bluuebunny/crossref_metadata_2025 huggingface dataset:
Suicide in Police—A Critical Review
Authors: Hem Erlend , Berg Anne Marie , Ekeberg Øivind
Published: December 2003

Police officers are commonly referred to as a high‐risk group for suicide. So far no comprehensive review has been published about epidemiologic studies among police. This article systematically explores the worldwide literature on suicide in police. None of the recent nationwide studies show elevated suicide rates among police. Other studies show inconsistent results. Conclusively, it is not documented that there is an elevated suicide rate in police. A particular problem in previous research has been methodological shortcomings. There is need for further systematic research, and this review points out some strategies of research.
Effective Problem Solving in Suicide Attempters Depends on Specific Autobiographical Recall
Authors: Pollock Leslie R. , Williams J. Mark G.
Published: December 2003

The relationship between over‐general autobiographical memory and inter‐personal problem solving was investigated by comparing a group of suicide attempters with a nonsuicidal psychiatric control group and a normal control group. Results showed that suicide attempters were more over‐general in memory and displayed significantly poorer problem solving than the other two groups. Furthermore, suicide attempters who were more over‐general displayed greater deficits in problem solving. It was concluded that effective problem solving in suicide attempters depends on specific autobiographical recall.
Does Suicidal History Enhance Acceptance of Other Suicidal Individuals?
Authors: Knott Ena , Range Lillian M.
Published: December 2003

Suicide is stigmatized, so suicidal people may be especially hard to accept. To see if moderately suicidal outpatients were more accepting of a suicidal person than never‐suicidal or severely suicide outpatients, 105 respondents completed measures of suicidality, depression, acceptance, and empathy. A curvilinear ANCOVA was nonsignificant, but a linear ANCOVA significantly adjusted for depression, and indicated, unexpectedly, that net of depression, never‐suicidal people were more accepting of a suicidal person than moderately or severely suicidal people. Empathy and acceptance were moderately related. An implication is that social support for suicidal individuals might best be obtained from those who were never suicidal themselves.
Suicidal Ideation in Hispanic and Mixed‐Ancestry Adolescents
Authors: Olvera Rene L.
Published: December 2003

This survey examined differences in suicidal ideation, depressive symptomatology, acculturation, and coping strategies based on ethnicity. The author gathered data from a self‐report questionnaire administered to students in an ethnically diverse middle school (grades 6–8, N = 158). Hispanic (predominantly Mexican American) and mixed‐ancestry adolescents displayed significantly higher risk of suicidal ideation compared to Anglo peers, even when socioeconomic status, age, and gender were controlled for. Suicidal ideation was associated with depressive symptoms, family problems, lower levels of acculturation, and various coping strategies. Using multivariate analysis, Hispanic ancestry, depressive symptoms, family problems, and the use of social coping remained in the model.
Assault Victimization and Suicidal Ideation or Behavior Within a National Sample of U.S. Adults
Authors: Simon Thomas R. , Anderson Mark , Thompson Martie P. , Crosby Alex , Sacks Jeffrey J.
Published: December 2003

Data from a nationally representative sample of 5,238 U.S. adults were used to examine the extent to which physical assault victimization was associated with suicidal ideation or behavior (SIB). The results from multivariable logistic regression analyses indicate that physical assault victimization was positively associated with SIB after adjusting for sociodemographic characteristics and alcohol use (OR = 3.6; 95% CI = 2.4–5.5). Those who were injured during the most recent physical assault (OR = 2.7; 95% CI = 1.2–6.0) and those who were assaulted by a relative (OR = 3.4; 95% CI = 1.0–11.0) or intimate partner (OR = 7.7; 95% CI = 2.7–22.5) were significantly more like to report SIB than victims who were not injured or were assaulted by a stranger. Also, those who were victimized but not injured (OR = 5.6; 95% CI = 3.8–8.2) and those who were victimized by a stranger (OR = 2.9; 95% CI = 1.4–6.0) were more likely to report SIB than non‐victims. These results highlight the need for legal, medical, mental health, and social service providers to address the co‐occurrence of violent victimization and suicidal ideation, particularly, but not exclusively, victimization by family members and intimates.
Suicidal Ideation and Somatic Symptoms of Patients with Mind/Body Distress in a Japanese Psychosomatic Clinic
Authors: Nakao Mutsuhiro , Yamanaka Gaku , Kuboki Tomifusa
Published: December 2003

To examine associations of suicidal ideation with somatic symptoms, 863 outpatients were studied in a psychosomatic clinic in Japan. All subjects were diagnosed according to the third and fourth editions of the Diagnostic and Statistical Manual of Mental Disorders (DSM‐III‐R and DSM‐IV). They completed the Cornell Medical Index Questionnaire to assess suicidal ideation and 15 major somatic symptoms. Mood states were rated using the Profile of Mood States (POMS). In the study, 266 patients (31%) reported suicidal ideation. The age‐ and sex‐adjusted odds ratios (typically in the range of 1.5 to 2.5) of somatic symptoms for suicide ideation showed significant differences (all ps < .05) for 13 of 15 symptoms. The total number of somatic symptoms predicted suicidal ideation (p < .05), controlling for the significant effects of sex, education, marital status, and the POMS Depression scale scores through multiple regression analysis. Evaluation of somatic symptoms might be important to assess suicidal ideation in a psychosomatic medicine population.
Suicidal Behavior Among Urban, African American Young Adults
Authors: Ialongo Nicholas , McCreary Beth K. , Pearson Jane L. , Koenig Amy L. , Wagner Barry M. , Schmidt Norman B. , Poduska Jeanne , Kellam Sheppard G.
Published: December 2003

The objectives of the present study were four‐fold. First, to determine the lifetime, last year, and 6‐month prevalence and demographic correlates of suicidal behavior in a defined population of urban, African American young adults. Second, to determine the degree of mental health service utilization among attempters. Third, to study the comorbidity between mental disorders and suicidal behavior, along with the variation in the numbers and types of psychiatric disorders associated with attempts versus ideation only. Fourth, to examine gender differences in the psychiatric diagnoses associated with attempts and ideation. Data relevant to each of these objectives were gathered through structured interviews of 1,157 economically disadvantaged, African American young adults. Lifetime, last year, and 6‐month prevalence rates for attempts were 5.3%, 1.2%, and 0.4%, respectively, whereas the lifetime and 6‐month prevalence of ideation were 14% and 1.9%, respectively. Approximately two thirds of those who reported lifetime ideation, and a similar proportion of those who reported lifetime attempts, had a history of at least one lifetime psychiatric disorder. There were no gender differences in terms of the degree of risk for suicidal behavior (ideation or attempts) associated with any of the comorbid psychiatric diagnoses assessed. Despite the severity of most attempts, few attempters received mental health services in their lifetime or at the time of their most recent attempt.
Domains and Rafts in Lipid Membranes
Authors: Binder Wolfgang H. , Barragan Veronique , Menger Fredric M.
Published: December 2003

“It takes a membrane to make sense out of disorder in biology. You have to be able to catch energy and hold it, storing precisely the needed amount and releasing it in measured shares”. So wrote Lewis Thomas in The Lives of Cells. Domains and rafts are shown in the present Review to play an important role in this amazing behavior of lipid membranes. Topics touched upon include the experimental detection of domains, their composition, domain induction, properties of rafts (a special form of domain), and the relationship of rafts to human diseases. Lipids, polymers, and proteins can contribute to this type of micro‐ and nanostructuring within membranes, thus imposing a new structural hierarchy on top of the classical bilayer membrane. The purpose of this Review is to develop an appreciation for the multiple organizational levels in self‐assembling systems.
Cover Picture: Breaking Down Barriers: The Liaison Between Sigmatropic Shifts, Electrocyclic Reactions, and Three‐Center Cations (Angew. Chem. Int. Ed. 47/2003)
Authors: Hoffmann Roald , Tantillo Dean J.
Published: December 2003

Orbital‐symmetry control was initially explored almost 40 years ago. However, new principles can still be discovered: There is a striking congruence in the geometries of the transition states (not reactants and products) of electrocyclic reactions and sigmatropic shifts related by a proton. A link between these reactions and three‐center hydride transfers in a cation is forged, and the idea of a transition‐state proton affinity is reintroduced by R. Hoffmann and D. J. Tantillo in their Communication on page 5877 ff.
Geoelectric prospection of a city wall by multi‐electrode resistivity image survey at the prehistoric site of Asea (southern Greece)
Authors: Dogan M. , Papamarinopoulos S.
Published: December 2003

Electric resistivity imaging survey was carried out at the archaeological site of Asea as part of a programme of cooperative research between the Swedish Institute at Athens and the University of Patras. This paper presents the geophysical results of the first field season 2001. It is intended to explore the buried extension of the city wall in order to contribute to progressive research on the responses of the resistivity method to intact subsurface archaeological features (wall, void, tunnel, etc.). The survey was performed by means of a Geopulse imager system with 25 electrodes and an electrode spacing of 1 m. The Wenner–Schlumberger array was selected for measurements. The city wall was imaged in both north and south directions. The results indicate that the resistivity method can provide a clear pseudo‐image of medium to large size walls with high accuracy on archaeological sites. Copyright © 2003 John Wiley & Sons, Ltd.
Geophysical surveys of Bury Walls hill fort, Shropshire
Authors: Murdie Ruth E. , White Roger H. , Barratt Glynn , Gaffney Vince , Goulty Neil R.
Published: December 2003

The hill fort of Bury Walls in Shropshire has been surveyed extensively by topographical and geophysical methods with the aims of recovering evidence for occupation, characterising the use of the hill fort and clarifying the chronological development of the site. Topographic surveys delineated the current extent of the fort and its massive fortifications. Resistance surveys showed several interesting features inside the fort, including extensive use of the geology to make flattened ledges in an otherwise quite uneven fort interior, a possible cross dyke, interior roads and traces of possible dwellings. Magnetic gradient surveys again showed clearly the possible cross dyke. Additional geophysical surveys attempted to define the depths of these features found in the resistance and magnetic gradient maps. This study, although not fully answering the original aims, provides a useful basis for future excavation. Copyright © 2003 John Wiley & Sons, Ltd.
A method to solve the multilayer non‐continuity problem for heat and moisture transfer in building structures
Authors: Su X. , Ang H.
Published: December 2003

In this paper a finite‐difference method is proposed for the first time for the solution of coupled heat and moisture transfer problems of transient nature in 1‐D multilayer building elements. Transient boundary conditions are specified for both heat and moisture transfer at external surfaces, while constant values are assumed for material properties of each layer of the structure. The calculations for a typical three layers wall are conducted to obtain the dynamic distributions of the relative humidity at the interfaces of every layer during 24 h by use of the mentioned method, and the results agree with the transfer function method in (ASHRAE Trans. 1999; 105(2) : 954–961). The method can be extended to 2‐D and 3‐D coupled heat and moisture transfer problems. Copyright © 2003 John Wiley Sons, Ltd.
P‐wave and S‐wave decomposition in boundary integral equation for plane elastodynamic problems
Authors: Perrey‐Debain Emmanuel , Trevelyan Jon , Bettess Peter
Published: December 2003

The method of plane wave basis functions, a subset of the method of Partition of Unity, has previously been applied successfully to finite element and boundary element models for the Helmholtz equation. In this paper we describe the extension of the method to problems of scattering of elastic waves. This problem is more complicated for two reasons. First, the governing equation is now a vector equation and second multiple wave speeds are present, for any given frequency. The formulation has therefore a number of novel features. A full development of the necessary theory is given. Results are presented for some classical problems in the scattering of elastic waves. They demonstrate the same features as those previously obtained for the Helmholtz equation, namely that for a given level of error far fewer degrees of freedom are required in the system matrix. The use of the plane wave basis promises to yield a considerable increase in efficiency over conventional boundary element formulations in elastodynamics. Copyright © 2003 John Wiley & Sons, Ltd.
Computation of the Laplace inverse transform by application of the wavelet theory
Authors: Wang Jizeng , Zhou Youhe , Gao Huajian
Published: December 2003

An efficient and robust method of solving Laplace inverse ransform is proposed based on the wavelet theory. The inverse function is expressed as a wavelet expansion with rapid convergence. Several examples are provided to demonstrate the methodology. As an example of application, the proposed inversion method is applied to the dynamic analysis of a single‐degree‐of‐freedom spring–mass–damper system whose damping is described by a stress–strain relation containing fractional derivatives. The results are compared with previous studies. Copyright © 2003 John Wiley Sons, Ltd
Numerical homogenization of active material finite‐element cells
Authors: Buehler Markus J. , Bettig Bernhard P. , Parker Gordon G.
Published: December 2003

We present the homogenization of a parametrically defined periodic microstructure in which it is possible to separately control the volume fractions of conventional material, active material and void. The effective material properties from the homogenization reduce the necessary finite‐element model complexity and also allow for topology optimization of smart structures or optimization of the microstructure itself. Homogenization equations for piezoelectric material including thermal effects are derived with a first‐order asymptotic approach. The homogenization problem is solved numerically for discrete values of the design parameters. An interpolation technique is used to find analytical, continuously derivable functions for material properties of the design parameters. Consideration is given to planar microstructures and the treatment of microstructures consisting of dielectrically distinct materials. Copyright © 2003 John Wiley & Sons, Ltd.
Security Maintenance Mediation: a technology for preventing unintended security breaches
Authors: King Roger (Buzz)
Published: December 2003

Web‐resident information is becoming ‘smarter’, in the sense that emerging technology will support the annotation of it with ontological terms, which will be used to locate and reuse information. This will pose a great security risk in the form of unintended breaches (as distinct from deliberate invasions). Web‐resident information will be far more readily available and relevant, thus causing inadvertent releases of secure information to potentially cause it to be diffusely spread across the Internet. Then as this information is iteratively transformed and integrated with other information, it will become irretrievable and potentially used in a myriad of unpredictable ways. The problem is that ontological annotations, while making information more understandable in its original form, do not provide a means for easily capturing the complex semantics of information that has been transformed via abstraction, aggregation, and integration. This demands the development of a semantically rich way of specifying ‘views’ of Web information, to which security controls can be attached. Also needed is a way for users of secure information to easily and voluntarily blend—and thereby propagate—security controls as information is transformed. Information mediators designed by collaborative teams of experts are proposed as the vehicle for wrapping information, so that at each step of reuse, high‐level views and their corresponding integrity controls can be made easily accessible to trusted users who will then be able to ensure their proper maintenance. Copyright © 2004 John Wiley & Sons, Ltd.
Parallel operation of CartaBlanca on shared and distributed memory computers
Authors: Padial‐Collins N. T. , VanderHeyden W. B. , Zhang D. Z. , Dendy E. D. , Livescu D.
Published: December 2003

We describe the parallel performance of the pure Java CartaBlanca code on heat transfer and multiphase fluid flow problems. CartaBlanca is designed for parallel computations on partitioned unstructured meshes. It uses Java's thread facility to manage computations on each of the mesh partitions. Inter‐partition communications are handled by two compact objects for node‐by‐node communication along partition boundaries and for global reduction calculations across the entire mesh. For distributed calculations, the JavaParty package from the University of Karlsruhe is demonstrated to work with CartaBlanca. Copyright © 2004 John Wiley & Sons, Ltd.
Investigation of the Crystallization Stages of LTA‐Type Zeolite by Complementary Characterization Techniques
Authors: Smaihi Monique , Barida Olivier , Valtchev Valentin
Published: December 2003

This paper reports on the physicochemical reorganizations, at 40 °C, of a template‐free aluminosilicate system yielding an LTA‐type zeolite. The events that take place in the system during the transformations of the amorphous material into a crystalline material were monitored by various characterization techniques which provide information from the molecular to the micrometer scale. High‐resolution solid‐state 29Si and 27Al MAS NMR spectroscopy, small‐angle X‐ray scattering (SAXS), X‐ray diffraction (XRD), and scanning electron microscopy (SEM) were used in order to achieve a better understanding of the structural properties of the precursor gel and its transformation into a crystalline zeolite‐type material. The experimental results show that the first crystallization stage proceeds by reorganization of the amorphous aluminosilicate units formed during the mixing of the precursors. This reorganization involves an ordering of the Si−O−Al bond angles and operates on aggregates of constant volume. The crystallization process takes place in the volume of the aggregates by propagation through the gel phase. This propagation through the gel continues to complete the transformation of the particles into crystalline zeolite Na‐A nanocrystals with a rough surface. After this stage, the growth in the system is dominated by the solution‐mediated transport, which leads to the formation of well‐shaped zeolite A crystals. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Thermal Stability and Absorption Spectroscopic Behavior of (μ‐Peroxo)dicopper Complexes Regulated with Intramolecular Hydrogen Bonding Interactions
Authors: Yamaguchi Syuhei , Wada Akira , Funahashi Yasuhiro , Nagatomo Shigenori , Kitagawa Teizo , Jitsukawa Koichiro , Masuda Hideki
Published: December 2003

In order to clarify the effect of hydrogen bonding on the stabilities of (μ‐peroxo)dicopper complexes with a trans‐μ‐1,2‐peroxo form, novel copper complexes with intramolecular hydrogen bonding interaction sites have been synthesized, and their spectroscopic properties and thermal stabilities studied. The selected tripodal tetradentate ligands were tris(2‐pyridylmethyl)amine (TPA) derivatives bearing pivalamido and amino groups at the 6‐position of the pyridine ring in TPA, {[6‐(pivalamido)pyrid‐2‐yl]methyl}bis(pyrid‐2‐ylmethyl)amine (MPPA) and [(6‐aminopyrid‐2‐yl)methyl]bis(pyrid‐2‐ylmethyl)amine (MAPA). The single‐crystal X‐ray structure of a monomeric CuII complex with N3− namely [Cu(mppa)N3]ClO4 (1a), revealed an interligand hydrogen bonding interaction between the substituent NH group of MPPA and the azide nitrogen atom in the axial position. The CuI complexes of MPPA and MAPA were immediately oxygenated with dioxygen in acetone solution at −78 °C to give the μ‐peroxo dinuclear copper(II) complexes [{Cu(mppa)}2(O2)]2+ (1b) and [{Cu(mapa)}2(O2)]2+ (2b). These complexes exhibited two kinds of characteristic absorption bands (π*σ⇄dσ, π*v⇄dσ) originating from the ligand−metal charge transfer (LMCT) of O22− to Cu. Affected by the hydrogen bonding interaction, the π*σ⇄dσ CT band shifted significantly to a higher energy region and the π*v⇄dσ CT absorbance decreased due to stabilization of the π*σ orbital and restriction of the Cu−O bond rotation. The thermal stabilities of the (μ‐peroxo)dicopper(II) complexes were estimated from their decomposition rates which decreased in the order, 2b ≈︁ [{Cu(tpa)}2(O2)]2+ (3b) > 1b >> [{Cu(6‐metpa)}2(O2)]2+ (4b) {6‐MeTPA = [(6‐methylpyrid‐2‐yl)methyl]bis(pyrid‐2‐ylmethyl)amine}. The above findings indicate that the interligand hydrogen bonding interaction, although overcome to some extent by the adverse effect of the steric bulk of the NH group, is inclined to stabilize (μ‐peroxo)dicopper(II) complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis and Reaction of MnII Iodides Bearing the β‐Diketiminate Ligand: the First Divalent Manganese N‐Heterocyclic Carbene Complexes [{HC(CMeNAr)2}MnI{C[N(iPr)CMe]2}] and [{HC(CMeNAr)2}MnNHAr{C[N(iPr)CMe]2}] (Ar = 2,6‐iPr2C6H3)
Authors: Chai Jianfang , Zhu Hongping , Most Kerstin , Roesky Herbert W. , Vidovic Denis , Schmidt Hans‐Georg , Noltemeyer Mathias
Published: December 2003

The manganese mono‐iodide [HC(CMeNAr)2]MnI(THF) (Ar = 2,6‐iPr2C6H3) (3) was prepared in good yield from the reaction of [HC(CMeNAr)2]K with MnI2 in THF. Treatment of 3 under reflux in toluene and removing all the volatiles in vacuo afforded the dimeric compound [{HC(CMeNAr)2}Mn]2(μ‐I)2 (4). Displacement of the coordinated THF in 3 by a strong Lewis base C[N(iPr)CMe]2 or by adding C[N(iPr)CMe]2 to the toluene solution of 4 readily gave the N‐heterocyclic carbene adduct [{HC(CMeNAr)2}]MnI{C[N(iPr)CMe]2} (5). Reduction of 5 with sodium/potassium alloy at room temperature unexpectedly resulted in the formation of the monomeric compound [{HC(CMeNAr)2}]MnNHAr{C[N(iPr)CMe]2} (6). Alternatively 6 was obtained by the salt elimination reaction of 5 with LiNHAr. Compounds 5 and 6 are the first examples of divalent manganese N‐heterocyclic carbene adducts and the first manganese non‐carbonyl carbene complexes. The single crystal X‐ray structural analyses reveal that compounds 3 and 6 are monomeric and compound 4 is dimeric in the solid state. The manganese centers in these compounds exhibit a distorted tetrahedral geometry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
η1‐Vinylidene to η2‐Alkyne Isomerization of Tungsten and Molybdenum Complexes
Authors: Ipaktschi Junes , Mohsseni‐Ala Javad , Uhlig Sascha
Published: December 2003

The thermal isomerizations of η1‐vinylidene complexes [(η5‐C5H5)(CO)(NO)W=C=CHR] [5a, R = Si(CH3)2C(CH3)3; 5c, R = C(CH3)3] as well as [(η5‐C5H5)(CO)(NO)Mo=C=CHC(CH3)3] (8), to the corresponding η2‐1‐alkyne complexes [(η5‐C5H5)(CO)(NO)W(η2‐H−C≡C−R)] [7a, R = Si(CH3)2C(CH3)3; 7c, R = C(CH3)3] and [(η5‐C5H5)(CO)(NO)Mo{η2‐H−C≡C−CHC(CH3)3}] (9) has been investigated. Activation parameters for the isomerization of 5a in [D6]benzene and 8 in [D8]toluene and [D5]ethanol were determined. In [D8]toluene η1‐vinylidene complex 5a undergoes a single step 1,2‐shift of the silyl group from Cβ to Cα. However, complex 8 shows dichotomous behavior. The isomerization 8 ⇄ 9, dependent upon the solvent applied, occurs by means of two different pathways: in a nonpolar solvent, 8 tautomerizes via the 1,2‐migration of the hydrogen atom to 9 and in ethanol this tautomerization proceeds by a multi‐step process via deprotonation‐protonation and subsequent reductive elimination. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Structure, and Biological Activity of New Azine‐Bridged Dinuclear Platinum(II) Complexes − a New Class of Anticancer Compounds
Authors: Kalayda Ganna V. , Komeda Seiji , Ikeda Kyoko , Sato Takaji , Chikuma Masahiko , Reedijk Jan
Published: December 2003

A recently described new class of dinuclear platinum anticancer compounds, represented so far by the isomeric azine‐bridged complexes [{cis‐Pt(NH3)2Cl}2(µ‐pzn)]Cl2 (1) (pzn = pyrazine), [{cis‐Pt(NH3)2Cl}2(µ‐pmn)]Cl2 (2) (pmn = pyrimidine) and [{cis‐Pt(NH3)2Cl}2(µ‐pdn)](NO3)2 (3) (pdn = pyridazine), has been added to. Three new dinuclear complexes of this type, [{cis‐Pt(NH3)2Cl}2(µ‐2,5pzn)]Cl2 (4) (2,5pzn = 2,5‐dimethylpyrazine), [{cis‐Pt(NH3)2Cl}2(µ‐qzn)]Cl2 (5) (qzn = quinazoline), and [{cis‐Pt(NH3)2Cl}2(µ‐pht)](NO3)2 (6) (pht = phthalazine), have been newly synthesized and characterized by 1H and 195Pt NMR spectroscopy. The interaction of the new compounds with 2 equiv. of 9EtG in D2O at 310 K has been investigated. Complexes 4 and 5 undergo substitution of both chloride ligands by 9EtG similarly to the related complexes 1 and 2, respectively. The methyl substituents on the pyrazine ring induce steric hindrance in 4 resulting in a slower reaction rate as compared to 1. Similarly to the case of 3, interaction of complex 6 with 9EtG results in cleavage of the Pt−N(pht) bond and subsequent formation of the polymeric species. A cytotoxicity assay of 4−6 has been performed on seven human tumor cell lines and on L1210 murine leukemia cell lines, sensitive and resistant to cisplatin. Compounds 4 and 5 exhibit lower cytotoxicity than the analogous complexes with unsubstituted azines. Complex 6 is more active: its cytotoxicity in the L1210 cell lines is similar to that of cisplatin. Analysis of nuclear DNA fragmentation in L1210 cells treated with the azine‐bridged complexes 1−6 has been carried out. The results clearly indicate induction of apoptosis by all the compounds, implying considerable anticancer potential. The structure‐activity relationship for this class of dinuclear platinum(II) complexes is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Non‐Oxo Vanadium(IV) Complexes of Aminebis(phenolate) [O,N,O] Donor Ligands and Solution Studies of Isostructural VIV and MnIV Complexes
Authors: Paine Tapan K. , Weyhermüller Thomas , Bill Eckhard , Bothe Eberhard , Chaudhuri Phalguni
Published: December 2003

Mononuclear non‐oxo vanadium(IV) complexes, [VIVLMe2] (1) and [VIVLtBu2] (2), with a tridentate bis(phenol) ligand H2L bearing the O2N donor atoms and with either dimethyl or di‐tert‐butyl substituents have been synthesized and the X‐ray structures of 1 and 2 are reported. Additionally, 3, an MnIV complex [MnIVLMe2], and 4, the anion containing the MnIII center [MnIIILMe2]−, are discussed. The X‐ray structure of 4 present as an anion in 4a, [(Me3tacn)2MnII2(μ‐OOCCH3)3][MnIIILMe2], where Me3tacn = 1,4,7‐trimethyl‐1,4,7‐triazacyclononane, confirms the magnetic susceptibility results of the high‐spin d4 nature of the manganese center in 4. The compounds were characterized by elemental analysis, IR, UV/Vis, mass spectrometry, EPR spectroscopy, electrochemical and variable‐temperature (2−295 K) magnetic susceptibility measurements. The electrochemical results of 1 and 2 suggest the metal‐centered oxidation, i.e. the generation of a VV−phenolate species, prior to the second oxidation attributable to the formation of a VV−phenoxyl radical species. Isomerization of the meridional form for the bis(ligand)metal species to the facial form has been observed for 1 and 3 in solution. The EPR spectroscopic data of 1 and 2 clearly show a considerable increase in the in‐plane π bonding, as is expected for a phenolate ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
High Molecular Weight Phosphazene Copolymers Having Chemical Functions Inside Chiral Pockets Formed by (R)‐(1,1′‐Binaphthyl‐2,2′‐dioxy)phosphazene Units
Authors: Carriedo Gabino A. , García Alonso Francisco J. , Presa‐Soto Alejandro
Published: December 2003

The polyphosphazene {[NPCl2]x[NP(O2C20H12)]1−x}n (O2C20H12 = 1,1′‐binaphthyl‐2,2′‐dioxy) reacted in refluxing THF in the presence of Cs2CO3 with HOC5H4N or para‐substituted phenols HOC6H4R to give the random copolymers {[NP(OC5H4N)2]x[NP(O2C20H12)]1−x}n (1) or {[NP(OC6H4R)2]x[NP(O2C20H12)]1−x}n [R = CN (2), COMe (3), CO2nPr (4), PPh2 (5)] and with H2NnBu to give {[NP(NHnBu)2]x[NP(O2C20H12)]1−x}n (6). The reaction of the polymer {[NPCl2]x[NP(O2C20H10Br2)]1−x}n (O2C20H10Br2 = 6,6′‐dibromo‐1,1′‐binaphthyl‐2,2′‐dioxy) with HOC6H4PPh2 and Cs2CO3 gave {[NP(OC6H4PPh2)2]x[NP(O2C20H10Br2)]1−x}n (7). Those polymers have a very high glass‐transition temperature (Tg) and a chemical function or ligand that is in the interior of a chiral pocket. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
New Diphosphane Ligands Based on Bisphenol A Backbones − Synthesis and Coordination Chemistry
Authors: van der Vlugt Jarl Ivar , Grutters Michiel M. P. , Mills Allison M. , Kooijman Huub , Spek Anthony L. , Vogt Dieter
Published: December 2003

A series of easily accessible diphosphane compounds 1−4, based on bisphenol A derived backbones, has been prepared. A straightforward two‐step synthetic route has been employed to obtain these new ligands in good yields from cheap starting materials. Molecular structures for both compound 2 and its oxidized form (5·H2O) have been determined and are discussed in detail. The coordination of ligand 2 to palladium, platinum, and rhodium precursors has been studied by NMR spectroscopy as well as X‐ray crystallography. The molecular structures of the face‐to‐face dimeric species [{PdCl(CH3)(2)}2] (6), [{PtCl2(2)}2] (7), and [{RhCl(CO)(2)}2] (8) are described in detail. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The First Chemical Achievements and Publications by Justus von Liebig (1803−1873) on Metal Fulminates and Some Further Developments in Metal Fulminates and Related Areas of Chemistry
Authors: Beck Wolfgang
Published: December 2003

The first chemical investigations and publications by Justus von Liebig dealt with the fulminates of silver and mercury. Even as a boy Liebig had learnt how to prepare silver fulminate, and as student of chemistry in Erlangen (1821) he studied the properties and reactions of silver fulminate. In Paris in 1823 (together with Gay‐Lussac) he succeeded in analyzing quantitatively the highly explosive silver compound. This great experimental success with the dangerous silver fulminate was most important in three respects: i. The development of the experimental method later culminated in Liebig’s perfected and well‐known C,H,N analysis of organic compounds (1830). ii. It led to the concept of isomerism when F. Wöhler found that silver cyanate had the same composition as silver fulminate. iii. It was decisive for furthering the scientific career of Liebig, since Alexander von Humboldt was highly impressed by the great skill and talent of Liebig and — by recommendation of Humboldt — Liebig became Professor in Gießen in 1824 (at the young age of 21). The first (fulminato)metal complex, K[Ag(CNO)2], was also isolated by Liebig. Later, explosive (fulminato)metal complexes were prepared by Nef, Wieland, and especially by Lothar Wöhler and co‐workers. In Munich the HCNO structure of fulminic acid was established by its IR spectrum and the spectroscopic properties of (fulminato)metal complexes were studied. A series of new nonexplosive complexes could be obtained by dilution of the energy‐rich species with large cations or ligands. Recent X‐ray structure determinations have revealed the almost perfect linear, tetrahedral, square‐planar, or octahedral structures of these complexes with linear metal−C≡NO bonds, e.g. [Au(CNO)2]−, [Zn(CNO)4]2−, [Ni(CNO)4]2−, [Co(CNO)6]3−. DFT calculations have given very good agreement between the calculated and experimental structural parameters and CNO stretching frequencies. The (fulminato)metal complexes closely resemble the analogous cyano compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The Metastable, Glasslike Solid‐State Phase of HAlO and Its Transformation to Al/Al2O3 Using a CO2 Laser
Authors: Veith Michael , Andres Kathrin , Stefan Faber  , Blin Joel , Zimmer Michael , Wolf Yan , Schnöckel Hansgeorg , Köppe Ralf , de Masi Remo , Hüfner Stefan
Published: December 2003

Bis(tert‐butoxyaluminum dihydride) (tBuOAlH2)2 decomposes on metal surfaces heated to 250 °C (Fe, Ni, Cu, Pt) and under reduced pressures of 0.01−0.1 atm with elimination of dihydrogen and isobutene to form a glasslike, amorphous film, which is composed of equimolar parts of hydrogen, aluminum and oxygen (elemental analysis, EDX analysis). The gases eliminated during this process were characterized by mass spectroscopy (H2, isobutene) or by infrared matrix techniques (isobutene). The exclusive binding of hydrogen to aluminum is deduced from IR spectroscopy of the HAlO film and of its deuterated form DAlO. The HAlO layer (which shows no X‐ray diffraction pattern), when heated to 450 °C or when exposed to a CO2 laser, loses hydrogen and transforms to an almost stoichiometric composite with nanoscale crystalline aluminum and aluminum oxide (Al/Al2O3) as ingredients. This transformation may be followed by IR spectroscopy, by 27Al MAS NMR or by XPS, the latter showing different signals (Al, 2p electrons, Mg‐Kα, θ = 0°) for HAlO (74.2 eV) and for the composite (Al: 72.1 eV, Al2O3: 75.3 eV). Microstructures that are characterized by different chemical compositions and different optical contrasts of the “drawing”, relative to the surrounding matrix, may be generated with an X/Y‐table and a CO2 laser. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Stoichiometric Control of the Magnetic Properties in Copper(II) Cyano‐Bridged Bimetallic Complexes
Authors: Coronado Eugenio , Giménez‐Saiz Carlos , Nuez Alicia , Sánchez Víctor , Romero Francisco M.
Published: December 2003

Control of the Cu2+ ion coordination environment affords a 1D, magnetically diluted compound, [Cu(cis‐chxn)2]3[Fe(CN)6]2·7H2O (1) and the 2D ferromagnetic material [Cu(cis‐chxn)]3[Fe(CN)6]2·6H2O (2) with a critical temperature, Tc, of 3.5 K. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Structure and Magnetic Properties of a New Iron Arsenate, [C10N4H28][{FeF(OH)(HAsO4)}4], with a Layer Structure
Authors: Chakrabarti Sandip , Pati Swapan K. , Green Mark A. , Natarajan Srinivasan
Published: December 2003

The reaction of FeCl3·6H2O, H3AsO4, HF and 1,4‐bis(3‐aminopropyl)piperazine under solvothermal conditions gives rise to a new iron arsenate, [C10N4H28][{FeF(OH)(HAsO4)}4] (I) with a layered structure. The cell parameters are monoclinic, space group = P21/n (no.14), M = 1143.08, a = 9.6320(3), b = 8.3598(3), c = 10.7794(1) Å, β = 115.036(1)°, V = 786.42(4) Å3, Z = 4, R1 = 0.0492, wR2 = 0.1227 [1114 observed reflections with I > 2σ(I)]. The connectivity between FeO3F2(OH) octahedra and HAsO4 tetrahedra forms a secondary building unit (SBU) of the type SBU‐4. The SBU‐4 units are linked together to form a layer structure with apertures formed by 8‐T atoms (T = Fe, As). The amine molecules are disordered and occupy the inter‐lamellar region. To the best of our knowledge, I is the first example of an iron arsenate structure formed from only one type of secondary building unit, SBU‐4. A dimer model has been used to describe the magnetic behavior. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Theoretical Gas‐Phase Stabilities of α‐Trimethylsilyl‐Substituted Tertiary Carbenium Ions
Authors: Grunenberg Jörg , Laschat Sabine , Dickner Tim
Published: December 2003

Theoretical hydride ion affinities in the gas phase are presented for α‐SiMe3‐substituted tertiary carbenium ions. Thermodynamic stabilization of the ”nascent“ ions by a single trimethylsilyl group is weaker than by atert‐butyl group but comparable to the effect of a methyl group. In the case of the cyclopropenylium cation, the stabilization by a trimethylsilyl group even exceeds the effectiveness of atert‐butyl group. Compliance constants are used to quantify the chemical concept of hyperconjugation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Expanding the Field of Phosphorus‐Containing Fatty Acid Derivatives: Synthesis of 1,2‐Oxaphospholene Derivatives and Alkenyl Phosphonates from α‐Keto Allenes
Authors: Fürmeier Sandra , Lau Maureen M. L. , Lie Ken Jie Marcel S. F. , Lützen Arne , Metzger Jürgen O.
Published: December 2003

The first successful preparation of phosphorus‐containing heterocyclic fatty acid derivatives is described. Reaction of the C18 α‐keto allene 1 and the C18 α‐keto chloroallene 2 with trimethyl phosphite gave the 1,2‐oxaphospholene derivatives 4 and 6, respectively. Hydrolysis of 4 and 6 furnished the corresponding alkenyl phosphonate 5 and alkenyl chlorophosphonate 7, respectively. α‐Chloro‐α′‐keto allene 3 gave the oxaphospholene derivative 8. The various intermediates and products were identified by a combination of spectroscopic and spectrometric techniques. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
New β,β‐Bis(benzo[b]thienyl)dehydroalanine Derivatives: Synthesis and Cyclization
Authors: Abreu Ana S. , Silva Natália O. , Ferreira Paula M. T. , Queiroz Maria‐João R. P. , Venanzi Mariano
Published: December 2003

The methyl ester of β,β‐dibromo‐N‐(tert‐butoxycarbonyl)dehydroalanine was synthesized by treating the methyl ester of N,N‐bis(tert‐butoxycarbonyl)dehydroalanine with trifluoroacetic acid, N‐bromosuccinimide and triethylamine. This compound was then used in Suzuki cross‐coupling reactions with several (benzo[b]thienyl)boronic acids to give the corresponding β,β‐bis(benzo[b]thienyl)dehydroalanine derivatives in good to high yields (55−90 %). After several experiments, the best conditions were shown to be: (benzo[b]thienyl)boronic acid (5 equiv.), [Pd(PPh)2Cl2] (20 mol %), Na2CO3 (4 equiv.) in DME/H2O (10:1). The Suzuki cross‐coupling products were treated with Pd(OAc)2 and Cu(OAc)2 in DMF at 160 °C to give the (benzo[b]thienyl)pyrroles in moderate to good yields (25−62 %). Other attempts were carried out using only Cu(OAc)2, the thienylpyrroles being, in some cases, isolated in lower yields. Preliminary fluorescence studies show that the (benzo[b]thienyl)pyrroles can be used as biomarkers. All of these compounds are non‐proteinogenic amino acids that can have biological activity or can be used in conformational studies in order to establish structure‐activity relationships. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Catalytic Asymmetric Hydroboration: Recent Advances and Applications in Carbon−Carbon Bond‐Forming Reactions
Authors: Crudden Cathleen M. , Edwards David
Published: December 2003

The metal‐catalyzed hydroboration reaction provides access to functionalized organoboron derivatives that cannot be easily prepared using traditional reagents. New developments in this reaction including neoteric reaction media and novel ligands are described in this review. A key aspect of the hydroboration reaction is the ability to further derivatize the product. Thus the conversion of boronate esters into amines, esters, alcohols, carboxylic acids and amino acids is described. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Adenylate Deaminase (5′‐Adenylic Acid Deaminase, AMPDA)‐Catalyzed Deamination of 5′‐Deoxy‐5′‐Substituted and 5′‐Protected Adenosines: A Comparison with the Catalytic Activity of Adenosine Deaminase (ADA)
Authors: Ciuffreda Pierangela , Loseto Angela , Alessandrini Laura , Terraneo Giancarlo , Santaniello Enzo
Published: December 2003

The enzyme adenylate deaminase (AMPDA) is able to catalyze the hydrolytic deamination of 5′‐substituted and 5′‐protected 5′‐deoxyadenosines, whereas limited or no activity is shown by adenosine deaminase (ADA) towards the same substrates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Cerium‐Catalyzed Reaction of β‐Dicarbonyl Compounds with Styrene and Atmospheric Oxygen
Authors: Christoffers Jens , Werner Thomas , Frey Wolfgang , Baro Angelika
Published: December 2003

The cerium‐catalyzed C−C coupling reaction of carbo‐ and heterocyclic β‐dicarbonyl compounds 1 with styrenes 4, using oxygen (air) as the oxidant, at ambient temperature, is reported. The reaction afforded a mixture of diastereoisomeric hydroperoxides 5 which could be transformed into the unique dioxo compounds 6 by disproportionation of the peroxo function under treatment with acetyl chloride/pyridine. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Sustainable Epoxidation of Electron‐Poor Olefins with Hydrogen Peroxide in Ionic Liquids and Recovery of the Products with Supercritical CO2
Authors: Bortolini Olga , Campestrini Sandro , Conte Valeria , Fantin Giancarlo , Fogagnolo Marco , Maietti Silvia
Published: December 2003

An efficient procedure is described for the epoxidation of electron‐deficient olefins, in particular Vitamin K3 and analogues, with aqueous basic solutions of hydrogen peroxide in different ambient temperature ionic liquids (ILs) [bmim+][X−] {[bmim+] = 1‐butyl‐3‐methylimidazolium; [X−] = [BF4−], [CF3SO3−], [PF6−], [N(CF3SO2)2−]}. Various factors affecting epoxide yield (in the range 80−99%), reaction rate and reproducibility have been examined. The almost quantitative extraction of the epoxides from the reaction media has been obtained with supercritical CO2. The ionic liquid was then recovered and reused in subsequent cycles. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Mono‐N‐glycosidation of β‐Cyclodextrin − Synthesis of 6‐(β‐Cyclodextrinylamino)‐6‐deoxy‐D‐galactosides and of N‐(6‐Deoxy‐β‐cyclodextrinyl)galacto‐azepane
Authors: Bonnet Véronique , Duval Raphaël , Tran Vinh , Rabiller Claude
Published: December 2003

An easy route to 6‐oxogalactose and to 6‐oxogalactosides through an oxidation reaction mediated by galactose oxidase allowed the N‐glycosidation of 6‐amino‐6‐deoxy‐β‐cyclodextrin by reductive amination in the presence of NaBH3CN in DMSO. When methyl α‐D‐ and p‐nitrophenyl α‐ and β‐D‐galacto‐hexodialdo‐1,5‐pyranosides (1, 2 and 3, respectively) were used as substrates, 6‐(β‐cyclodextrinylamino)‐6‐deoxy‐D‐galactopyranosides were obtained in 25−50% yields. The same was true in the cases of 6II‐oxolactose 4 and of 6II‐oxomelibiose 5, for which the anomeric carbon was shown to be unreactive in complexation with DMSO. This reaction was also successfully applied in water with an oxidized polygalactomannan 6. The behaviour of galacto‐hexodialdo‐1,5‐pyranose 7 was different, since further intramolecular cyclisation and reduction resulted in a N‐(6‐deoxy‐β‐cyclodextrinyl)‐galacto‐azepane in good yield. Molecular modelling was also used to explain the course of this reaction. Calculations indicated that the formation of the cis D‐form of the intermediate N‐β‐CD imine of 7 was strongly preferred. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Supramolecular Complex Formation: A Study of the Interactions between β‐Cyclodextrin and Some Different Classes of Organic Compounds by ESI‐MS, Surface Tension Measurements, and UV/Vis and 1H NMR Spectroscopy
Authors: Guernelli Susanna , Laganà Maria Francesca , Mezzina Elisabetta , Ferroni Fiammetta , Siani Gabriella , Spinelli Domenico
Published: December 2003

The ability of several organic compounds [alcohols 1 and 2, the corresponding phosphate esters 3 and 4 and their sodium salts 5 and 6 as well as some commercial surfactants such as C14DMAO (7, zwitterionic), SDS (8, anionic) and CTABr (9, cationic)] to produce supramolecular complexes with β‐cyclodextrin has been investigated by four different techniques (ESI‐MS, surface tension measurements, UV/Vis and 1H NMR spectroscopy). The data collected have allowed information about the formation of complexes and the location of the guest in the host to be gained. Comparison of the results obtained for phosphate esters and their salts, for both saturated and unsaturated derivatives, has made it possible to evaluate the factors that affect the stability of the supramolecular complexes under the different experimental conditions used. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Hydrolysis of the Phosphonamidate Bond in Phosphono Dipeptide Analogues — the Influence of the Nature of the N‐Terminal Functional Group
Authors: Mucha Artur , Grembecka Jolanta , Cierpicki Tomasz , Kafarski Paweł
Published: December 2003

Phosphonamidate pseudodipeptides, designed as transition state analogue inhibitors of leucine aminopeptidase, revealed unexpected instability in aqueous solutions of pH values varying from acidic up to highly basic. This reaction has been studied in some detail by means of NMR spectroscopy and it was found that the phosphonamidate stability depended strongly on the solution pH, relying on the protonation state of two crucial functional groups of the molecule — the phosphonamidate and amino moieties. Protonation of the free N‐terminal amino moiety is required for the occurrence of rapid P−N bond decomposition; N‐protected derivatives are significantly more stable. The mechanisms of the cleavage of the phosphonamidate bond have been proposed and discussed. The observed instability of unblocked P−N peptides may be the cause of the substantial limitations of their practical application as aminopeptidase inhibitors. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Topochemical [2+2] Dimerization of Kinetically Stabilized 1‐Phosphaallenes in the Solid State
Authors: Ito Shigekazu , Sekiguchi Satoshi , Yoshifuji Masaaki
Published: December 2003

The thermolysis of two bulky 1‐phosphaallenes in the solid state afforded diphosphanylidenecyclobutane or 2,4‐dimethylene‐1,3‐diphosphacyclobutane. The regioselectivity of the [2+2] dimerization depends largely on the crystal structure of the 1‐phosphaallenes, and the reaction path seems to be affected by the presence of bulky 2,4,6‐tri‐tert‐butylphenyl (Mes*) group. This topochemical reaction was also controlled by the substituents at the 3‐position of the 1‐phosphaallene skeleton. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Developing Molecular Diversity in the Construction of a Family of Bicyclic Isoxazolines Scaffolds: Control of Regio‐and Diastereoselectivities
Authors: Giorgi Gianluca , Lampariello L. Raffaella , Minetto Giacomo , Paoli M. Laura , Riello Vincenzo , Rodriquez Manuela , Sega Alessandro
Published: December 2003

A completely regioselective approach to bicyclic isoxazolines has been found starting from 4‐cyclopentene‐1,3‐dione or 2‐cyclopentenones. 1,3‐Dipolar cycloaddition with nitrile oxides gave different semirigid bicyclic scaffolds with at least four points of elaboration for molecular diversity. From these intermediates, two families of regioisomer isoxazolines can be prepared with complete control of their relative stereochemistry. Further elaboration of functional groups was demonstrated in order to exploit a successive parallel preparation of arrays of compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)