Fingerprint quality control of Tianjihuang by high-performance liquid chromatography-photodiode array detection

A novel, simple and accurate fingerprint method was developed using high-performance liquid chromatography-photodiode array detection (HPLC-DAD) for the quality control of Hypericum japonicum thunb (Tianjihuang), a Chinese herbal medicine used for the treatment of several bacterial diseases, infectious hepatitis, gastrointestinal disorder, internal hemorrhage and tumors. For the first time, the feasibility and advantages of employing chromatographic fingerprint were investigated and demonstrated for the evaluation of Tianjihuang by systematically comparing chromatograms with a professional analytical software recommended by State Food and Drug Administration (SFDA). Our results revealed that the chromatographic fingerprint combining similarity evaluation could efficiently identify and distinguish raw herbs of Tianjihuang from different sources. The effects resulted from collecting locations, harvesting time and storage time on herbal chromatographic fingerprints were also examined.     

Simultaneous determination of polycarboxylic acids by capillary electrophoresis with a copper electrode

The simultaneous determination of polycarboxylic acids including oxalic acid, citric acid, malonic acid, malic acid, tartaric acid, aspartic acid and glutamic acid was achieved by capillary electrophoresis with a copper disk electrode (d = 200 microm). In the system. 0.2 mmol/l cetylpridinium bromide (CPB) was used as an electroosmotic flow (EOF) modifier to reverse the direction of EOF. The effects of the solution pH and CPB concentration on separation were evaluated to achieve the optimum separation conditions. At the working potential of +0.14 V (vs. saturated calomel electrode), the calibration curves for all polycarboxylic acids studied were linear with 2 approximately 3-orders of magnitude and all the detection limits (S/N = 3) were below 15 fmol except malonic acid. Furthermore, the oxalic and citric acids in urine were successfully separated and determined with high sensitivity.     

Rational design of an “all-in-one” phototheranostic

We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd³⁺ and Lu³⁺. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.

We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.     

Synthesis and characterization of highly ordered Ni-MCM-41 mesoporous molecular sieves

Highly ordered Ni-MCM-41 samples with nearly atomically dispersed nickel ions were prepared reproducibly and characterized. Similar to the Co-MCM-41 samples, the pore diameter and porosity can be precisely controlled by changing the synthesis surfactant chain length. Nickel was incorporated by isomorphous substitution of silicon in the MCM-41 silica framework, which makes the Ni-MCM-41 a physically stable catalyst in harsh reaction conditions such as CO disproportionation to single wall carbon nanotubes or CO2 methanation. X-ray absorption spectroscopy results indicate that the overall local environment of nickel in Ni-MCM-41 was a tetrahedral or distorted tetrahedral coordination with surrounding oxygen anions. Hydrogen TPR revealed that our Ni-MCM-41 samples have high stability against reduction; however, compared to Co-MCM-41, the Ni-MCM-41 has a lower reduction temperature, and both the H2-TPR and in situ XANES TPR reveal that the reducibility of nickel is not clearly correlated with the pore radius of curvature, as in the case of Co-MCM-41. This is probably a result of nickel being thermodynamically more easily reduced than cobalt. The stability of the structural order of Ni-MCM-41 has been investigated under SWNT synthesis and CO2 methanation reaction conditions as both require catalyst exposure to reducing environments leading to formation of metallic Ni clusters. Nitrogen physisorption and XRD results show that structural order was maintained under both SWNT synthesis and CO2 methanation reaction conditions. EXAFS results demonstrate that the nickel particle size can be controlled by different prereduction temperatures but not by the pore radius of curvature as in the case of Co-MCM-41.     

H2S-induced reorganization of mixed monolayer of carboxylic derivatives on silver surface

The structure of self-assembled monolayers ofp-terphenyl-4-carboxylic acid and the mixed monolayers of this acid with n-hexadecanoic acid on silver surface were studied by reflection-IR spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) measurement, X-ray photoemission electron microscopy (X-PEEM), and atomic force microscopy. Exposure of the p-terphenyl-4-carboxylate monolayer to H2S vapor resulted in reorganization of the film structure into clusters of the corresponding free acids, in tens of nanometer dimension. Exposure of the mixed monolayer to H2S resulted in reorganization of the mixed monolayer film into phase-separated clusters of respective component molecules. The saturated aliphatic acid formed clusters of submicrometer size, whereas the p-terphenyl-4-carboxylic acid formed clusters of tens of nanometer size, presumably due to different surface mobility and/or intermolecular interaction of the two types of molecule. Restoration of the monolayer film from the clusters, driven by the reaction between the free acid molecules and the basic surface sites, proceeded at different speeds for the two types of molecules. The saturated acid monolayer was restored much faster than the p-terphenyl-4-carboxylic acid monolayer. A domain-separated monolayer in several micrometers scale was obtained. The process was imaged by tapping mode atomic force microscopy.     

Synthesis of (+)-zeylenone from shikimic acid

Starting from shikimic acid, the total synthesis of zeylenone was studied. The product was proved to be the (+)antipode of zeylenone through analysis and comparison of their respective spectra (including NMR, MS, IR and CD) and optical data. The absolute configuration of the natural product was thus determined to be (1S,2S,3R).     

Modulation of the lifespan of C. elegans by the controlled release of nitric oxide

The frontier of nitric oxide biology has gradually shifted from mechanism elucidation to biomanipulation, e.g. cell-proliferation promotion, cell-apoptosis induction, and lifespan modulation. This warrants biocompatible nitric oxide (NO) donating materials, whose NO release is not only controlled by a bioorthogonal trigger, but also self-calibrated allowing real-time monitoring and hence an onset/offset of the NO release. Additionally, the dose of NO release should be facilely adjusted in a large dynamic range; flux and the dose are critical to the biological outcome of NO treatment. Via self-assembly of a PEGylated small-molecule NO donor, we developed novel NO-donating nanoparticles (PEG-NORM), which meet all the aforementioned criteria. We showcased that a low flux of NO induced cell proliferation, while a high flux induced cell oxidative stress and, ultimately, death. Notably, PEG-NORM was capable of efficiently modulating the lifespan of C. elegans. The average lifespan of C. elegans could be fine-tuned to be as short as 15.87 ± 0.29 days with a high dose of NO, or as long as 21.13 ± 0.41 days with a low dose of NO, compared to an average life-span of 18.87 ± 0.46 days. Thus, PEG-NORM has broad potential in cell manipulation and life-span modulation and could drive the advancement of NO biology and medicine.

Schematic illustration of modulating the longevity of the C. elegans by PEG-NORM nanoparticles.     

Design of a calcium-binding protein with desired structure in a cell adhesion molecule

Ca2+, "a signal of life and death", controls numerous cellular processes through interactions with proteins. An effective approach to understanding the role of Ca2+ is the design of a Ca2+-binding protein with predicted structural and functional properties. To design de novo Ca2+-binding sites in proteins is challenging due to the high coordination numbers and the incorporation of charged ligand residues, in addition to Ca2+-induced conformational change. Here, we demonstrate the successful design of a Ca2+-binding site in the non-Ca2+-binding cell adhesion protein CD2. This designed protein, Ca.CD2, exhibits selectivity for Ca2+ versus other di- and monovalent cations. In addition, La3+ (Kd 5.0 microM) and Tb3+ (Kd 6.6 microM) bind to the designed protein somewhat more tightly than does Ca2+ (Kd 1.4 mM). More interestingly, Ca.CD2 retains the native ability to associate with the natural target molecule. The solution structure reveals that Ca.CD2 binds Ca2+ at the intended site with the designed arrangement, which validates our general strategy for designing de novo Ca2+-binding proteins. The structural information also provides a close view of structural determinants that are necessary for a functional protein to accommodate the metal-binding site. This first success in designing Ca2+-binding proteins with desired structural and functional properties opens a new avenue in unveiling key determinants to Ca2+ binding, the mechanism of Ca2+ signaling, and Ca2+-dependent cell adhesion, while avoiding the complexities of the global conformational changes and cooperativity in natural Ca2+-binding proteins. It also represents a major achievement toward designing functional proteins controlled by Ca2+ binding.     

Synthesis and near infrared luminescence of a tetrametallic Zn2Yb2 architecture from a trinuclear Zn3L2 Schiff base complex

Near infrared luminescence is observed in tetrametallic [Zn2Yb2L2(mu-OH)2Cl4].2MeCN which is obtained from the Zn3 Schiff-base complex [Zn3L2(NO3)2].MeOH, (H2L =N,N'-bis(5-bromo-3-methoxysalicylidene)propylene-1,3-diamine).     

Preparative SEC column packed with microporous particles prepared from cellulose

New microporous particles with large pore size (mean pore diameter of 820 nm) are successfully prepared from a mixture of cellulose and konjac glucomannan (RC-KGM3) in 1.5 M NaOH-0.65 M thiourea aqueous solution by coagulating with 5 weight percentage (wt%) CaCl(2), and then 2 wt% HCl aqueous solution. A preparative size-exclusion chromatographic (SEC) column packed with the gel particles is used for the fractionation of a dextran in water. The exclusion limit and fractionation range of the stationary phase are molecular masses of 125 yen 104 g/mol and 5.6 yen 104 to 125 yen 104 g/mol, respectively. The dextran [dextran 50, weight-average molecular mass (M(w)) = 40.1 yen 104 g/mol, polydispersity index (d) = 3.5] is fractionated by the preparative SEC column to obtain six fractions, and four of them are refractionated twice by the same preparative SEC column. The refractionated samples F-3-3 and F-4-3 are characterized by analytical SEC combined with laser light scattering and light scattering to obtain M(w) of 91.8 and 61.9 yen 104 g/mol, as well as d of 1.3 and 1.4, respectively. The results indicate that the fractions having narrow molecular mass distribution are satisfactorily prepared with the SEC column. The described SEC column can be successfully used to fractionate polymers in aqueous solution.