bluuebunny/crossref_metadata_2025 huggingface dataset:
Relationships between polychlorinated biphenyls and health status in harbor porpoises (Phocoena phocoena) stranded in the United Kingdom
Authors: Jepson Paul D. , Bennett Peter M. , Deaville Robert , Allchin Colin R. , Baker John R. , Law Robin J.
Published: December 2004

To investigate possible relationships between polychlorinated biphenyl (PCB) exposure and infectious disease mortality in harbor porpoises (Phocoena phocoena) in United Kingdom waters, summed blubber concentrations of 25 chlorobiphenyl congeners (Σ25CB) in healthy harbor porpoises that died of acute physical trauma (mainly by-catch; n = 175) were compared with Σ25CB values in animals that died of infectious disease (n = 82). The infectious disease group had significantly greater Σ25CB values (mean, 27.6 mg/kg lipid) than the physical trauma group (mean, 13.6 mg/kg lipid;p < 0.001). This association occurred independently of other potentially confounding variables, including age, sex, two indices of nutritional status, season, region, and year found. Total blubber PCB levels (as Aroclor 1254) were also calculated, enabling direct comparison with a proposed threshold for adverse health effects (including immunosuppression) in marine mammals of 17 mg/kg lipid. In porpoises with total PCB levels greater than 17 mg/kg lipid (n = 154), total PCB levels were significantly higher in the infectious disease group compared to the physical trauma group (p < 0.001). This association was no longer significant in porpoises with total PCB levels of less than 17 mg/kg lipid (n = 103; p > 0.55). These findings are consistent with a causal (immunotoxic) relationship between PCB exposure and infectious disease mortality, and they provide a framework for future quantitative risk-assessment analyses of porpoise populations of known size and PCB exposure.
Mobilization of pesticides on an agricultural landscape flooded by a torrential storm
Authors: Donald David B. , Hunter Fraser G. , Sverko Ed , Hill Bernard D. , Syrgiannis Jim
Published: December 2004

Mobilization of pesticides into surface waters of flooded agricultural landscapes following extreme precipitation events has not been previously investigated. After receiving 96 mm of rain in the previous 45 d, the Vanguard area of southeastern Saskatchewan, Canada, was subjected to a torrential storm on July 3, 2000, that produced as much as 375 mm of rain in 8 h. The majority of herbicides, but no insecticides, would have been applied to crops in the Vanguard area during the four weeks preceding the storm. After the storm, 19 herbicides and insecticides were detected in flooded wetlands, with 14 of them detected in 50% or more of wetlands. Average concentrations ranged from 0.43 ng/L (endosulfan) to 362 ng/L (2,4-dichlorophenoxyacedic acid). The pesticides probably were from long-range transport, followed by deposition in rain, and from herbicides applied to crops within the area subjected to the storm (1,700 km2). In the following year, when only 62 mm of rain fell in the same 45 d, only five pesticides were detected in 50% or more of wetlands. We estimated that for the 1,700-km2 storm zone, 278 kg of herbicide were mobilized into rain and by runoff into surface waters, and 105 kg were removed from the Vanguard area by discharge into Notukeu Creek. Significant quantities of herbicides are mobilized to aquatic environments when prairie agricultural landscapes are subjected to torrential storms. In these circumstances, flooded wells and small municipal reservoirs used as sources of drinking water may be compromised by 10 or more pesticides, some at relatively high concentrations.
Single versus multiple occupancy—effects on toxcityp parameters measured on Eisenia fetida in lead nitrate–treated soil
Authors: Currie Mark , Hodson Mark E. , Arnold Rebecca E. , Langdon Caroline J.
Published: December 2004

The mortality (7 and 14 d), weight change (7 and 14 d), and metal uptake of Eisenia fetida (Savigny, 1826) kept in Pb(NO3)2-treated Kettering loam soil in single- and multiple-occupancy (10 earthworms) test containers were determined. The number of earthworms to dry mass (g) ratio of soil was 1:50 in both sets of test containers. Lead concentrations were in the nominal range of 0 to 10,000 mg Pb/kg soil (mg/kg hereafter). Levels of mortality at a given concentration were statistically identical between the single- and multiple-occupancy tests, except at 1,800 mg/kg, at which significantly (p ≤ 0.05) more mortality occurred in the multiple-occupancy tests. Death of individual earthworms in the multiple-occupancy tests did not trigger death of the other earthworms in that soil. The LC50 values (concentration statistically likely to kill 50% of the population) were identical between the multiple- and single-occupancy soils: 2,662 mg/kg (2,598–2,984, 7 d) and 2,589 mg/kg (2,251–3,013, 14 d) for the multiple-occupancy soils and 2,827 mg/kg (2,443–3,168, both 7 and 14 d) for the single-occupancy soils (values in brackets represent the 95% confidence intervals). Data were insufficient to calculate the concentration statistically likely to reduce individual earthworm mass by 50% (EC50), but after 14 d, the decrease in earthworm weight in the 1,800 and 3,000 mg/kg tests was significantly greater in the multiple- than in the single-occupancy soils. At 1,000, 1,800, and 3,000 mg/kg tests, earthworm Pb tissue concentration was significantly (p ≤ 0.05) greater in earthworms from the multiple-occupancy soils. The presence of earthworms increased the NH3 content of the soil; earthworm mortality increased NH3 concentrations further but not to toxic levels.
Effect of coexisting compounds on the sorption and reduction of trichloroethylene with iron
Authors: Cho Hyun-Hee , Park Jae-Woo
Published: December 2004

Batch experiments were performed to study the effect of coexisting compounds on trichloroethylene (TCE) dechlorination and sorption in the presence of iron. Competitive sorption of TCE was observed with naphthalene as a coexisting contaminant, but the TCE reduction rate slightly increased with naphthalene, which is hardly subject to reduction. With carbon tetrachloride, nitrate, and chromate as reducible cocontaminants, the competitive reduction of TCE was observed in binary-contaminant systems. The reduction rate constant of TCE by iron filings decreased 1.5 times with carbon tetrachloride because of the competition for electrons. The TCE reduction rate with nitrate decreased five times because of the competition for electrons and the enhanced passivation. The sorbed mass of TCE on iron surface with chromate increased more than that without chromate because of the formation of (Cr, Fe)(OH)3 precipitations.
Comparative thresholds for acetylcholinesterase inhibition and behavioral impairment in coho salmon exposed to chlorpyrifos
Authors: Sandahl Jason F. , Baldwin David H. , Jenkins Jeffrey J. , Scholz Nathaniel L.
Published: December 2004

Chlorpyrifos is a common organophosphate insecticide that has been widely detected in surface waters that provide habitat for Pacific salmon in the western United States. Although chlorpyrifos is known to inhibit acetylcholinesterase (AChE) in the brain and muscle of salmonids, the relationship between sublethal AChE inhibition and more integrative indicators of neuro-behavioral impairment are poorly understood. This is particularly true for exposures that reflect the typical range of pesticide concentrations in the aquatic environment. To directly compare the effects of chlorpyrifos on AChE activity and salmon behavior, we exposed juvenile coho salmon (Oncorhynchus kisutch) to chlorpyrifos (0–2.5 μg/L) for 96 h. A computer-assisted, three-dimensional video imaging system was used to measure spontaneous swimming and feeding behaviors in control and chlorpyrifos-exposed fish. After the behavioral trials, brain and muscle tissues were collected and analyzed for AChE activity. Chlorpyrifos inhibited tissue AChE activity and all behaviors in a dose-dependent manner. Moreover, brain AChE inhibition and reductions in spontaneous swimming and feeding activity were significantly correlated. Benchmark concentrations for sublethal neurotoxicity (statistical departure values) were <0.5 μg/L and were similar for both neurochemical and behavioral endpoints. Collectively, these results indicate a close relationship between brain AChE inhibition and behavioral impairment in juvenile coho exposed to chlorpyrifos at environmentally realistic concentrations.
No association of the GABAA receptor genes on chromosome 5 with alcoholism in the collaborative study on the genetics of alcoholism sample
Authors: Dick Danielle M. , Edenberg Howard J. , Xuei Xiaoling , Goate Alison , Hesselbrock Victor , Schuckit Marc , Crowe Raymond , Foroud Tatiana
Published: December 2004

A substantial body of literature suggests that γ‐aminobutyric acid (GABA) may be involved in the neurochemical pathways contributing to alcohol use and related disorders. Chromosome 5 contains a cluster of GABAA receptor genes, GABRA1, GABRA6, GABRB2, and GABRG2, which have been among the most extensively studied in relation to alcohol use. These studies have yielded mixed results. Using data from large, multiplex alcoholic families collected as part of the Collaborative Study on the Genetics of Alcoholism (COGA), we sought to provide more conclusive evidence regarding the role of the GABAA receptor genes on chromosome 5. Multiple single nucleotide polymorphisms (SNPs) were tested in each of the four chromosome 5q GABAA receptor genes, and we conducted both classic trio‐based association analyzes and extended pedigree analyzes. We found no consistent evidence of association with alcohol dependence or alcohol dependence comorbid with antisocial personality disorder (ASPD) for any of the regions tested in the chromosome 5 GABAA receptor genes. These analyses suggest that the GABAA receptor genes on chromosome 5 do not play a strong role in alcohol dependence. Future studies are planned to test whether these genes are more important in influencing behavioral endophenotypes related to the risk of alcohol dependence. © 2004 Wiley‐Liss, Inc.
The Use of the l1 and l∞ Norms in Fitting Parametric Curves and Surfaces to Data
Authors: Al‐Subaihi I. , Watson G. A.
Published: December 2004

Given a family of curves or surfaces in Rs, an important problem is that of finding a member of the family which gives a “best” fit to m given data points. There are many application areas, for example metrology, computer graphics, pattern recognition, and the most commonly used criterion is the least squares norm. However, there may be wild points in the data, and a more robust estimator such as the l1 norm may be more appropriate. On the other hand, the object of modelling the data may be to assess the quality of a manufactured part, so that accept/reject decisions may be required, and this suggests the use of the Chebyshev norm.

We consider here the use of the l1 and l∞ norms in the context of fitting to data curves and surfaces defined parametrically. There are different ways to formulate the problems, and we review here formulations, theory and methods which generalize in a natural way those available for least squares. As well as considering methods which apply in general, some attention is given to a fundamental fitting problem, that of lines in three dimensions. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Approximating Solutions of Equations Using Two‐Point Newton Methods
Authors: Argyros Ioannis K.
Published: December 2004

We provide a local as well as a semilocal convergence analysis for two‐point Newton methods under very general conditions. Our equation contains a Fréchet differentiable operator F and another operator G whose differentiability is not assumed. Using more precise majorizing sequences than before we provide sufficient convergence conditions for Newton methods to a locally unique solution of equation F (x) + G(x) = 0. In the semilocal case we show under weaker conditions that our error estimates on the distances involved are finer and the information on the location of the solution at least as precise as in earlier results [17]. In the local case a larger radius of convergence is obtained [21]. Several applications are provided to show that our results compare favorably with earlier ones [11]–[14], [17], [21], [23], [25]. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Phase Space Stability Error Control with Variable Time‐stepping Runge‐Kutta Methods for Dynamical Systems
Authors: Humphries Tony , Vigneswaran R.
Published: December 2004

We consider a phase space stability error control for numerical simulation of dynamical systems. We illustrate how variable time‐stepping algorithms perform poorly for long time computations which pass close to a fixed point. A new error control was introduced in [9], which is a generalization of the error control first proposed in [8]. In this error control, the local truncation error at each step is bounded by a fraction of the solution arc length over the corresponding time interval. We show how this error control can be thought of either a phase space or a stability error control. For linear systems with a stable hyperbolic fixed point, this error control gives a numerical solution which is forced to converge to the fixed point. In particular, we analyze the forward Euler method applied to the linear system whose coefficient matrix has real and negative eigenvalues. We also consider the dynamics in the neighborhood of saddle points. We introduce a step‐size selection scheme which allows this error control to be incorporated within the standard adaptive algorithm as an extra constraint at negligible extra computational cost. Theoretical and numerical results are presented to illustrate the behavior of this error control. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Optimal Control of Geodesics in Riemannian Manifolds
Authors: Rozsnyo Roland , Semmler Klaus‐Dieter
Published: December 2004

In this paper, we present a method based on an optimal control technique for numerical computations of geodesic paths between two fixed points of a Riemannian Manifold under the assumption of existence. In this method, the control variable is the tangent vector to the geodesic we are looking for. Defining a cost function corresponding to the requested control, we explain how to derive the optimal control algorithm by the use of an adjoint state method for the calculation of the gradient of that cost function. We then give a geometrical interpretation of the adjoint state. After having introduced the discrete optimal control algorithm, we show an application to wooden roof design. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A Moment‐Based Method for Large‐Scale Generalized Eigenvalue Problems
Authors: Sakurai Tetsuya , Tadano Hiroto , Inadomi Yuichi , Nagashima Umpei
Published: December 2004

In this paper we consider a method for finding several eigenvalues and corresponding eigenvectors of large‐scale generalized eigenvalue problems. In this method, a small matrix pencil that has only the desired eigenvalues is derived using complex moments obtained via numerical integration. Since the process to derive the moments can be performed in parallel and we do not need to exchange data between processes, the presented method is suitable for master‐worker programming models. We have implemented and tested the proposed method in a grid RPC (remote procedure call) system. Numerical examples illustrate the properties of our approach. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Efficient Implementation of the Nelder–Mead Search Algorithm
Authors: Singer Saša , Singer Sanja
Published: December 2004

The Nelder–Mead or simplex search algorithm is one of the best known algorithms for unconstrained optimization of non–smooth functions. Even though the basic algorithm is quite simple, it is implemented in many different ways. Apart from some minor computational details, the main difference between various implementations lies in the selection of convergence (or termination) tests, which are used to break the iteration process. A fairly simple efficiency analysis of each iteration step reveals a potential computational bottleneck in the domain convergence test. To be efficient, such a test has to be sublinear in the number of vertices of the working simplex. We have tested some of the most common implementations of the Nelder–Mead algorithm, and none of them is efficient in this sense.

Therefore, we propose a simple and efficient domain convergence test and discuss some of its properties. This test is based on tracking the volume of the working simplex throughout the iterations. Similar termination tests can also be applied in some other simplex–based direct search methods. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Optimal Ship Routing Based on Wind and Wave Forecasts
Authors: Vlachos D. S.
Published: December 2004

Short term accurate wind and wave forecasts can be used for optimal ship routing. In this work, a method is presented for manipulating the POSEIDON [1] system forecasts for the Greek seas and for producing optimal routes for small and medium size ships. The method is composed from a geometrical calculation of all possible routes between two points and from an iterative algorithm which approximates the optimal (or an almost optimal) route. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Modern Synthetic Methods for Fluorine‐Substituted Target Molecules
Authors: Shimizu Masaki , Hiyama Tamejiro
Published: December 2004

Fluorine has come to be recognized as a key element in materials science: in heat‐transfer agents, liquid crystals, dyes, surfactants, plastics, elastomers, membranes, and other materials. Furthermore, many fluorine‐containing biologically active agents are finding applications as pharmaceuticals and agrochemicals. Progress in synthetic fluorine chemistry has been critical to the development of these fields and has led to the invention of many novel fluorinated molecules as future drugs and materials. As a result of the electronic effects of fluorine substituents, fluorinated substrates and reagents often exhibit unusual and unique chemical properties, which often make them incompatible with established synthetic methods. Thus, the problem of how to control the unusual properties of compounds with fluorine substituents deserves much attention, so as to promote the design of facile, efficient, and environmentally benign methods for the synthesis of valuable organofluorine targets.
Polyol recovery from biomass‐based polyurethane foam by glycolysis
Authors: Lee Seung‐Hwan , Ohkita Tsutomu , Teramoto Yoshikuni
Published: December 2004

Biomass‐based polyurethane foams (PUFs) were degraded by glycolysis and the polyols recovered were reused to prepare a rigid polyurethane foam. Biomass‐based PUFs were prepared from liquefied wood or starch polyols and grafted products with polycaprolactone. The glycolysis was conducted using diethylene glycol (DEG) as a solvent and potassium acetate as a catalyst under various reaction conditions. The effects of reaction conditions on the properties of the polyols recovered were examined. The average‐weight molecular weight (Mw) and viscosity decreased as the reaction time, temperature, and ratio of DEG/PUF increased, whereas the hydroxyl value increased. It was found from IR measurements that the conversion of the urethane functional group (NCOO) increased as the glycolysis proceeded. The PUF prepared from the recovered polyols had properties comparable to those of the raw PUF used in glycolysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 975–980, 2005
Melt index modeling with support vector machines, partial least squares, and artificial neural networks
Authors: Han In‐Su , Han Chonghun , Chung Chang‐Bock
Published: December 2004

This article presents the application of three black‐box modeling methods to two industrial polymerization processes to predict the melt index, which is considered an important quality variable determining product specifications. The modeling methods covered in this study are support vector machines (SVMs; known as state‐of‐the‐art modeling methods), partial least squares (PLS), and artificial neural networks (ANNs); the processes are styrene–acrylonitrile (SAN) and polypropylene (PP) polymerizations currently operated for commercial purposes in Korea. Brief outlines of the modeling procedure are presented for each method, followed by the procedures for training and validating the models. The SVM models yield the best prediction performances for both the SAN and PP polymerization processes. However, the ANN models fail to accurately predict the melt index when sufficient data are not available for model training in the PP polymerization process. The PLS models are not effective either when applied to the SAN polymerization process, for which the melt index has strong nonlinear functionality with the process variables. The good prediction performance that the SVM models show despite the insufficient data or strong process nonlinearity suggests that SVMs can be effectively used as alternative to PLS or ANNs for modeling the melt indices in other polymerization processes as well. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 967–974, 2005
Low molecular weight block copolymers as plasticizers for polystyrene
Authors: Hansen Kristoffer K. , Nielsen Charlotte Juel , Hvilsted Søren
Published: December 2004

Polystyrene‐b‐alkyl, polystyrene‐b‐polybutadiene‐b‐polystyrene, and polystyrene‐b‐poly(propylene glycol)monotridecyl ether were synthesized using macro initiators and atom transfer radical polymerization or by esterifications of homopolymers. The aim was a maximum molecular weight of 4 kg/mol and minimum polystyrene content of 50 w/w %, which by us is predicted as the limits for solubility of polystyrene‐b‐alkyl in polystyrene. DSC showed polystyrene was plasticized, as seen by a reduction in glass transition temperature, by block copolymers consisting of a polystyrene block with molecular weight of approximately 1 kg/mol and an alkyl block with a molecular weight of approximately of 0.3 kg/mol. The efficiency of the block copolymers as plasticizers increases with decreasing molecular weight and polystyrene content. In addition, polystyrene‐b‐alkyl is found to be an efficient plasticizer also for polystyrene‐b‐polyisoprene‐b‐polystyrene (SIS) block copolymers. The end use properties of SIS plasticized with polystyrene‐b‐alkyl, measured as tensile strength, is higher than for SIS plasticized with dioctyl adipate. The polystyrene‐b‐polybutadiene‐b‐polystyrene and polystyrene‐b‐poly(propylene glycol)monotridecyl ether series were only partially soluble in polystyrene and insoluble in the polystyrene phase of SIS. For the lowest molecular weight samples, this leads to measurable plasticization of polystyrene but no plasticization of SIS. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 981–991, 2005
Surface photografting polymerization of vinyl acetate, maleic anhydride, and their charge‐transfer complex. V. Charge‐transfer complex (1)
Authors: Jianping Deng , Wantai Yang
Published: December 2004

In previous studies, the photografting polymerization of vinyl acetate (VAC) and maleic anhydride (MAH) was investigated systematically. After that, to increase the grafting rate and efficiency and make the project more practicable, a VAC–MAH binary monomer system was employed for simultaneous photografting onto the surface of low‐density polyethylene film. The effects of several crucial factors, including the composition and total concentration of the monomer solution and different types of photoinitiators and solvents, on the grafting polymerization were investigated in detail. The conversion percentage (CP), grafting efficiency (GE), and grafting percentage were measured by gravimetry. The results showed that the monomer composition played a big part in this binary system; appropriately increasing the content of MAH in the monomer feed was suited for grafting polymerization. The growth of the total monomer concentration, however, made the copolymerization faster and was unfavorable for grafting polymerization. The three photoinitiators—2,2‐dimethoxy‐2‐phenylacetophenone (Irgacure 651), benzoyl peroxide, and benzophenone (BP)—led to only slight differences in CP, but for GE, BP was the most suitable. As for the different solvents—acetone, ethyl acetate, tetrahydrofuran (THF), and chloroform—using those able to donate electrons (acetone and THF) resulted in relatively higher CPs; on the contrary, the use of the other solvents made GE obviously higher, and this should be attributed to the charge‐transfer complex (CTC) that formed in this system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 903–909, 2005
Validation of a model of information seeking over multiple search sessions
Authors: Lin Shin‐jeng , Belkin Nick
Published: December 2004

Most information systems share a common assumption: information seeking is discrete. Such an assumption neither reflects real‐life information seeking processes nor conforms to the perspective of phenomenology, “life is a journey constituted by continuous acquisition of knowledge.” Thus, this study develops and validates a theoretical model that explains successive search experience for essentially the same information problem. The proposed model is called Multiple Information Seeking Episodes (MISE), which consists of four dimensions: problematic situation, information problem, information seeking process, episodes. Eight modes of multiple information seeking episodes are identified and specified with properties of the four dimensions of MISE. The results partially validate MISE by finding that the original MISE model is highly accurate, but less sufficient in characterizing successive searches; all factors in the MISE model are empirically confirmed, but new factors are identified as well. The revised MISE model is shifted from the user‐centered to the interaction‐centered perspective, taking into account factors of searcher, system, search activity, search context, information attainment, and information use activities.
Effect in rats of simultaneous prenatal exposure to ochratoxin A and aflatoxin B1. I. Maternal toxicity and fetal malformations
Authors: Wangikar P.B. , Dwivedi P. , Sinha Neeraj
Published: December 2004

Ochratoxin A (OA) and Aflatoxin B1 (AFB1), the food borne mycotoxins are produced by several fungal species of the genera Aspergillus and Penicillium. To determine the teratogenic effects, these mycotoxins were administered orally either individually or in combination to the pregnant Wistar rats on days 6–15 of gestation. OA and AFB1 were dissolved in corn oil and different doses of OA (0.125, 0.25, 0.50, and 0.75 mg/kg), AFB1 (0.125, 0.25, 0.50, and 1.00 mg/kg), and a combination of OA+AFB1 (0.125+0.125; 0.25+0.50; 0.50+0.25 mg/kg) were given by gastric intubation to rats. During dosing period, the body weight and body weight gains significantly decreased at a higher dosage, in both individual and combined treatments. In all the combination treatments, the percent implants resorbed, fetal body weights, and crown‐rump lengths were comparable to those of controls and with the individual mycotoxin treatment. The number of dead fetuses was significantly increased in the high OA combination (OA+AFB1 0.50+0.25) group as compared with the other two combinations. OA and AFB1 alone and in combination caused various gross, skeletal, and visceral anomalies. The occurrence was considerably less pronounced in fetuses of AFB1 and combination groups as compared with those of OA group fetuses. The exencephaly, incomplete closure of skull, wavy and fused ribs, agenesis of the ischium bone, and enlarged renal pelvis, recorded in OA treatment and ear abnormality and incomplete ossification of skull bones observed in AFB1 when given individually, were not seen in combination groups. However, new manifestations, such as gastroschisis and syndactyly were observed and the incidence of cardiac defects was increased in fetuses due to the combined treatment. The results of the present study indicated that there is some interaction between these mycotoxins that resulted in reduced teratogenic activity of OA in the presence of AFB1. Apparently, new manifestations observed in combination treatment points to the potential threat of teratogenicity in terms of public health hazards. Birth Defects Res B 71:343–351, 2004. © 2004 Wiley‐Liss, Inc.
Making the links: child abuse, animal cruelty and domestic violence
Authors: Becker Fiona , French Lesley
Published: December 2004

The paper sets out the research evidence on the correlation, or the ‘links’, between child abuse, animal abuse and domestic violence, explores the evidence base available to professionals working with animals or children and describes the process of establishing a national multidisciplinary group known as the Links Group. The paper goes on to consider the challenges in setting up a working group of this kind and its subsequent progress in terms of inﬂuencing policy and practice. Finally, the authors make a series of recommendations aimed at continuing the process of change within organizations charged with the welfare of animals, children and vulnerable families. Copyright © 2004 John Wiley & Sons, Ltd.
From the Linden Flower to Linden Honey – Volatile Constituents of Linden Nectar, the Extract of Bee‐Stomach and Ripe Honey
Authors: Naef Regula , Jaquier Alain , Velluz Alain , Bachofen Boris
Published: December 2004

Honey is produced by honeybees (Apis mellifera), which collect nectar from flowers, digest it in their bodies, and deposit it in honeycombs, where it develops into ripe honey. We studied the evolution of the volatile constituents from the nectar of linden blossoms (Tilia cordata) to honey via the ‘intermediate’ honeybee.

The sampling of the contents of the honey stomach or honey sack of the bee is unique. Extracts were prepared from nectar, from the liquid of the honey stomach, and from ripe honey. The chemistry is extremely complex, and compounds spanning from monoterpenes (hydrocarbons, ethers, aldehydes, acids, and bifunctional derivatives), isoprenoids, aromatic compounds (phenylpropanoids, phenols), and products degraded from fatty acids to alkaloids, were identified. Some compounds definitely stem from the plants, whereas other interesting constituents can be attributed to animal origin. Two derivatives of decanoic acid, 9‐oxodec‐2‐enoic acid (12) and 9‐hydroxydec‐2‐enoic acid, identified in the honey are known to be constituents of the so‐called ‘Queen's pheromone’. Two metabolites of these acids were identified in the extract of the honey stomach: 8‐oxononanal (10), a new natural product, and 8‐oxononanol (11). There structures were confirmed by synthesis.

Nectar and honey stomach contain many aldehydes, which, due to the highly oxidative atmosphere in the honeycomb, are found as corresponding acids in the honey. Two acids were newly identified as 4‐isopropenylcyclohexa‐1,3‐diene‐1‐carboxylic acid (14) and 4‐(1‐hydroxy‐1‐methylethyl)‐cyclohexa‐1,3‐diene‐1‐carboxylic acid (15).
14‐Methylpentadecano‐15‐lactone (Muscolide): A New Macrocyclic Lactone from the Oil of Angelica archangelicaL.
Authors: Lopes Daíse , Strobl Herbert , Kolodziejczyk Paul
Published: December 2004

The chemical composition of seed and root oils from Angelica archangelica L. was investigated. Analyses were performed by GC/MS and GC using two columns of different polarities (polyethylene glycol (DB‐Wax) and 5% phenyl/95% polydimethylsiloxane (HP‐5)), for the separation of several co‐eluting components. A total of 58 compounds were identified, accounting for 96.3% (seed) and 93.5% (root) of the oils, respectively. A high content of β‐phellandrene (74.7%) was found in Angelica seed oil. Root oil contained a larger amount of macrocyclic lactones (1.3%) in comparison to the seed oil (0.4%). Different harvest dates produced only slight changes in the root‐oil composition. In root oil harvested in summer, the β‐phellandrene content increased by ca. 36%, but no significant changes in the relative compositions of other components were observed. Fresh root oils were collected in five fractions (constant time intervals) during steam distillation (see Table). The highest‐boiling fraction contained 9.3% of macrocyclic lactones such as tridecano‐13‐lactone (5.0%), 12‐methyltridecano‐13‐lactone (0.4%), tetradecano‐14‐lactone (0.1%), pentadecano‐15‐lactone (3.5%), 14‐methylpentadecano‐15‐lactone (1; trace), hexadecano‐16‐lactone (trace), and heptadecano‐17‐lactone (0.2%). This is the first report of the occurrence of 14‐methylpentadecano‐15‐lactone (muscolide; 1) in a natural product.
Silylating Reagents: A Powerful Tool for the Construction of Isosteric Analogs of Highly Branched Odorants
Authors: Doszczak Leszek , Gasperi Tecla , Saint‐Dizier Alexandre , Loreto M. Antonietta , Enders Dieter
Published: December 2004

We have discovered that α‐[dimethyl(thexyl)silyl]acetaldehyde (=[dimethyl(1,1,2‐trimethylpropyl)silyl]acetaldehyde; 31) has a strong, woody odor. Structural analysis has shown resemblance to known odorants with similar organoleptic properties. On the basis of structureodor relationships, new and more‐powerful woody and ambery sila odorants were prepared. Further derivatization led to a set of compounds with very interesting organoleptic properties. Selected chiral compounds were also prepared stereoselectively. The influence of the absolute configuration on the olfactory properties was in agreement with theoretical assumptions. We also designed other groups of organosilicon odorants. The compounds discovered can be obtained in a few simple steps from commercially available reagents, and may find application in the fragrance and flavor industry. Their structures provide interesting data for further research on structureodor relationships.
New Woody and Ambery Notes from Cedarwood and Turpentine Oil
Authors: Panten Johannes , Bertram Heinz‐Jürgen , Surburg Horst
Published: December 2004

The development of a new product in the chemical industry is still driven by needs like technical properties, price/performance ratio, biodegradability, or product safety. However, in terms of improving more and more on ecological criteria, summarized under such catchphrases as sustainable development or green chemistry, another important aspect is to use renewable resources as starting materials. This is not significantly new in fragrance chemistry, and there are a lot of raw materials in the perfume oils that are derived from molecules of renewable resources. Two commonly used materials are: longifolene (from turpentine oil) and cedrene (from cedarwood oil). These compounds are very suitable for the synthesis of woody and ambery notes, and even though it seemed that all possibilities were exhausted, it is actually still feasible to discover new molecules with excellent olfactory properties such as Ambrocenide® (50a), which is available in three steps from α‐cedrene. Some of these molecules will be treated in this review, both with respect to synthesis as well as structural and sensory aspects.
New Macrocyclic Musk Compounds
Authors: Matsuda Hiroyuki , Watanabe Shinya , Yamamoto Kenichi
Published: December 2004

The syntheses and olfactory evaluations of eight new macrocyclic musks with a 1,6‐dioxa structure (1a–d and 1′a–d) as well as of twelve optically active 3‐methyl macrolides (5a–c and 5′a–c) are reported. These macrocycles were synthesized via intramolecular metathesis mediated by the Grubbs catalyst. Despite the absence of a CO function, the 1,6‐dioxa compounds, both unsaturated (1) and saturated (1′), possess musky odors similar to those of macrocyclic ketones and lactones. Especially 16‐membered rings were found to display an intense and pleasant musk character. However, in the case of optically active 3‐methyl macrolides (5, 5′), only the (R)‐configured 15‐ and 16‐membered rings had intense and pleasant musk notes.
Gold Liquid Crystals Displaying Luminescence in the Mesophase and Short F⋅⋅⋅F Interactions in the Solid State
Authors: Bayón Rocio , Coco Silverio , Espinet Pablo
Published: December 2004

Rodlike gold(I) complexes, [Au(C6F4OCmH2m+1)(CNC6H4C6H4OCnH2n+1)] (m=2, n=4, 10; m=6, n=10; m=10, n=6, 10), display interesting features. They are liquid crystals and show photoluminescence in the mesophase, as well as in the solid state and in solution. The single‐crystal, X‐ray diffraction structure of [Au(C6F4OC2H5)(CNC6H4C6H4OC4H9)] confirms its rodlike structure, with a linear coordination around the gold atom, and reveals the absence of any Au⋅⋅⋅Au interactions (such interactions are often present in luminescent gold complexes). Well‐defined, intermolecular Fortho⋅⋅⋅Fmeta interactions, with remarkably short intermolecular F⋅⋅⋅F distances (2.66 Å), are observed; these interactions seem to be responsible for the crystal packing, which consists of an antiparallel arrangement of molecules. Experiments under different conditions support the explanation that the photoluminescence has an intramolecular origin.
Investigations on the Iron‐Catalyzed Asymmetric Sulfide Oxidation
Authors: Legros Julien , Bolm Carsten
Published: December 2004

The development of an enantioselective sulfide oxidation involving a chiral iron catalyst and aqueous hydrogen peroxide as oxidant is described. In the presence of a simple carboxylic acid, or a carboxylate salt, the reaction affords sulfoxides with remarkable enantioselectivities (up to 96 % ee) in moderate to good yields. The influence of the structure of the additive on the reaction outcome is reported. In the sulfoxide‐to‐sulfone oxidation a kinetic resolution (with s=4.8) occurs, which, however, plays only a negligible role in the overall enantioselective process. Furthermore, a positive nonlinear relationship between the ee of the product and that of the catalyst has been found. On the basis of these observations, a possible catalyst structure is proposed.
SrFe2(PO4)2: Ab initio Structure Determination with X‐Ray Powder Diffraction Data and Unusual Magnetic Properties.
Authors: Belik Alexei A. , Azuma Masaki , Takano Mikio , Lazoryak Bogdan I.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
The Henicosaphosphide Iodides of Potassium and Rubidium, K4P21I and Rb4P21I.
Authors: Hoenle Wolfgang , Schmettow Walter , Peters Karl , Chang Jen‐Hui , von Schnering Hans Georg
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Electronic Absorption and Vibrational IR and Raman Studies of Binary Phosphate β‐K4Ce2P4O15.
Authors: Szczygiel I. , Macalik L. , Znamierowska T. , Hanuza J.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
The Counterion Effect in the Phase‐Transfer Catalyzed Asymmetric Synthesis of α‐Amino Acids Promoted by Anthryl‐Derived Dimeric Cinchona Ammonium Salts.
Authors: Chinchilla Rafael , Mazon Patricia , Najera Carmen , Ortega Francisco J.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
N‐Allyl‐N‐tert‐butyldimethylsilylamine for Chiral Ligand‐Controlled Asymmetric Conjugate Addition to tert‐Butyl Alkenoates.
Authors: Doi Hirohisa , Sakai Takeo , Yamada Ken‐ichi , Tomioka Kiyoshi
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Copper(II) Triflate‐Mediated Addition Reaction of α‐Sulfurated Alkylstannanes to Imines: Facile Synthesis of Vicinal‐amino Sulfides.
Authors: Kagoshima Hirotaka , Takahashi Naoshi
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Palladium Catalyzed Cross‐Coupling Reactions of Silylamines.
Authors: Smith Catherine J. , Early Tessa R. , Holmes Andrew B. , Shute Richard E.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Ionic Liquid Media Resulted in More Efficient Regio‐ and Stereoselective Aminohalogenation of Cinnamic Esters.
Authors: Kotti S. R. S. Saibabu , Xu Xin , Wang Yining , Headley Allan D. , Li Guigen
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Sequential Assembly Strategy for Tetrasubstituted Olefin Synthesis Using Vinyl 2‐Pyrimidyl Sulfide as a Platform.
Authors: Itami Kenichiro , Mineno Masahiro , Muraoka Nobuhiro , Yoshida Jun‐ichi
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Efficient Synthesis of 3‐Substituted Indazoles Using Pd‐Catalyzed Intramolecular Amination Reaction of N‐Tosylhydrazones.
Authors: Inamoto Kiyofumi , Katsuno Mika , Yoshino Takashi , Suzuki Ikue , Hiroya Kou , Sakamoto Takao
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
1,3‐Dipolar Addition of Diethyl Diazomethylphosphonate onto a C=N Double Bond. Synthesis of Triazolinyl and Aziridinyl Phosphonates.
Authors: Bartnik Romuald , Lesniak Stanislaw , Wasiak Piotr
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Chain Elongation of Primary Alcohols of Carbohydrates.
Authors: Clavel Caroline , Barragan‐Montero Veronique , Montero Jean‐Louis
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Synthesis of Enantiomerically Pure D‐FDOC, an anti‐HIV Agent.
Authors: Mao Shuli , Bouygues Martin , Welch Christopher , Biba Mirlinda , Chilenski Jen , Schinazi Raymond F. , Liotta Dennis C.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Stereospecific Synthesis of all Four Isomeric 6,8‐Heneicosadien‐11‐ones: Sex Pheromone Components of the Painted Apple Moth Teia anartoides.
Authors: Comeskey Daniel J. , Bunn Barry J. , Fielder Simon
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
The Chemistry of the Heaviest Elements: Theory and Experiment
Authors: Pershina V. , Hoffman D. C.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Explorations into New Reaction Chemistry
Authors: Mukaiyama Teruaki
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Oxidation of Heterocyclic Compounds by Permanganate Anion
Authors: Soldatenkov A. T. , Temesgen A. V. , Kolyadina N. M.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Non‐Stabilized Transition Metal Carbenes as Intermediates in Intramolecular Reactions of Alkynes with Alkenes
Authors: Echavarren Antonio M. , Nevado Cristina
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Studies Based on Deuterium Isotope Effect on 13C Chemical Shifts
Authors: Dziembowska T. , Hansen P. E. , Rozwadowski Z.
Published: December 2004

For Abstract see ChemInform Abstract in Full Text.
Wie schmutzig ist der Rhein??
Authors: Malle Karl‐Geert
Published: December 2004

Die Rheinanliegerstaaten haben im gemeinsamen Bemühen um die Qualität des Rheinwassers schon 1963 die „Internationale Kommission zum Schutze des Rheins gegen Verunreinigung”︁ (IKSR) ins Leben gerufen. Die IKSR überwacht die Wasserqualität und gibt einen jährlichen Bericht mit Analysendaten heraus. Außerdem erarbeitet sie Vorschläge für Maßnahmen zum Schutze des Stroms. In Ergänzung der jeweiligen nationalen Gewässerschutzmaßnahmen haben die Rheinanliegerstaaten 1976 das Übereinkommen zum Schutze des Rheins gegen chemische Verunreinigung (Chemieabkommen) abgeschlossen. Das Chemieakbkommen, durch das die Ableitung bestimmter gefährlicher Stoffe aus den Stoffgruppen und ‐familien: Queck‐silber‐ und Cadmiumverbindungen, organische Halogen‐, Phosphor‐ und Zinnverbin‐dungen, cancerogene Stoffe so weit wie möglich verhindert und aus weiteren Stoffgruppen und ‐familien, darunter den meisten Metallen, streng überwacht und eingeschränkt werden soll, hat einen langfristigen präventiven Charakter. Das Chloridabkommen soll dagegen sofort zu Maßnahmen führen. Zu diesen Abkommen der Rheinanliegerstaaten treten eine Reihe weiterer internationaler Abkommen und Vereinbarungen mit Auswirkungen auf den Rhein, verschiedene Richtlinien der Europäischen Gemeinschaft, ein geplantes Abkommen der Länder im Europarat, ein Abkommen zum Schutze der Nordsee und des Nordatlantiks gegen die Verschmutzung vom Lande aus.
Moderne Verfahren der Großchemie: Chlor und Natronlauge
Authors: Minz Franz‐Rudolf , Schliebs Reinhard
Published: December 2004

Neue technische Entwicklungen, Änderungen im Rohstoffangebot oder bei den Rohstoffpreisen, aber auch Forderungen des Umwelt‐ und Arbeitsschutzes führen dazu, daß die technische Herstellung von anorganischen und organischen Basisprodukten weit stärkeren Veränderungen unterworfen ist, als die Lehrbücher vermuten lassen. „Chemie in unserer Zeit”︁ setzt mit dem vorliegenden Beitrag eine lockere Folge von Berichten über aktuelle Verfahren zur Herstellung industrieller Basischemikalien fort.
Neuere Erkenntnisse der Pflanzenernährung
Authors: Isermann Klaus
Published: December 2004

Dies ist Teil I einer zweiteiligen Aufsatzfolge. Teil II wird „Neuentwicklungen der Düngemittelforschung”︁ behandeln und im nächsten Heft erscheinen.
Neuentwicklungen aus der Düngemittelforschung
Authors: Isermann Klaus
Published: December 2004

Teil I dieser zweiteiligen Folge handelte von „Neueren Erkenntnissen der Pflanzenernährung”︁ [diese Zeitschr. 13, 97 (1979)].
Das Experiment: Farbreaktionen zur Klassifizierung von Lösungsmitteln I
Authors: Soukup Rudolf Werner
Published: December 2004

„We lehrt nun die Natur zu geben und zu empfangen? Es gibt der Kupfermensch, und es nimmt der Wasserstein; es gibt das Erz, und es nimmt die Pflanze; es geben die Sterne, und es nehmen die Blüten; es gibt der Himmel, und es nimmt die Erde.”︁ [Aus einem alchemistischen Traktat des Zosimos (um 400 n. Chr.) „Über die Kraft”︁ (Coll. des Alch. Grecs)]
Das Experiment: Farbreaktionen zur Klassifizierung von Lösungsmitteln II
Authors: Soukup Rudolf Werner
Published: December 2004

Experimente zur Lewis‐Basizität: Ein Nikkelkomplex als Indikator für die Lösungsmittel‐Basizität
Selen in der enzymatischen Katalyse
Authors: Flohé Leopold , Straßburger Wolfgang , Günzler Wolfgang A.
Published: December 2004

Selen ist als Bestandteil mehrerer Enzyme biologisch wirksam. Im tierischen Organismus spielt es als Bestandteil der Glutathion‐Peroxidase eine zentrale Rolle beim Schutz des Gewebes gegen die schädigende Wirkung von Hydroperoxiden. Soweit bekannt ist, wird Selen in Form der Aminosäure Selenocystein cotranslational, also unmittelbar während der Proteinbiosyn‐these, in die Proteinkette inkorporiert. Als Codon für diese Aminosäure dient das bislang als Stopp‐Codon bekannte Basentriplett TGA.
Farbige Komplexe: das Charge‐Transfer‐Phänomen
Authors: Kaim Wolfgang , Ernst Sylvia , Kohlmann Stephan
Published: December 2004

Zu den elementarsten chemischen Vorgängen gehört die Elektronenübertragung (Elektron‐Transfer, ET [1]), für deren Verständnis das Studium der lichtinduzierten Ladungsübertragung innerhalb einer „komplexen”︁ Verbindung von großer Bedeutung ist. Bei einem solchen „Charge Transfer”︁ (CT)‐Übergang

Das Charge‐Transfer‐Konzept wurde von R. S. Mulliken (1896‐1986) ursprünglich für Molekülkomplexe entwickelt.

wird durch Absorption eines Lichtquants geeigneter Energie eine intramolekulare Übertragung von Elektronenladung zwischen zwei verschiedenen Bestandteilen der „Komplex”︁‐Verbindung angeregt. Koordinationsverbindungen mit CT‐Absorptionen stellen exzellente Anschauungsbeispiele für die Wechselwirkung zwischen chemischen Verbindungen und Photonen sowie für deren Folgereaktionen dar. Das zweifellos attraktivste und vor allem in den letzten Jahren in den Vordergrund gerückte Ziel solcher Untersuchungen ist dabei eine effektive und selektive Nutzung von sichtbarem Licht, etwa der Sonnenstrahlung, für katalytisch geführte, „saubere”︁ chemische Prozesse.