DNA-directed formation of peptide bond: a model study toward DNA-programmed peptide ligation

A model study of DNA-directed peptide ligation has been developed by transferring fluorescent reporting group from small molecule thioester to a DNA strand (template DNA) in the presence of a thiol-functionalized DNA strand (auxiliary DNA), mimicking the Native Chemical Ligation (NCL) reaction. This DNA-directed transfer shows dependence on the sequence complementarity of the two DNA strands, with in situ generated 4-thiolphenylmethyl functionalized oligonucleotide as the auxiliary DNA strand, under mild basic condition (pH=8.5), and with tris(2-carboxyethyl) phosphine hydrochloride (TCEP) as a reducing agent. Reactions with different amino acid α-thioesters resulted in varied transfer efficiencies from glycine to α-substituted amino acids. This study has provided the basic foundation to use DNA-programmed chemistry toward the chemical synthesis or unnatural modification of protein molecules.     

pH‐ and Thiol‐Responsive BODIPY‐Based Photosensitizers for Targeted Photodynamic Therapy

A diiodo distyryl boron dipyrromethene (BODIPY) core was conjugated to two ferrocenyl quenchers through acid‐labile ketal and/or thiol‐cleavable disulfide linkers, of which the fluorescence and photosensitizing properties were significantly quenched through a photoinduced electron‐transfer process. The two symmetrical analogues that contained either the ketal or disulfide linkers could only be activated by a single stimulus, whereas the unsymmetrical analogue was responsive to dual stimuli. Upon interaction with acid and/or dithiothreitol (DTT), these linkers were cleaved selectively. The separation of the BODIPY core and the ferrocenyl moieties restored the photoactivities of the former in phosphate buffered saline and inside the MCF‐7 breast cancer cells, rendering these compounds as potential activable photosensitizers for targeted photodynamic therapy. The dual activable analogue exhibited the greatest enhancement in intracellular fluorescence intensity in both an acidic environment (pH 5) and the presence of DTT (4 mm ). Its photocytotoxicity against MCF‐7 cells also increased by about twofold upon preincubation with 4 mm of DTT. The activation of this compound was also demonstrated in nude mice bearing a HT29 human colorectal carcinoma. A significant increase in fluorescence intensity in the tumor was observed over 9 h after intratumoral injection.     

Synthesis and Characterization of Polymers Derived from the Copolymerization of 1,1′-Dihydroxyethyl-2,2′-Biimidazole and the Diglycidyl Ether of Bisphenol A

Abstract

1,1′-Dihydroxyethyl-2,2′-biimidazole has been used as a copolymerizing monomer with the diglycidyl ether of bisphenol A in the preparation of biimidazole-containing epoxy polymers. Polymerization reactions were studied in bulk, with and without catalyst, and in N,N-dimethylforma-mide and anisole solvents, with and without catalyst. FT-IR and NMR spectra, molecular weight, thermal and solubility characteristics were obtained. Polymers isolated as amorphous light brown solids were found to be only sparingly soluble in THF or in highly polar nitrogen-containing solvents (DMF, NMP, pyridine). These materials exhibited molecular weights up to 37 000 for SnC1₄-catalyzed polymerization carried out in DMF. A glass-transition temperature of 391°C was observed for polymers obtained under uncatalyzed solventless conditions. The glass transition temperature was 373°C for product obtained under SnC1₄-catalyzed, solventless conditions. Thermogravimetric analysis in air of polymers obtained under varying solvent and catalyst conditions showed less than 25% weight loss below 330°C and greater than 75% weight loss above 400°C.     

Photophysics of Silicon Phthalocyanines in Aqueous Media

Phthalocyanines have been used as photodynamic therapy (PDT) agents because of their uniquely favorable optical properties and high photostability. They have been shown to be highly successful for the treatment of cancer through efficient singlet‐oxygen (¹O₂) production. However, due to their hydrophobic properties, the considerations of solubility and cellular location have made understanding their photophysics in vitro and in vivo difficult. Indeed, many quantitative assessments of PDT reagents are undertaken in purely organic solvents, presenting challenges for interpreting observations during practical application in vivo. With steady‐state and time‐resolved laser spectroscopy, we show that for axial ligated silicon phthalocyanines in aqueous media, both the water:lipophile ratio and the pH have drastic effects on their photophysics, and ultimately dictate their functionality as PDT drugs. We suggest that considering the presented photophysics for PDT drugs in aqueous solutions leads to guidelines for a next generation of even more potent PDT agents.     

Adsorption behavior of uranium on polyvinyl alcohol-g-amidoxime: Physicochemical properties, kinetic and thermodynamic aspects

Amidoxime-based adsorbents are widely studied as the main adsorbent in the recovery of uranium from seawater.However,the adsorption rate and loading capacity of such adsorbents should be further improved due to the economic viability consideration.In this paper,polyvinyl alcohol functionalized with amidoxime(PVA-g-AO)has been prepared as a new adsorbent for uranium(Ⅵ)adsorption from aqueous solution.The physicochemical properties of PVA-g-AO were investigated using infrared spectroscopy(IR),scanning electron microscope(SEM),X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).Results showed that the ligand monomers were successfully grafted onto the matrixes.The XRD and XPS analysis showed that uranium was adsorbed in metal ionic form rather than in crystal form.Uranyl(U(Ⅵ))adsorption properties onto PVA-g-AO were evaluated.The adsorption of U(Ⅵ)by PVA-g-AO was fast,with an equilibrium time of less than 50 min.Additionally the maximum adsorption capacity reached 42.84 mg/g at pH 4.0.     

Trigonal‐Bipyramidal and Square‐Pyramidal Chromium?Manganese Chalcogenide Clusters, [E2CrMn2(CO)n]2− (E=S,Se, Te; n=9, 10): Synthesis,Electrochemistry, UV/Vis Absorption,and Computational Studies

The reactions of E powder (E=S, Se) with a mixture of Cr(CO)₆ and Mn₂(CO)₁₀ in concentrated solutions of KOH/MeOH produced two new mixed Cr? Mn? carbonyl clusters, [E₂CrMn₂(CO)₉]^2? (E=S, 1 ; Se, 2 ). Clusters 1 and 2 were isostructural with one another and each displayed a trigonal‐bipyramidal structure, with the CrMn₂ triangle axially capped by two μ₃‐E atoms. The analogous telluride cluster, [Te₂CrMn₂(CO)₉]^2? ( 3 ), was obtained from the ring‐closure of Te₂Mn₂ ring complex [Te₂Mn₂Cr₂(CO)₁₈]^2? ( 4 ). Upon bubbling with CO, clusters 2 and 3 were readily converted into square‐pyramidal clusters, [E₂CrMn₂(CO)₁₀]^2? (E=Se, 5 ; Te, 6 ), accompanied with the cleavage of one Cr? Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue ( 5 ) was spectroscopically proposed to be diamagnetic, as verified by TD‐DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn? Mn bond to produce a new arachno‐cluster, [Te₂CrMn₂(CO)₁₁]^2? ( 7 ). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations.     

A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure,Redox Properties,and Oxidation Reactions Investigated by DFT Calculations

The electronic structure and redox properties of the highly oxidizing, isolable Ru^V?O complex [Ru^V(N₄O)(O)]²⁺, its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol^?1, respectively. The overall free energy activation barrier (ΔG^≠=25.5 kcal mol^?1) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru^III(N₄O)(HOCl)]²⁺ (ΔG=15.0 kcal mol^?1) and the substitution of HOCl by a water molecule (ΔG^≠=10.5 kcal mol^?1). For water oxidation, nucleophilic attack on Ru^V?O by water, leading to O? O bond formation, has a free energy barrier of 24.0 kcal mol^?1, the major component of which comes from the cleavage of the H? OH bond of water. Intermolecular self‐coupling of two molecules of [Ru^V(N₄O)(O)]²⁺ leads to the [(N₄O)Ru^IV? O₂? Ru^III(N₄O)]⁴⁺ complex with a calculated free energy barrier of 12.0 kcal mol^?1.     

Understanding the electronic energy transfer pathways in the trimeric and hexameric aggregation state of cyanobacteria phycocyanin within the framework of Förster theory

In the present study, the electronic energy transfer pathways in trimeric and hexameric aggregation state of cyanobacteria C‐phycocyanin (C‐PC) were investigated in term of the Förster theory. The corresponding excited states and transition dipole moments of phycocyanobilins (PCBs) located into C‐PC were examined by model chemistry in gas phase at time‐dependent density functional theory (TDDFT), configuration interaction‐singles (CIS), and Zerner's intermediate neglect of differential overlap (ZINDO) levels, respectively. Then, the long‐range pigment‐protein interactions were approximately taken into account by using polarizable continuum model (PCM) at TDDFT level to estimate the influence of protein environment on the preceding calculated physical quantities. The influence of the short‐range interaction caused by aspartate residue nearby PCBs was examined as well. Only when the protonation of PCBs and its long‐ and short‐range interactions were properly taken into account, the calculated energy transfer rates (1/K) in the framework of Förster model at TDDFT/B3LYP/6‐31+G* level were in good agreement with the experimental results of C‐PC monomer and trimer. Furthermore, the present calculated results suggested that the energy transfer pathway in C‐PC monomer is predominant from β‐155 to β‐84 (1/K = 13.4 ps), however, from α‐84 of one monomer to β‐84 (1/K = 0.3–0.4 ps) in a neighbor monomer in C‐PC trimer. In C‐PC hexamer, an additional energy flow was predicted to be from β‐155 (or α‐84) in top trimer to adjacent β‐155 (or α‐84) (1/K = 0.5–2.7 ps) in bottom trimer. © 2013 Wiley Periodicals, Inc.