Metachromins R--T, new sesquiterpenoids from marine sponge Spongia sp

Three new sesquiterpenoids, metachromins R--T (1--3), have been isolated from an Okinawan marine sponge Spongia sp. The structures and stereochemistry of 1--3 were elucidated on the basis of the spectroscopic data. Metachromins S (2) and T (3) showed modest cytotoxicity.     

Color Bricks: Building Highly Organized and Strongly Absorbing Multicomponent Arrays of Terpyridyl Perylenes on Metal Oxide Surfaces

Terpyridine‐substituted perylenes containing cyclic anhydrides in the peri position were synthesized. The anhydride group served as an anchor for assembly of the terpyridyl‐crowned chromophores as monomolecular layers on metal oxide surfaces. Further coordination with Zn²⁺ ions allowed for layer‐by‐layer formation of supramolecular assemblies of perylene imides on the solid substrates. With properly selected anchor and linker molecules it was possible to build high quality structures of greater than ten successive layers by a simple and straightforward procedure. The prepared films were stable and had a broad spectral coverage and high absorbance. To demonstrate their potential use, the synthesized dyes were employed in solid‐state dye‐sensitized solar cells, and electron injection from the perylene antennas to titanium dioxide was observed.     

Superhydrophobic polyolefin surfaces: controlled micro- and nanostructures

Superhydrophobic polyolefin surfaces were prepared by simultaneous micro- and nanostructuring. Electropolished aluminum foil was microstructured with a micro working robot and then anodized in polyprotic acid. The surface microstructure can be tailored by adjusting the settings of the micro working robot and the nanostructure by adjusting the parameters of the anodization procedure. Surface structuring was done by injection molding where a microstructured anodized aluminum oxide mold insert was used to pattern the surfaces. Structuring had a marked effect on the contact angle between the injection-molded polyolefins and water. When the optimized microstructure was covered with nanostructure, the static contact angle between polypropylene and water obtained a value of about 165 degrees and the sliding angle decreased to about 2.5 degrees. The superhydrophobic state was achieved.     

Detection of environmental chemicals by SPR assay using branched cyclodextrin as sensor ligand

We obtained the association constants Ka of estrogen (E2) and environmental chemicals by the surface plasmon resonance (SPR) assay using the immobilized mono-6-O-α-maltosyl-β-CD (G₂βCD) compared with the immobilized β-CD and the immobilized estrogen receptor (ER). The association behavior of G₂βCD was shown as a ER model compound. The calibration curve was determined by the initial rate of association depending on the various concentrations, and the minimum detectable concentrations in the order of parts per billion were calculated. The SPR assay has advantages that the pre-treatment of the sample is not necessary and the immobilized ligand is stable and useful for the repeated measurement.     

Surface modification with well-defined biocompatible triblock copolymers Improvement of biointerfacial phenomena on a poly(dimethylsiloxane) surface

To improve interfacial phenomena of poly(dimethylsiloxane) (PDMS) as biomaterials, well-defined triblock copolymers were prepared as coating materials by reversible addition-fragmentation chain transfer (RAFT) controlled polymerization. Hydroxy-terminated poly(vinylmethylsiloxane-co-dimethylsiloxane) (HO–PV_lD_mMS–OH) was synthesized by ring-opening polymerization. The copolymerization ratio of vinylmethylsiloxane to dimethylsiloxane was 1/9. The molecular weight of HO–PV_lD_mMS–OH ranged from (1.43 to 4.44) × 10⁴, and their molecular weight distribution (M_w/M_n) as determined by size-exclusion chromatography equipped with multiangle laser light scattering (SEC-MALS) was 1.16. 4-Cyanopentanoic acid dithiobenzoate was reacted with HO–PV_lD_mMS–OH to obtain macromolecular chain transfer agents (macro-CTA). 2-Methacryloyloxyethyl phosphorylcholine (MPC) was polymerized with macro-CTAs. The gel-permeation chromatography (GPC) chart of synthesized polymers was a single peak and M_w/M_n was relatively narrow (1.3–1.6). Then the poly(MPC) (PMPC)–PV_lD_mMS–PMPC triblock copolymers were synthesized. The molecular weight of PMPC in a triblock copolymer was easily controllable by changing the polymerization time or the composition of the macro-CTA to a monomer in the feed. The synthesized block copolymers were slightly soluble in water and extremely soluble in ethanol and 2-propanol.

Surface modification was performed via hydrosilylation. The block copolymer was coated on the PDMS film whose surface was pretreated with poly(hydromethylsiloxane). The surface wettability and lubrication of the PDMS film were effectively improved by immobilization with the block copolymers. In addition, the number of adherent platelets from human platelet-rich plasma (PRP) was dramatically reduced by surface modification. Particularly, the triblock copolymer having a high composition ratio of MPC units to silicone units was effective in improving the surface properties of PDMS.

By selective decomposition of the Si–H bond at the surface of the PDMS substrate by irradiation with UV light, the coating region of the triblock copolymer was easily controlled, resulting in the fabrication of micropatterns. On the surface, albumin adsorption was well manipulated.     

Synthesis of 3-substituted indazoles and benzoisoxazoles via Pd-catalyzed cyclization reactions: application to the synthesis of nigellicine

Syntheses of 3-substituted indazoles and benzoisoxazoles were efficiently accomplished with the aid of Pd-catalyzed intramolecular carbon-nitrogen and carbon-oxygen bond formations. The catalyst system described herein allows the cyclization to proceed under very mild conditions and thus could be applied to a wide range of substrates with acid- or base-sensitive functional groups. A total synthesis for the indazole ring-containing natural product nigellicine is also described.     

Accurate solubility prediction with error bars for electrolytes: a machine learning approach

Accurate in silico models for predicting aqueous solubility are needed in drug design and discovery and many other areas of chemical research. We present a statistical modeling of aqueous solubility based on measured data, using a Gaussian Process nonlinear regression model (GPsol). We compare our results with those of 14 scientific studies and 6 commercial tools. This shows that the developed model achieves much higher accuracy than available commercial tools for the prediction of solubility of electrolytes. On top of the high accuracy, the proposed machine learning model also provides error bars for each individual prediction.     

Effect of compression on interaction between 1,4-dihydropyridine compounds and lactose monohydrate

Manidipine dihydrochloride or benidipine hydrochloride will change to hydrate form in part, when differential scanning calorimetric (DSC) measurement is carried out together with lactose monohydrate. This interaction was accelerated by compressing their mixture. It can be suggested that the interaction may cause by the disruption of crystal structure of lactose monohydrate due to compression to set free of water molecules. A new DSC peak at 170 degrees C, which was not observed in each component, appeared in DSC measurement of a mixture. This will be based on hydrate formed by the interaction, i.e., movement of water molecules. The profile of the plotting of the DSC peak area ratio before and after compression against the compression force changed by the molar ratio of lactose monohydrate in a mixture. In the case of low molar ratio of lactose monohydrate, profiles for manidipine dihydrochloride and benidipine hydrochloride differed from each other. This will be because manidipine dihydrochloride is stickier than benidipine hydrochloride. The profile for manidipine dihydrochloride became more gradual and showed lag compression force region when the amount of addition of the lubricant, magnesium stearate in a mixture increased. The endothermic peak area at 170 degrees C for manidipine dihydrochloride was larger than that for benidipine hydrochloride. It should be suggested that benidipine hydrochloride is easier to be transformed to its hydrate than manidipine dihydrochloride.     

Iron(II)‐ and Cobalt(II) Complexes with Tridentate Bis(imino)pyridine Nitrogen Ligands Bearing Chiral Bulky Aliphatic and Aromatic Substituents: Crystal Structure of [CoCl2{2, 6‐bis[R‐(+)‐(bornylimino)methyl]pyridine}]

Iron(II) and cobalt(II) complexes ( 7 ‐ 15 ) based on new aldimine 2, 6‐bis[(imino)methyl]pyridine ( 1 , 2 , 4 , 6 ) and ketimine (2, 6‐bis[(imino)ethyl]pyridine ( 3 , 5 ) ligands with bulky chiral aliphatic or aromatic terminal groups have been prepared and characterized by ¹H NMR, ¹³C NMR, IR‐, mass spectroscopy (EI), and elemental analysis. The complex [CoCl₂(BBoMP)]·¹/₂ CHCl₃ ( 13 ) (BBoMP: 2, 6‐bis{(R‐(+)‐(bornylimino)‐methyl}pyridine) crystallizes in monoclinic space group P2₁ with cell dimensions: a = 7.6603(11) Å, b = 28.3153(14) Å, c = 13.537(2) Å, V = 2908.1(6) ų, Z = 4. The coordination sphere around Co is distorted trigonal bipyramidal.