A dihydro-benzo[4,5]imidazo[1,2-c]quinazoline-based probe with aggregation-induced ratiometric emission for the ratiometric fluorescent detection of peroxynitrite in living cells and zebrafish.

As a significant kind of reactive oxygen species (ROS), peroxynitrite (ONOO-) plays an indispensable role in many physiological and pathological processes. This study aimed to synthesize a novel dihydro-benzo[4,5]imidazo[1,2-c]quinazoline-based probe 1 for detecting ONOO-. In 99.5% H2O solution, probe 1 displayed a distinct aggregation-induced ratiometric emission (AIRE), and would selectively respond toward ONOO-via a ratiometric fluorescent signal, along with a short response time (<30 s) and ultra-sensitivity (LOD = 17.6 nM). Moreover, the probe was applied for monitoring the concentration fluctuations of ONOO- in HeLa cells and zebrafish.

A novel AIRE-based fluorescent ratiometric probe with endoplasmic reticulum-targeting ability for detection of hypochlorite and bioimaging.

Hypochlorite (ClO-) plays an important role in the human immune defense system, but high concentrations of ClO- in the endoplasmic reticulum (ER) damage cellular proteins, causing ER stress, cell death, and various diseases. Herein, we developed a simple hydrazone probe (1) featuring aggregation-induced ratiometric emission, which would quickly (within 20 s) and sensitively (detection limit of 15.4 µM) respond to ClO- in an almost pure aqueous solution via a fluorescent ratiometric output. Furthermore, the probe was employed to track the level of ClO- in the ER of HeLa cells and zebrafish.

A novel indene-chalcone-based fluorescence probe with lysosome-targeting for detection of endogenous carboxylesterases and bioimaging.

An indene-chalcone-based fluorescence probe 1 was synthesized and characterized. Under physiological conditions (containing 5% DMSO), probe 1 showed satisfactory stability with a low background signal and recognized carboxylesterases (CEs) based on the catalytic hydrolysis of ester groups, releasing a significant green fluorescence. Probe 1 presents several features including a short response time (within 20 min), low detection limit (1.3 × 10-4 U/mL) and large stokes shift (over 155 nm). Notably, commercial lysosomal dye co-staining experiments illustrated the lysosomal localization function of 1, with the probe also being used for cell and zebrafish imaging of endogenous CEs.

TLR4 Knockout Attenuates BDL-induced Liver Cholestatic Injury through Amino Acid and Choline Metabolic Pathways.

The exact mechanism by which knockout of Toll-like receptor 4 (TLR4) attenuates the liver injury remains unclear. The present study aimed to examine the role of TLR4 in the pathogenesis of bile duct ligation (BDL)-induced liver cholestatic injury and the underlying mechanism. Wild type (WT) mice and TLR4 knockout (TLR4-KO) mice were used for the establishment of the BDL model. Metabolomics were applied to analyze the changes of small molecular metabolites in the serum and liver of the two groups. The serum biochemical indexes and the HE staining results of liver tissue showed that liver damage was significantly reduced in TLR4-KO mice after BDL when compared with that in WT mice. The metabolite analysis results showed that TLR4 KO could maintain the metabolisms of amino acids- and choline-related metabolites. After BDL, the amino acids- and choline-related metabolites, especially choline and 3-hydroxybutyrate, were significantly increased in WT mice (both in serum and liver), but these metabolites in the liver of TLR4-KO mice after BLD were not significant different from those before BLD. In conclusion, TLR4 KO could attenuate BDL-induced liver cholestatic injury through regulating amino acid and choline metabolic pathways.

[Three-dimensional Fluorescence Spectral Characteristics of Different Molecular Weight Fractionations of Dissolved Organic Matter in the Water-level Fluctuation Zones of Three Gorges Reservoir Areas].

The study of the molecular weight (MW) fractions of dissolved organic matter (DOM) in aquatic environment is of interests because the size plays an important role in deciding the biogeochemical characteristics of DOM. Thus, using ultrafiltration ( UF) technique combined with three-dimensional fluorescence spectroscopy, DOM samples from four sampling sites in typical water-level fluctuation zones of Three Gorge Reservoir areas were selected to investigate the differences of properties and sources of different DOM MW fractions. The results showed that in these areas, the distribution of MW fractions was highly dispersive, but the approximately equal contributions from colloidal (Mr 1 x 10³-0.22 µm) and true dissolved fraction (Mr < 1 x 10³) to the total DOC concentration were found. Four fluorescence signals (humic-like A and C; protein-like B and T) were observed in all MW fractions including bulk DOM, which showed the same distribution trend: true dissolved > low MW (Mr 1 x 10³-10 x 10³) > medium MW (Mr 10 x 10³-30 x 10³) > high MW (Mr 30 x 10³-0.22 µm). Additionally, with decreasing MW fraction, fluorescence index (FI) and freshness index (BIX) increased suggesting enhanced signals of autochthonous inputs, whereas humification index ( HIX) decreased indicating lowe humification degree. It strongly suggested that terrestrial input mainly affected the composition and property of higher MW fractions of DOM, as compared to lower MW and true dissolved fractions that were controlled by autochthonous sources such as microbial and alga activities, instead of allochthonous sources. Meanwhile, the riparian different land-use types also affected obviously on the characteristics of DOM. Therefore, higher diversity of land-use types, and also higher complexity of ecosystem and landscapes, induced higher heterogeneity of fluorescence components in different MW fraction of DOM.

[Characteristics of absorption and fluorescence spectra of dissolved organic matter from confluence of rivers: case study of Qujiang River-Jialing River and Fujiang River-Jialing River].

Three-dimensional fluorescence spectroscopy combined with ultraviolet-visible (UV-Vis) absorption spectra was used to investigate the change characteristics of dissolved organic matter (DOM) in confluences water of Qujiang River-Jialing River and Fujiang River-Jialing River, respectively. The results suggested that DOM showed a significant terrestrial input signal in all the sampling sites, FI < 1.4, HIX > 0.8, possibly representing remarkable signals of humus resulted from humic-like component. Moreover, the mixing zone of this study showed a non-conservative mixed behavior, which had a limited contribution, and was not the dominant factor to interpret the change characteristics of DOM in confluences zones. Different land-use types along all the rivers had an obvious impact on DOM inputs. Results of cluster analysis showed that a higher degree of aromaticity and humification components was observed as the predominant contributor to DOM when the land-use type was forest and farmland ecosystem, for example the confluences of Qujiang River-Jialing River. On the other hand, high concentrations of DOM with relative simple structures were found in the water when the urban land-use type was predominant, for example the confluences of Fujiang River-Jialing River. Meanwhile, a new fluorescent signal of protein-like components (peak T) appeared, which manifested a significant effect on the water quality resulted from anthropogenic activities.

[Ultraviolet-visible (UV-Vis) and fluorescence spectral characteristics of soil dissolved organic matter (DOM) in typical agricultural watershed of Three Gorges Reservoir Region].

As an important geo-factor to decide the environmental fate of pollutants in watershed, soil dissolved organic matter (DOM) sampled from a typical agricultural watershed in the Three Gorges Reservoir area was investigated using ultraviolet-visible (UV-Vis) and fluorescence spectroscopies, to analyze and discuss the effect of different land uses including forest, cropland, vegetable field and residence, on soil DOM geochemical characteristics. The results showed that significant differences in DOM samples amongst different land uses were observed, and DOM from forest had the highest aromaticity and humification degree, followed by DOM from cropland. Although DOM from vegetable field and residence showed the highest dissolved organic carbon (DOC) concentration (average values 0.81 g x kg(-1) and 0.89 g x kg(-1), respectively), but the aromaticity was lower indicating lower humification, which further suggested that the non-chromophoric component in these DOM samples contributed significantly to total DOM compositions. Additionally, in all DOM samples that were independent of land uses, fluorescence index (FI) values were between 1.4 (terrigenous) and 1.9 (authigenic) , evidently indicating both the allochthonous and autochthonous sources contributed to DOM characteristics. Meanwhile, r(T/C) values in most of samples were higher than 2.0, suggesting that soil DOM in this agricultural watershed was heavily affected by anthropogenic activities such as agricultural cultivation, especially, vegetable field was a good example. Additionally, sensitivities of different special spectral parameters for reflecting the differences of DOM characteristics amongst different land uses were not identical. For example, neither spectral slope ratio (S(R)) nor humification index (HIX) could clearly unveil the various geochemical characteristics of soil DOM from different sources. Thus, simple and single special spectral parameter cannot comprehensively provide the detailed information of DOM, and combined application of UV-Vis and fluorescence spectroscopies is highly recommended.

[Absorption and fluorescence characteristics of dissolved organic matter (DOM) in rainwater and sources analysis in summer and winter season].

This study aimed at evaluating the variability of the optical properties including UV-Vis and fluorescence characteristics of dissolved organic matter (DOM) from rainwater in summer and winter seasons. UV-Vis and fluorescence spectroscopy, together with Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and fire events map, were conducted to characterize DOM and investigate its sources and contributions. The results showed that as compared with aquatic and soil DOM, rainwater DOM showed similar spectral characteristics, suggesting DOM in precipitation was also an important contributor to DOM pool in terrestrial and aquatic systems. The concentrations of DOC in rainwater were 0.88-12.80 mg x L(-1), and the CDOM concentrations were 3.17-21.11 mg x L(-1). Differences of DOM samples between summer and winter were significant (P < 0.05). In comparison to summer, DOM samples in winter had lower molecular weight and aromaticity, and also lower humification. Input of DOM in winter was predominantly derived from local and short-distance distances, while non-special scattering sources were identified as the main contributors in summer. Although absorption and fluorescence spectroscopy could be used to identify DOM composition and sources, there were obvious differences in spectra and sources analysis between rainwater DOM and the others from other sources. Thus, the classic differentiation method by "allochthonous (terrigenous) and autochthonous (authigenic)" is possibly too simple and arbitrary for characterization of DOM in rainwater.

[Ultraviolet-visible (UV-Vis) and fluorescence spectral characteristics of dissolved organic matter (DOM) in soils of water-level fluctuation zones of the Three Gorges Reservoir Region].

Ultraviolet-visible (UV-Vis) absorption spectroscopy and three-dimensional fluorescence spectroscopy, combined with fluorescence regional integration were conducted to investigate the geochemical characteristics of DOM extracted from soils of water-level fluctuation zones of the Three Gorges Reservoir Region. The results showed that the average CDOM concentrations in soils were in order of Zhongxian > Fengdu > Fuling > Wanzhou > Wushan > Yunyang > Fengjie > Kaixian. Additionally, in Zhongxian, Fengdu and Fuling, the CDOM concentration [a (355)], aromaticity (SUVA254) and hydrophobicity (SUVA260) were all much higher than those at the other sampling sites, but the humification index (HIX) was lower. Four fluorophores were observed in all soil DOM samples, including three humic-like fluorescence peaks (A, C and M respectively) and one tryptophan-like fluorescence peak (T). Proportion of fluorescence regional integration of ultraviolet region humic-like A fluorophore was the highest as compared with the others. More importantly, tryptophan-like fluorophore (T) and a(355) showed significant correlation (r = 0.674, P < 0.01), indicating the variance of CDOM concentration was possibly dependent on T fluorophore. Meanwhile, the total integrated fluorescence intensity(TOT) of 3D- EEM was an appropriate parameter to characterize the total contributions of fluorophores in DOM. Furthermore, the humification degree of DOM in soils was low in comparison with higher biological availability. Conclusively it seemed that the influence of "alternation of wetting and drying" resulted from water-level fluctuation on the geochemical characteristics of soil DOM was not significant as expected. It might be related to local agricultural activity, littoral plant growth and DOM mineralization process.

[Photobleaching of dissolved organic matter (DOM) from confluence of two rivers under natural solar radiation: a case study of Fujiang River-Jialingjiang River].

Three-dimensional fluorescence spectroscopy combined with ultraviolet-visible absorption spectra was used to investigate the photobleaching process of dissolved organic matter (DOM) sampled from Fujiang River (FJ), Jialingjiang River (JLJ) and the confluence (FJ-JLJ) under natural solar radiation. The results indicated that obvious photochemical degradation of colored dissolved organic matter (CDOM) concentration [ α(280) ] and all fluorescence peaks intensity (A, C, M and T) occurred under natural solar radiation, and the degradation degree was in order of JLJ > FJ-JLJ > FJ. Photobleaching properties of DOM samples from different locations showed significant differences, which could be partially explained by the sampling sites surroundings including various landuse types, and dilution effect of river confluence. Light-induced bleaching activity of JLJ samples, which was mainly terrestrial input from forest system, was the highest as compared to the lowest activity of FJ samples, which was predominated by urban inputs. Samples from confluence were in the middle. Additionally, the spectrum slope(S) and absorbance ratio (A250/A350) were increased, while the humification index(HIX) was decreased with increasing irradiation time, which can be used as important indicators for photobleaching properties changes during the process. More importantly, the predominantly allochthonous (terrigenous) characteristics of DOM almost showed a tendency of transferring to autochthonous (authigenic) characteristics due to photobleaching. Especially, IT/Ic firstly decreased and then increased significantly in the process. Thus the photodegradation process may exaggerate DOM autochthonous contribution, and further interfere with the assessment of anthropogenic impacted-water quality by using IT/Ic. In addition, mechanisms of light-induced DOM degradation process consistently showed by absorption and fluorescence spectrum parameters suggested the validation of analyzing DOM geochemical characteristics by the two important spectra tools.

[Using ultraviolet-visible ( UV-Vis) absorption spectrum to estimate the dissolved organic matter (DOM) concentration in water, soils and sediments of typical water-level fluctuation zones of the Three Gorges Reservoir areas].

Dissolved organic matter (DOM) is a very important component in terrestrial ecosystem. Chromophoric dissolved organic matter (CDOM) is a significant constituent of DOM, which can be measured by ultraviolet-visible (UV-Vis) absorption spectrum. Thus the relationship between CDOM and DOM was investigated and established by several types of models including single-wavelength model, double-wavelength model, absorption spectrum slope (S value) model and three-wavelength model, based on the UV-Vis absorption coefficients of soil and sediment samples (sampled in July of 2012) and water samples (sampled in November of 2012) respectively. The results suggested that the three-wavelength model was the best for fitting, and the determination coefficients of water, soil and sediment data were 0. 788, 0. 933 and 0. 856, respectively. Meanwhile, the nominal best model was validated with the UV-Vis data of 32 soil samples and 36 water samples randomly collected in 2013, showing the RRMSE and MRE were 16. 5% and 16. 9% respectively for soil DOM samples, 10. 32% and 9. 06% respectively for water DOM samples, which further suggested the prediction accuracy was higher in water DOM samples as compared with that in soil DOM samples.

[Ultraviolet-visible (UV-Vis) spectral characteristics of dissolved organic matter (DOM) in soils and sediments of typical water-level fluctuation zones of Three Gorges Reservoir areas].

Dissolved organic matter (DOM) is a very important component in terrestrial ecosystem, which also plays a key role in geo-environmental chemistry. A number of DOM samples were extracted from soils and sediments samples obtained from typical water-level fluctuation zones of Three Gorges reservoir areas. Ultraviolet-visible (UV-Vis) absorption spectra were recorded for unveiling the geochemical characteristics of DOM based on specific absorption parameters and fitting models. Through the results of specific absorption parameters, it was suggested that the aromaticity, hydrophobicity and humification degree were lower in soils than in the surface sediments, which were also independent of the sampling location height and land-use types. Among the four absorption models selected, model 2 was the optimal. Meanwhile, different models and fitting wavelengths also significantly affected the absorption spectral slope (S value): S increased with the decreasing wavelength. Additionally, the correlation among different S values obtained from different fitting wavelength ranges was significantly different suggesting that the S values in various wavelength ranges only indicated the tip of the iceberg of DOM characteristics instead of the entirety. Furthermore, the ratio of specific spectral slope (S(R)) indicated lower degradation (photo-bleaching or microbial degradation) degree in the surface sediments as compared to those in soils and older sediments. The surface sediments had higher aromaticity, hydrophobicity, molecular weight and photochemical/ biodegradation activity potentials, suggesting fresher DOM, lower effect of photobleaching and microbial degradation activities.

[Characteristics of phosphorus forms and the effects of UV light in the confluences water of Qujiang-Jialing River and Fujiang-Jialing River].

The confluences water of Qujiang-Jialing River and Fujiang-Jialing River was investigated in this paper for understanding the characteristics of phosphorus (P) forms and the effects of ultraviolet (UV) irradiation. Through analysis of P speciation, the results showed that the concentration of total P was above the Eutrophication threshold (0.2 mmol x m(-3)) in this study. Meanwhile, total dissolved P (TDP) and dissolved inorganic P (DIP) were the predominant forms of total P (TP) and TDP respectively at all sampling sites, which was independent of confluences. After confluences of Fujiang-Jialing River and Qujiang-Jialing River, the concentration of all forms of P in main stream increased, among which particulate P (PP) showed the greatest increase of up to 129%. Furthermore, water was fractionated by relative molecular weight (M(r)) of composition, and the results showed the predominant forms of dissolved P (DP, < 0.22 µm) was in the soluble high M(r) fraction (0.5 x 10(3)-10 x 10(3)), which was ranged from 47%-61% of DP. After confluences, no significant changes of P contents in different M(r) fraction of water were observed in the main stream (Jialing River). Moreover, UV irradiation experiment was conducted, and it suggested that P in free forms of water (< 0.5 x 10(3)) increased by 10% - 29%, as compared with the decreasing P in the other two M(r) fractions of M(r) 10 x 10(3)-0.22 µm and 0.5 x 10(3)-10 x 10(3). Additionally, in comparison with confluence site samples of Fujiang-Jialing River, the decreasing trend of P in colloid fraction (10 x 10(3)-0.22 µm) was higher in Qujiang-Jialing River. Thus, it confirmatively indicated that UV was an important environmental factor influencing the geochemical fate of P in aquatic system.

[Effects of light irradiation on phosphorous releases from typical submerged soils of water-level fluctuation zones of Three Gorges Reservoirs areas].

For understanding the impact of light irradiation on the phosphorus (P) releases from soil-water interface, two types of typical soils sampled from water-level fluctuation zones of Three Gorges Reservoir areas were selected as research objectives, and simulated light irradiation experiment in lab was conducted for unveiling the underlying mechanisms of P releases from submerged soils in the presence of light irradiation. The results showed that light irradiation could inhibit P releases from submerged soils by a certain degree. Under light condition, total P (TP) concentrations in underlying water of submerged purple soil ranged from 0.018 to 0.033 mg x L(-1), as compared to the range of 0.02-0.057 mg x L(-1) in darkness treatment. Additionally, for gray-brown purple soil, TP was in a range of 0.028-0.045 mg x L(-1) when light irradiated, but in the range of 0.04-0. 084 mg x L(-1) under darkness condition. Meanwhile, changes of iron oxides in soils due to light irradiation were possibly to be the important reason to explain the inhabitation of light irradiation on P releases. Moreover, light irradiation resulted in decreasing saturation degree of iron oxides in soils, which further inhibited the iron reduction and production of amorphous iron, further enhanced the underlying mechanisms of decreasing P releases in presence of light irradiation. Further, CO2 and CH4 could reflect decomposition of soil organic carbon (SOC) in submerged condition. Light irradiation significantly decreased SOC transformation into carbon gases. Stimulating consumption of inorganic electron acceptors in submerged soils could also be used to explain the changes of iron oxides under light irradiation condition. Thus, inhabitation of light irradiation on P releases from submerged soils obviously related with iron minerals reduction and decomposition of organic matter in soils.

(1-Oxo-2,6,7-trioxa-1-phosphabicyclo-[2.2.2]octan-4-yl)methyl 4-methyl-benzene-sulfonate.

In the title compound, C(12)H(15)O(7)PS, the P atom has a distorted tetra-hedral environment. The P-O-C-C torsion angles deviate significantly from zero [average = 12.0 (3)°], indicating that the bicyclic OP(OCH(2))(3)C cage is strained. In the crystal, weak C-H⋯O inter-actions consolidate the packing.

Enhanced removal of bilirubin on molecularly imprinted titania film.

Titania film imprinted by bilirubin molecule at the surface of quartz crystal was prepared using molecular imprinting and surface sol-gel process. The molecularly imprinted titania film was characterized by FTIR spectra, and the interaction between bilirubin and imprinted film was investigated using quartz crystal microbalance (QCM) technique. Compared with pure titania film, the molecularly imprinted titania film exhibits a much higher adsorption capacity for the target molecule, and the adsorption kinetic parameter estimated from the in situ frequency measurement is about 1.6×10(8) M(-1), which is ten times higher than that obtained on pure titania film. The photocatalytic measurements indicate that the bilirubin adsorbed on molecularly imprinted titania film can be completely removed under UV illumination. Moreover, our study indicates that the molecularly imprinted titania film possesses a better stability and reusability.

Isolation, identification and degradation characterization of a p-chloroaniline degrading strain.

A bacterium (strain ycsd02) was isolated from rhizosphere soil in phragmites wetland using the enrichment culture contaminated with p-Chloroaniline (p-CA). Morphology, physio-biochemical characteristics and phylogenetic analysis based on 16S rDNA sequence indicated that the shape of the single cell is pole, which clearly belongs to Bacillus licheniformis. The optimal conditions for satisfactory degradation of p-CA were also studied. A dynamic test indicated that the biodegradation had no lag phase at concentrations from 0 to 20 mg/L in minimal medium culture fluids at vaccination of 15%, pH 7.0 and 32°C, and the growth of strain ycsd02 cells met the first-order kinetics.

1-Methyl-3-trifluoro-methyl-1H-pyrazol-5-ol.

In the title compound, C(5)H(5)F(3)N(2)O, the F atoms are disordered over two sets of sites in a 0.64 (3):0.36 (3) ratio. In the crystal structure, O-H⋯N hydrogen bonds link the mol-ecules into chains and a short C-H⋯F contact also occurs.

[The clinical analysis of with 106 cases aortic dissection].

OBJECTIVE: To explore the risk factors clinical appearance and examination methods of aortic dissection (AD). METHOD: The clinical data of 106 AD patients admitted from the January, 2001 to July, 2004 were retrospectively reviewed. RESULTS: The symptoms and physical signs of the 106 AD patients were diverse. Chest pain was a common initial symptoms but some patients initial symptoms were atypical. The origins of AD was in ascending aorta when patients had clinical appearance mimicking myocardial infarction, and in descending aorta when patients had pain involving shoulders, dorsum, waist, abdomen or lower limbs. Hypertension was the most important cause of AD. The combination use of echocardiography, CT and MRI may help to make rapid diagnosis. CONCLUSIONS: The symptoms and physical signs of AD were diverse. Clinical symptom had some relationship with the origin of AD, the form of AD and hypertension had obvious relations. An obvious correlation exited between the occurrence of AD and hypertension.