DICHLORO(ETA(5)-CYCLOPENTADIENYL)([1-(4-METHOXYPHENYL)CYCLOHEXYL]-ETA(5)-CYCLOPENTADIENYL)TITANIUM(IV)

The title molecule, [TiCl2(C5H5)(C18H21O)], has a pseudotetrahedral bent metallocene structure in which the cyclopentadienyl ring is symmetrically bonded to Ti [range of Ti-C distances 2.36(1)-2.41(1)Angstrom], but the substituted cyclopentadienyl ring adopts asymmetrical bonding [Ti-C 2.33(1)-2.48(1)Angstrom] due to the interaction of the large substituent with the Cl(2) atom. The angle C(11)-C(1)-C(21) is 111.1(8)degrees with the large substituent occupying a cis position with respect to the substituted ring.

UNIMOLECULAR DISSOCIATION REACTIONS OF DOUBLY-CHARGED IONS [C12H12N2O](2+) AND [C12H12N2S](2+) IN GAS-PHASE

The unimolecular dissociation reactions of doubly charged ions were reported, which resulted from a tandem mass spectrometer and a reversed geometry double focusing mass spectrometer by electron impact, Mass analyzed ion kinetic energy spectrometry (MIKES) was used to obtain the kinetic energy releases in charge separation reactions of doubly charged ions, The intercharge distances between the two charges at transition states can be calculated from the kinetic energy releases, Transition structures of unimolecular dissociation reactions were infered from MIKES and MS/MS.

A STUDY OF ION KINETIC-ENERGY SPECTROMETRY OF ORTHO-DICHLORO, META-DICHLORO AND PARA-DICHLORO BENZENE DOUBLY CHARGED IONS [C6H4CL2]2+ AND [C6H3CL]2+ IN GAS-PHASE

The unimolecular Charge separation reactions of the doubly charged ions [C6H4Cl2]2+, [C6H3Cl]2+ produced in the ion source by electron impact from o-, m-, and p-dichloro benzene have been studied using mass analysed ion kinetic energy spectrometry. The values of kinetic energy releases (T) can be calculated from the energy dispersion of product ions. As T essentially reflects the release of coulombic energy, which can be used to calculate the approximate distances R between the two charges immediately before decomposition of the ions. From these data, some structural information about transiton states could be provided. The ECID and CID processes of above doubly charged ions, have also been studied. We found that the CID reactions of (C6H4Cl2)2+ could be used to distinguish three dichloro benzene isomers.

SYNTHESIS, THERMAL-STABILITY AND X-RAY CRYSTAL-STRUCTURE OF THE BIS(CYCLOPENTADIENYL)YTTERBIUM NAPHTHOXIDE DERIVATIVE (C5H5)2YB(OC10H7)(THF)

Cp3Yb (Cp = C5H5) reacts with a-naphthol (HNP) in THF to form Cp2Yb(NP)(THF) (1), which crystallizes in the space group P2(1)/n with unit cell dimensions a = 8.084(2), b = 15.996(6), c = 15.973(7) angstrom, beta = 98.95(3), V = 2040.3 angstrom and D(calc.) = 1.69 g cm-3 for Z = 4. Least-squares refinement based on 2242 observed reflections converged to a final R value of 0.081. The average Yb-C(Cp) distance is 2.60(2) angstrom and Yb-O(THF) and Yb-O(NP) distances are 2.30(1) and 2.06(1) angstrom, respectively. The title compound loses the coordinated THF molecule readily by heating under vacuum to give dimeric [Cp2Yb(NP)]2 (2), which undergoes disproportionation to give Cp3Yb and Yb(NP)3 on heating above 230-degrees-C.

ANALYSIS OF ANGULAR OVERLAP PARAMETERS FOR EU3+ - LN2O2S (LN = LU, Y, GD, LA) CRYSTAL SERIES

The angular overlap model (AOM) is applied to 4f6 electron systems. The crystal field parameters are interpreted and covalency between 4f electrons and ligands is investigated based on the experimental energy levels. For Eu3+:Ln2O2S (Ln = Lu, Y, Gd, La) crystal series, we adopt two computational schemes. First of all, we assume that the distances to all ligands are equal, and then the distances to all ligands are divided into two groups, namely, oxygens as one group, sulfurs as the other. Of course, much information about covalency will be obtained from the latter case. Obviously, our results show that the covalency of Ln-O bonding is stronger than that of Ln-S bonding in line with much shorter bondlength for the former than that for the latter. The two schemes yield the same results, that is, for sigma and pi bonding, ligands are strong donors as well as sigma, pi effects are dominant over delta, phi effects.

SYNTHESES OF METHYLCYCLOPENTADIENYL DERIVATIVES OF LANTHANIDES (LN = LA-ND) AND CRYSTAL-STRUCTURES OF [(THF)2LI(MU-CL)2]2[MECPND(THF)] AND [LI(DME)3][MECPLA(NPH2)3]

The reaction of LnCl3.2LiCl with 1 equiv of MeCpNa in THF gives the complexes [(THF)2Li(mu-Cl)2]2[MeCpLn(THF)] (Ln = Nd (1), La (2)) in good yield. These precursors react further with 2 equiv of LiNPh2 to produce the new complexes [Li(DME)3][MeCpLn(NPh2)3] (Ln = La (3), Pr (4), Nd (5)). They have been characterized by elemental analyses and IR and NMR spectra, as well as by structural analyses of 1 and 3. The chloride 1 crystallizes in the monoclinic space group P2(1)/n (No. 14) with a = 12.130 (5) angstrom, b = 17.343 (5) angstrom, c = 17.016 (5) angstrom, beta = 108.54 (3)-degrees, V = 3393.87 angstrom3, Z = 4, and D(c) = 1.45 g/cm3. Least-squares refinement led to a final R value of 0.051 (I greater-than-or-equal-to 3-sigma(I(o))) for 2004 independent reflections. Complex 3 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 18.335 (6) angstrom, b = 16.576 (5) angstrom, c = 17.461 (6) angstrom, beta = 96.04 (3)-degrees, V = 5277.17 angstrom3, D(c) = 1.26 g/cm3, Z = 4, and R = 0.057 (I greater-than-or-equal-to 2.5-sigma(I(o))) for 3378 reflections. The structure of 3 consists of discrete ion pairs [Li(DME)3]+ and [MeCpLa(NPh2)3]- with average La-N and La-C(ring) distances of 2.459 (8) and 2.84 (1) angstrom, respectively.

STRUCTURE-ANALYSIS OF MOLTEN CACL2-KCL SYSTEM BY X-RAY-DIFFRACTION

Radial distribution function of CaCl2-KCl (1:2 mol) melt was measured by X-ray scattering of high temperature liquid. The nearest neighbour distances of Ca2+-Cl-, K+-Cl- and Cl--Cl- ionic pairs are 0.278, 0.306 and 0.380 nm, respectively, Discussion on the relation between structure and physicochemical properties in the melt was simply done in this paper.

A STUDY OF ION KINETIC ENERGY SPECTROMETRY OF FERROCENE DOUBLY CHARGED IONS IN GAS PHASE

The unimolecular charge separation reactions of the doubly charged ions FeC10H102+, FeC10H theta 2+, FeC10H82+ produced in the ion source by electron impact from ferrocene have been studied using Mass analyzed Ion Kinetic Energy Spectrometry (MIKES) technique. From the values of the kinetic energy releases (T), the intercharge distances (R) of the exploding doubly charged ions in their transition structures have been estimated and some structural informations about the transition states can be obtained. The collision induced reactions of the FeC10H102+ ion with Ar have been studied using MIKES, we postulate a new type of continuing reaction which may be "collisional charge separation induced dissociation".

SYNTHESIS AND MOLECULAR-STRUCTURE OF THE 5-COORDINATE ZIRCONIUM COMPLEX (CH3C5H4)2ZRCL(ALPHA-C10H7COO)

Bis(methylcyclopentadienyl)chloro(alpha-naphthoyloxy)zirconium, (CH3C5H4)2Zr Cl(alpha-C10H7COO), has been synthesized by the reaction between (MeCp)2ZrCl2 and equimolar sodium alpha-naphthoate in toluene at room temperature. The molecular structure of the title complex was determined by X-ray diffraction. The molecules have a five-coordinate bent metallocene structure in which the alpha-naphthoxyligand is bidentate [Zr-O, 2.317(2), 2.260(2) angstrom]. The remaining distances are [Zr-Cl, 2.521(1) angstrom; Zr-C, 480-2, 565 angstrom; Zr-cent-CH3C5H4 2.217 and 2.230 angstrom].

STRUCTURE OF HEXAMETHYLENETETRATELLURAFULVALENE DIIODIDE

C12H12I2Te4, M(r) = 920.44, monoclinic, P2(1)/n, a = 10.942 (2), b = 14.924 (2), c = 11.415 (2) angstrom, beta = 104.32 (1)-degrees, V = 1806.0 (5) angstrom 3, Z = 4, D(x) = 3.38 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 100.7 cm-1, F(000) = 1592, T = 294 K, R = 0.033 for 1828 observed reflections. One of the Te atoms is bonded to the two I atoms, which are on either side of the molecular plane. The Te-I distances are 2.963 (1) and 2.961 (1) angstrom, which means oxidation at the Te atom instead of at the C = C bonds.

Assessment of genetic diversities of selected Laminaria (Laminariales, Phaeophyta) gametophytes by inter-simple sequence repeat analysis

Inter-simple sequence repeat (ISSR) analysis was used to assess genetic diversity among 10 pairs of male and female Laminaria gametophytes. A total of 58 amplification loci was obtained from 10 selected ISSR primers, of which 34 revealed polymorphism among the gametophytes. Genetic distances were calculated with the Dice coefficient ranging from 0.006 to 0.223. A dendrogram based on the unweighted pair-group method arithmetic (UPGMA) average showed that most male and female gametophytes of the same species were clustered together and that 10 pairs of gametophytes were divided into four groups. This was generally consistent with the taxonomic categories. The main group consisted of six pairs of gametophytes, which were selected from Laminaria japonica Aresch. by intensive inbreeding through artificial hybridization. One specific marker was cloned, but was not converted successfully into a sequence characterized amplified region (SCAR) marker. Our results demonstrate the feasibility of applying ISSR markers to evaluate Laminaria germplasm diversities.

Molecular phylogeny and species identification of pufferfish of the genus Takifugu (Tetraodontiformes, Tetraodontidae)

The phylogenetic relationships and species identification of pufferfishes of the genus Takifugu were examined by use of randomly amplified polymorphic DNA (RAPD) and sequencing of the amplified partial mitochondrial 16S ribosomal RNA genes. Amplifications with 200 ten-base primers under predetermined optimal reaction conditions yielded 1962 reproducible amplified fragments ranging from 200 to 3000 bp. Genetic distances between 5 species of Takifugu and Lagocephalus spadiceus as the outgroup were calculated from the presence or absence of the amplified fragments. Approximately 572 bp of the 16S ribosonial RNA gene was amplified, using universal primers, and used to determine the genetic distance values. Topological phylogenic trees for the 5 species of Takifugu and outgroup were generated from neighbor-joining analysis based on the data set of RAPD analysis and sequences of mitochondrial 16S rDNA. The genetic distance between Takifugu rubripes and Takifugu pseudommus was almost the same as that between individuals within cacti species, but much smaller than that between T. rubripes, T. pseudommus, and the other species. The molecular data gathered from both analysis of mitochondria and nuclear DNA strongly indicated that T. rubripes and T. pseudommus should be regarded as the same species. A fragment of approximately 900 bp was amplified from the genome of all 26 T. pseudommus individuals examined and 4 individuals of intermediate varieties between T. rubripes and T. pseudommus. Of the 32 T. rubripes individuals, only 3 had the amplified fragment. These results suggest that this fragment may be useful in distinguishing between T. rubripes and T. pseudommus.

An estimate of divergence time of parazoa and eumetazoa and that of cephalochordata and vertebrata by aldolase and triose phosphate isomerase clocks

Previously we suggested that four proteins including aldolase and triose phosphate isomerase (TPI) evolved with approximately constant rates over long periods covering the whole animal phyla. The constant rates of aldolase and TPI evolution were reexamined based on three different models for estimating evolutionary distances, It was shown that the evolutionary rates remain essentially unchanged in comparisons not only between different classes of vertebrates but also between vertebrates and arthropods and even between animals and plants, irrespective of the models used, Thus these enzymes might be useful molecular clocks for inferring divergence times of animal phyla, To know the divergence time of Parazoa and Eumetazoa and that of Cephalochordata and Vertebrata, the aldolase cDNAs from Ephydatia fluviatilis, a freshwater sponge, and the TPI cDNAs from Ephydatia fluviatilis and Branchiostoma belcheri an amphioxus, have been cloned and sequenced, Comparisons of the deduced amino acid sequences of aldolase and TPI from the freshwater sponge with known sequences revealed that the Parazoa-Eumetazoa split occurred about 940 million years ago (Ma) as determined by the average of two proteins and three models, Similarly, the aldolase and TPI clocks suggest that vertebrates and amphioxus last shared a common ancestor around 700 Ma and they possibly diverged shortly after the divergence of deuterostomes and protostomes.

Seeding nets with neutral spores of the red alga Porphyra umbilicalis (L.) Kutzing for use in integrated multi-trophic aquaculture (IMTA)

Nets in traditional Porphyra mariculture are seeded with conchospores derived from the conchocelis phase, and spend a nursery period in culture tanks or calm coastal waters until they reach several centimeters in length. Some species of Porphyra can regenerate the foliose phase directly through asexual reproduction, which suggests that the time, infrastructure, and costs associated with conchocelis culture might be avoided by seeding nets with asexual spores. Here, we present work from a short-term mariculture study using nets seeded with asexual spores (neutral spores) of a native Maine species of Porphyra. Porphyra umbilicalis (L.) Kutzing was selected for this proof of concept research because of its reproductive biology, abundance across seasons in Maine, and evidence of its promise as a mariculture crop. We studied the maturation, release, and germination of the neutral spores to develop an appropriate seeding protocol for nets, followed by development of a nursery raceway to provide an easily manipulated environment for the seeded nets. Neutral spores were produced throughout the year on the central Maine coast,however, there was a temporal variability in the number and survival of released neutral spores, depending upon thallus position in the intertidal zone. Small thalli were strictly vegetative, but most thalli reproduced by neutral spores- sexual reproduction was absent. Neutral spores germinated quickly at 10 and 15 'C, but germination was delayed at 5 degrees C. Unlike some algal zygotes and spores, neutral spores of R umbilicalis required light to germinate; however, irradiances of 25 and 100 mu mol photons M-2 S-1 were equally sufficient for germination. Rafts of seeded nets were deployed in Cobscook Bay, Maine, at two distances from salmon aquaculture pens and at a control site on a nearby, fallow aquaculture site (no salmon). There was no difference in nitrogen content of harvested thalli; however, both the density and the surface area of harvested thalli were different among the sites. The possible causes of these differences are discussed in the context of potential use of P umbilicalis in IMTA. (C) 2007 Elsevier B.V. All rights reserved.

Inter-simple sequence repeat (ISSR) analysis of genetic variation of Chondrus crispus populations from North Atlantic

ISSR analysis was used to investigate genetic variations of 184 haploid and diploid samples from nine North Atlantic Chondrus crispus Stackhouse populations and one outgroup Yellow Sea Chondrus ocellatus Holmes population. Twenty-two of 50 primers were selected and 163 loci were scored for genetic diversity analysis. Genetic diversity varied among populations, percentage of polymorphic bands (PPB) ranged from 27.0 to 55.8%, H(Nei's genetic diversity) ranged from 0.11 to 0.20 and I(Shannon's information index) ranged from 0.16 to 0.30. Estimators PPB, H and I had similar values in intra-population genetic diversity, regardless of calculation methods. Analysis of molecular variance (AMOVA) apportioned inter-population and intra-population variations for C crispus, showing more genetic variance (56.5%) occurred in intra-population, and 43.5% variation among nine populations. The Mantel test suggested that genetic differentiation between nine C. crispus populations was closely related with geographic distances (R = 0.78, P = 0.002). Results suggest that, on larger distance scale (ca. > 1000 km), ISSR analysis is useful for determining genetic differentiations of C crispus populations including morphologically inseparable haploid and diploid individuals. (c) 2007 Elsevier B.V. All rights reserved.