Iodine-Mediated Difunctionalization of Imidazopyridines with Sodium Sulfinates: Synthesis of Sulfones and Sulfides.

Novel iodine-induced sulfonylation and sulfenylation of imidazopyridines have been described using sodium sulfinates as the sulfur source. This strategy enables highly selective difunctionalization of imidazo[1,2-a]pyridine to access sulfones and sulfides in good yields. A wide range of substrates and functional groups were well-tolerated under optimized conditions. Moreover, control experiments have been conducted, indicating a radical pathway involved in the reaction mechanisms.

Reactivity of p-Toluenesulfonylmethyl Isocyanide: Iron-Involved C-H Tosylmethylation of Imidazopyridines in Nontoxic Media.

A novel iron-involved tosylmethylation of imidazo[1,2-α]pyridines with p-toluenesulfonylmethyl isocyanide in a solvent mixture of H2O and PEG400 under an Ar atmosphere has been developed. This protocol provides a facile synthetic route for the functionalization of the imidazo[1,2-α]pyridine scaffold with broad substrate compatibility, which is less expensive and environmentally friendly. The current methodology could further enable regioselective C-H tosylmethylation of indole at the C3 position. Also, p-toluenesulfonylmethyl isocyanide was utilized as the tosylmethylating reagent for the first time.

[Contribution Analysis of External Source Pollution Load and Environmental Capacity Estimation of Reservoirs in Central Yunnan Plateau].

To explore the source of the pollution load and its contribution rate in the upper reaches of the plateau reservoir and to analyze the water environment capacity of the reservoir, we selected the Chaishitan Reservoir in the Yunnan Plateau as the research object, applied the pollutant discharge coefficient method to estimate the source of external pollution in the upstream basin of the reservoir, used the simultaneous monitoring data of hydrology and water quality to calculate pollution load into the reservoir, and used the eutrophication model to calculate the maximum capacity of TN and TP in the reservoir under different water quality target scenarios. The results showed that:① the main characteristic pollutants in Chaishitan Reservoir and the above basin were TN and TP. ② COD and TP in the upper reaches of the reservoir mainly came from rural non-point source pollution, with contribution rates of 49.40% and 50.11%, respectively; NH4+-N and TN mainly came from urban domestic pollution sources, with contribution rates of 45.76% and 33.77%, respectively. Among the contributions of rural non-point source pollution, the contribution rates of COD and TP in Luliang District were 34.82% and 36.82%, respectively. The contributions of COD, NH4+-N, TN, and TP to urban domestic pollution were the highest in Qilin District, all of which were up to 65%. ③ The inflows of COD, NH4+-N, TN, and TP were 28050.90, 2465.16, 4680.54, and 870.93 t·a-1, respectively. The inflow of TN and TP pollution load was 4637.80 t·a-1 and 125.04 t·a-1, respectively. ④ When the target of water quality was Class Ⅲ, and the requirements of the Water Function Zoning of Yunnan province were met, the environmental capacities of TN and TP were 1102.62 t·a-1 and 54.85 t·a-1, respectively. Rural non-point source pollution and urban domestic pollution sources were the main sources of pollution in the upper reaches of Chaishitan Reservoir, which were priority control sources. These research results can provide a scientific theoretical basis for pollution source treatment in the plateau reservoir basin.

Study on the supramolecular system of 5-(p-hydroxyphenyl)-10,15,20-tris-(4-chlorophenyl)porphyrin with cyclodextrins and its analytical characteristics.

The supramolecular systems of 5-(p-hydroxyphenyl)-10,15,20-tris-(4-chlorophenyl)porphyrin (p-HTClPP) with beta-cyclodextrin (beta-CD), heptakis(2,3,6-tri-O-methyl)-beta-CD (TM-beta-CD), carboxymethyl-beta-cyclodextrin (CM-beta-CD) and sulfurbutylether-beta-CD (SBE-beta-CD) have been investigated by means of absorption, fluorescence and (1)H NMR spectroscopy. The formation of inclusion complexes has been confirmed on the base of changes of spectroscopy properties. "The double reciprocal method" has been used to determine the stoichiometry and the inclusion constants of p-HTClPP with the four cyclodextrins (CDs). The results show that p-HTClPP can form 1:1 inclusion complexes with the four CDs. Compared with parent native beta-CD, the inclusion abilities of modified beta-CDs with p-HTClPP are stronger. It indicates that the hydrophobic effect plays an important role in the inclusion procedure. The mechanism of inclusion interaction was examined by (1)H NMR technique. During the study of p-HTClPP-TM-beta-CD supramolecular complex, an efficient enhancement of fluorescence intensity was observed. Based on this phenomenon, fluorometric method for the determination of p-HTClPP was developed. The relationship between fluorescence intensity and the concentration of p-HTClPP is linear from 1.0 x 10(-9) to 7.0 x 10(-6)mol L(-1). The limit of detection is 8.3 x 10(-10)mol L(-1) and the relative standard deviation (R.S.D.) is 1.3% (n=8). This research will provide useful information for further application of p-HTClPP.

[The relative contributions of plant quality, simulated rising temperature, and habitat to litter decomposition.] / 植物质量、模拟增温及生境对凋落物分解的相对贡献.

With litter bag methods, we examined mass loss rates and different chemical fractions of litters from two wetland plant species, Zizania caduciflora and Hippuris vulgaris. Those two species examined here varied significantly in their initial litter chemical traits. Experiment was performed under simulated rising temperature (1.5-2.0 ℃), and under three different habitats (air, air-water interface and water-soil interface). The results showed that, during one-year decomposition period, the mass resi-dual rates exhibited distinct seasonal dynamics, and there were strong interactive effects between seasonal dynamics and environmental factors. Different factors contributed differently for the variation of litter decomposition, 28.8% of which being explained by litter quality, 6.3% of which being explained by rising temperature, and 34.9% being explained by habitat. Along with the decomposition, the contents of different chemical fractions (easy or hard to decompose) varied greatly. Among them, nitrogen contents in H. vulgaris decreased by 53.1%, while the lignin contents increased by 45.4%. Overall, habitat was the most important factor driving litter decomposition, the second was litter quality, and rising temperature had minor effect.

Study on the interaction of 5-pyridine-10,15,20-tris-(p-chlorophenyl)porphyrin with cyclodextrins and DNA by spectroscopy.

The interaction of 5-pyridine-10,15,20-tris-(p-chlorophenyl)porphyrin (PyTPP) with beta-CD and TM-beta-CD were examined by UV-vis absorption, fluorescence and (1)H NMR spectroscopy. PyTPP prefers to form the 1:1 inclusion complex with TM-beta-CD but hardly form inclusion complex with beta-CD. An inclusion constant (K) for the formation of PyTPP-TM-beta-CD inclusion complex has been evaluated to be 4.4x10(3)L/mol from the absorbance changes. This K value is nearly the same as that 4.5x10(3)L/mol obtained from the fluorescence intensity changes. Compared to beta-CD, the inclusion ability of TM-beta-CD with PyTPP is stronger. It indicates that the hydrophobic effect plays an important role in the inclusion procedure. The mechanism of inclusion interaction was carried out by 1H NMR technique. Furthermore, the interaction of PyTPP with DNA is shown here. It can bind DNA by out-side stacking along the DNA helix but not by intercalation because of the high electron density in the porphyrin core. The binding constant and binding number of PyTPP to DNA are 4.3x10(3) and 1.3, respectively. The interaction of PyTPP with DNA was further carried out in the presence of TM-beta-CD. The significant decrease of the binding constant and binding number were observed and the interaction of porphyrin-bound DNA has been inhibited, which was due to the fact that PyTPP inter into the cavity of TM-beta-CD and influence binding affinity of PyTPP to DNA.

Study on the supramolecular systems of 5-(2-hydroxy phenyl)-10,15,20-tris (4-methoxy phenyl) porphyrin with cyclodextrins.

In neutral phosphate buffer solutions of pH 7.4, the inclusive complexation of 5-(2-hydroxy phenyl)-10,15,20-tris(4-methoxy phenyl) porphyrin (o-HTPP) with alpha-cyclodextrin (alpha-CD), beta-CD, heptakis (2,3,6-tri-O-methyl)-beta-CD (TM-beta-CD), SBE-beta-CD, HP-beta-CD and gamma-CD has been examined by means of UV-vis and fluorescence spectroscopy. The formation of inclusion complexes has been confirmed on the base of changes of spectroscopy properties. The o-HTPP forms 1:2 inclusion complexes with TM-beta-CD and 1:1 inclusion complexes with the other five cyclodextrins. The formation constants (K) of o-HTPP for the formation of the inclusion complexes have been estimated from the absorbance and fluorescence intensity changes in neutral phosphate buffer solutions. The K value (2.89x10(7)), which is the formation constant for the formation of the 1:2 inclusion supramolecular, is nearly 10(4) times than those of the 1:1 inclusion complexes. Compared to the other five cyclodextrins, the strongest inclusion ability of TM-beta-CD can be explained that the hydrogen bond plays significant role in the inclusion process. UV-vis experiments also showed that the cavity of TM-beta-CD causes the transform of the state of o-HTPP. In addition (1)H NMR data and 2D-ROSEY NMR spectra support the inclusion conformation of the o-HTPP-CD supramolecular system, indicating the interaction mechanism of inclusion processes.

Electroanalytical method for TPPS4, the interaction of TPPS4 with BSA and the influence of CDs on it by fluorescence spectroscopy.

AIM: To establish a simple, rapid and accurate electroanalytical method for water soluble porphyrin meso-tetrakis-(4-sulfonatophenyl) porphyrin (TPPS4); to clarify the reaction between water soluble porphyrins and bovine serum albumin (BSA); and to determine the interaction of TPPS4 with BSA in the absence of presence of cyclodextrins (CDs), separately. METHODS: Three methods including LSV, UV spectroscopy and fluorescence spectroscopy had been employed to the relevant experiments. The way of employing three methods at the same time could make the experiment results more reliable. RESULTS: In the supporting electrolyte of NaH2 PO4-Na2 HPO4 (pH 7.18), a sensitive reduction peak of TPPS4 was found by linear sweep voltammetry (LSV), the peak potential (Ep) was -0.70 V (vs SCE). The relationship between the second derivative peak of LSV (ip") and the concentration of TPPS4 was linear from 1.0 x 10(-7) mol x L(-1) to 1.0 x 10(-5) mol x L(-1), the square of correlation coefficients (r2) were 0.998 3 and 0.999 3, respectively. The relative standard deviation (RSD) was 0.56% (n = 5). The mean recovery of TPPS4 was 99.59%. In NH4Cl-NH3 x H2O buffers (pH 9.05), it was proved that BSA and TPPS4 could interact with each other and form 1 : 1 TPPS4-BSA supramolecular system. Moreover, the interaction between TPPS4 and BSA had been investigated by adding cyclodextrins (CDs). The interaction of TPPS4 with BSA was facilitated both by hydroxypropyl-beta-CD (HP-beta-CD) and sulforbutylether-beta-CD (SBE-beta-CD). CONCLUSION: An electroanalytical method for TPPS4 has been established by LSV. The porphyrin drugs included by CDs could react with protein existing inside the human body easier. The consequences of this article also show that CDs will play important role in controlling and releasing the porphyrin drugs.

Assemblies of brilliant cresyl violet to DNA in the presence of gamma-cyclodextrin.

The interactions of brilliant cresyl violet (BCV) with herring sperm DNA in gamma-cyclodextrin (gamma-CD) supramolecular system were studied by UV-vis absorption spectroscopy and cyclic voltammetry (CV). Both UV-vis absorption and CV data show that the interaction of BCV with DNA depends on the concentration ratio of BCV to DNA (R), the initial concentration of BCV and gamma-CD. The binding constants of BCV monomer, (BCV)(2) dimer and (BCV)(2)-gamma-CD inclusion complex with DNA are 1.64x10(5), 2.56x10(4) and 2.32x10(3) M(-1), respectively. It was observed that gamma-CD can affect the interactive mode of BCV with DNA. If R is larger than 0.5, the (BCV)(2)-gamma-CD inclusion complex will retain intact and bind to DNA via the electrostatic attraction forces. By contrast, when R is smaller than 0.5, the inclusion complex will be partially dissociated and the free BCV monomer is intercalated into the double-helix structure of DNA attributing to the more favorable microenvironment of DNA for the BCV monomer. Our work postulates the importance of the initial concentration of dye and host molecule on the interaction of dye with DNA in living bodies.

Electrochemical studies of the interaction of Basic Brown G with DNA and determination of DNA.

A new method of electrochemical probe has been proposed for the determination of Herring Sperm DNA (DNA) based on its interaction with Basic Brown G (BBG). The electrochemical behavior of interaction of BBG with DNA was investigated on Hg electrode. In 0.1molL(-1) NH(3)-NH(4)Cl buffer solution (pH 8.0), BBG can be reduced on Hg electrode with a well-defined voltammetric peak at -0.67V (versus SCE). In the presence of DNA, the reduction peak current of BBG decreases and the peak potential shifts to a more positive potential without the appearance of new peak. The study shows that a new BBG-DNA complex is formed by linear sweep voltammetry (LSV) and spectrophotometry. The decrease of the second order derivative of reductive peak current (Delta i(")(p)) of BBG is proportional to the concentration of DNA in the range of 0.10-36microg mL(-1). Limit of detection of DNA is 0.04microg mL(-1). DNA of Hepatitis B Virus in serum samples was determined satisfactorily. Additionally, the binding mechanism was preliminarily discussed. The mode of interaction between BBG and DNA was found to be intercalation binding.