Study on the BODIPY-triazine-based tripod fluorescent systems: various structures from similar procedure

We report a small library of fluorophore-triazine tripod fluorescent system that can accommodate a combination of three different functional groups, such as fluorophore (BODIPY), ligand (or ligands) and auxiliary group. Syntheses, photophysical properties as well as binding properties towards metal ions of these BODIPY-triazine derivatives are described.     

Detection of layer‐by‐layer self‐assembly multilayer films by low‐temperature plasma mass spectrometry

The detection of layer‐by‐layer self‐assembly multilayer films was carried out using low‐temperature plasma (LTP) mass spectrometry (MS) under ambient conditions. These multilayer films have been prepared on quartz plates through the alternate assembling of oppositely charged 4‐aminothiophenol (4‐ATP) capped Au particles and thioglycolic acid (TGA) capped Ag particles. An LTP probe was used for direct desorption and ionization of chemical components on the films. Without the complicated sample preparation, the structure information of 4‐ATP and TGA on films was studied by LTP‐MS. Characteristic ions of 4‐ATP (M) and TGA (F), including [M]^+?, [M‐NH₂]⁺, [M‐HCN‐H]⁺, and [F + H]⁺, [F‐H]⁺, [F‐OH]⁺, [F‐COOH]⁺ were recorded by LTP‐MS on the films. However, [M‐CS‐H]⁺ and [F‐SH]⁺ could not be observed on the film, which were detected in the neat sample. In addition, the semi‐quantitative analysis of chemical components on monolayer film was carried out, and the amounts of 4‐ATP and TGA on monolayer surface were 45 ng/mm² and 54 ng/mm², respectively. This resulted the ionization efficiencies of 72% for 4‐ATP and 54% for TGA. In order to evaluate the reliability of present LTP‐MS, the correlations between this approach and some traditional methods, such as UV–vis spectroscopy, atomic force microscope and X‐ray photoelectron spectroscopy were studied, which resulted the correlation coefficients of higher than 0.9776. The results indicated that this technique can be used for analyzing the films without any pretreatment, which possesses great potential in the studies of self‐assembly multilayer films. Copyright © 2013 John Wiley & Sons, Ltd.     

One inorganic-organic hybrid derived from reduced molybdophosphate and trinuclear cadmium(Ⅱ) fragment

One new polyoxometalate (POM)-based inorganic-organic hybrid [Cd3Ⅱ(HPO4)(Hbpp)(H2O)2]{CdⅡ[P4- Mo6O28H3.5(OH)3]2} (H4tpb)·7H2O (1) (bpp = 1,3-bis-(4-pyridyl)propane, tpb = 1,2,4,5-tetra(4-pyridyl)-benzene) constructed from reduced molybdophosphate [P4Mo6O28H3.5(OH)3]5.5- (P4Mo6), trinuclear CdⅡ-phosphate-Hbpp fragment and protonated tpb has been hydrothermally synthesized and structurally characterized by IR, elemental analyses and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system with the space group P21/c and cell parameters of a = 15.672(12)Å, b = 23.839(19)Å, c = 27.654(2)Å, β = 115.850(10)8, V = 9297.9(12) Å3, Z = 4, R1 = 0.0534 and wR2 = 0.1135. In complex 1, the P4Mo6 units are bridged by CdⅡ ions to form the classic sandwich-type [Cd(P4Mo6)2] dimers, which are further connected into a two dimensional network via the trinuclear CdⅡ subunits. The tpb is synthesized in situ from the bpp ligands and connects the adjacent 2D layers into a 3D supramolecular framework through hydrogen bonding interactions. The electrochemical and fluorescent properties of complex 1 have been investigated.     

Simultaneous quantitation of seven alkaloids in processed Fuzi decoction by rapid resolution liquid chromatography coupled with tandem mass spectrometry

A rapid analytical method based on rapid resolution LC coupled with MS/MS was first established to quantify seven alkaloids in processed Fuzi decoction. The chromatographic method was optimized to allow simultaneous analysis of all analytes in 5 min and demonstrated good linearity (r > 0.9995), repeatability (RSD < 4.36%), intra‐ and interday precisions (RSD < 5.07%) with good accuracies (97.76–105.08%) and good recovery (95.0–107.5%) of seven alkaloids, namely higenamine, benzoylhypaconine, benzoylmesaconine, benzoylaconine, aconitine, hypaconitine, and mesaconitine. The LODs for these markers were in the range of 2.30–17.00 pg/mL. Quantitative analysis of the seven alkaloids in Baifupian decoction and Heishunpian decoction showed that the content of the seven marker chemicals varied significantly and concluded that the quality of Fuzi was greatly affected by different processed methods. The developed method could be used as a rapid, sensitive, and reliable approach for assessment of the quality of processed Fuzi and related decoction.     

Two Lanthanide(III)?Copper(II) Organic Frameworks Based on {OLn6} Clusters that Exhibited a Large Magnetocaloric Effect and Slow Relaxation of the Magnetization

Two new 3D lanthanide(III)? copper(II) organic frameworks based on unusual {OLn₆} clusters have been successfully synthesized and fully characterized. Crystallographic studies showed that the {OLn₆} clusters acted as 12‐connected nodes that were linked together by [CuL₂] (H₂L=3‐hydroxypyrazine‐2‐carboxylic acid) moieties to construct an interesting 4,12‐c net with the point symbol {4³⁶.6³⁰}{4⁴.6²}₃. Magnetic studies revealed that these two isostructural heterometallic frameworks exhibited different magnetic properties, depending on the different anisotropies of the lanthanide spin carriers: Gd‐Cu showed a large magnetocaloric effect, with an entropy change (?ΔS_m) of 35.76 J kg^?1 K^?1, which is one of the largest values in high‐dimensional complexes, whilst Dy‐Cu exhibited slow relaxation of the magnetization at low temperatures.     

Preparation of biodegradable and thermoresponsive enzyme–polymer conjugates with controllable bioactivity via RAFT polymerization

The preparation of biodegradable and thermoresponsive enzyme–polymer bioconjugates with controllable enzymatic activity via reversible addition−fragmentation chain transfer (RAFT) polymerization and amidation conjugation reaction is presented. A new 2-mercaptothiazoline ester functionalized RAFT agent with intra-disulfide linkage was synthesized and used as chain transfer agent (CTA) to generate a biocompatible homopolymer, poly(ethyleneglycol) acrylate (polyPEG-A) and a thermoresponsive copolymer of poly(ethyleneglycol) acrylate with di(ethyleneglycol)ethyl ether acrylate [poly(PEG-A-co-DEG-A)]. These biodegradable and thermoresponsive polymers were then conjugated to the surface of glucose oxidase (GOx) under mild condition to afford the biodegradable and thermoresponsive enzyme–polymer conjugates. Cleavage of the polymer chains from the GOx surface obviously recovered the enzymatic activity. The thermoresponsive test of GOx-poly(PEG-A-co-DEG-A) revealed that the bioconjugate exhibited regular enzymatic activity fluctuation upon the temperature change below or above the lower critical solution temperature (LCST). The as-prepared enzyme–polymer conjugates were also characterized using ¹H NMR, UV–vis spectroscopy, polyacrylamide gel electrophoresis (PAGE) and biocatalytic activity tests. These smart enzyme–polymer conjugates would envision promising applications in biotechnology and biomedicine.     

Colorimetric detection of peroxynitrite-induced DNA damage using gold nanoparticles, and on the scavenging effects of antioxidants

We describe a rapid and convenient colorimetric method for the detection of oxidative DNA damage caused by peroxynitrite (ONOO^?) using unmodified gold nanoparticles (AuNPs). AuNPs are stable in the presence of single-stranded DNA (ssDNA) against the aggregation induced by a high ionic strength. If adsorbed ssDNA are cleaved by ONOO^? to form smaller fragments, the AuNPs rapidly aggregate due to electrostatic attraction. As a result, the color of the solution changes from red to blue, and this can be seen with bare eyes. We also have evaluated the activity of the antioxidants gallic acid, ascorbic acid and caffeic acid to scavenge ONOO^?. This method therefore also can be applied to screen for anti-oxidation drugs and agents.

Preparation of self-supporting molecularly imprinted films via transition layer construction and RAFT polymerization, and their use in HPLC

Molecularly imprinted films with self-supporting property (SS-MIFs) have been prepared by using the strategy of transition layer construction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. The structure, composition and selectivity of the SS-MIFs as well as the mechanism of mass transfer were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform IR spectrometry, specific surface area analysis, thermogravimetric analysis, and HPLC. Surface area analysis showed the samples possessed specific surface areas as high as 80.5 m².g^?1. This is almost 9 times more than that of the original porous anodic aluminum oxide substrate. Thermogravimetric analysis also showed the samples to be thermally stable up to 350 °C. The separating power was investigated by HPLC and revealed a selective separation effect for the target molecules theobromine. The separation factor is 5.37.

Solubility of Icariin in a Binary Solvent System of Ethanol and Water

The solubility of icariin in the binary solvent system of ethanol and water was measured by UV–Vis spectrophotometry from 288.2 to 328.2 K. The solubility of icariin in the system increased with increasing temperature. A synergistic effect appeared at x ₂ = 0.4 (equivalent to 68.34 % ethanol, v/v) binary mixture. Solubility data were correlated with the modified Apelblat equation. The enthalpy and entropy of solution were evaluated using van’t Hoff plots.     

Terbinafine hydrochloride intercalated in montmorillonite: synthesis and characterization

The novel antifungal hybrid of terbinafine hydrochloride (TER-HCl)/montmorillonite was synthesized by the intercalation method under mechanical stirring. Intercalation of TER-HCl in the MMT galleries was characterized by X-ray diffraction (XRD), Fourier transform infrared spectra, elemental analysis (EA). and thermogravimetric analysis (TGA). The results from IR, TGA, and EA showed a difference in chemical composition of the MMT and the TER-HCl/MMT. XRD analysis showed that the basal spacing of montmorillonite significantly expanded from 1.53 to 2.79 nm. TER-HCl was successfully intercalated into the interlayer of MMT, and 28 % of TER-HCl was released after 48 h in 0.9 % (w/v) NaCl aqueous solution (pH 7) at 37 ± 0.5 °C. The antifungal activity of the hybrid against Candida albicans was evaluated using the inhibitory zone method and the minimum inhibitory concentration. The TER-HCl/MMT strongly inhibited C. albicans. These results show that TER-HCl/MMT can be useful in biomedical applications.