bluuebunny/crossref_metadata_2025 huggingface dataset:
Full‐scale in situ bioremediation of hexachlorocyclohexane‐contaminated soil
Authors: Phillips Theresa M , Lee Hung , Trevors Jack T , Seech Alan G
Published: October 2005

Daramend bioremediation technology was used to treat 1100 tonnes of hexachlorocyclohexane (HCH)‐contaminated soil at a former lindane manufacturing plant. Half of the site (area A) was treated using a cycled anoxic/oxic treatment, and the other half (area B) was treated under oxic conditions. Each area was divided east to west into five zones. A control area (area C) consisted of strips of soil along the north and east edges of the site. Total HCH concentrations along a west to east gradient ranged from 22 430 to 1069 mg kg−1 in area A and from 21 100 to 730 mg kg−1 in area B. Concentrations in area C ranged from 52 to 1427 mg kg−1. The soil was treated for 371 days, during which time seven anoxic/oxic cycles were completed in area A and regular tillage was performed on area B. Soil samples (one per zone) were collected after 154 and 371 days of treatment. After 371 days, total HCH concentrations were reduced in the most highly contaminated zones of areas A and B by 60% (from 22 430 to 8910 mg kg−1) and 75% (from 21 100 to 5120 mg kg−1), respectively. The average HCH reductions for all five zones of areas A and B were 40 and 47%, respectively, with the data indicating decreased concentrations of selected isomers in certain zones of both areas. Less substantial changes in HCH concentrations were observed in control area C. Elevated chloride ion concentrations were observed in zones that had demonstrated HCH removal. This full scale project demonstrated the potential for solid phase bioremediation treatment of soil containing high HCH concentrations. Copyright © 2005 Society of Chemical Industry
Detoxification of synthetic industrial wastewaters using electrochemical oxidation with boron‐doped diamond anodes
Authors: Cañizares Pablo , Sáez Cristina , Lobato Justo , Rodrigo Manuel A
Published: October 2005

The electrochemical oxidation on boron‐doped diamond (BDD) anodes of synthetic industrial wastewaters polluted with different aromatic compounds has been studied. This technology reduces significantly the organic load and the toxicity of treated aqueous wastes. The shape of the toxicity vs time curve depends strongly on the nature of the phenolic compounds, and especially on the substituent groups contained in the phenol molecule. For the oxidation of hydroxybenzenes a complex shape is obtained, with a plateau zone in the first stages of the electrolyses. This plateau zone is transformed into a maximum in the electrolyses of chlorophenols. In the case of nitrophenols, the toxicity index decreases at the same time as the chemical oxygen demand (COD) concentration, although the decrease in the toxicity is less significant than the decrease in the COD. All these toxicity profiles can be justified in terms of the nature of the intermediates generated during the electrolyses, but they cannot be directly related to the COD variation, which shows an exponential decrease. Copyright © 2005 Society of Chemical Industry
Optimized lipopolyplex formulations for gene transfer to human colon carcinoma cells under in vitro conditions
Authors: Pelisek Jaroslav , Gaedtke Lars , DeRouchey Jason , Walker Greg F. , Nikol Sigrid , Wagner Ernst
Published: October 2005

Background

Polycation (PC, polyplex), cationic lipid (CL, lipoplex), and a combination of PC/CL (lipopolyplex) formulations were investigated for gene transfer to slow‐proliferating human colon carcinoma cell lines (COGA).

Methods

The luciferase reporter gene was complexed with either PC, CL, or PC/CL. PCs included linear (PEI22lin, 22 kDa) and branched polyethylenimine (PEI2k, 2 kDa; PEI25br, 25 kDa) and poly‐L‐lysine (PLL18 with 18 lysine monomers). CLs included DOCSPER, DOSPER and DOTAP. Lipopolyplexes were formed by either sequentially first mixing DNA with PC or CL, followed by addition of CL or PC, respectively, or simultaneously with both PC and CL. Particle size and zeta‐potential were determined and gene transfer and cytotoxicity were quantified on COGA‐3, ‐5, ‐12, HeLa and Sw480 cells.

Results

The highest gene transfer was achieved when DNA was first complexed with PC followed by CL. At low ionic strength, particles were small (50–130 nm) with a zeta‐potential of +20–40 mV. At physiological ionic strength, only lipoplexes of DOCSPER or DOSPER and their respective lipopolyplexes with PEI25br were stable to aggregation (140–220 nm). Lipopolyplexes of PEI25br were between 5‐ to 400‐fold more efficient compared to the corresponding lipoplexes or polyplexes in all cases. Chloroquine did not significantly affect lipopolyplex‐mediated gene transfer.

Conclusions

Lipopolyplex formulations of PEI25br in combination with multivalent CLs (DOCSPER, DOSPER) are promising tools for in vitro and potentially also in vivo gene transfer to colorectal cancer cells. Copyright © 2005 John Wiley & Sons, Ltd.
Ambient mass spectrometry using desorption electrospray ionization (DESI): instrumentation, mechanisms and applications in forensics, chemistry, and biology
Authors: Takáts Zoltán , Wiseman Justin M. , Cooks R. Graham
Published: October 2005

Analytical characteristics of DESI are summarized. Examples of applications to small and large molecules, to in situ analysis, and to high‐throughput analyses are presented. Evidence is provided for both a heterogeneous charge‐transfer mechanism and a droplet pick‐up mechanism of ionization. The speed, lack of the need for sample preparation, selectivity, and sensitivity of DESI are all demonstrated and discussed. Instrumentation is also discussed. Forensic applications as well as emerging areas of application including tissue imaging are given emphasis. Copyright © 2005 John Wiley & Sons, Ltd.
Lipopolysaccharide and proinflammatory cytokines require different astrocyte states to induce nitric oxide production
Authors: Kozuka Nagisa , Itofusa Rurika , Kudo Yoshihisa , Morita Mitsuhiro
Published: October 2005

Nitric oxide (NO) production by astrocytes is a significant factor affecting brain physiology and pathology, but the mechanism by which it is regulated is not known. Previous studies using different specimens and stimuli might have described different aspects of a complex system. We investigated the effect of culture and stimulus conditions on NO production by cultured astrocytes and identified two combinations of these allowing NO production. Lipopolysaccharide (LPS)‐induced NO production required a high seeding cell density and was independent of the serum concentration, whereas that induced by proinflammatory cytokines required simultaneous treatment with interleukin‐1β, tumor necrosis factor‐α, and interferon‐γ and low‐serum conditions but was less affected by the seeding density. These two pathways showed differential sensitivity to protein kinase inhibitors. Both LPS and cytokines induced expression of inducible nitric oxide synthase (iNOS). Although LPS‐induced iNOS expression required a high seeding cell density, cytokine‐induced iNOS expression, in contrast to NO production, was not affected by the serum concentration. These results suggest that astrocytes interact with the environment and alter their responsiveness to NO production‐inducing stimuli by regulating iNOS expression and activity. This is the first evidence for the selective use of two different regulatory pathways in any cell type. © 2005 Wiley‐Liss, Inc.
Ischemic preconditioning ameliorates excitotoxicity by shifting glutamate/γ‐aminobutyric acid release and biosynthesis
Authors: Dave Kunjan R. , Lange‐Asschenfeldt Christian , Raval Ami P. , Prado Ricardo , Busto Raul , Saul Isabel , Pérez‐Pinzón Miguel A.
Published: October 2005

Excitotoxicity is recognized to play a major role in cerebral ischemia‐induced cell death. The main goal of the present study was to define whether our model of ischemic preconditioning (IPC) promotes a shift from excitatory to inhibitory neurotransmission during the test ischemia to diminish metabolic demand during the reperfusion phase. We also determined whether γ‐aminobutyric acid (GABA) played a role in IPC‐induced neuroprotection. Ten minutes of cerebral ischemia was produced by tightening the carotid ligatures bilaterally following hypotension. Samples of microdialysis perfusate, representing extracellular fluid, were analyzed for amino acid content by HPLC. IPC promoted a robust release of GABA after lethal ischemia compared with control rats. We also observed that the activity of glutamate decarboxylase (the predominant pathway of GABA synthesis in the brain) was higher in the IPC group compared with control and ischemic groups. Because GABAA receptor up‐regulation has been shown to occur following IPC, and GABAA receptor activation has been implicated in neuroprotection against ischemic insults, we tested the hypothesis that GABAA or GABAB receptor activation was neuroprotective during ischemia or early reperfusion by using an in vitro model (organotypic hippocampal slice culture). Administration of the GABAB agonist baclofen during test ischemia and for 1 hr of reperfusion provided significant neuroprotection. We concluded that increased GABA release in preconditioned animals after ischemia might be one of the factors responsible for IPC neuroprotection. Specific activation of GABAB receptor contributes significantly to neuroprotection against ischemia in organotypic hippocampal slices. © 2005 Wiley‐Liss, Inc.
A mid‐shelf, mean wave direction climatology for southeastern Australia, and its relationship to the El Niño—Southern Oscillation since 1878 A.D.
Authors: Goodwin Ian D.
Published: October 2005

Coastal systems behave on timescales from days to centuries. Shelf and coastal wave climatological data from the Tasman Sea are only available for the past few decades. Hence, the records are too short to investigate inter‐ and multidecadal variability and their impact on coastal systems. A method is presented to hindcast monthly mid‐shelf mean wave direction (MWD) for southeastern Australia, based on the monthly, trans‐Tasman mean sea‐level pressure (MSLP) difference between northern NSW (Yamba) and the north island of New Zealand (Auckland). The MSLP index is calibrated to instrumental (Waverider buoy) MWD data for the Sydney shelf and coast. Positive/negative trans‐Tasman MSLP difference is significantly correlated to southerly/easterly Sydney MWD, and to long/short mean wave periods. The 124‐year Sydney annual (MWD) time series displays multidecadal variability, and identifies a significant period of more southerly annual MWD during 1884 to 1914 than in the period since 1915. The Sydney MWD is significantly correlated to the Southern Oscillation Index (SOI). The correlation with the SOI is enhanced during periods when the Interdecadal Pacific Oscillation (IPO) is in its negative state and warm SST anomalies occur in the southwest Pacific region. The Sydney MWD was found to be associated with Pacific basin‐wide climate fluctuations associated with the El Niño‐Southern Oscillation (ENSO). Southerly/easterly Sydney MWD is correlated with low/high MSLP anomalies over New Zealand and the central Pacific Ocean. Southerly/easterly Sydney MWD is also correlated with cool/warm SST anomalies in the southwest Pacific, particularly in the eastern Coral Sea and Tasman Sea. Copyright © 2005 Royal Meteorological Society.
Features of cross‐Pacific climate shown in the variability of China and US precipitation
Authors: Li Q. , Yang S. , Kousky V. E. , Higgins R. W. , Lau K.‐M. , Xie P.
Published: October 2005

In this study, we have analyzed the climate features of China and the United States with a focus on the differences, similarities, connectivity, and predictability of precipitation and the relationships between precipitation and large‐scale patterns of natural variability. China precipitation is characterized by large seasonality, with a maximum in summer and a minimum in winter. The seasonality of precipitation shows an increasing linear tendency in northwest China, with a change of about 20% from 1901 to 1998. A relatively weaker increasing tendency also appears in the Big Bend of Yellow River (BBYR) and the Tibetan Plateau, while southwest China experiences a decreasing tendency. Furthermore, the seasonality in the BBYR shows particularly significant interdecadal variability, while that of southern and eastern China has decreased slightly in the recent decades.

Compared to China, the United States as a whole has less precipitation in summer but more precipitation in other seasons. Here, the seasonality of precipitation is only about 24% of that in China. The annual mean precipitation is 64.1 mm per month in the United States, compared to 54.6 mm per month in China. The seasonality of precipitation exhibits a decreasing tendency in the southeast, Pacific Northwest, and Gulf Coast and an increasing tendency in the Great Lakes. The seasonality in the Great Plains exhibits large interdecadal variability.

The long‐term variations of precipitation are highly seasonally dependent. In summer, a decreasing trend is observed in north China and an increasing trend is found in eastern‐central China. However, these trends are almost opposite in spring. In addition, the fall precipitation decreases with time nearly everywhere in China except for the middle and lower reaches of the Yangtze River Valley.

Results also indicate that the El Niño/Southern Oscillation (ENSO), the Arctic Oscillation (AO), the North Atlantic Oscillation (NAO), the Pacific Decadal Oscillation (PDO), and the North Pacific (NP) fluctuation affect strongly the variations of China and US precipitation. Although these influences vary with regions and seasons, we in particular emphasize the importance of AO and NAO for China precipitation and NP and PDO for US precipitation. In fall, ENSO and PDO are the two phenomena that influence predominantly precipitation variability in both China and the United States We also identify the common phenomena that influence China and US regional precipitation and provide a better understanding of the physical mechanism for precipitation variability through the associated changes in atmospheric and oceanic conditions. Furthermore, we develop a linear regression model, based on multiple regression method by combining the regionally and seasonally varying impacts, to increase the skill of precipitation prediction. Copyright © 2005 Royal Meteorological Society
Synthesis of poly(p‐methoxyphenylacetylene) with the vanadium acetylacetonate‐aluminum triethyl Ziegler–Natta catalyst system: Cyclotrimers/polymer ratio analysis
Authors: Rodríguez J. Gonzalo , Lafuente Antonio , Martín‐Villamil Rosa
Published: October 2005

Poly(p‐methoxyphenylacetylene) was obtained by the reaction of p‐methoxyphenylacetylene (MOPA) with the vanadium acetylacetonate‐aluminum triethyl V(acac)3‐AlEt3 homogeneous catalyst system. The crude product was always a mixture of 1,2,4‐ and 1,3,5‐tris(p‐methoxyphenyl)benzene and poly(MOPA) of low averaged molecular weight. The 1,2,4‐ and 1,3,5‐cyclotrimers versus poly(MOPA) ratio was analyzed. The poly(MOPA) obtained under different conditions, on the basis of the spectroscopic data, always shows a cis–transoidal stereo‐regular structure. Molecular mass of poly(MOPA) was determined by vapor pressure osmometry, high pressure liquid chromatography (HPLC), and gel permeation chromatography (GPC) techniques. The kinetics of the reaction has been also analyzed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5987–5997, 2005
Synthesis of novel crosslinkable polymers by atom transfer radical polymerization of cardanyl acrylate
Authors: Suresh Kattimuttathu I. , Jaikrishna M.
Published: October 2005

In this work, the successful application of atom transfer radical polymerization (ATRP) to cardanyl acrylate, a polymerizable monomer derived from a renewable resource cardanol, is reported. Polycardanyl acrylate and poly(methylmethacrylate)‐cardanyl acrylate copolymers were prepared in bulk ATRP, using Copper(I) bromide/N, N, N′, N′, N″‐pentamethyl diethylene triamine (PMDETA) catalyst system at 95 °C in combination with ethyl‐2‐bromo isobutyrate initiator. The copolymers had mol. wt. (Mn) in the range 8300–2400 g/mol and polydispersity index (PDI) 1.27–2.00, depending upon the [M]0/[I]0 ratio. 1H NMR analysis of the copolymer showed that unsaturation in the side chain of cardanyl acrylate is unaffected under the conditions of ATRP. This was further confirmed by studying the curing reaction of polycardanyl acrylate by supported dynamic mechanical thermal analysis (DMTA) in dual cantilever mode. The thermogravimetric analysis shows that the copolymers have improved thermal stability, by about 35 °C, in comparison with pure PMMA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5953–5961, 2005
Transfer of indoxacarb among workers of Coptotermes formosanus (Isoptera: Rhinotermitidae): effects of dose, donor:recipient ratio and post‐exposure time
Authors: Hu Xing Ping , Song Dunlun , Scherer Clay W
Published: October 2005

Horizontal transfer of indoxacarb among workers of the Formosan subterranean termite, Coptotermes formosanus Shiraki, was examined under laboratory conditions. The effects of dose (0, 10, 20, 50, 100 or 200 ng AI per donor), donor:recipient ratio (1:1, 1:4 or 1:9) and post‐exposure time (2, 4, 8, 16, 20 and 24 days) on lethal transfer of indoxacarb were investigated using a donor/recipient model in groups of 100 workers. Transfer of lethal doses from donors to recipients was evidenced by significant recipient mortality in 13 out of 15 treatments within 24 days post‐exposure. Dosage significantly affected indoxacarb transfer. Higher doses resulted in greater recipient mortality than lower doses. The highest dose tested resulted in 100% death of recipients and donors within 20 days. A dose of 100 ng resulted in recipient mortalities ranging from 68 to 100%, whereas doses ≤50 ng killed <60% of recipients within 24 days. Donor:recipient ratio also had considerable effect on indoxacarb transfer. At 24 days post‐exposure, greater recipient mortalities were observed at ratios ≥1:4 at doses ≥20 ng, but only at a ratio 1:1 at dose 10 ng. Recipient mortality increased significantly as post‐exposure time increased. The higher the doses applied on donors, the shorter were the times required for the onset of recipient mortality to occur and for recipients to reach maximum mortality. Significantly greater recipient mortalities were not observed at doses 20 and 50 ng until more than 20 days post‐exposure, indicating a delayed activity of indoxacarb. Possible transfer mechanisms are discussed. Copyright © 2005 Society of Chemical Industry
Evaluation of the time–concentration–mortality responses of Plutella xylostella larvae to the interaction of Beauveria bassiana with a nereistoxin analogue insecticide
Authors: Tian Li , Feng Ming‐Guang
Published: October 2005

Six bioassays were conducted to evaluate the interaction between Beauveria bassiana SG8702 and a nereistoxin analogue insecticide, diammonium S,S′‐(2‐dimethylaminotrimethylene)di(thiosulfate), which is highly compatible with the fungal biocontrol agent against diamondback moth Plutella xylostella (L.). Second‐instar larvae were exposed to sprays of B. bassiana alone (assay 1) at concentrations of 21–38, 157–232 and 822–1133 conidia mm−2 or together with the insecticide at the low application rates of 5, 10, 25, 50 and 100 µg AI ml−1 (assays 2–6), and then maintained at 25 °C and 12:12 h light:dark photoperiod for daily monitoring of mortality for 8 days. Based on the modelling of the resultant time–concentration–mortality data sets, the fungal agent was highly virulent to P. xylostella with an LC50 decreasing from 269 conidia mm−2 on day 4 to 107 on day 8. Lower lethal concentrations or shorter median lethal times resulted from fungal sprays including the tested chemical rates; the latter never caused higher mortalities than the fungal treatments alone. The fungal action over 3–7 days after spray was significantly enhanced by including in the fungal sprays the chemical at rates of ≥25 µg ml−1 for 2.6‐ to 1756‐fold reduction of LC50 values, ≥50 µg ml−1 for 4‐ to 274‐fold reduction of LC70 values and 100 µg ml−1 for 9‐ to 33‐fold reduction of LC90 values respectively. These rates were equivalent to 5–20% of the chemical rate labelled for field application. The fungal and chemical interaction outlined above highlights the feasibility of combined formulation or application of B. bassiana and the chemical insecticide for P. xylostella control. Copyright © 2005 Society of Chemical Industry
Magnetoresistive hybrid transistor in vertical architecture
Authors: Meruvia M. S. , Benvenho A. R. V. , Hümmelgen I. A. , Gomez J. A. , Graeff C. F. O. , Li R. W. C. , Aguiar L. H. J. M. C. , Gruber J.
Published: October 2005

We report the development of a hybrid semiconductor–metal–semiconductor permeable‐base transistor in vertical architecture, which operates by positive charge carrier transport. This transistor has a p‐type silicon collector, a thin tin layer as base and a conjugated polymer, poly(9,9‐dioctyl‐2,7‐ fluorenylenevinylene), as emitter material. The transistor transport characteristics are dependent on the applied magnetic field and the base transport factor for positive charge carriers is nearly ideal. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Reflectance difference spectroscopy RDS/RAS combined with spectroscopic ellipsometry for a quantitative analysis of optically anisotropic materials
Authors: Rossow U. , Goldhahn R. , Fuhrmann D. , Hangleiter A.
Published: October 2005

We discuss various aspects of the characterization of optically anisotropic materials by spectroscopic ellipsometry (SE) and reflectance‐difference/anisotropy‐spectroscopy (RDS/RAS). The main focus is on the limitation of quantitative analysis, and will be discussed in detail for two different examples: group‐III‐nitride layers and ZnO. We suggest that a combination of SE and RDS is a good choice to determine the components of the dielectric tensor (here ε‖, ε⊥) and allows also to determine important parameters such as thickness or sample orientation. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Investigation of molecule chemisorption on Si(001)2 × 1 surfaces by surface reflectance spectroscopies
Authors: Pluchery O. , Witkowski N. , Borensztein Y.
Published: October 2005

Several examples are given on the investigation of adsorption of atoms and molecules on Si(001)2 × 1 in ultra‐high vacuum, by means of two different surface optical spectroscopies, the Surface Differential Reflectance Spectroscopy and the Reflectance Anisotropy Spectroscopy. Hydrogen, water, oxygen, benzene and pyridine adsorptions are presented. Specific spectra are obtained, which are interpreted as a function of the mode of adsorption of the adsorbates. In particular, it is possible to discriminate between adsorption on the dangling bonds of the Si dimers and adsorption inducing a breaking of the dimers. Moreover, quantitative information is obtained from these optical techniques which yields the determination of the absolute number of surface Si atoms involved in the bonding. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
MEP–MPE potential energy surface for the Cl + CH4 → HCl + CH3 reaction
Authors: Garcia Ernesto , Sánchez Carlos , Rodríguez Aurelio , Laganà Antonio
Published: October 2005

A potential energy functional based on a many‐process expansion minimum energy path approach has been fitted to the ab initio potential energy values of the Cl + CH4 system. The functional form adopted, the parameters of the fitted surface, and the variation of the cone of acceptance as a function of relevant parameters are discussed. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006
Reactivity of dialkylzirconium species and solvent polarity
Authors: Derat Etienne , Bouquant James , Bertus Philippe , Szymoniak Jan , Humbel Stéphane
Published: October 2005

The specific solvent effect of dimethylether is studied for two possible chemical reactions involving dialkylzirconium (ZrCl2Et2) and formaldehyde (H2CO). Using Density Functional Theory (B3LYP) and qualitative arguments, it is shown that such a polar solvent favors the ZrCl2(Alkene) formation by coordinating to the metal. Such a stable system can react further through alkene—solvent—formaldehyde exchange to spontaneously give the cyclization product. In a polar solvent, where such coordination cannot be envisaged, the preferred path gives the hydrometalated product directly from the dialkylzirconium reagent. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006
The effects of performance anxiety on salivary ultra‐weak chemiluminescence
Authors: Takagi Kuniaki , Hasunuma Tsuyoshi , Goi Nobuhiro , Harada Hitoshi , Ikari Akira , Hiramatsu Mitsuo , Nakamura Kimitsugu , Tsuboi Hirohito
Published: October 2005

Response of ultra‐weak chemiluminescence (UCL) in saliva before and after an experimental examination was explored in 10 healthy undergraduate students. Participants were asked to perform a task under supervision that consisted of a serial aseptic manipulation for cell culture. Saliva was collected 30 min before, immediately after, 30 min after and 60 min after the stress exposure. One‐way repeated measures ANOVA for UCL revealed a significant difference across the four measurement occasions (F = 4.45, p < 0.05). Post hoc Dunnett's test clarified that UCL levels right after the stress exposure was significantly greater than that 30 min before the exposure (p < 0.05). The concentrations of secretory immunoglobulin A (sIgA) and cortisol in saliva were also measured. Two‐way ANOVA with repeated measures indicated that UCL and sIgA exhibited the same change pattern in the four occasions (F = 0.28, p = 0.84), whereas UCL changed differently from cortisol (F = 5.82, p < 0.005). It was suggested that salivary UCL may be a sensitive biomarker for acute psychological changes. Copyright © 2005 John Wiley & Sons, Ltd.
Post‐traumatic reactions among rescue personnel 96 hours after the Hilton Hotel bombing in Sinai: The effect of previous exposure
Authors: Ben‐Ezra Menachem , Essar Nir , Saar Ronen
Published: October 2005

This paper considers the immediate post‐traumatic reactions of rescue personnel who were exposed to the Hilton Hotel bombing in Sinai. The entire rescue personnel (n = 26) were assessed and separated into two groups on the basis of previous exposure to the same type of trauma. The results suggest that among rescue personnel, those with previous exposure had a lower level of post‐traumatic symptoms than those who were being exposed for the first time. This supports the hypothesis that previous exposure to the same type of trauma has an immunizing effect for subsequent same type of traumatic event among rescue personnel. Copyright © 2005 John Wiley & Sons, Ltd.
Synthesen, Kristallstrukturen und spektroskopische Eigenschaften des Melem‐Adduktes C6N7(NH2)3 · H3PO4 sowie der Melemium‐Salze (H2C6N7(NH2)3)SO4 · 2 H2O und (HC6N7(NH2)3)ClO4 · H2O
Authors: Sattler Andreas , Seyfarth Lena , Senker Jürgen , Schnick Wolfgang
Published: October 2005

Syntheses, Crystal Structures and Spectroscopic Properties of the Melem Adduct C6N7(NH2)3 · H3PO4 and the Melemium Salts (H2C6N7(NH2)3)SO4 · 2H2O and (HC6N7(NH2)3)ClO4 · H2O

The melem adduct C6N7(NH2)3 · H3PO4 (1) and the melemium salts (H2C6N7(NH2)3)SO4 · 2H2O (2) and (HC6N7(NH2)3)ClO4 · H2O (3) were obtained by the reactionof melem, 2,6,10‐triamino‐s‐heptazine, C6N7(NH2)3 with the corresponding acids in aqueous solution. The crystal structures of these compounds were solved by single‐crystal X‐ray diffraction (1: R3c, Z = 6, a = 1024.7(1), c = 1848.1(4) pm; 2: P21/n, Z = 4, a = 690.3(1), b = 2026.4(4), c = 961.7(2) pm, β = 98.96(3)°; 3: $P{\bar 1}$, Z = 2, a = 726.1(2), b = 757.5(2), c = 1207.0(2) pm, α = 71.76(3), β = 76.31(3), γ = 71.06(3)°). All three compounds have layer‐like structures consisting of melem (1) or melemium ions (2 and 3) and the acid (1) or acid anions (2 and 3), respectively. The building units and the crystal water molecules (in 2 and 3) are connected through extended hydrogen bridging networks. IR and Raman spectroscopic investigations have been performed. Solid‐state NMR experiments prove that there is no complete proton transfer from the phosphoric acid to the melem molecules. Therefore compound (1) has to be classified as an adduct C6N7(NH2)3 · H3PO4.
Polysulfonylamine. CLXXIV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 17 [2] Silber(I)‐di(methansulfonyl)amid: Ein diamantoides Netzwerk aus Ag2N2‐Vierringen und verbrückenden Mesylgruppen
Authors: Zerbe Eva‐Maria , Jones Peter G. , Moers Oliver , Blaschette Armand
Published: October 2005

Polysulfonylamines. CLXXIV. Crystal Structures of Metal Di(methanesulfonyl)amides. 17. Silver(I) Di(methanesulfonyl)amide: A Diamondoid Network of Four‐Membered Ag2N2 Rings and Bridging Mesyl Groups

The crystal structure of silver(I) dimesylamide (orthorhombic, space group Fddd, Z = 16, Z′ = 1/2, single‐crystal X‐ray diffraction at −140 °C) consists of dinuclear Ag2[N(SO2Me)2]2 complexes, in which the nitrogen atoms are μ2‐bonded to the silver ions at distances of 241.83(15) pm to form planar rhombic Ag2N2 rings; the short Ag···Ag ring diagonal, 285.36(4) pm, is consistent with weak argentophilic interaction. In the packing, the ring centres lie on 222 sites, conferring crystallographic D2 symmetry on the complex and crystallographic C2 symmetry on the anions. Moreover, each complex is connected to four adjacent complexes by centrosymmetric pairs of silver‐oxygen bonds at distances 245.35(13) pm. In the resulting three‐dimensional coordination polymer, the ring centres represent the nodes of a distorted diamondoid network, whereby the high packing efficiency prevents the interpenetration of networks that is frequently observed in diamondoid solids. The primary N2O2 coordination of the cation corresponds to a distorted tetrahedron with bond angles in the range 103.62(3)–118.57(3)°; including the short Ag···Ag contact and four secondary silver‐oxygen contacts at distances of 300.18(13) pm (2×) and 333.10(13) pm (2×), the coordination number is increased to nine.
Crystallization by Slow Halogen Exchange in Hypercoordinate Silicon Chelates and the first X‐ray Structure of a trans‐Featured Hexacoordinate Difluorosilicon‐bis‐Chelate
Authors: Schley Michael , Wagler Jörg , Roewer Gerhard
Published: October 2005

Starting from silicon tetrahalides SiCl4 and SiBr4, respectively, and the bidentate 2‐iminomethylphenol‐type ligand HO‐C6H3‐2‐[C(C6H5)=N(CH2‐C6H5)]‐5‐OCH3, three novel complexes with hypercoordinate silicon atom were synthesized. Their coordination spheres consist of two halogen atoms (F, Cl, Br) and two six membered ring systems created by chelating bidentate ligands of 2‐iminomethylphenolate type. Demonstrated by crystal structure analysis, the dichloro‐ and difluorosilicon complexes {O‐C6H3‐2‐[C(C6H5)=N(CH2‐C6H5)]‐5‐OCH3}SiX2 (X = Cl, F) reveal all‐trans‐configuration in solid state. The difluorosilicon complex {O‐C6H3‐2‐[C(C6H5)=N(CH2‐C6H5)]‐5‐OCH3}SiF2 is the first X‐ray crystallographically proven example of a trans‐featured difluorosilicon‐bis‐chelate. Its all‐trans‐configuration, however, is not retained after dissolution. The formation of an octahedral complex with cis‐arranged fluorine atoms is 1H NMR spectroscopically proven by the coupling pattern of diastereotopic benzyl methylene protons of the chelating ligands.
Platinum(II) Complexes with 1‐Cyclohepta‐2,4,6‐trienyl‐diphenylphosphane, Ph2P(C7H7), and Alkyn‐1‐yl Ligands
Authors: Wrackmeyer Bernd , Ullmann Bettina , Kempe Rhett , Herberhold Max
Published: October 2005

[1‐Cyclohepta‐2,4,6‐trienyl‐diphenylphosphane]platinum(II) dichloride (4) was prepared by the 1:1 reaction of (cod)PtCl2 (cod = η4‐cycloocta‐1,5‐diene) with the phosphane. The reaction of 4 with di(alkyn‐1‐yl)dimethylstannanes, Me2Sn(C≡C‐R)2 [R = H (a), Me (b), Ph (c), SiMe3 (d)], in boiling THF gave selectively in high yield the monoalkynyl complexes [Ph2P(C7H7)]Pt(Cl)C≡C‐R (6b,c,d), in which the alkyn‐1‐yl group is arranged in cis position with respect to the phosphorus atom, and the C7H7 ring is η2‐coordinated to platinum through the central C=C bond. The same reaction at room temperature afforded, again selectively and in high yield, the dialkynyl complexes [Ph2P(C7H7)]Pt(C≡C‐R)2 (7a‐d). The new complexes were characterised in solution by 1H, 13C, 29Si, 31P and 195Pt NMR spectroscopy, and the molecular structures of 4 and 7d were determined by X‐ray crystallography.
The Synthesis of a Homoleptic Lanthanoid Complex of the 8‐Quinolinolate Ion Directly from the Metal
Authors: Leary Stuart G. , Deacon Glen B. , Junk Peter C.
Published: October 2005

Reaction of 8‐hydroxyquinoline (HOQ) with holmium metal in the presence strontium metal and metallic mercury at 190 °C under vacuum in a 1,3,5‐tri‐tert‐butylbenzene flux yielded (η2‐8‐quinolinolato‐κ:N,O(Ho(2))bis(η2‐8‐quinolinolato‐κ:N,O(Ho(1)))hexakis(μ‐(O)‐8‐quinolinolato‐κ:N,O(Ho(1))trisholmium(III) as an 8‐hydroxyquinoline solvate (1) (C2/c, a = 17.336(4) Å, b = 23.464(5), c = 18.038(4) Å, β = 92.92(3)°, V = 7328(3) Å3, R1 = 0.0622). The complex was resynthesised after preactivation of the metals by mercury and then heating them with HOQ at 190 °C.
Complete Nitrogen Coordination in Rare Earth Bipyridine Pyrrolate Complexes from Pyrrole under Solvothermal Conditions: [Ln(Pyr)3(Bipy)2], Ln = Pr, Yb
Authors: Quitmann Catharina C. , Müller‐Buschbaum Klaus
Published: October 2005

The compounds [Ln(Pyr)3(Bipy)2], Ln = Pr (1), Yb (2), (Pyr– = pyrrolate anion, C4H4N−; Bipy = 2,2′‐bipyridyl, C10H8N2) were obtained by the solvothermal reaction of pyrrole with praseodymium and ytterbium metal and the amine bipyridine. Yellow‐green single crystals of 1 and yellow crystals of 2 are formed next to dark green solutions. 1 and 2 are isotypic and exhibit monomeric molecules with a complete nitrogen coordination of three pyrrolate anions and two bipyridine molecules around the trivalent rare earth ions. Thus co‐coordination with Bipy renders unsubstituted pyrrolates of the rare earth elements feasible from solvothermal conditions in addition to previous low‐temperature syntheses. The products were investigated by X‐ray single crystal diffraction, Mid IR and Far IR spectroscopy.
Synthesis and X‐ray Structure of n‐Propylimidodiphosphonic Anhydride, a New Precursor for the Hydrothermal or Solvothermal Synthesis of Zinc Phosphates
Authors: Chivers Tristram , Fu Zhiyong , Grebinski James , Parvez Masood
Published: October 2005

n‐Propylimidodiphosphonic anhydride [O(OH)P(μ‐O)PO(OH)(μ‐NnPr)]2·2NH2nPr (1) is prepared by hydrolysis of trichloro‐n‐propylimidophosphorane with three equivalents of water. X‐ray analysis shows that 1 forms an eight‐membered P4N2O2 ring in a chair conformation. These heterocycles are linked via extensive hydrogen‐bonding to form a three‐dimensional network. Hydrothermal reactions of 1 with zinc chloride give rise to P‐N bond cleavage and the formation of the hydrated zinc phosphates, {Zn3(PO4)2·H2O}n and {Zn3(PO4)2·4H2O}n, whereas the solvothermal reaction in isopropyl alcohol produces the anionic network [ZnCl(HPO4)−]n with [nPrNH3]+ counter‐ions.
Über die Umsetzung von (TAS)+[P4N4F9]− mit Me3SiCF3
Authors: Kingston Melanie , Lork Enno , Mews Rüdiger
Published: October 2005

On the Reaction of (TAS)+[P4N4F9]− with Me3SiCF3

From the reaction of (TAS)+[P4N4F9]− with Me3SiCF3 in CH3CN (TAS+)2[{NP(CF3)2F}(NPF2)2{NP(N‐C≡C‐SiMe3)F}]2− (1) was isolated and characterized by X‐ray crystallography. The by‐products (TAS+)2 [{NP(CF3)2F}(NPF2)2{NP(CF3)(N‐C≡C‐SiMe3)}]2− (2) and (TAS+) [{NP(CF3)2F}(NPF2)3]− (3) were identified by nmr spectroscopy. In the reaction described, Me3SiCF3 reacts in the presence of fluoride ions towards the phosphazene as trifluoromethylating‐, towards the solvent CH3CN as deprotonating‐ and silylating reagent.
Organoplatinum Complexes of the N,N‐Diisopropyl‐diazabutadiene Ligand: A Structural and Spectroscopic Study
Authors: Klein Axel , Schurr Thilo , Záliš Stanislav
Published: October 2005

Organoplatinum complexes [Pt(R)2(iPr‐DAB)], [PtCl(R)(iPr‐DAB)] or [PtCl2(iPr‐DAB)] (R = methyl or 2,4,6‐trimethylphenyl = mesityl, iPr‐DAB = N,N′‐diisopropyl‐1,4‐diazabutadiene) have been investigated by a combination of multiple spectroscopy (NMR, UV/VIS), single crystal XRD and quantum chemical calculations. Excellent agreement of calculated and experimental structural data from XRD or NMR provide a good basis for the quantum mechanical calculations. DFT calculations reveal the contributions of the DAB ligand and the co‐ligands to the electronic ground state. Methyl acts more or less purely as a σ‐donor, Cl or mesityl provide strong contributions (p or π) to the highest occupied molecular orbital (HOMO) whereas the lowest unoccupied molecular orbital (LUMO) is mainly centred to the DAB ligand. The TD‐DFT calculated electronic transitions were in excellent agreement with the experimental ones and allow reliable assignment of the absorption bands.
Mononuclear Metal Phosphinates with Ancillary Pyrazole Ligands. Synthesis and X‐ray Crystal Structures of [M(Ph2PO2)2(3,5‐DMPZ)2] (M = Co, Zn)
Authors: Chandrasekhar Vadapalli , Boomishankar Ramamoorthy , Sasikumar Palani , Nagarajan Loganathan , Cordes A. Wallace
Published: October 2005

The reaction of diphenylphosphinic acid, [Ph2P(O)(OH)], with CoCl2 or ZnCl2 and 3,5‐dimethylpyrazole (DMPZ) in the presence of triethylamine affords the mononuclear phosphinates, M(Ph2PO2)2(DMPZ)2 (M= Co(1), Zn(2)). The molecular structures of 1 and 2 reveal a tetrahedral environment around the metal. The phosphinate ligands are monoanionic and bind to the metal in a monodentate manner, while the pyrazole ligands act as neutral monodentate ligands. Intermolecular C‐H‐O and π–π interactions in 1 and 2 result in the generation of two dimensional supramolecular polymeric sheets in the solid state.
2‐Amino‐substituted 1,3,2‐Diazaphospholenes
Authors: Burck Sebastian , Gudat Dietrich , Lissner Falk , Nättinen Kalle , Nieger Martin , Schleid Thomas
Published: October 2005

2‐Amino‐substituted 1,3,2‐diazaphospholenes 2 ‐ 4 were synthesised by treatment of 1,3‐dimesityl‐2‐chloro‐1,3,2‐diazaphospholene with one equivalent of lithium N,N′‐dimesityl‐2,4‐pentanedioniminate, sodium amide, or a mixture of 3,5‐diphenylpyrazole and NEt3. In contrast, 1,3‐di‐tert.butyl‐1,3,2‐diazaphospholene reacted with sodium amide in a 2:1 molar ratio to afford the bis‐diazaphospholenyl‐imine 5. All products were characterised by spectroscopic data and single‐crystal X‐ray diffraction studies. Evaluation of trends in bond lengths suggest the presence of similar residual π‐delocalisation effects as had previously established in P‐Cl or P‐H substituted diazaphospholenes but disclosed that 2 ‐ 5 differ from these compounds in lacking all signs for a concomitant lengthening of the exocyclic P‐X bonds. The results of computational studies allowed to conclude that the deviating behaviour of diazaphospholenes with different P‐X substituents is attributable to a shift in the balance between n(N)→σ*(P‐X)‐ and n(X)→σ*(P‐N)‐hyperconjugation interactions.
The Simple Hexapyridine Cluster [Mo6Br8Py6][OSO2CF3]4 and Substituted Hexapyridine Clusters Including a Cluster‐cored Polyolefin Dendrimer
Authors: Méry Denise , Plault Lauriane , Nlate Sylvain , Astruc Didier , Cordier Stéphane , Kirakci Kaplan , Perrin Christiane
Published: October 2005

The yellow octahedral molybdenum cluster [n‐Bu4N]2[Mo6Br8(CF3SO3)6], (1); undergoes substitution of all six terminal triflate ligands by pyridine ligands in pyridine/THF at 60 °C to yield the orange hexapyridine cluster [Mo6Br8(Py)6][CF3SO3]4, (2). The cluster 1 also reacts in THF at 60 °C with excessof the para‐substitued pyridines 4‐tert‐Bupy and 4‐vinylpy to give the orange para‐substituted hexapyridine clusters [Mo6Br8(p‐Py‐R)6][CF3SO3]4 (3: R = tert‐Bu; 4: R = vinyl) and with the new dendronic pyridine derivative 3,3′‐{CH2Op‐C6H4C(CH2CH=CH2)3}2Py, (5) (7 d), to give the orange relatively air stable Mo6‐cluster‐cored 36‐allyl dendrimer [Mo6Br8(3,5‐{CH2OC6H4C(CH2CH=CH2)3}2Py)6][CF3SO3]4, (6). All these substitution reactions were easily monitored by 1H NMR in CDCl3 using the comparison between the intensities of the tetrabutylammonium cation and deshielded coordinated pyridine signals.
Pentahydrido‐, Trihydrido‐ und Dihydrido‐Iridiumkomplexe mit bifunktionellen Phosphanen als Liganden
Authors: Steinert P. , Werner H.
Published: October 2005

Pentahydrido‐, Trishydrido‐, and Bishydridoiridium Complexes with Bifunctional Phosphanes as Ligands

The pentahydridoiridium(V) complexes [IrH5{κ(P)‐iPr2PX}2] (4‐6) with X = CH2CO2Me, (CH2)2OMe and (CH2)3NMe2 were prepared from iridium(I) or iridium(III) precursors and hydride donors such as NaBH4 or LiAlH4. While attempts to obtain the iridium(III) compounds [IrH3(iPr2PX)2] failed, the complex [IrH3(CO){κ(P)‐iPr2PCH2CO2Me}2] (7) was formed from 4 and CO. The reactions of 4‐6 with acetic acid led, by elimination of two equivalents of H2, to the bishydrido compounds [IrH2(κ2‐O2CCH3){κ(P)‐iPr2PX}2] (8‐10), which are rigid in solution. In contrast, the corresponding complex [IrH2(κ1‐O2CCF3){κ(P)‐iPr2PCH2CO2Me}{κ2‐(P,O)‐iPr2PCH2CO2Me}] (11) is fluxional in solution, the trifluoracetato ligand, however, being not involved in the change of the hapticity.
Thioether Functionalized Pyrazolate Ligands and their Dicopper(II) Complexes – Structures and Magnetic Properties
Authors: Teichgräber Jörg , Leibeling Guido , Dechert Sebastian , Meyer Franc
Published: October 2005

A bis(bidentate) compartmental pyrazolate ligand HL with appended methylthiomethyl substituents in the 3‐ and 5‐positions of the heterocycle has been synthesized. It forms doubly pyrazolato bridged dicopper(II) complexes [L2Cu2]X2 (X = NO3− (3a), ClO4− (3b)) with the metal ions in square planar {S2N2} environment and additional weak axial interactions with the respective counteranions. Magnetic measurements reveal strong antiferromagnetic coupling with J = −243 or −231 cm−1 (Ĥ = −2J·S1S2), which is at the upper limit of what has previously been observed for bis(μ‐pyrazolato)dicopper(II) complexes.
Synthesis and Characterization of the Novel AlI Compound Al(C5Me4Ph): Comparison of the Coordination Chemistry of Al(C5Me5) and Al(C5Me4Ph) at d10 Metal Centers1)
Authors: Buchin Beatrice , Steinke Tobias , Gemel Christian , Cadenbach Thomas , Fischer Roland A.
Published: October 2005

The synthesis of the novel AlI compound AlCp*Ph (Cp*Ph = C5Me4Ph) is presented. This compound is characterized by 1H, 13C, 27Al NMR spectroscopy, elemental analysis as well as its reactivity towards the α,ω‐diolefin dvds (dvds = tetramethyl‐divinyl‐disiloxane). Also the reactivity of AlCp* towards dvds is investigated and the product [(dvds)(μ2‐AlCp*)2] characterized by NMR spectroscopy, elemental analysis as well as X‐ray crystallography. Furthermore, two new coordination compounds of AlCp* to d10 metal centers are synthesized and characterized. [Pd(AlCp*)4] is obtained by reaction of [(tmeda)PdCl2] with AlCp*, and [Ni(AlCp*)4] is synthesized from [Ni(cod)2] and AlCp* via ligand substitution. Both complexes are spectroscopically and crystallographically characterized. Finally, preliminary results on the coordination of AlCp*Ph to Ni0 and Pd0 centers will be discussed.
Polymer Two‐Dimensional Networks of Au55 Clusters
Authors: Schmid Günter , Vidoni Olivia , Torma Viktoria , Pollmeier Klaus , Rehage Heinz , Vassiliev Andrei
Published: October 2005

Monolayers and thin films of Au55 clusters, linked by different dithiol spacer molecules and by polymerization between functionalized ligands, were prepared and investigated by TEM and AFM. Due to spacer molecules of different lengths, the cluster‐cluster distances could be varied from 1.3 up to 3.8 nm, enabling later investigations of electron transport processes in two dimensions. Film formation was carried out using either Langmuir‐Blodgett techniques or spin‐coating processes in the presence of the spacer molecules. Polymerization reactions between neighboured clusters in monolayers or thin films succeeded by the use of vinyl‐substituted ligand molecules. (Vinyl)8Si8O11(OH)2 and p‐styryl‐diphenylphosphine modified Au55 clusters could be linked by light‐induced polymerization via the vinyl functions.
Copper(I) Chloride Cluster Complexes with Pentaphenyl‐Cyclopentaphosphane as Ligand
Authors: Scherer Markus , Stein Daniel , Breher Frank , Geier Jens , Schönberg Hartmut , Grützmacher Hansjörg
Published: October 2005

Pentaphenylcyclopentaphosphane, c‐(P5Ph5) is conviently prepared from PhPCl2 and thermally activated zinc powder in thf. Hydrolysis of c‐(P5Ph5) in the presence of ZnCl2 gives to an equimolar distribution of PhPH2, PhP(=O)H2, and PhP(=O)(OH)H. Reaction of c‐(P5Ph5) with CuICl leads to the tetranuclear copper(I) chloride complex [Cu4(μ4‐Cl)2(μ2‐Cl)2{c‐(P5Ph5)}2] with a Cu4(μ4‐Cl)2(μ2‐Cl)2 cluster core and the hexanuclear [Cu6(μ3‐Cl)2(μ2‐Cl)2{c‐(P5Ph5)}2(thf)2]. Hydrolysis of the copper c‐(P5Ph5) complexes leads to significantly higher amounts of the primary phosphane oxide PhP(=O)H2.
First Examples of Metal Cyclohexylphosphonates: Influence of the Choice of Synthetic Route on the Product
Authors: Murugavel Ramaswamy , Davis Paul , Walawalkar Mrinalini G.
Published: October 2005

The first divalent metal cyclohexylphosphonate derivative, [Co(O3PCy)·H2O]n (1) has been synthesized using four different synthetic methodologies in the presence of added amines. The new phosphonates have been characterized with the aid of analytical, thermoanalytical, spectroscopic, and powder XRD studies. The nature and particle size of the product formed is highly dependent on the method employed (viz. (a) room temperature synthesis, (b) hydrothermal synthesis, (c) microwave assisted synthesis, and (d) a biphasic reaction) as revealed by SEM and TEM studies. While in most cases the metal phosphonates were isolated as insoluble crystalline powders directly from the reaction mixture, the use of 3,5‐dimethylpyrazole (DMP) as co‐ligand leads to the isolation of soluble compound [{Co(H2O)4(DMP)2}{CyPO3H}2]n (2) as single crystals. The X‐ray diffraction studies on 2 reveal a hydrogen‐bonded polymeric structure for this compound. Crystal data: C22H48CoN4O10P2, monoclinic, P21/c, a = 12.147(2), b = 11.607(2), c = 11.872(2) Å, β = 104.00(3)°, V = 1624.2(5) Å3, Z = 2, R1(all data) = 0.050, wR2 (all data) = 0.145.
Experimental and Theoretical Approaches to the Protonation of Thiourea: A Convenient Nucleophile in Coordination Chemistry Revisited
Authors: Schiessl Wolfgang C. , Summa Nadine K. , Weber Christian F. , Gubo Sonja , Dücker‐Benfer Carlos , Puchta Ralph , van Eikema Hommes Nico J. R. , van Eldik Rudi
Published: October 2005

The protonation of thiourea was reinvestigated in aqueous and non‐aqueous media using potentiometric, UV‐vis, NMR, MS spectroscopy, as well as DFT calculations. In aqueous medium, no evidence for protonation could be found in the pH range 0 to 7, in agreement with typical pKa values (acid dissociation constants of protonated thiourea) quoted in the literature of around ‐1.2. Most of the protonation constants quoted in the literature are incorrect and apparently refer to pKa values. Protonation of thiourea occurs at a much higher pKa value in methanol and in water‐dioxane mixtures, which must be related to the stabilization of the protonated species in such media.