Interfacial Charge Transfer Regulates Photoredox Catalysis.

Photoredox catalytic processes offer the potential for precise chemical reactions using light and materials. The central determinant is identified as interfacial charge transfer, which simultaneously engenders distinctive behavior in the overall reaction. An in-depth elucidation of the main mechanism and highlighting of the complexity of interfacial charge transfer can occur through both diffusive and direct transfer models, revealing its potential for sophisticated design in complex transformations. The fundamental photophysics uncover these comprehensive applications and offer a clue for future development. This research contributes to the growing body of knowledge on interfacial charge transfer in photoredox catalysis and sets the stage for further exploration of this fascinating area of research.

In Situ Metal-Assisted Ligand Modification Induces Mn4 Cluster-to-Cluster Transformation: A Crystallography, Mass Spectrometry, and DFT Study.

Dehydration of (S,S)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethane-1,2-diol (H4 L) to (Z)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethenol) (H3 L') was found to be metal-assisted, occurs under solvothermal conditions (H2 O/CH3 OH), and leads to [MnII 4 (H3 L)4 Cl2 ]Cl2 ⋅5 H2 O⋅5 CH3 OH (Mn4 L4 ) and [MnII 4 (H2 L')6 (µ3 -OH)]Cl⋅4 CH3 OH⋅H2 O (Mn4 L'6 ), respectively. Their structures were determined by single-crystal XRD. Extensive ESI-MS studies on solutions and solids of the reaction led to the proposal consisting of an initial stepwise assembly of Mn4 L4 from the reactants via [MnL] and [Mn2 L2 ] below 80 °C, and then disassembly to [MnL] and [MnL2 ] followed by ligand modification before reassembly to Mn4 L'6 via [MnL'], [MnL'2 ], and [Mn2 L'3 ] with increasing solvothermal temperature up to 140 °C. Identification of intermediates [Mn4 Lx L'6-x ] (x=5, 4, 3, 2, 1) in the process further suggested an assembly/disassembly/in situ reaction/reassembly transformation mechanism. These results not only reveal that multiple phase transformations are possible even though they were not realized in the crystalline state, but also help to better understand the complex transformation process between coordination clusters during "black-box" reactions.

Thermally Induced trans-to-cis Isomerization and Its Photoinduced Reversal Monitored using Absorption and Luminescence: Cooperative Effect of Metal Coordination and Steric Substituent.

For ethene derivatives with large groups the cis-isomer is often quite unstable and unavailable. Herein, we report an exception of two stable coordination complexes, (cis-L)ZnCl2 , starting from trans-1,2-bis(1-R-benzo[d]imidazol-2-yl)ethene (R=H, L1; R=CH3 , L2) ligands under solvothermal condition (T ≥140 °C). Using the intensity of the absorption and luminescence spectra as probes we proposed its progressive cis-to-trans reversal upon irradiation with UV light, which was confirmed by powder X-ray diffraction (PXRD). Similar results observed in the series of (cis-L2)MII Cl2 [M=Fe (4), Co (5), Ni (6)] demonstrate the universal strategy. The results of PXRD, NMR spectroscopy, ESI-MS and DFT calculations support the above conclusion. NMR spectroscopy indicates that irradiation of 1 converts an optimized 71 % of the cis-isomer to trans, whereas the free trans-L1 ligand transforms to only 15 % cis-isomer under similar conditions.

Incidence of allergic rhinitis and meteorological variables: Non-linear correlation and non-linear regression analysis based on Yunqi theory of chinese medicine.

OBJECTIVE: To analyze the correlations between the incidence of allergic rhinitis (AR) and meteorological variables of previous periods, so as to establish non-linear prediction equations of AR in Beijing area. METHODS: AR patients (10,478 cases) collected from Beijing Tongren Hospital during 2007-2010 and meteorological data (including daily average temperature, daily maximum temperature, daily minimum temperature, daily relative humidity, daily average vapor pressure, daily dew point temperature, daily precipitation, daily average wind speed, sea level pressure, and degree of comfort) collected from Beijing Municipal Meteorological Observatory in the same periods were used for the analysis. Non-linear correlation and regression were adopted to analyze the relationship between AR incidence and meteorological variables of former six-qi stage which was defined according to Yunqi theory of Chinese medicine. Comprehensive meteorological parameter was introduced to establish the predictive model. RESULTS: The high incidence of AR appeared in the 4th qi stage (from the Beginning of Autumn to Autumn Equinox), while the changes of meteorological variables appeared in the 3rd qi stage (from Grain in Beard to Greater Heat), which advanced one phase. The incidence of AR was closely associated with vapor pressure. The correlation coeffifi cients of two predictive models were between 0.8931-0.9176 and all of them have passed signififi cant statistical tests, which showed a satisfactory fifi tting effect. CONCLUSION: Comprehensive meteorological parameters can be used to forecast AR incidence, which is benefifi cial to AR prevention.

Relationship between haze and acute cardiovascular, cerebrovascular, and respiratory diseases in Beijing.

Haze is an atmospheric phenomenon in which dry particulate pollutants obscure the sky. Haze has been associated with chronic diseases, but its relationship with acute diseases is less clear. We aimed to determine the association between haze and acute cardiovascular, cerebrovascular, and respiratory diseases, in order to determine the influence of haze on human health. We compared the number of cases of acute cardiovascular, cerebrovascular, and respiratory diseases in Beijing Emergency Center between 2006 and 2013, with haze data from Beijing Observatory. The relationship between the number of hazy days and the number of cases of the above types of diseases was analyzed using univariate analyses. Both the number of cases and the number of hazy days showed a rising trend. The average number of cases per day for all three diseases was higher on hazy days than on non-hazy days. There was a positive correlation between the number of hazy days and the number of cases, and this correlation showed a hysteretic quality. Haze has an influence on acute cardiovascular (CVDs), cerebrovascular (CBDs), and respiratory system (RSDs) diseases. Haze seems to have an additive effect, since the associations between haze and number of cases were stronger in the following month than in the preceding month. The increasing trend in the number of hazy days might worsen the problem of haze-related diseases.

[Grading forecast research for pathogenesis of allergic rhinitis directed by meteorological elements].

OBJECTIVE: To analyze the correlation between meteorological factors and onset of allergic rhinitis (AR), and to establish the prediction of AR epideminlogical trend. METHODS: According to skin prick test (SPT) data of AR from Beijing Tongren Hospital and meteorological data of Beijing Observatory (2007 -2010) , analyzed the relationship between meteorological factors and onset in patients with AR. To analyze the probability distribution of onset in AR patients, and establish the grade of AR epideminlogical trend index. SPSS 16. O software was used to analyze the data. RESULTS: The peak of onset in patients with AR appeared in 15 - 30 th August. There was significant correlation between the onset of AR patients and air temperature and vapor pressure(r = 0. 7473, F = 206. 13; r =0. 8465, F = 321. 04; all P < 0. 001) , and the peak of air temperature and vapor pressure were one month earlier than the peak of onset AR patients in 4 years. According to the above correlation, nonlinear prediction models of AR were established; used probability grading method, onset index of AR was divided into 4 grades. CONCLUSION: Index grade forecast of AR onset has important guiding significance for AR diagnosis and prophylaxis, offers objective reference information for health departments.

[Correlation between symptoms of pollen allergic rhinitis and pollen grain spreading in summer and autumn].

OBJECTIVE: To analyze the correlation between airborne pollen concentrations and symptoms in patients with pollen allergic rhinitis. METHODS: Durhum sampler was used to collect the pollen concentration and species from June to September in 2011. The clinical skin prick test (SPT) data were analyzed. The patients with pollen allergic rhinitis were divided into pure pollen allergic rhinitis group (pollen group) and pollen combined perennial allergens allergic rhinitis group (combined group). Symptom scores of patients were assessed, and correlation between pollen concentration and onset of symptoms of patients were analyzed. SPSS 16.0 software was used to analyse the data. RESULTS: While the peak of Summer-Autumn pollen concentration appeared from August 20 to September 15, the major pollen included Artemisia L, Chenopodium album and Humulus scandens. The peak of pollen concentration in one day reached 638/1000 mm(2). The patients taken SPT from June to September accounted for 51.9% of the patients in whole year, among which SPT pollen positive patients were 1509, 60.7% of all SPT positive patients. The amount and rate of SPT positive patients showed significant correlation with pollen concentration(r value were 0.90 and 0.99, both P < 0.05). Onset of symptoms in two groups was correlated with pollen concentration in Summer-Autumn. Symptoms of cough in combined group showed more severe compared with patients with pollen group (t = 2.36, P < 0.05). CONCLUSIONS: Pollen concentration has a major effect on onset of symptoms of allergic rhinitis. Airborne pollen monitoring has important preventive and therapeutic significance on patients with allergic rhinitis.

Correlation analysis for the attack of respiratory diseases and meteorological factors.

OBJECTIVE: To investigate the relationship between respiratory diseases onset and the meteorological factors in the same period and in a specific environment. METHODS METHODS: By using the data of daily incidence of respiratory diseases obtained from Dongzhimen Hospital Affiliated to Beijing University of Chinese Medicine from January 1, 1998 to December 31, 2007, and the data of 16 items of meteorological factors (such as the average, maximum, and minimum temperatures, etc., including meteorological factors derived) obtained from the Beijing Municipal Meteorological Observatory, mathematical statistical methods were applied to achieve the non-linear correlation analysis, or the correlation test, between the incidence of respiratory diseases and the time-related meteorological factors. RESULTS: The simple correlation coefficients of the relationship between the incidence of respiratory diseases and 9 meteorological elements, including the average values of temperature, maximum temperature, minimum temperature, degree of comfort, precipitation, vapor pressure, low cloud cover, change of vapor pressure, and change of wind speed, were all greater than 0.8286, in which one of the relationship between the incidence of respiratory diseases and the maximum temperature is as high as 0.9670. Statistical tests showed R>Rα=0.05 and F>Fα=0.05. CONCLUSIONS: The incidence of respiratory diseases was closely correlated to meteorological factors, such as air temperature, vapor pressure, precipitation, wind speed, etc. To a certain extent, this conclusion confirmed the scientificity and objectivity of the theory of five evolutive phases and six climatic factors (Wu Yun Liu Qi ) in Huang Di Nei Jing (The Yellow Emperor's Canon of Internal Medicine).

[The effect of Hongjingtian (Gadol) injection on cardiac hemodynamics and myocardial oxygen consumption of dogs].

OBJECTIVE: To study the effect of Hongjingtian (Gadol) injection on cardiac hemodynamics and myocardial oxygen consumption for analyzing its underlying mechanism in the treatment of coronary heart disease. METHOD: A total of 20 dogs anesthetized with pentobarbital sodium (30 mg x kg(-1), i.v.) were evenly randomized into control group, low-dose Gadol (LDG) group, high-dose Gadol (HDG) group and Herbesser Injection group. The blood flow volume (BFV) of the left coronary artery and cardiac output (CO), left ventricular pressure (LVP), maximum ascending rate (dp/dtmax) of LVP, mean arterial pressure (MAP) of the femoral artery, oxygen contents of the coronary artery and coronary vein (venous sinus), oxygen consumption index (OCI), cardiac index (CI), coronary artery resistance (CAR) and total peripheral resistance (TPR) as well as oxygen utilization rate (OUR) were detected respectively. RESULT: After venous injection of Gadol, CAR, MAP, TPR, OCI, myocardial oxygen consumption and heart rate lowered significantly (P < 0.05-0.01), while BFV and blood oxygen content of the venous sinus increased considerably (P < 0.05-0.01) in comparison with pre-injection. No significant differences were found in LVP and myocardial contractivity between control group and LDG, and between control and HDG groups respectively. CONCLUSION: It showed dilation of the coronary artery and reduction of the cardiac afterload after injection of Gadol. Besides, CO and stroke volume increased considerably and the cardiac effective work was raised without any significant simultaneous increase of both myocardial contractility and LVP. A decrease in the myocardial oxygen consumption and reduction of OCI indicates an improvement of the oxygen supply of the myocardium, and a favorable regulation of the compliance of the cardiac vessels. As a result, the cardiovascular performance was ameliorated. The abovementioned improvement of these indexes may contribute to the therapeutic effect of Gadol in the treatment of coronary heart disease in clinic.