A Sublimable Dinuclear Cuprous Complex Showing Selective Luminescence Vapochromism in the Crystalline State.

A new sublimable dicopper(I) complex bearing 1,2-bis(diphenylphosphino)ethane and 5-trifluoromethyl-3-(2'-pyridyl)pyrazolate ligands has been designed and synthesized, and its crystalline solvated and nonsolvated compounds have also been obtained and investigated. It is shown that only the crystalline solvated compound exhibits reversible and selective luminescence vapochromism, arising from its unique "pyridyl/CH2Cl2/pyridyl" organic sandwich-like stacking arrangement revealed by X-ray crystallography, as supported by time-dependent density functional theory calculations. Additionally, the neutral Cu(I) complex has excellent thermal stability and sublimability, good solid-state luminescence properties, and TADF character, and it is suggested to be a good emitter for vapor-deposited organic light-emitting diodes.

[Multiple time-scale analysis of nitrogen retention characteristics and influencing factors in Shanmei Reservoir, Fujian, China.] / å±±ç¾Žæ°´åº“æ°®è¥å »ç›æ»žç•™ç‰¹å¾åŠå ¶å½±å“å› ç´ çš„å¤šæ—¶é—´å°ºåº¦åˆ†æž.

The retention effect of reservoir on nitrogen is an important influence factor on the eutrophication prevention and control. In order to reveal the differences of nitrogen retention characteristics and the influence factors at multiple timescales, an ecological dynamic model was developed in Shanmei Reservoir watershed. Based on the retention flux and retention rate calculation, the nitrogen retention effect was analyzed at three time scales of yearly, monthly and daily, respectively. Furthermore, multiple linear correlation analysis was conducted to analyze the influence of inflow runoff, ratio of inflow to outflow, residence time, velocity and temperature on the retention of nitrogen in the reservoir. The results showed that the process of nitrogen retention always displayed fluctuant characteristic at different time scales. On a yearly scale, the reservoir mainly played a role of nitrogen sink; on a monthly scale, seasonal variation of nitrogen retention and release effect made the reservoir as nitrogen sink in wet period and as nitrogen source in dry period; on a daily scale, the nitrogen retention process fluctuated intensely, with the retention rate ranging from -300% to 100% in dry year. At different time scales, ratio of inflow to outflow and velocity were always the important factors to affect nitrogen retention in the reservoir, with significant correlation coefficients consistently. With the time scale changing from yearly to monthly, daily, the influence degree of inflow runoff and temperature on nitrogen retention was gradually strengthened. The correlations between the residence time and retention rate could be positive or negative at different time scales.

[Multiple time scales analysis of spatial differentiation characteristics of non-point source nitrogen loss within watershed].

Identification of the critical source areas of non-point source pollution is an important means to control the non-point source pollution within the watershed. In order to further reveal the impact of multiple time scales on the spatial differentiation characteristics of non-point source nitrogen loss, a SWAT model of Shanmei Reservoir watershed was developed. Based on the simulation of total nitrogen (TN) loss intensity of all 38 subbasins, spatial distribution characteristics of nitrogen loss and critical source areas were analyzed at three time scales of yearly average, monthly average and rainstorms flood process, respectively. Furthermore, multiple linear correlation analysis was conducted to analyze the contribution of natural environment and anthropogenic disturbance on nitrogen loss. The results showed that there were significant spatial differences of TN loss in Shanmei Reservoir watershed at different time scales, and the spatial differentiation degree of nitrogen loss was in the order of monthly average > yearly average > rainstorms flood process. TN loss load mainly came from upland Taoxi subbasin, which was identified as the critical source area. At different time scales, land use types (such as farmland and forest) were always the dominant factor affecting the spatial distribution of nitrogen loss, while the effect of precipitation and runoff on the nitrogen loss was only taken in no fertilization month and several processes of storm flood at no fertilization date. This was mainly due to the significant spatial variation of land use and fertilization, as well as the low spatial variability of precipitation and runoff.

3-(3-Methyl-phen-yl)-5-(quinolin-8-yl-meth-oxy)-1,2,4-oxa-diazole monohydrate.

In the title compound, C19H15N3O2·H2O, the oxa-diazole ring and the quinoline unit are almost coplanar, making a dihedral angle of 7.66 (8)°. The dihedral angle between the benzene ring and the quinoline system is 25.95 (8)° while that between the benzene and the oxa-diazole rings is 18.88 (9)°. The water mol-ecule is hydrogen bonded to an oxa-diazole N atom and to the quinoline N atom. In the crystal, these units are linked via C-H⋯O hydrogen bonds, forming two-dimensional net-works lying parallel to the ab plane.

Synthesis, supramolecular behavior, and in vitro photodynamic activities of novel zinc(II) phthalocyanines "side-strapped" with crown ether bridges.

Two new tetra- or di-α-substituted zinc(II) phthalocyanines 5 and 6 have been prepared through a "side-strapped" method. In the molecules, the adjacent benzene rings of the phthalocyanine core are linked at α-position through a triethylene glycol bridge to form a hybrid aza-/oxa-crown ether. The tetra-α-substituted phthalocyanine 5 shows an eclipsed self-assembly property in CH2Cl2 and the effect on the di-α-substituted analogue 6 is significantly weakened. Furthermore, the crown ethers of these compounds can selectively complex with Fe(3+) or Cu(2+) ion in DMF, leading to formation of J-aggregated nano-assemblies, which can be disaggregated in the presence of some organic or inorganic ligands, such as triethylamine, tetramethylethylenediamine, CH3COO(-), or OH(-). In addition, both compounds are efficient singlet oxygen generators with the singlet oxygen quantum yields (Φ(Δ)) of 0.54-0.74 in DMF relative to unsubstituted zinc(II) phthalocyanine (Φ(Δ)=0.56). They exhibit photodynamic activities toward HepG2 human hepatocarcinoma cells, but the compound 6, which has more than 40-fold lower IC50 value (0.08 µM) compared to the analogue 5 (IC50=3.31 µM), shows remarkablely higher in vitro photocytotoxicity due to its significantly higher cellular uptake and singlet oxygen generation efficiency. The results suggest that these compounds can serve as promising multifunctional materials both in (opto)electronic field and photodynamic therapy.

[Coupling SWAT and CE-QUAL-W2 models to simulate water quantity and quality in Shanmei Reservoir watershed].

A coupled watershed-reservoir modeling approach consisting of a watershed distributed model (SWAT) and a two-dimensional laterally averaged model (CE-QUAL-W2) was adopted for simulating the impact of non-point source pollution from upland watershed on water quality of Shanmei Reservoir. Using the daily serial output from Shanmei Reservoir watershed by SWAT as the input to Shanmei Reservoir by CE-QUAL-W2, the coupled modeling was calibrated for runoff and outputs of sediment and pollutant at watershed scale and for elevation, temperature, nitrate, ammonium and total nitrogen in Shanmei Reservoir. The results indicated that the simulated values agreed fairly well with the observed data, although the calculation precision of downstream model would be affected by the accumulative errors generated from the simulation of upland model. The SWAT and CE-QUAL-W2 coupled modeling could be used to assess the hydrodynamic and water quality process in complex watershed comprised of upland watershed and downstream reservoir, and might further provide scientific basis for positioning key pollution source area and controlling the reservoir eutrophication.

[History of pregnancy induced hypertension is linked with increased risk of cardio-cerebral vascular events].

OBJECTIVE: To compare the incidence of cardio-cerebral vascular events between pregnancy induced hypertension (PIH) women and non-PIH(NPIH) women. METHODS: Ambispective cohort study method was used and 4630 pregnant women giving birth during October 1976 to December 2008 in our hospital and participated the healthy examination between July 2006 and October 2007 at Kailuan medical group were included and divided into PIH group (n = 694) and NPIH group (n = 3936) by the history of PIH. Incidence of cardio-cerebral vascular events (myocardial infarction, cerebral infarction and cerebral hemorrhage) was obtained during follow-up. Multivariable Cox proportional hazards regression models was used to assess the relative risk of cardio-cerebral vascular events. RESULTS: (1) The follow-up time was 2 to 34 (15.32 ± 7.94) years. (2) The childbearing age, systolic blood pressure and diastolic blood pressure before delivery were significantly higher while gestational weeks and weight of newborn were significantly less in PIH group than in NPIH group (all P < 0.01). Levels of systolic blood pressure, diastolic blood pressure, waist circumference, body mass index, triglyceride, total cholesterol and fasting blood glucose during healthy examination between July 2006 and October 2007 were significantly higher in PIH group than in NPIH group (P < 0.05 or P < 0.01). (3) There were 71 cardio-cerebral vascular events during the follow-up. In PIH group, the incidence rate of cardio-cerebral vascular events, myocardial infarction and cerebral infarction was 20.64%, 11.08% and 8.67%, respectively, while the corresponding incidence rate was 7.82%, 4.02% and 2.67% in NPIH group (all P < 0.01). After adjustment for other traditional cardiovascular risk factors, the risk of total cardio-cerebral vascular events, myocardial infarction and cerebral infarction in PIH group was 2.99 fold (95%CI: 1.80 - 4.95), 3.91 fold (95%CI: 1.71 - 8.91) and 3.96 fold (95%CI: 1.95 - 8.05) higher than in NPIH group. CONCLUSION: PIH is an independent risk factor for cardio-cerebral vascular events.

Improved absorption of salmon calcitonin by ultraflexible liposomes through intranasal delivery.

The objective of this work was to explore the potential of ultraflexible liposomes as carriers for improving the absorption of salmon calcitonin (sCT) through intranasal administration. The average diameters of positively charged ultraflexible liposomes ranged from about 73 to 99 nm, while those of negatively charged ones were 114 and 157.6 nm, respectively. The content of sodium deoxycholate in liposomes markedly affected the size and encapsulated efficiency of liposomes. The absorption of sCT through intranasal administration was evaluated by hypocalcemic efficacy in rats. The total Ca decrease D% of sCT-loaded ultraflexible liposomes with positive and negative charges were significantly bigger than that of sCT solution, while there was no significant difference in the hypocalcemic efficacy between plain liposome and sCT solution. Unexpectedly, the hypocalcemic efficacy of sCT-loaded ultraflexible liposomes with positive charges was not significantly better than those with negative charges. The decrease rate and extent of the serum calcium level for subcutaneous injection of sCT solution were almost equivalent to those for intranasal administration of negatively and positively charged ultraflexible liposomes within the first 2h, indicating that the ultraflexible liposomes could quickly enhance the penetration of the drug during their residence in the nasal cavity. The results of the toxicity of sCT-loaded ultraflexible liposomes to nasal mucosa demonstrated that the ultraflexible liposomes exerted slight toxicity on the nasal mucosa. On an overall evaluation, the ultraflexible liposomes may be a useful vehicle for intranasal delivery of sCT.

[Preparation of brain targeted immunoliposomes].

To prepare a kind of effective non-viral transduction vector, which can deliver exogenous gene into the brain, this vector can be injected through vein system and has the ability to penetrate blood brain barrier. Several groups of materials proportion, type of oil phase, water-oil ratio, phosphatides-cholesterol ratio, temperature of steaming, ultrasonic temperature and time were compared for optimization. Well-constructed immunoliposomes encapsuling LacZ gene were infused into rats through tail vein. 48 h after injection, expression product beta-galactosidase of LacZ gene was detected by histochemistry staining to convince the validity of immunoliposomes as non-viral vectors. The best proportion of synthesis immunoliposomes is as following: phosphatides-cholesterol ratio is 1:1, lipids/drug is 100:1, the type of oil phrase is dichloromethane, oil-water ratio is 4:1, temperature of steaming is 30 degrees C, ultrasonic temperature and time is 10 degrees C and 5 min. At last, 10% trehalose was added as a stabilizer. The entrapment rate is 87.24% and antibody coupling rate is 69%. When immunoliposomes were infused into rats, the expression of LacZ gene could be observed in the brain and periphery organs. Through the best proportion of materials, gene delivering immunoliposomes had been synthesized successfully. This non-viral vector can deliver exogenous gene penetrating blood brain barrier and express in the brain, and will be well-used in the field of gene therapy of cerebral diseases.