher than control group. (2) Regard of age, the efficiency of NGF treatment group was significantly higher than control group. (3) For the patients whose duration were less than 7 d, or the PTA < or = 60 dBHL, the efficiency of NGF group were significantly higher. For the patients whose duration were more than 7 d, or the PTA>60 dBHL, the efficiency of NGF therapy was not superior to the traditional treatment. CONCLUSION: NGF can significantly improve the symptom of patients with short duration or low PTA. For this kind of patients, NGF adjuvant therapy should be recommended. For the patients with longer duration and higher level of PTA, NGF therapy is not advocated. NGF treatment should not be in consideration of the age.

Reductive electropolymerization of bis-tridentate ruthenium complexes with 5,5''-divinyl-4'-tolyl-2,2':6',2''-terpyridine.

Four bis-tridentate ruthenium complexes with 5,5''-divinyl-4'-tolyl-2,2':6',2''-terpyridine (dvtpy) have been synthesized. Among them, 3(PF6) ([(dvtpy)Ru(Mebib)](PF6)) and 4(PF6) ([(dvtpy)Ru(dpb)](PF6)) are cyclometalated, and 5(PF6)2 ([(dvtpy)Ru(Mebip)](PF6)2) and 6(PF6)2 ([(dvtpy)Ru(tpy)](PF6)2) are noncyclometalated, where Mebib is 2-deprotonated-1,3-bis(N-methylbenzimidazolyl)benzene, dpb is 2-deprotonated-1,3-di(2-pyridyl)benzene, Mebip is 2,6-bis(N-methylbenzimidazolyl)pyridine, and tpy is 2,2':6',2''-terpyridine, respectively. Reductive electropolymerization of these complexes and copolymerization of 4(PF6) and 5(PF6)2 proceeded smoothly, both on glassy carbon and ITO glass electrodes, to afford stable metallopolymeric films with well-defined redox processes. On the basis of the monomer structures, electrochemical properties, and polymerization mechanism, the polymer chains of these materials are supposed to be composed of organic frameworks with the metal ions laterally chelated to the main backbones. The polymeric films on ITO surfaces display promising electrochromism in the visible region with good reversibility and moderate contrast ratio. Besides, the apparent diffusion constants of films of 3(PF6)­6(PF6)2 were measured by potential step chronoamperometry and the typical surface morphology of poly-5(PF6)2/ITO film was studied using SEM.