Electronic structure in five-coordinate complexes of nickel(II) with heavy-donor ligands

I.

Various studies designed to elucidate the electronic structure of the arsenic donor ligand, o-phenylenebisdimethylarsine (diarsine), have been carried out. The electronic spectrum of diarsine has been measured at 300 and 77˚K. Electronic spectra of the molecular complexes of various substituted organoarsines and phosphines with tetracyanoethylene have been measured and used to estimate the relative ionization potentials of these molecules.

Uv photolysis of arsines in frozen solution (96˚K) has yielded thermally labile, paramagnetic products. These include the molecular cations of the photolyzed compounds. The species (diars)⁺ exhibits hyper-fine splitting due to two equivalent ⁷⁵As(I=3/2) nuclei. Resonances due to secondary products are reported and assignments discussed.

Evidence is presented for the involvement of d-orbitals in the bonding of arsines. In (diars)⁺ there is mixing of arsenic “lone-pair” orbitals with benzene ring π-orbitals.

II.

Detailed electronic spectral measurements at 300 and 77˚K have been carried out on five-coordinate complexes of low-spin nickel(II), including complexes of both trigonal bipyramidal (TBP) and square pyramidal (SPY) geometry. TBP complexes are of the form NiLX⁺ (X=halide or cyanide,

L = Qƭ(CH₂)₃As(CH₃)₂]₃ or

P [hexagon - Q'CH₃] , Q = P, As,

Q’=S, Se).

The electronic spectra of these compounds exhibit a novel feature at low temperature. The first ligand field band, which is asymmetric in the room temperature solution spectrum, is considerably more symmetrical at 77˚K. This effect is interpreted in terms of changes in the structure of the complex.

The SPY complexes are of the form Ni(diars)₂X^z (X=CL, Br, CNS, CN, thiourea, NO₂, As). On the basis of the spectral results, the d-level ordering is concluded to be xy ˂ xz, yz ˂ z² ˂˂ x² - y². Central to this interpretation is identification of the symmetry-allowed ¹A₁ → ¹E (xz, yz → x² - y²) transition. This assignment was facilitated by the low temperature measurements.

An assignment of the charge-transfer spectra of the five-coordinate complexes is reported, and electronic spectral criteria for distinguishing the two limiting geometries are discussed.

The structure specificity of alpha-chymotrypsin. I. Polypeptides as substrates. II. N-acylated peptide esters as substrates. III. Some reactive esters of N-acylated amino acids as substrates

The structural specificity of α-chymotrypsin for polypeptides and denatured proteins has been examined. The primary specificity of the enzyme for these natural substrates is shown to closely correspond to that observed for model substrates. A pattern of secondary specificity is proposed.

A series of N-acetylated peptide esters of varying length have been evaluated as substrates of α-chymotrypsin. The results are interpreted in terms of proposed specificity theories.

The α-chymotrypsin-catalyzed hydrolyses of a number of N-acetylated dipeptide methyl esters were studied. The results are interpreted in terms of the available specificity theories and are compared with results obtained in the study of polypeptide substrates. The importance of non-productive binding in determining the kinetic parameters of these substrates is discussed. A partial model of the locus of the active site which interacts with the R’₁CONH- group of a substrate of the form R’₁CONHCHR₂COR’₃ is proposed.

Finally, some reactive esters of N-acetylated amino acids have been evaluated as substrates of α-chymotrypsin. Their reactivity and stereo-chemical behavior are discussed in terms of the specificity theories available. The importance of a binding interaction between the carboxyl function of the substrate and the enzyme is suggested by the results obtained.

The Riesz space structure of an Abelian W*-algebra

Let M be an Abelian W*-algebra of operators on a Hilbert space H. Let M₀ be the set of all linear, closed, densely defined transformations in H which commute with every unitary operator in the commutant M’ of M. A well known result of R. Pallu de Barriere states that if ɸ is a normal positive linear functional on M, then ɸ is of the form T → (Tx, x) for some x in H, where T is in M. An elementary proof of this result is given, using only those properties which are consequences of the fact that ReM is a Dedekind complete Riesz space with plenty of normal integrals. The techniques used lead to a natural construction of the class M₀, and an elementary proof is given of the fact that a positive self-adjoint transformation in M₀ has a unique positive square root in M₀. It is then shown that when the algebraic operations are suitably defined, then M₀ becomes a commutative algebra. If ReM₀ denotes the set of all self-adjoint elements of M₀, then it is proved that ReM₀ is Dedekind complete, universally complete Riesz spaces which contains ReM as an order dense ideal. A generalization of the result of R. Pallu de la Barriere is obtained for the Riesz space ReM₀ which characterizes the normal integrals on the order dense ideals of ReM₀. It is then shown that ReM₀ may be identified with the extended order dual of ReM, and that ReM₀ is perfect in the extended sense.

Some secondary questions related to the Riesz space ReM are also studied. In particular it is shown that ReM is a perfect Riesz space, and that every integral is normal under the assumption that every decomposition of the identity operator has non-measurable cardinal. The presence of atoms in ReM is examined briefly, and it is shown that ReM is finite dimensional if and only if every order bounded linear functional on ReM is a normal integral.

Diversity, abundance distribution and secondary production of intertidal and subtidal benthic macrofauna of Bushehr Province with emphasis on annelida groups

The present investigation was undertaken to establish a reference situation for future use, to identify temporal and spatial composition of macrofauna and estimate some ecological indices in the sub tidal waters along the Bushehr coastal waters in Persian Gulf. Six transects were selected including Genaveh, Farakeh, Shif, Bandargah, Rostami and Asalouyeh, at each transect 3 station were sampled in depths of zero, 5 and 10 metres. Sampling was seasonally carried out by a VAN VEEN grab 0.0225 m2, during summer 2008 until spring 2009. Samples were wet sieved immediately using 0.5 mm mesh size sieves and sediment retained in the sieve was preserved in 4% buffered formalin solution. Macrofauna specimen were separated from the sediments using decantation and elutriation methods, enumerated and identified up to the Genus level. Environmental factors such as temperature. pH, and salinity were recorded in field using sensitive probs and refractometer (for salinity) and also sediment samples were taken for TOM and grain size analysis in all the stations. 5611 specimens belonging to 66 genera were collected during the present study. Polychaetes were dominant both in terms of genus number (31) and relative abundance (74 % of total macrofaunal abundance). The other dominant groups were Artheropoda, (16.1%), Molusca (2.8%), Echinodermata (1.29%) and others including Nematoda, Nemertina, Echiura and Turbellaria (5.8%). Thirty one Genera belong of 27 families of polychaeta, one genus and family of Subphylum Chlicerata,19 genera belong to 14 families of Crustacea, 8 genera belong to 6 families of Molusca, were indentified in the studied region. 1 family (Polygordidae) and 3 genera (Flabeligera, Pilargis and Polygordius) of Polychaeta, 1 family (Nymphonidae) and genus (Nymphon) of Chelicerata, 1 Family (Nematoplanidae) and genus (Nematoplana) of Turbellaria, were identified for the first time in Persian Gulf area. The result indicated that macrofauna organism have strong relationship with the grain size characteristics of the sediments they inhabit. The most surface deposit feeder specimens such as Prionospio and Cossura were found in zero meters depth of Genaveh, Farakeh, Bandargah, Rostami and Asalouyeh stations with sandy substratum, however the most burrowing deposit feeder and scavenger specimens such as Capitella and Petaloproctus were collected in 5 and 10 meter depths of stations with silty–clay substratum. The annual mean abundance, Shanon- weiner diversity and evenness of macrofauna were estimated1152.73 N/ m² , 2.72 and 0.792 respectively .The annual average biomass and secondary production were computed 1.797 gDW m² and 3.594 gDW m² y-1 .The average of water temperature, salinity, pH and oxygen concentration were recorded between 16.37-36.05 °C, 38-42 g/l, 7.89-8.76 and 4.23-8.23 mg/l, respectively during this study in 6 studied region. Among of investigated stations Asalouyeh adjacent of effluent canal of Gas and petrochemical industry sewage and Farakeh regions adjacent the Helleh estuary had the lowets and the highest community indices. The average of diversity and density in 5 meters depth stations with moderate of sand, silt and clay were slightly more than 2 other depths stations, it seems that 5 meters stations are made a transition habitats between 2 sandy and clay habitats, that can be used by 2 groups of surface and borrowing deposit feeders. Based on the data provided in this survey, the temperature variation, sediment texture, TOM, type habitat and manmade factors of Gas and petrochemical industries have had the most effect on the macrofauna community structure in the studied region during sampling periods.

Assessment of pelagic primary and secondary production in Sefidrud River estuary

Sefid-Rood River Estuary (SRE) is the most important riverine ecosystem in the south Caspian Sea along the Iranian coast lines. The aim of this study was to examine spatial and temporal variability in Phytoplankton and Zooplankton abundance and diversity in SRE. Variability of Chlorophyll a and inorganic nutrient concentration were determined during a year (November 2004– October 2005) in five sampling stations. Primary and secondry production were determined during a year. Total chlorophyll a concentration during the investigation ranged between zero to 22.8 μgl-1 and the highest levels were consistently recorded during summer and the lowest during winter with a annual mean concentration 4.48 μgl-1. Nutrient concentration was seasonally related to river flow with annual mean concentration: NO2 0.05±0.2 mgl-1, NO3 1.13±0.57 mgl-1, NH4 0.51±0.66 mgl-1, total phosphate 0.13±0.1mgl-1 and SiO2 5.68±1.91 mgl-1. Bacillariophytes, Cyanophytes, Chlorophytes, Pyrophytes and Euglenophytes were the dominant phytoplankton groups in this shallow and turbid estuary. The diversity and abundance of phytoplankton had a seasonal pattern while Diatomas and Chrysophytes were dominant throughout the year but Cyanophytes observed only during the summer. Zooplankton community structure was dominated by copepods which 68% of the total zooplankton. In the winter and summer seasons two increased in the number of zooplankton community and usually toward the sea had occurred. Zooplankton also showed a significant spatial and temporal variation. The high turbidity and temperature prime characteristics of SRE seem to be determining factors acting directly on phytoplankton and zooplankton temporal variability and nutrient fluctuations. Everywhere in this estuary nutrients appeared to be in excess of algal requirement and did not influence a phytoplankton and zooplankton composition. Also there was a positive correlation between chlorophyll a and temperature and a negative one with DIN and TP. Primary production determined in this estuary by dark and light butter method and G.P.P. 38.27±34.12 mgcm-2h-1 and N,PP 201.6±289.9 mgcm-2d-1. secondry production determined 15/128 mgc/m3/year. Everywhere in this estuary nutrients appeared to be in excess to algal requirement and did not influence in Chl. a and primary production. The most important factor influence on Chl. a was water temperature.

Molecular phylogeography and population structure of a mid-elevation montane frog Leptobrachium ailaonicum in a fragmented habitat of southwest China

Leptobrachium ailaonicum is a vulnerable anuran restricted to a patchy distribution associated with small mountain streams surrounded by forested slopes at mid-elevations (approximately 2000-2600 m) in the subtropical Mount Wuliang and Mount Ailao ranges in southwest China (Yunnan Province) and northern Vietnam. Given high habitat specificity and lack of suitable habitat in lower elevations between these ranges, we hypothesized limited gene flow between populations throughout its range. We used two mitochondrial genes to construct a phylogeographic pattern within this species in order to test our hypothesis. We also examined whether this phylogeographic pattern is a response to past geological events and/or climatic oscillations. A total of 1989 base pairs were obtained from 81 individuals of nine populations yielding 51 unique haplotypes. Both Bayesian and maximum parsimony phylogenetic analyses revealed four deeply divergent and reciprocally monophyletic mtDNA lineages that approximately correspond to four geographical regions separated by deep river valleys. These results suggest a long history of allopatric separation by vicariance. The distinct geographic distributions of four major clades and the estimated divergence time suggest spatial and temporal separations that coincide with climatic and paleogeographic changes following the orogeny and uplift of Mount Ailao during the late Miocene to mid Pliocene in southwest China. At the southern distribution, the presence of two sympatric yet differentiated clades in two areas are interpreted as a result of secondary contact between previously allopatric populations during cooler Pleistocene glacial cycles. Analysis of molecular variance indicates that most of the observed genetic variation occurs among the four regions implying long-term interruption of maternal gene flow, suggesting that L ailaonicum may represent more than one distinct species and should at least be separated into four management units corresponding to these four geographic lineages for conservation. (C) 2009 Elsevier Inc. All rights reserved.

Community structure of small fishes in a shallow macrophytic lake (Niushan Lake) along the middle reach of the Yangtze River, China

This study describes the current status of the small fish community in Niushan Lake in China, and examines the spatial and seasonal variations of the community in relation to key environmental factors. Based on macrophyte cover conditions, the lake was divided into three major habitat types: (1) Potamogeton maackianus habitat, (2) Potamogeton maackianus and Myriophyllum spicatum habitat, and (3) uncovered or less-covered habitat. Fish were sampled quantitatively in the three habitat types by block nets seasonally from September 2002 to August 2003. A total of 10 469 individuals from 27 fish species were caught, among which 20 species were considered as small fishes. Rhodeus ocellatus, Paracheilognathus imberbis, Pseudorasbora parva, Micropercops swinhonis and Cultrichthys erythropterus were recognized as dominant small fishes according to their abundance and occurrence. It was noted that (1) small fishes predominated the total number of fish species in the lake, which reflected to some degree the size diminution phenomenon of fish resources; (2) many small fishes had plant detritus as their food item, which was consistent with the abundance of macrophyte detritus in the lake and implied the importance of detritus in supporting small fish secondary production. Canonical correspondence analysis suggested that the spatial distributions of most small fishes were associated with complex macrophyte cover conditions. Macrophyte biomass was positively correlated with species richness, diversity index and the catch per unit of effort (CPUE) of the fish community. Water depth had no significant effects on species diversity and distribution of the small fishes. Correspondence analysis revealed a higher occurrence of the small fishes and higher abundance of individuals in summer and autumn. Seasonal length-frequency distributions of several species indicated that more larval and juvenile individuals appeared in spring and summer. This study provides some baseline information which will be essential to long-term monitoring of small fish communities in the Yangtze lakes.

Photoelectric characteristics of metal/InGaN/GaN heterojunction structure

A heterojunction structure photodetector was fabricated by evaporating a semitransparent Ni/Au metal film oil the InGaN/GaN structure. The photocurrent (PC) spectra show that both the Schottky junction (NiAu/InGaN) and the InGaN/GaN isotype heterojunction contribute to the PC signal which suggests that two junctions are connected in series and result in a broader spectral response of the device. Secondary electron, cathodoluminescence and electron-beam-induced current images measured from the same area of the edge surface clearly reveal the profile of the layer structure and distribution of the built-in electric field around the two junctions. A band diagram of the device is drawn based oil the consideration of the polarization effect at the InGaN/GaN interface. The analysis is consistent with the physical mechanism of a tandem structure of two junctions connected in series.

Growth of a novel periodic structure of SiC/AlN multilayers by low pressure chemical vapour deposition

A novel 10-period SiC/AlN multilayered structure with a SiC cap layer is prepared by low pressure chemical vapour deposition (LPCVD). The structure with total film thickness of about 1.45 mu m is deposited on a Si (111) substrate and shows good surface morphology with a smaller rms surface roughness of 5.3 nm. According to the secondary ion mass spectroscopy results, good interface of the 10 period SiC/AlN structure and periodic changes of depth profiles of C, Si, Al, N components are obtained by controlling the growth procedure. The structure exhibits the peak reflectivity close to 30% near the wavelength of 322 nm. To the best of our knowledge, this is the first report of growth of the SiC/AlN periodic structure using the home-made LPCVD system.

The difference of Si doping efficiency in GaN and AlGaN in GaN-based HBT structure

An AlGaN/GaN HBT structure was grown by low-pressure metalorganic chemical vapor deposition (MOCVD) on sapphire substrate. From the high-resolution x-ray diffraction and transmission electron microscopy (TEM) measurements, it was indicated that the structure is of good quality and the AlGaN/GaN interfaces are abrupt and smooth. In order to obtain the values of Si doping and electronic concentrations in the AlGaN emitter and GaN emitter cap layers, Secondary Ion Mass Spectroscopy (SIMS) and electrochemical CV measurements were carried out. The results showed that though the flow rate of silane (SiH4) in growing the AlGaN emitter was about a quarter of that in growing GaN emitter cap and subcollector layer, the Si sputtering yield in GaN cap layer was much smaller than that in the AlGaN emitter layer. The electronic concentration in GaN was about half of that in the AlGaN emitter layer. It is proposed that the Si, Al co-doping in growing the AlGaN emitter layer greatly enhances the Si dopant efficiency in the AlGaN alloy. (c) 2006 WILEY-VCH Verlag GmbH & Co KGaA, Weinheim.

Effects of rare earth on the structure and properties of Mg–6Zn–5Al–4Gd–1RE (RE = Ce or Y) alloys

The microstructures and mechanical properties of Mg-6Zn-5Al-4Gd-1RE (RE = Ce or Y) alloys were investigated. The addition of Ce or Y obviously refines the grain size for the Mg-6Zn-5Al-4Gd-based alloy, while the Y element has a better refining effect. The Ce and Y show different grain-refining mechanisms: Ce addition mostly promotes the growth of secondary dendrite, while Y addition mainly increases the heterogeneous nucleation sites.

Structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30-LaNi5 hydrogen storage alloys

The structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30+x% LaNi5 (x=0, 1, 5 and 10) hydrogen storage alloys have been investigated systematically. XRD shows that the matrix phase structure of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure is not changed after adding LaNi5 alloy. However, the amount of the secondary phase increases with increasing LaNi5 content. Field emission scanning electron microscopy-energy dispersive spectroscopy (FESEM-EDS) shows that the C14 Laves phase contains more Zr and the white lard phase has a composition close to (Zr, Ti)(V, Cr, Ni, La)(2).

Structure and mechanical properties of extruded Mg-Gd based alloy sheet

The Mg-8Gd-2Y-1Nd-0.3Zn-0.6Zr (wt.%) alloy sheet was prepared by hot extrusion technique, and the structure and mechanical properties of the extruded alloy were investigated. The results show that the alloy in different states is mainly composed of alpha-Mg solid solution and secondary phases of Mg5RE and Mg24RE5 (RE = Gd, Y and Nd). At aging temperatures from 200 degrees C to 300 degrees C the alloy exhibits obvious age-hardening response. Great improvement of mechanical properties is observed in the peak-aged state alloy (aged at 200 degrees C for 60 h), the ultimate tensile strength (sigma(b)), tensile yield strength (sigma(0.2)) and elongation (epsilon) are 376 MPa, 270 MPa and 14.2% at room temperature (RT), and 206 MPa. 153 MPa and 25.4% at 300 degrees C, respectively, the alloy exhibits high thermal stability.

A three-dimensional metal-organic framework based on a triazine derivative: syntheses, structure analysis, and sorption studies

A novel metal-organic framework [Cu-3(m-TATB)(2)Py(CH3OH)(2)] (1) constructed of a triazine-based trigonal-planar ligand, 3,3',3 ''-s-triazine-2,4,6- triyltribenzoate (m-H(3)TATB), has been synthesized and structurally characterized. Compound 1 features three-dimensional (3D) channels and cavities together, and exhibits high carbon dioxide sorption at normal pressure.