Nagelamide J, a novel dimeric bromopyrrole alkaloid from a sponge Agelas species

A novel dimeric bromopyrrole alkaloid, nagelamide J (1), with antimicrobial activity has been isolated from an Okinawan marine sponge Agelas species, and the structure and stereochemistry were elucidated from spectroscopic data. Nagelamide J (1) is the first bromopyrrole alkaloid possessing a cyclopentane ring fused to an amino imidazole ring.     

Infrared spectroscopy of ozone-water complex in a neon matrix

Matrix isolation infrared spectroscopy has been applied to study an ozone-water complex of atmospheric interest. The complex was identified in the spectral region of three normal modes of ozone and water. Ab initio calculation at MP4(SDQ), QCISD, and CCSD(T) levels indicates the existence of only one stable conformer, which accords with the present experimental result. This conformer belongs to the Cs symmetry group where two molecular planes of ozone and water are perpendicular to the Cs symmetry plane. The binding energy was calculated to be 1.89 kcal/mol at the CCSD(T)/6-311++G(3df,3pd)//CCSD(T)/6-311++G(d,p) level of theory. The formation constant and atmospheric abundance of the ozone-water complex are estimated using the thermodynamic and spectroscopic data obtained.     

Crystal chemistry and thermodynamic properties of anisotropic Ce2Ni7H4.7 hydride

A new intermetallic deuteride Ce₂Ni₇D_4.7 with an anomalous volume expansion has been studied. Its structure was solved on the basis of in situ neutron diffraction data. Expansion proceeds along the c-axis and within the CeNi₂ slabs only. All D atoms are located inside these slabs and on the border between CeNi₂ and CeNi₅. Ordering of D atoms in the bulk of CeNi₂ is accompanied by substantial deformation of these slabs thus lowering the hexagonal symmetry to orthorhombic [space group Pmcn (No. 62); a=4.9251(3) Å, b=8.4933(4) Å, c=29.773(1) Å]. Inside the CeNi₂ layer the hydrogen sublattice is completely ordered; all D-D distances exceed 2.0 Å. Local coordination of Ni by D inside the CeNi₂ blocks is of “open”, saddle-like type. Hydrogen ordering is mainly determined by Ce-H and H-H interactions. The pressure-composition-temperature measurements yielded the following thermodynamic parameters of the formation of the hydride: ΔH=−22.4 kJ/mol_H, ΔS=−59.9 J/(K mol_H).     

Effects of silica nanoparticle addition on polymer semiconductor wettability and carrier mobility in solution‐processable organic transistors on hydrophobic substrates

The effects of the addition of silica nanoparticles (SNPs) on wettability of regioregular poly(3‐hexylthiophene) (P3HT) organic semiconductor solutions on hydrophobic substrates and the carrier mobility in organic field‐effect transistors (OFETs) made of these films are investigated. The dewetting of films made from P3HT solutions on hydrophobic substrates modified with octadecyltrichlorosilane (ODTS) is markedly suppressed after the addition of SNPs with phenyl surfactants. This enables us to fabricate continuous P3HT/SNPs films with high crystallinity by the conventional spin‐coating technique, leading to higher mobility compared with P3HT FETs fabricated on non‐modified substrates. Moreover, the addition of SNPs with larger diameters compensates for the degradation of mobility associated with the increase in the concentration of SNPs. Solution‐processed P3HT/SNPs FETs on ODTS‐modified substrates exhibit a field‐effect mobility of 1.3 × 10^?2 cm² V^?1 s^?1, which is almost comparable to that of P3HT FETs without SNPs (2.1 × 10^?2 cm² V^?1 s^?1). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 509–516     

Self-assembled light-harvesting systems: Ru(II) complexes assembled about Rh-Rh cores

Ru(II) polypyridine species have been assembled about dirhodium(II, II) tetracarboxylate cores. The complexes prepared have general formulas [{(terpy)Ru(La)}n{Rh2(CH3COO)4-n(CH3CN)2}]2n+ (a-type compounds: terpy = 2,2':6',2' '-terpyridine; La = 4'-(p-carboxyphenyl)-2,2':6',2' '-terpyridine; n = 1, 1a; n = 2, cis-2a and trans-2a-cis and trans refer to the arrangement of the Ru(II) species around the dirhodium core; n = 3, 3a), [{(Lb)Ru(La)}n{Rh2(CH3COO)4-n(CH3CN)2}]2n+ (b-type compounds: Lb = 6-phenyl-2,4-di(2-pyridyl)-s-triazine; n = 1, 1b; n = 2, an inseparable mixture of cis-2b and trans-2b; n = 3, 3b; n = 4, 4b), and [{(terpy)Ru(Lc)}{Rh2(CH3COO)3(CH3CN)2}]2+ (1c; Lc = 6-(p-carboxyphenyl)-2,4-di(2-pyridyl)-s-triazine). As model species, also the mononuclear [(terpy)Ru(La)]2+ (5a), [(La)Ru(Lb)]2+ (5b), and [(terpy)Ru(Lc)]2+ (5c) have been prepared. All of the complexes have been characterized by several techniques, including NMR and mass spectra, and the stability of the various species is discussed. The absorption spectra of all of the compounds are dominated by the Ru(II) polypyridine moieties, showing intense ligand-centered (LC) bands in the UV region and intense metal-to-ligand charge-transfer (MLCT) bands in the visible. The compounds exhibit several metal-centered oxidation and ligand-centered reduction processes, which have been assigned to specific subunits. Both absorption and redox data indicate a supramolecular nature of the assembled systems. Efficient energy transfer from the MLCT triplet state of the Ru-based components to the lowest-energy excited state of the dirhodium core takes place for the a-type compounds at 298 K in acetonitrile solution, whereas such a process is inefficient for the b-type and c-type species, which exhibit the typical MLCT emission. At 77 K in butyronitrile matrix, Ru-to-Rh2 energy transfer is partly efficient for both the a-type and the b-type compounds and is inefficient for 1c. The reasons for such behavior are discussed by taking into account arguments concerning the driving force and reorganization energy of the complexes.     

Nepalensinols D-G, new resveratrol oligomers from Kobresia nepalensis (Cyperaceae) as potent inhibitors of DNA topoisomerase II

Four new resveratrol oligomers, nepalensinols D-G, were isolated from the stem of Kobresia nepalensis (Cyperaceae). The structures were determined by detailed NMR spectral analysis. The compounds were assessed for their inhibitory activity against human topoisomerase II, a potential target of anti-tumor agents. These stilbenoids showed potent inhibitory activity against human topoisomerase II with IC50 values of 5-15 microM.     

Synthesis, structures and reactions of cyclometallated gold complexes containing (2-diphenylarsino-n-methyl)phenyl (n = 5, 6)

Reaction of (C6H3-2-AsPh2-n-Me)Li (n = 5 or 6) with [AuBr(AsPh3)] at -78 degrees C gives the corresponding cyclometallated gold(I) complexes [Au2[(mu-C6H3-n-Me)AsPh2]2] [n = 5, (1); n = 6, (9)]. 1 undergoes oxidative addition with halogens and with dibenzoyl peroxide to give digold(II) complexes [Au2X2[(mu-C6H3-5-Me)AsPh2]2] [X = Cl (2a), Br (2b), I (2c) and O2CPh (3)] containing a metal-metal bond between the 5d9 metal centres. Reaction of 2a with AgO2CMe or of 3 with C6F5Li gives the corresponding digold(II) complexes in which X = O2CMe (4) and C6F5 (6), respectively. The Au-Au distances increase in the order 4 < 2a < 2b < 2c < 6, following the covalent binding tendency of the axial ligand. Like the analogous phosphine complexes, 2a-2c and 6 in solution rearrange to form C-C coupled digold(I) complexes [Au2X2[mu-2,2-Ph2As(5,5-Me2C6H3C6H3)AsPh2]] [X = Cl (5a), X = Br (5b), X = I (5c) and C6F5 (7)] in which the gold atoms are linearly coordinated by As and X. In contrast, the products of oxidative additions to 9 depend markedly on the halogens. Reaction of 9 with chlorine gives the gold(I)-gold(III) complex, [ClAu[mu-2-Ph2As(C6H3-6-Me)]AuCl[(6-MeC6H3)-2-AsPh2]-kappa2As,C] (10), which contains a four-membered chelate ring, Ph2As(C6H3-6-Me), in the coordination sphere of the gold(III) atom. When 10 is heated, the ring is cleaved, the product being the digold(I) complex [ClAu[mu-2-Ph2As(C6H3-6-Me)]Au[AsPh2(2-Cl-3-Me-C6H3)]] (11). Reaction of 9 with bromine at 50 degrees C gives a monobromo digold(I) complex (12), which is similar to 11 except that the 2-position of the substituted aromatic ring bears hydrogen instead halogen. Reaction of 9 with iodine gives a mixture of a free tertiary arsine, (2-I-3-MeC6H3)AsPh2 (13), a digold diiodo compound (14) analogous to 11, and a gold(I)-gold(III) zwitterionic complex [I2Au(III)[(mu-C6H3-2-AsPh2-6-Me)]2Au(I)] (15) in which the bridging units are arranged head-to-head between the metal atoms. The structures of 2a-2c and 4-15 have been determined by single-crystal X-ray diffraction analysis. The different behaviour of 1 and 9 toward halogens mirrors that of their phosphine analogues; the 6-methyl substituent blocks C-C coupling of the aryl residues in the initially formed oxidative addition product. In the case of 9, the greater lability of the Au-As bond in the initial oxidative addition product may account for the more complex behaviour of this system compared with that of its phosphine analogue.     

The development of an automated continuous measurement system for the monitoring of HCHO and CH3CHO in the atmosphere by using an annular diffusion scrubber coupled to HPLC

An automated continuous measurement system for the monitoring of formaldehyde (HCHO) and acetaldehyde (CH₃CHO) in the urban atmosphere was developed by using an annular diffusion scrubber in conjunction with a high-performance liquid chromatograph (HPLC). With this technique, atmospheric HCHO and CH₃CHO were effectively collected by the annular diffusion scrubber which consists of a porous polytetrafluoroethylene (PTFE) tube disposed concentrically within a Pyrex-glass tube and a scrubbing solution. 2,4-Dinitrophenylhydrazine (DNPH) was selected as the scrubbing solution for collecting HCHO and CH₃CHO, which are derivatized to 2,4-dinitrophenylhydrazone-formaldehyde (DNPH-HCHO) and 2,4-dinitrophenylhydrazone-acetaldehyde (DNPH-CH₃CHO), respectively. An aliquot of the sample solution was automatically injected into an HPLC equipped with a semi-micro ODS column and a UV-VIS detector for separating and determining DNPH-HCHO and DNPH-CH₃CHO. All the operations are sequenced by a programmable controller, and automated continuous measurements are performed with a typical temporal resolution of 1 h. The collection efficiencies of HCHO and CH₃CHO were about 97% and 93%, respectively, at an air flow rate of 0.2 L/min. The lower detection limits (3σ of the blank hydrazones) of HCHO and CH₃CHO were 0.05 ppbv and 0.10 ppbv, respectively, in the case of 12-L air sample volume. Analytical response of a standard solution of DNPH-HCHO and DNPH-CH₃CHO by the HPLC during a 10-day continuous measurement was unchanged and the relative standard deviation (RSD) was < 1.0%. Interferences from O₃ and NO₂ were insignificant in this annular diffusion scrubber method. Both for HCHO and CH₃CHO measurements, concentrations from this developed system well agreed with those measured by a DNPH Silica cartridge method. Received: 15 July 1998 / Revised: 5 October 1998 / Accepted: 7 October 1998     

Action Spectrum for the Photophobic Response of Ciona intestinalis (Ascidieacea, Urochordata) Larvae Implicates Retinal Protein

Ascidian tadpole larvae change swimming behavior during the course of development. The photic behavior of the larvae of Ciona intestinalis was monitored by a computerized cell-tracking system with a time resolution of 0.1 s. Newly hatched larvae swim at an average speed of 1.4 mm/s but show no response to light stimuli. The swimming speed of the larvae became slower (0.4 mm/s) 3 h after hatching and they were induced to swim more rapidly by a sudden decrease in light intensity 4 h after hatching. During the course of development, the maximal speed of swimming behavior increased with time until 8 h after hatching and then plateaued. The action spectrum for the step-down photophobic response of the larvae was determined at around 8 h after hatching and was fitted to Dartnall's nomogram with the absorbance maximum of the pigment located at 505 nm. These results suggest retinal proteins in the ocellus of the larvae are the photoreceptors for the photobehavior.