Photodynamic effect in near-IR light by a photocytotoxic iron(III) cellular imaging agent

A red light for cancer cells: an iron(III) complex (1, see picture) that contains an anthracenyl fluorophore moiety and a catecholate ligand is a potent, metal-based PDT agent that efficiently photocleaves DNA in near-infrared light, has significant nuclear uptake, and high photocytotoxicity in red light by an apoptotic pathway in HeLa and MCF-7 cancer cells.     

Synthesis of a cyclic dinuclear organotin carboxylate via simultaneous debenzylation and decarbonylation reactions: X-ray crystal structure of [(PhCH2)2{O2CC6H4{N(H)N(C6H3-4(O)-5-O)}-o}Sn]2

The complex, [(PhCH₂)₂{O₂CC₆H₄{N(H)N(C₆H₃-4(O)-5-O)}-o}Sn]₂ (1), is obtained as the exclusive reaction product from the reaction of sodium 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyl]benzoate and (PhCH₂)₃SnCl. The reaction possibly proceeds via Dakin type rearrangements where arylazosalicylaldehyde is oxidized to arylazocatechol, followed by facile Sn-C bond cleavage. Complete assignments were achieved by ¹H, ¹³C, 2D ¹H-¹¹⁹Sn HMQC (¹¹⁹Sn chemical shift), 1D gs ¹H-¹⁵N HMQC (¹J(¹⁵N, ¹H) coupling constant) NMR and ESI-MS. The crystal structure of compound 1 as determined by X-ray diffraction analyses shows a cyclic centrosymmetric dinuclear moiety linked into extended chains by pairs of long Sn?O contacts of approximately 3.2 Å. Two polymorphs were identified and their structures differ primarily in the packing arrangement afforded by the benzyl groups. In one polymorph, when viewed along the Sn?Sn vector, the benzyl groups at each Sn-atom are oriented to form an S-shape, while they form a U-shape in the second polymorph.     

Activation of Nucleotide-Binding Oligomerization Domain 1 (NOD1) Receptor Signaling in Labeo rohita by iE-DAP and Identification of Ligand-Binding Key Motifs in NOD1 by Molecular Modeling and Docking

The nucleotide-binding oligomerization domain 1 (NOD1) receptor recognizes various pattern-associated structures of microbes through its leucine-rich repeat (LRR) domain and activates signaling cascades to induce innate immunity. This report describes the activation of NOD1 receptor signaling by gamma-d-glutamyl-meso-diaminopimelic acid (or γ-D-Glu-mDAP [iE-DAP]) in a commercially important fish species, rohu (Labeo rohita). It also described critical motifs in the NOD1-LRR domain that could be involved in binding iE-DAP, lipopolysaccharide (LPS), and polyinosinic:polycytidylic acid (poly I:C). The activation of NOD1 receptor signaling was studied by injecting iE-DAP, and analysis of tissue samples for NOD1 and receptor-interacting serine/threonine kinase (RICK) expression was done by quantitative real-time polymerase chain reaction (qRT-PCR) assay. To identify ligand-binding motifs in NOD1, the 3D model of NOD1-LRR was generated, followed by a 6-ns molecular dynamics simulation. Molecular docking of LPS with NOD1-LRR was executed at the Hex and PatchDock servers, and iE-DAP and poly I:C in the AutoDock 4.2, FlexX 2.1, Glide 5.5, and GOLD 4.1 programs. The results of qRT-PCR revealed significant (p?<?0.05) upregulation of NOD1 and RICK expression. Molecular docking revealed that the amino acid residues at LRR1–2, LRR3–7, and LRR8–9 could be involved in poly I:C, LPS, and iE-DAP binding, respectively. In fish, this is the first report describing the 3D structure of NOD1-LRR and its critical ligand-binding motifs.     

Simple and Advantageneous Stereoselective Synthesis of (Z)-Allyl Phosphonates Starting from Baylis–Hillman Adducts

Baylis–Hillman adducts 3-hydroxyl-2-methylene alkanoates have been converted in one pot into the corresponding (Z)-allyl phosphonates by treatment with FeCl₃ and trialkyl phosphites in toluene under reflux. The products are formed in excellent yields (88–98%) within 1–1.5 h. The process is highly convenient and efficient, cost-effective, and remarkably stereoselective.     

Synthesis of glycopeptides from glucosaminic acid

We report on the synthesis of polypeptides with saccharide side chains starting from d ‐glucosaminic acid. The hydroxyl groups were first protected by benzylation, followed by N‐carboxyanhydride formation, which was polymerized by ring opening to form a high molecular weight polyamide. De‐protection of the benzyl groups yields a polypeptide with fully de‐protected saccharide side chains. The resulting new non‐ionic, water soluble, and optically active polymers possessing the properties of both peptides and saccharides have potential use as scaffolds for tissue engineering and drug carriers. The method described here may be extended to any saccharide α‐amino acid. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2657–2662     

Synthesis of crescent shaped heterocycle-fused aromatics via Garratt-Braverman cyclization and their DNA-binding studies

Three crescent shaped heterocycle-fused phenanthrene based systems 1–3 have been synthesized starting from benzene (or substituted benzene) 1,2-bis-propargyl alcohols. Bis-alkylation with propargylic bromides provided the key intermediate, the bis-propargyl bis-ethers. In spite of the possibility of many competing reactions, the latter underwent facile double Garratt-Braverman cyclization to provide compounds 1–3 in near quantitative yield, in a striking reaction involving the formation of four C–C bonds in a single step. Compounds 1–3 showed binding interaction with DNA, predominantly, via groove binding along with partial intercalation (combilexins). Molecular docking study supported the proposed binding modes.     

用于流化床燃烧脱硫的石灰石的反应活性评价和测试研究

对用于燃煤流化床燃烧脱硫的脱硫剂石灰石的反应活性进行了研究，提出了易于进行数学处理的石灰石硫盐化模型，得出了评价石灰石反应活性的两个指标－最大转化率和反应速率常数。研究方法除采用了传统的热天平法和鼓泡流化床外，还根据循环流化床燃烧技术的特点，发展了提出了湍流床法和石英棉法，并进行了不同试验条件下的实验研究，对不同反应活性温度技术进行了试验比较。     

Monitoring of trace levels of p-dioxan in high purity benzene feedstock by capillary gas chromatography

Summary A procedure has been standarized for the determination of p-dioxan (1,4-dioxan) in benzene feedstock in the range of 1 to 100 ppm by capillary GC. The GC conditions such as oven temperature, length of the column etc were optimized to achieve better resolution of p-dioxan from hydrocarbons. The standard addition method of quantitation, was used to determine the amount of p-dioxan and was found to give better results than those obtained by external standardization. Prior to analysis the identity of the p-dioxan peak was established by GC-MS. The proposed method has been applied for the monitoring of p-dioxan in high purity benzene feedstock produced by the Udex extraction process in the refinery. The data were used for optimization of plant conditions for the production of high purity benzene feedstock. By using this method, the p-dioxan content down to 0.5 ppm can be determined in the benzene feedstock.     

Kinetics and mechanisms of the reactions of thiosulphato-amine complexes of cobalt(III). Part I. Isomerization and base hydrolysis ofcis andtrans isomers of dithiosulphatobis(ethylenediamine) cobalt(III) ion in aqueous solution

Summary Investigations were carried out on the isomerization and base hydrolysis ofcis andtrans forms of dithiosulphatobis-(ethylenediamine)cobalt(III) ions. Thecis form isomerizes to thetrans form in neutral aqueous medium, rates being 1.15, 2.30 and 4.0×10^–5s^–1, respectively at 42, 50 and 58 °C. Thetrans complex isomerizes to thecis form in basic solution only, the rate varying with pH in a sigmoid pattern. In presence of OH^–, an acid-base equilibrium of the complex ion sets in, but only the basic form takes part in the isomerization reaction. Hydrolysis of thecis isomer proceeds through a base-dependent path only, but that of thetrans isomer proceeds both through base-dependent and base-independent paths. The mechanisms are associative in nature. Thetrans form reacts faster thancis in all cases.