bluuebunny/crossref_metadata_2025 huggingface dataset:
Focused motor stereotypies do not require enhanced activation of neurons in striosomes
Authors: Glickstein Sara B. , Schmauss Claudia
Published: December 2003

Stereotypic motor behavior is a widespread phenomenon of many neurologic and psychiatric disorders. Studies on the mechanisms controlling motor stereotypies have focused on the role of dopamine in modulating the activity of basal ganglia neuronal circuits, and recent results demonstrated that stereotypic motor responses characteristic of psychomotor stimulant sensitization correlate with an enhanced activation of neurons located in striatal striosomes that substantially exceeds that of the surrounding matrix. The present study tested whether predominant striosomal activation is a general predictor for stereotypy. Wild‐type and dopamine D2 and D3 receptor knockout mice were treated either three times with methamphetamine (METH; 3 × 5 mg/kg every 2 hours) or once with a full D1 agonist. Depending on the genotype, both treatments elicit the same focused stereotypy (taffy pulling). Repeated METH‐treatment elicits intense stereotypy in wild‐type and D3 mutants but not in D2 single and D2/D3 double mutants. The stereotypic response of wild‐type and D3 mutants correlates with a predominant activation of neurons located in striosomes. No striosomal predominance is detected in METH‐treated D2 single and D2/D3 double mutants. In contrast, D2 single and D2/D3 double mutants exhibited the most severe stereotypic response to D1‐agonist treatment. However, this treatment did not result in enhanced striosomal activation. Thus, whereas the expression of stereotypy in response to repeated METH treatment requires D2 receptor expression, D2 receptor expression diminishes stereotypic responses to an acute dose of a D1 agonist. Enhanced striosomal activation, however, is a reliable indicator of D1‐ and D2‐receptor coactivation but not a predictor for repetitive motor behavior in general. J. Comp. Neurol. 469:227–238, 2004. © 2003 Wiley‐Liss, Inc.
Actions of a histaminergic/peptidergic projection neuron on rhythmic motor patterns in the stomatogastric nervous system of the crab Cancer borealis
Authors: Christie Andrew E. , Stein Wolfgang , Quinlan John E. , Beenhakker Mark P. , Marder Eve , Nusbaum Michael P.
Published: December 2003

Histamine is a neurotransmitter with actions throughout the nervous system of vertebrates and invertebrates. Nevertheless, the actions of only a few identified histamine‐containing neurons have been characterized. Here, we present the actions of a histaminergic projection neuron on the rhythmically active pyloric and gastric mill circuits within the stomatogastric ganglion (STG) of the crab Cancer borealis. An antiserum generated against histamine labeled profiles throughout the C. borealis stomatogastric nervous system. Labeling occurred in several somata and neuropil within the paired commissural ganglia as well as in neuropil within the STG and at the junction of the superior oesophageal and stomatogastric nerves. The source of all histamine‐like immunolabeling in the STG neuropil was one pair of neuronal somata, the previously identified inferior ventricular (IV) neurons, located in the supraoesophageal ganglion. These neurons also exhibited FLRFamide‐like immunoreactivity. Activation of the IV neurons in the crab inhibited some pyloric and gastric mill neurons and, with inputs from the commissural ganglia eliminated, terminated both rhythms. Focal application of histamine had comparable effects. The actions of both applied histamine and IV neuron stimulation were blocked, reversibly, by the histamine type‐2 receptor antagonist cimetidine. With the commissural ganglia connected to the STG, IV neuron stimulation elicited a longer‐latency activation of commissural projection neurons which in turn modified the pyloric rhythm and activated the gastric mill rhythm. These results support the hypothesis that the histaminergic/peptidergic IV neurons are projection neurons with direct and indirect actions on the STG circuits of the crab C. borealis. J. Comp. Neurol. 469:153–169, 2004. © 2003 Wiley‐Liss, Inc.
GABAergic projection from the ventral tegmental area and substantia nigra to the periaqueductal gray region and the dorsal raphe nucleus
Authors: Kirouac Gilbert J. , Li Sa , Mabrouk Gehan
Published: December 2003

Previous studies have shown that neurons in the ventral tegmental area (VTA) and substantia nigra (SN) project to the ventrolateral periaqueductal gray (PAGvl) and dorsal raphe nucleus (DR). Research has also shown that stimulation of neurons in the VTA/SN elicits cardiovascular depressor responses that are mediated by a projection to the PAGvl/DR. Anatomic and physiological experiments were done in the present study to determine the neurochemical identity of the VTA/SN projection to the PAGvl/DR. Experiments were done to characterize the origin and chemical nature of this projection by combining cholera toxin B tracing with immunofluorescence for the 67K isoform of glutamic acid decarboxylase (GAD) and tyrosine hydroxylase. The PAGvl/DR region was found to receive a substantial input from neurons in the VTA, SN, and deep mesencephalic nucleus. The DR was preferentially innervated by neurons in the VTA, whereas the PAGvl was preferentially innervated by neurons in the SN. A proportion of neurons in the VTA and the reticular portion of the SN found to project to the PAGvl/DR were GAD positive. In addition, experiments were done in urethane‐anesthetized rats to determine whether injections of a γ‐aminobutyric acid (GABA) antagonist in the region of the PAGvl/DR attenuated the cardiovascular depressor responses produced by glutamate stimulation of the VTA/SN. Injections of the GABA‐blocking agent picrotoxin (2.5 nmol, 500 nl) into the PAGvl/DR eliminated the cardiovascular responses from stimulation of the VTA/SN (0.01 M, 50 nl). The results of the present investigation provide evidence for a GABAergic projection from the VTA/SN to the PAGvl/DR. This projection may be an important regulator of the PAGvl/DR, an area of the midbrain involved in the production of behavioral and physiological responses to pain and stress. J. Comp. Neurol. 469:170–184, 2004. © 2003 Wiley‐Liss, Inc.
Morphology and connections of nucleus isthmi pars magnocellularis in chicks (Gallus gallus)
Authors: Wang Yuan , Major Daniel E. , Karten Harvey J.
Published: December 2003

The nucleus isthmi pars magnocellularis (Imc) and pars parvocellularis (Ipc) influence the receptive field structure of neurons in the optic tectum (TeO). To understand better the anatomical substrate of isthmotectal interactions, neuronal morphology and connections of Imc were examined in chicks (Gallus gallus). Cholera toxin B injection into TeO demonstrated a coarse topographical projection from TeO upon Imc. Retrogradely labeled neurons were scattered throughout Imc and in low density within the zone of anterogradely labeled terminals, suggesting a heterotopic projection from Imc upon TeO. This organization differed from the precise homotopic reciprocal connections of Ipc and the nucleus isthmi pars semilunaris (SLu) with TeO. By using slice preparations, extracellular biotinylated dextran amine injections demonstrated a dense projection from most neurons in Imc upon both Ipc and SLu. Intracellular filling of Imc neurons with biocytin revealed two cell types. The most common, Imc‐Is, formed a widely ramifying axonal field in both Ipc and SLu, without obvious topography. A less frequently observed cell type, Imc‐Te, formed a widely ramifying terminal field in layers 10–12 of TeO. No neurons were found to project upon both Ipc/SLu and TeO. Both types possessed local axon collaterals and flat dendritic fields oriented parallel to the long axis of Imc. Imc neurons contain glutamic acid decarboxylase, which is consistent with Imc participating in center‐surround or other wide‐field inhibitory isthmotectal interactions. The laminar and columnar pattern of isthmotectal terminals also suggests a means of interacting with multiple tectofugal pathways, including the stratified subpopulations of tectorotundal neurons participating in motion detection. J. Comp. Neurol. 469:275–297, 2004. © 2003 Wiley‐Liss, Inc.
Up‐regulation of phosphorylated CREB but not c‐Jun in bladder afferent neurons in dorsal root ganglia after cystitis
Authors: Qiao Li‐Ya , Vizzard Margaret A.
Published: December 2003

We examined the changes of two transcription factors, CREB and c‐Jun, in dorsal root ganglia (DRG) after acute (8 or 48 hours) or chronic (10 days) cyclophosphamide (CYP)‐induced cystitis. Results showed an increase in the number of p‐CREB‐immunoreactive (‐IR) cells in the L1 and L2 DRG (5–7‐fold; P ≤ 0.05) as well as L6 and S1 DRG (2–4‐fold; P ≤ 0.05) after acute and chronic cystitis. The number of p‐CREB‐IR cells in the L4–L5 DRG was not altered with cystitis. The number of c‐Jun‐IR cells increased in the L1–L2 DRG (L1: 10‐fold; L2: 8‐fold; P ≤ 0.05) only with chronic cystitis, although it increased in the L6–S1 DRG with CYP‐induced cystitis of acute (2–3‐fold; P ≤ 0.05) and chronic (6–10‐fold; P ≤ 0.05) duration. After CYP treatment, the percentage of bladder afferent cells expressing p‐CREB immunoreactivity (3–7‐fold; P ≤ 0.05) increased in L1, L2, L6, and S1 DRG. The increase occurred 8 hours post‐CYP injection and was maintained with chronic cystitis. There were few c‐Jun‐IR cells in the bladder afferent population. These results demonstrate that CYP induces p‐CREB and c‐Jun expression in DRG in a time‐dependent manner. However, c‐Jun expression is not associated with bladder afferent neurons. Resiniferatoxin reduced CYP‐induced up‐regulation of p‐CREB in DRG, suggesting that cystitis can reveal an altered CREB phosphorylation that may be mediated by capsaicin‐sensitive bladder afferents. Colocalization of p‐CREB and Trk receptor(s) showed that a subpopulation of p‐CREB‐IR cells expressed p‐Trk with cystitis. These results suggest that up‐regulation of p‐CREB may be mediated by a neurotrophin/Trk signaling pathway. J. Comp. Neurol. 469:262–274, 2004. © 2003 Wiley‐Liss, Inc.
An immunohistochemical and pathway tracing study of the striatopallidal organization of area X in the male zebra finch
Authors: Reiner Anton , Laverghetta Antonio V. , Meade Christopher A. , Cuthbertson Sherry L. , Bottjer Sarah W.
Published: December 2003

Area X is a nucleus within songbird basal ganglia that is part of the anterior forebrain song learning circuit. It receives cortical song‐related input and projects to the dorsolateral medial nucleus of thalamus (DLM). We carried out single‐ and double‐labeled immunohistochemical and pathway tracing studies in male zebra finch to characterize the cellular organization and circuitry of area X. We found that 5.4% of area X neuronal perikarya are relatively large, possess aspiny dendrites, and are rich in the pallidal neuron/striatal interneuron marker Lys8‐Asn9‐neurotensin8–13 (LANT6). Many of these perikarya were found to project to the DLM, and their traits suggest that they are pallidal. Area X also contained several neuron types characteristic of the striatum, including interneurons co‐containing LANT6 and the striatal interneuron marker parvalbumin (2% of area X neurons), interneurons containing parvalbumin but not LANT6 (4.8%), cholinergic interneurons (1.4%), and neurons containing the striatal spiny projection neuron marker dopamine‐ and adenosine 3′,5′‐monophosphate‐regulated phosphoprotein (DARPP‐32) (30%). Area X was rich in substance P (SP)‐containing terminals, and many ended on area X neurons projecting to the DLM with the woolly fiber morphology characteristic of striatopallidal terminals. Although SP+ perikarya were not detected in area X, prior studies suggest it is likely that SP‐synthesizing neurons are present and the source of the SP+ input to area X neurons projecting to the DLM. Area X was poor in enkephalinergic fibers and perikarya. The present data support the premise that area X contains both striatal and pallidal neurons, with the striatal neurons likely to include SP+ neurons that project to the pallidal neurons. J. Comp. Neurol. 469:239–261, 2004. © 2003 Wiley‐Liss, Inc.
Cell proliferation in the lamprey central nervous system
Authors: Vidal Pizarro Ivonne , Swain Gary P. , Selzer Michael E.
Published: December 2003

After spinal cord transection, axons regenerate both in larval and adult lampreys. It is not known to what degree cells proliferate, even in the uninjured animal. Therefore, we have determined the prevalence of mitosis in the lamprey central nervous system (CNS). Bromodeoxyuridine (BrdU) was injected and incorporated for 4 hours into 2‐ to 5‐year‐old larvae, animals undergoing metamorphosis, and young adults. Labeled cells were counted in the rhombencephalon (where most supraspinal projecting neurons are located) and spinal cord. A mitotic index (MI) was calculated as the percentage of nuclei that were labeled. There was a seasonal variation in mitotic activity, with higher MIs occurring in summer. Within the summer, there was an additional transient spike in mitosis, especially in the rhombencephalon. There was no correlation between age and MI within the range of developmental stages examined. Baseline MIs in the rhombencephalon and spinal cord were approximately 0.15% and 0.20%, respectively. In most animals, the highest mitotic rates in both the rhombencephalon and spinal cord were seen in the ependyma, but many labeled cells were found in nonependymal regions as well. During the summer spike, almost all of the additional mitosis in the rhombencephalon was in the ependyma, but this finding was not true in the spinal cord. Many BrdU‐labeled cells in the spinal cord and rhombencephalon were also stained by monoclonal antibodies specific for lamprey glial keratin but were never labeled by anti‐neurofilament antibodies. These results suggest that (1) neurogenesis is uncommon in the lamprey CNS; (2) during most of the year, baseline gliogenesis occurs mainly in the ependyma with substantial contribution by nonependymal areas. During the summer, a spike of mitotic activity occurs in the ependyma of the rhombencephalon and throughout the spinal cord. J. Comp. Neurol. 469:298–310, 2004. © 2003 Wiley‐Liss, Inc.
Aberrant transcription of unrearranged T‐cell receptor β gene in mouse brain
Authors: Nishiyori Atsushi , Hanno Yoko , Saito Michiko , Yoshihara Yoshihiro
Published: December 2003

The nervous system and the immune system share several functional molecules involved in various cell–cell interaction events. In this study, we used in situ hybridization to identify immune molecules that are expressed by a restricted population of neurons in the mouse brain and found that mRNA for the β subunit of T‐cell receptor (TCRβ) was predominantly and strongly localized to neurons in deep layers of the cerebral neocortex and weakly expressed in the thalamus. Developmentally, TCRβ mRNA expression started at embryonic day 15 in the thalamic nuclei and at postnatal day 1 in the cerebral neocortex. The level of TCRβ mRNA in the neocortex subsequently increased until postnatal day 21, and it remained high in the adult. Detailed analysis revealed that only the Cβ2 segment of TCRβ, not the Cβ1 or Vβ segments, was expressed by the brain neurons. By the 5′ rapid amplification of cDNA ends method, we determined a brain‐specific transcription start site in the Jβ2 region locus, not in the Vβ region locus. Furthermore, we confirmed that the aberrant transcription around the Jβ2 region took place only in neurons and lymphocytes in transgenic mice. These results demonstrate that the transcriptional machinery for unrearranged TCRβ expression is shared by the nervous and immune systems and raise a possibility of gene rearrangement in neurons under certain circumstances. J. Comp. Neurol. 469:214–226, 2004. © 2003 Wiley‐Liss, Inc.
Bridging evidence‐based practice and practice‐based evidence: developing a rigorous and relevant knowledge for the psychological therapies
Authors: Barkham Michael , Mellor‐Clark John
Published: December 2003

Four key areas of research work are identified: efficacy, effectiveness, practice, and service system. These research areas are placed within the paradigms of evidence‐based practice and practice‐based evidence. This article provides an introduction to these two paradigms and these four research areas together with examples of current work. From this basis, we argue for a knowledge base for the psychological therapies in which each area has a place within an overall research model and in which the interdependence of each area on the others is acknowledged. A cyclical model exemplifying the complementary relationship between evidence‐based practice and practice‐based evidence is presented as a means for furthering the delivery of a rigorous but relevant knowledge base for the psychological therapies. Copyright © 2003 John Wiley & Sons, Ltd.
Clinical practice guidelines in clinical psychology and psychotherapy
Authors: Parry Glenys , Cape John , Pilling Steve
Published: December 2003

Evidence‐based clinical practice guidelines have proliferated over the past two decades. Few are limited to psychological therapies or are targeted at clinical psychologists and psychotherapists – the UK guideline Treatment Choice in Psychotherapy and Counselling is a major exception. However, psychological therapies will increasingly be considered alongside medical treatments in diagnosis‐specific guidelines. There has been interest and debate about the place of guidelines in the psychological therapies, with views ranging from scepticism to enthusiasm. This paper defines clinical practice guidelines, describes major guideline programmes internationally, examines guidelines of specific interest to psychologists and psychotherapists, explores issues in their implementation, reviews evidence for their effectiveness in changing practice and improving therapy outcomes and draws out implications for practice. Guidelines are only one aspect of informing psychologists and psychotherapists about best practice. They need to be supplemented by other clinical support methods and with methods of monitoring what is actually done in practice. Copyright © 2003 John Wiley & Sons, Ltd.
Longitudinal analysis when the experimenter does not determine when treatment ends: what is dose–response?
Authors: Feaster Daniel J. , Newman Frederick L. , Rice Christopher
Published: December 2003

The most appropriate amount of psychotherapy to address a particular problem is of interest to clinicians, consumers and those responsible for funding of care. The dose–response relationship has been examined within the context of randomized clinical trials, meta‐analysis as well as naturalistic studies; however, each of these approaches has limits. Many of these approaches have conceptually blurred two distinct concepts: do participants with different characteristics need different amounts of therapy and do otherwise equal participants show different outcomes when given different levels of (a particular type of) therapy? For any study design, if the experimenter does not determine the duration of therapy, then the length of therapy is said to be endogenous. This endogeneity can bias any attempt to untangle the answer to these two questions. An extension of the biasing effect of this endogeneity involves the choice of times to assess outcome; if outcome assessment depends on when therapy is terminated (rather than exogenously chosen) then estimates of the trajectory of outcome may be biased. Design considerations to minimize this effect are discussed. Copyright © 2003 John Wiley & Sons, Ltd.
Waiting for supershrink: an empirical analysis of therapist effects
Authors: Okiishi John , Lambert Michael J. , Nielsen Stevan L. , Ogles Benjamin M.
Published: December 2003

Improving the effects of psychotherapy has been accomplished through a variety of methods. One infrequently used method involves profiling patient outcomes within therapist in order to find the empirically supported psychotherapist. This study examined data collected on 1841 clients seen by 91 therapists over a 2.5‐year period in a University Counseling Center. Clients were given the Outcome Questionnaire‐45 (OQ‐45) on a weekly basis. After analysing data to see if general therapist traits (i.e. theoretical orientation, type of training) accounted for differences in clients' rate of improvement, data were then analysed again using Hierarchical Linear Modeling (HLM), to compare individual therapists to see if there were significant differences in the overall outcome and speed of client improvement. There was a significant amount of variation among therapists' clients' rates of improvement. The therapists whose clients showed the fastest rate of improvement had an average rate of change 10 times greater than the mean for the sample. The therapists whose clients showed the slowest rate of improvement actually showed an average increase in symptoms among their clients. Use of this information for improving quality of patient outcomes is discussed. Copyright © 2003 John Wiley & Sons, Ltd.
Practice‐based evidence: benchmarking NHS primary care counselling services at national and local levels
Authors: Evans Chris , Connell Janice , Barkham Michael , Marshall Chris , Mellor‐Clark John
Published: December 2003

There are a number of problems for evidence‐based practice (EBP) including limited generalizability of efficacy research results, the consequent lack of confidence in the relevance of such research, and the conceptual distance of most practitioners from the research process. The result is that EBP, although sound in principle, often fails to achieve its aim of improving practice. Practice‐based evidence (PBE) provides a complementary bridge for the gap between research and practice to offset some of these problems, promoting collaboration between mental health services and academic institutions. This paper presents the initial results of such a collaboration via three phases: (1) the development of a referential database for primary care counselling services, (2) ‘practitioner‐friendly’ feedback on grouped data to services, and (3) the combination of the two to build an evidence base for work with ethnic minorities—an area in which research trials are not well adapted to provide much evidence. Copyright © 2003 John Wily & Sons, Ltd.
The Ohio mental health consumer outcomes system: reflections on a major policy initiative in the US
Authors: Brower Leslie A.
Published: December 2003

This article describes the key elements of Ohio's development and implementation of a statewide system of consumer outcomes measurement for adults and youth, 1996–2003. A complete history would include the view from each component of this decentralized mental health system and from its major participants: consumers and families, providers, and local boards. Copyright © 2003 John Wiley & Sons, Ltd.
Theory‐based training in constructive conflict for trauma relief personnel: The case of Croatia and Bosnia
Authors: Desivilya Helena Syna , Gal Reuven
Published: December 2003

This article presents an intervention designed to assist trauma relief personnel in their work with victims of protracted conflict among adversary ethnic groups. The training program presented here incorporates components of conflict escalation and deescalation models and is tailored to the Balkan conflict, especially victims of the Croatian and Bosnian‐Serbian conflict.
The impact of participation in a parent education program for divorcing parents on the use of court resources: An evaluation study
Authors: Ellis Desmond , Anderson Dawn Y.
Published: December 2003

This article assesses the impact of mandatory participation in family information sessions (FIS) and selected demographic and marital
experiences on the use of court resources such as motions, case conferences, and the number of days a divorce case remains active.The study, conducted
in Ontario, Canada, concludes with a number of policy‐practice recommendations.
Consensus building and “Smart Growth”
Authors: Brand Martha
Published: December 2003

Many local governments are implementing public processes in conjunction with new “Smart Growth” land use patterns that focus on
increasing
housing choices, encouraging compact new development and redevelopment in older areas, preserving environmentally sensitive lands and open space,
creating a unique sense of community, and providing more transportation options. This article examines nine Minnesota projects that used consensus
building processes and offers general strategies for designing and implementing future processes.
What's news? Reflections of intractable environmental conflicts in the news: Some promises, many premises
Authors: Vraneski Ariella , Richter Ravit
Published: December 2003

This article presents part of a research project aimed at improving the understanding of the framing and reframing processes of intractable
environmental conflicts. It introduces a hybrid typology for analyzing the media framing and reframing patterns, discussing the frames used by the
media while covering four Israeli case studies. The article also explores some premises and promises of the media framing and reframing processes
with regard to prevention and transformation of environmental conflict.
Deposition of II‐VI Thin Films by LP‐MOCVD Using Novel Single‐Source Precursors
Authors: Afzaal Mohammad , Crouch David , Malik Mohmmad A. , Motevalli Majid , O’Brien Paul , Park Jin‐Ho , Woollins J. Derek
Published: December 2003

Thin films of several zinc or cadmium chalcogenides have been deposited on glass substrates by low pressure metal‐organic chemical vapour deposition (LP‐MOCVD) using single‐source precursors, [M{(EPiPr2)2N}2] (M = CdII, ZnII and E = S, Se). X‐ray single crystal structures show that [Zn{(EPiPr2)2N}2] (E = S or Se) and [Zn{(SePPh2)2N}2] are tetrahedrally distorted. TGA analyses showed that the precursors are volatile, making them suitable for MOCVD studies. As‐deposited films were polycrystalline as confirmed by X‐ray powder diffraction (XRPD) and their morphologies were studied by scanning electron microscope (SEM). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Supramolecular Chemistry Based on [W3S4(H2O)6Cl3]+ − A Versatile Building Block
Authors: Sokolov Maxim N. , Gerasko Olga A. , Dybtsev Danil N. , Chubarova Elena V. , Virovets Alexander V. , Vicent Cristian , Llusar Rosa , Fenske Dieter , Fedin Vladimir P.
Published: December 2003

The cluster [W3S4(H2O)6Cl3]+ (which is present in solutions of [W3S4(H2O)9]4+ in 1−4 M HCl) reacts with the macrocyclic cavitand cucurbituril (C36H36N24O12) to form supramolecular adducts of 2:1 cluster/cucurbituril stoichiometry, where two portals of cucurbituril (which contains a water molecule in its cavity) are closed by two cluster cations. These aggregates are bound together in the solid by complementary hydrogen bonds between coordinated Cl− and the cations H9O4+ to give chains. Thus, a supramolecular architecture is achieved from three different but complementary building blocks. The packing of the chains affords a honeycomb structure (hexagonal symmetry) with channels (about 5.2 Å in diameter). The overall stoichiometry is (H9O4){[W3S4(H2O)6Cl3]2(C36H36N24O12)}Cl3·16.15H2O (1). [W3S4(H2O)6Cl3]+ reacts with SbCl3 in 6 M HCl to give cuboidal [W3(SbCl3)S4(H2O)6Cl3]+, which forms with the macrocyclic cavitand cucurbituril a 2:1 cluster/cucurbituril adduct − a discrete supramolecule consisting of five independent molecular units. In the solid it crystallizes as a salt of very rare anion [SbCl6]3− with the stoichiometry {[W3(SbCl3)S4(H2O)6Cl3]2(C36H36N24O12)}(SbCl6)2/3·12H2O (2). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Investigation of the Thermal Properties of [Cu20Se13(PEt3)12]
Authors: Eichhöfer Andreas , Fenske Dieter , Scheer Petra
Published: December 2003

The mixed‐valence cluster [Cu20Se13(PEt3)12] has been synthesized by the reaction of CuCl and PEt3with Se(SiMe3)2. A powder‐diffraction pattern has revealed its crystalline purity and UV/Vis reflectance spectra display an intervalence band around 1200 nm. The solid‐state conversion of the cluster upon heating yields, even at moderate temperatures of around 100 °C, α‐Cu2Se and not a Cu3Se2phase that should be favoured in terms of the Cu/Se ratio of 3.1:2 in the cluster complex. This thermogravimetric analysis, coupled with mass spectrometry, shows that in addition to the labile phosphane ligands selenium atoms are cleaved as SePEt3during the consolidation process. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Crystal Field Strengths, Nephelauxetic Effects, and Experimentally Based Molecular Orbital Schemes (in the f Range) of Selected Cyclopentadienyl Complexes of Samarium(III)
Authors: Amberger Hanns‐Dieter , Reddmann Hauke , Jank Stefan , Lopes Maria Irene , Marques Noémia
Published: December 2003

The absorption and luminescence spectra of pseudo (ψ) trigonal planar [Sm(η5‐C5H4tBu)3] (1), low symmetric [Sm(η5‐Cp)(η3‐Tp)(η2‐Tp)] (Cp = η5‐cyclopentadienyl; Tp= hydrotris(3,5‐dimethylpyrazolyl)borato) (2) as well as ψ trigonal pyramidal [Sm(η5‐C5H4tBu)3(THF)] (3), [Sm(η5‐Cp)3(THF)] (4) and [Sm(η5‐Cp)3(CNC6H11)] (5) have been measured at room and low temperatures. From the spectra obtained, truncated crystal field (CF) splitting patterns of these compounds could be derived, and simulated by fitting the parameters of a phenomenological Hamiltonian. On the basis of the CF parameters used, the global CF strengths experienced by the Sm3+central ions of complexes1−5, as well as the individual CF strength associated with one C5H4tBu−ligand are estimated. The obtained Slater parameters F2and the spin‐orbit coupling parameters ζ4fallow the insertion of compounds1−5into truncated nephelauxetic and relativistic nephelauxetic series. Besides, the experimentally based non‐relativistic and relativistic molecular orbital schemes (in the f range) of complexes1and, partly,3are set up and compared with the results of quantum chemical model calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Structure‐Dependent Electrochemical Behavior of Thienylplatinum(II) Complexes of N,N‐Heterocycles
Authors: Zhao Feng , Xu Xingling , Khoo Soo Beng , Hor T. S. Andy
Published: December 2003

trans‐[Pt(MeCN)(PPh3)2(2‐thienyl)]BF4 (1) serves as a convenient precursor to bifunctional mononuclear trans‐[Pt(PPh3)2(η1‐N‐N)(2‐thienyl)]BF4 [N‐N = pyrazine (2); 2‐chloropyrazine, (3)] and dinuclear trans,trans‐[Pt2(PPh3)4(μ‐N‐N)(2‐thienyl)2](BF4)2 [(N‐N = 4,4′‐bipyridine (4); 4,4′‐vinylenedipyridine (5)] complexes. The nuclear selectivity is conveniently controlled by the choice of the heterocyclic ligands or spacers. Both structural types 3 and 5 were confirmed by single‐crystal X‐ray crystallographic analyses. Their solution identities were established by positive‐ion Electrospray Mass Spectrometry (ESMS). The electroactivities of these complexes were studied by cyclic voltammetry (CV). Continuous CV scans of 4 and 5 revealed variations in the redox waves with the number of scans. While the initial oxidative scan exhibited only a broad, irreversible wave, further cycling showed the growth of two additional redox couples up to about the tenth cycle. The peak currents of these redox couples began to decay with prolonged potential cycling beyond the tenth cycle. These findings are consistent with the formation of electroactive oligomers/polymers, and this conclusion is supported by visible thin film formation on the electrodes. In contrast, the mononuclear complexes (2 and 3) do not show such behavior. The films formed were further studied by repetitive potential cycling and XPS. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Structure and Reactivity of Coordinatively Unsaturated Half‐Sandwich Iron, Ruthenium and Osmium Complexes
Authors: Jiménez‐Tenorio Manuel , Puerta M. Carmen , Valerga Pedro
Published: December 2003

This review deals with the study of coordinatively unsaturated half‐sandwich iron, ruthenium and osmium complexes, in particular those bearing bulky phosphane ligands. The synthesis, properties and structure of neutral complexes of the type [(C5R5)MX(L)] and their cationic derivatives [(C5R5)M(L)2]+, are described here. We will also refer to related compounds containing hydrotris(pyrazolyl)borate (Tp) ligands, given the formal relationship existing between these and those containing cyclopentadienyl groups. In addition, we discuss the reactivity of these unsaturated species towards small molecules and alkynes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Study of the Reaction of Tridentate Ligands with Ferrocenyl Boronic Acid
Authors: Barba Victor , Xochipa Rubí , Santillan Rosa , Farfán Norberto
Published: December 2003

Evaluation of the reactivity of eight tridentate ligands derived from amino alcohols and salicylaldehyde, 2‐hydroxyacetophenone, or 2‐hydroxybenzophenone with ferrocenyl boronic acid has shown that the reaction leads to both monomeric and dimeric ferrocenyl boronates. A coordinative N−B bond is essential to give the tetrahedral boron atoms that are responsible for the formation of heterobicyclic structures containing six, seven and ten members. The purity and identity of all compounds were unequivocally established by analytical and multinuclear (1H, 11B, 13C) magnetic resonance spectroscopic data. Furthermore, the structures of the dimeric (2a) and monomeric (5b) boron complexes were established by X‐ray diffraction analyses. The dimeric compound contains a ten‐membered ring in a boat−chair−boat conformation, while the monomeric compound has a seven‐membered ring with a chair conformation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
The Role of Spacers between Carboxylate Groups in Self‐Assembly Process: Syntheses and Characterizations of Two Novel Cadmium(II) Complexes Derived from Mixed Ligands
Authors: Wang Ruihu , Hong Maochun , Yuan Daqiang , Sun Yanqiong , Xu Lijin , Luo Junhua , Cao Rong , Chan Albert S. C.
Published: December 2003

Two novel cadmium(II) coordination polymers, [Cd2(bpda)2(dpe)]n (1) and [Cd2{(R)‐Hdmpa}2{(S)‐Hdmpa}2(dpe)3]n (2), [H2bpda = 1,1′‐biphenyl‐3,3′‐dicarboxylic acid, H2dmpa = 6,6′‐dimethyl‐1,1′‐biphenyl‐2,2′‐dicarboxylic acid, and dpe = 1,2‐di(4‐pyridyl)ethylene] have been prepared by hydrothermal reactions of both Cd(NO3)2·4H2O and dpe with H2bpda and H2dmpa, respectively. 1 is a threefold interpenetrating three‐dimensional coordination network composed of paddle‐wheel tetracarboxylate dicadmium(II) units bridged by dpe. 2 affords an example of ligand self‐discrimination in an assembly process, in which dpe connects the [Cd{(R)‐Hdmpa}{(S)‐Hdmpa}] building units to generate a one‐dimensional ladder structure. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Novel Supramolecular Frameworks Self‐Assembled from One‐Dimensional Polymeric Coordination Chains
Authors: Shi Xin , Zhu Guangshan , Fang Qianrong , Wu Gang , Tian Ge , Wang Renwei , Zhang Daliang , Xue Ming , Qiu Shilun
Published: December 2003

The novel supramolecular frameworks [Cd(BDC)(phen)(H2O)]n (2) and [Cd2(HBTC)2(phen)2]2n·nCd(HBTC)(phen)2 (3) have been synthesized by reaction of the metal source Cd(phen)2(NO3)2 (1) with benzene‐1,4‐dicarboxylic acid (H2BDC) and benzene‐1,3,5‐tricarboxylic acid (H3BTC), respectively in a mixed solution of DMF/C2H5OH/H2O. The three‐dimensional supramolecular structure of 2 is constructed through hydrogen‐bond and aromatic π−π interactions between adjacent metal‐organic polymeric coordination chains. Conversely, interestingly, the supramolecular architecture 3 is formed by extending 1‐D metal‐organic polymeric coordination chains into a 3‐D framework by hydrogen‐bond interactions between polymeric coordination chains and metal‐organic coordination complexes instead of by interchain hydrogen‐bond interactions. Additionally, these three compounds exhibit strong fluorescence at room temperature in the solid state. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Synthesis and Crystal Structure of {[HNEt3]2n[Ag8Ag4/2(SC6H4tBu‐4)12]n·nC2H5OH} and Its Reaction Product with CS2
Authors: Tang Kaluo , Xie Xiangjin , Zhao Liang , Zhang Yaohua , Jin Xianglin
Published: December 2003

By using an arylthiolate ligand with a substituent in the para‐position, 4‐tBuC6H4S−, the yellow silver‐thiolate complex {[HNEt3]2n[Ag8Ag4/2(SC6H4tBu‐4)12]n·nC2H5OH} (1) has been synthesized and structurally characterized. Complex 1 is ionic composed of [HNEt3]+ cations and a polymeric [Ag8Ag4/2(SC6H4tBu‐4)12]n2n− anion. Complex 1 reacts with CS2 in acetone to give a red pentaconta‐nuclear silver anionic cluster complex {[HNEt3]4[Ag50S7(SC6H4tBu‐4)40]·2CS2· 6C3H6O} (2). The core of the anionic cluster of 2 consists of fifty silver atoms and forty seven sulfur atoms, shaped like a discus with a diameter of ca. 2.0 nm. The factors influencing the structure and the formation mechanism of the large cluster are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Homo‐ and Heteronuclear Complexes of (Pentamethylcyclopentadienyl)rhodium(III) Bearing Bis(diphenylphosphanylmethyl)phenylphosphane
Authors: Yamamoto Yasuhiro , Kosaka Yosuke , Tsutsumi Yoshihiro , Kaburagi Yoshihiro , Kuge Katsuaki , Sunada Yusuke , Tatsumi Kazuyuki
Published: December 2003

Reaction of [Cp*RhCl2]2 (1) with bis(diphenylphosphanylmethyl)phenylphosphane (dpmp) in the presence of KPF6 generated the mono‐ or bi‐nuclear complexes [(Cp*RhCl)(dpmp‐P,P,P)(RhCl2Cp*)](PF6) (2) or [Cp*RhCl(dpmp‐P,P)](PF6) (3), depending on the reaction conditions. These complexes have two chiral centers at Rh and the central P atoms, and the diastereomers were separated by successive recrystallization. The structures of 2(B) with an RRhSP/SRhRP pair and 3(A) with an RRhSP/SRhRP pair were elucidated by X‐ray analyses. Reaction of 1 with an excess of dpmp in the presence of Ag(OTf) generated a hetero‐tetranuclear complex [{Cp*RhCl2(dpmp‐P,P,P)Ag}2](OTf)2 (4). An X‐ray analysis revealed that each Cp*RhCl2 moiety is connected by a terminal P1 atom of the dpmp ligand and each Ag atom is two‐coordinate and is surrounded by another terminal P3 atom, and a central P*2 atom of the other dpmp ligand. A mixture of 1 and dpmp was treated with Au(SC4H8) or CuCl in the presence of KPF6, generating the hetero‐tetranuclear complexes [{Cp*RhCl2(dpmp‐P,P,P)M}2](PF6)2 (7: M = Au; 8: M = Cu), in which the structures, except for the Cl‐bridged structure of 8, are fundamentally similar to that of 4. These complexes were also prepared by the reactions of 3 with Au(SC4H8) or CuCl. Complex 3 reacted with AgOTf to afford [Cp*Rh(dpmp‐P,P,P)](OTf)2 (5). Treatment of 3(A) (a diastereomer with an RRhSP2/SRhRP2 pair) with 1, [(p‐cymene)RuCl2]2 or PdCl2(cod) gave [Cp*RhCl(dpmp‐P,P,P)RhCl2Cp*](PF6) (2) or [Cp*RhCl(dpmp‐P,P,P)RuCl2(p‐cymene)](PF6) (6), respectively. These addition reactions proceeded stereoselectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Formation and Reactivity of Gaseous Iron‐Sulfur Clusters
Authors: Koszinowski Konrad , Schröder Detlef , Schwarz Helmut
Published: December 2003

The gas‐phase reactions of Fen+ clusters, n = 1−6, with COS and CS2 have been investigated by means of Fourier‐transform ion‐cyclotron resonance mass spectrometry. Whereas CS2 predominantly substitutes one Fe atom, COS exclusively affords multiple sulfur transfer and thus opens a synthetic route to gaseous FenSx+ clusters. In the final products such as Fe2S2+, Fe3S2+, and Fe4S4+, the sulfur atoms appear to occupy multiple coordination sites much like in the analogous biogeneous iron‐sulfur clusters. Bracketing experiments find IE(Fe2S2) = 7.2±0.3 eV besides providing upper limits for IE(Fe3S2) and IE(Fe4S4). In accordance with the low IE(Fe2S2), Fe2S2+ does not activate H2 or small hydrocarbons and only exhibits rather limited reactivity towards more reactive substrates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Functionalization of Polyoxometalates by a Negatively Charged Bridging Ligand: The Dimeric [(SiW11O39Ln)2(μ‐CH3COO)2]12− (Ln = GdIII, YbIII) Complexes
Authors: Mialane Pierre , Dolbecq Anne , Rivière Eric , Marrot Jérôme , Sécheresse Francis
Published: December 2003

The possibility of coupling lacunary polyoxometalates through a cationic center present in the vacancy by negatively charged organic ligands is demonstrated for the first time by single‐crystal X‐ray diffraction. The structure of the dimeric K12[{Yb(α‐SiW11O39)(H2O)}2(μ‐CH3COO)2]·38H2O complex, where two acetato ligands connect the ytterbium centers in a (η2, μ‐1,1) fashion, is reported. Using gadolinium instead of ytterbium, both the isostructural dimeric compound K12[{Gd(α‐SiW11O39)(H2O)}2(μ‐CH3COO)2]·38H2O and the mononuclear sandwich complex [Gd(SiW11O39)2]13− can be selectively isolated, depending on the synthetic conditions. The magnetic properties of the dimeric gadolinium complex are presented. The influence of the nature of the rare‐earth metal on the final compound is further highlighted by the fact that when praseodymium is used as the rare‐earth element, only the sandwich compound can be obtained. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Cover Picture: Functionalization of Polyoxometalates by a Negatively Charged Bridging Ligand: The Dimeric [(SiW11O39Ln)2(μ‐CH3COO)2]12− (Ln = GdIII, YbIII) Complexes (Eur. J. Inorg. Chem. 1/2004)
Authors: Mialane Pierre , Dolbecq Anne , Rivière Eric , Marrot Jérôme , Sécheresse Francis
Published: December 2003

The cover picture shows the synthetic pathway leading to the first polyoxometalate complex where two subunits are linked by negatively charged organic ligands via a cationic center present inside the polyoxometalate. The strategy used, together with the influence of the nature of the rare earth and the ligand concentration on the final product, are developed in the Short Communication by P. Mialane et al. on p. 33 ff.
Indicator Free DNA Hybridization Detection by Impedance Measurement Based on the DNA‐Doped Conducting Polymer Film Formed on the Carbon Nanotube Modified Electrode
Authors: Cai Hong , Xu Ying , He Pin‐Gang , Fang Yu‐Zhi
Published: December 2003

A new biosensing strategy for direct electrochemical detection of DNA hybridization by AC impedance measurement is described. The indicator or label free approach was developed on the basis of the carbon nanotubes coupled with a conductive polymer polypyrrole (PPy). Multi‐walled carbon nanotubes functionalized with carboxylic group (MWNTs‐COOH) were modified on the glassy carbon electrode (GCE) and the oligonucleotide probes were doped within the electro‐polymerized PPy films by serving as the sole counter anion during the growth of the conducting films. Before and after hybridization reaction with the complementary DNA sequences, a decrease of impedance values was observed as a result of the reduction of the electrode resistance. Hybridization amounts of the one‐base, two‐base and three‐base mismatched sequences were obtained only in a 51%, 18% and 8.2% response when compared to that for the complementary matched sequence. Such unique response is attributed to the concomitant conductivity changes of the PPy‐polymerized carbon nanotubes, and offers great promise for reagentless DNA hybridization analysis.
Performance of Poly(styrenesulfonate)‐Coated Thin Mercury Film Electrodes in the Determination of Lead and Copper in Estuarine Water Samples of High Salinity
Authors: Monterroso Sandra C. C. , Carapuça Helena M. , Duarte Armando C.
Published: December 2003

Thin mercury film electrodes coated with poly(styrenesulfonate) (PSS‐TMFE) were prepared by solvent evaporation of an aqueous solution of the polymer onto a glassy carbon electrode followed by electrolytic deposition of the mercury film through the polymer layer. The performance of these polymer modified mercury film electrodes is evaluated in a NaCl solution using lead(II) as a model heavy metal cation. This new methodology presents an improved sensitivity, mechanical stability, reproducibility, repeatibility and increased efficiency against surfactants when comparing to the conventional TMFE. Square‐wave anodic stripping voltammetry at the ex situ mercury plated PSS‐TMFE was successfully applied to the determination of total and labile amounts of lead and copper in estuarine water samples of variable and high salinity (23.5‰–35.0‰). Concentrations in the nanomolar region can be easily assessed using a 3 minutes accumulation time with low relative standard deviations (less than 3%).
Study on Catalytic Adsorptive Stripping Voltammetry of Trace Cobalt at Bismuth Film Electrodes
Authors: Krolicka Agnieszka , Bobrowski Andrzej , Kalcher Kurt , Mocak Jan , Svancara Ivan , Vytras Karel
Published: December 2003

Bismuth film electrodes (BiFE) prepared by plating a glassy carbon support ex situ from a solution containing 0.5 M LiBr and 1 M HCl was tested for the determination of cobalt traces using adsorptive stripping voltammetry (AdSV) and catalytic adsorptive stripping voltammetry (CAdSV). AdSV enables one to determine cobalt as the Co(II)‐dimethylglyoximate (Co‐DMG) complex down to 0.3 μg/L Co. Addition of NaNO2 to the solution containing dimethylglyoxime in ammonia buffer provides a 15‐fold enhancement of the voltammetric signal of cobalt due to the catalytic effect occurring during the reduction of Co(II)‐DMG. Utilization of the bismuth film electrode under optimized conditions assures a stable catalytic adsorptive stripping voltammetric response for Co, with an extremely high sensitivity (1.75 μA/(μg/L)), good precision (RSD=3%), and a low detection limit (0.07 μg/L Co with 60 s of adsorptive accumulation). The results of the measurement of the catalytic cobalt response in the presence of DMG and nitrite under hydrodynamic amperometric conditions have shown the BiFE to be an attractive and suitable tool for the rapid determination of cobalt at low μg/L level in both batch and flow systems.
Square‐Wave Quantification of Lead in Rainwater with Disposable Gold Electrodes Without Removal of Dissolved Oxygen
Authors: Richter Eduardo M. , Pedrotti Jairo J. , Angnes Lúcio
Published: December 2003

Only a few authors describe the use of gold electrodes for trace levels of lead quantification. In this work a sensitive and reliable procedure to the quantification of lead at trace levels by stripping analysis utilizing gold electrodes was developed. It was observed that the presence of chloride ions plays an essential role for lead deposition. Under this condition, the content of lead in rainwater was quantified utilizing disposable gold electrodes (CDtrodes), without removal of the dissolved oxygen. CDtrodes possess very flat surface, high crystalline homogeneity, very clean surface and present great performance for lead quantification in presence of hydrochloric acid. A special cell was designed to work with small volumes of samples (0.5 to 1.0 mL), an important condition to analyze small amounts of rain. Finally, the rapid scanning propitiated by the use of square‐wave stripping voltammetry, coupled with blank subtraction eliminates the effect of the dissolved oxygen on the final result. Various experimental parameters were optimized to allow convenient monitoring of lead concentrations (in trace levels) with relatively short deposition times. Linear calibration plots were obtained for different concentration ranges (using different deposition times). A detection limit of 80 ng L−1 (or 80 ppt) of lead was estimated when a deposition period of 300 s was used. During this work, a reliable procedure for electrochemical cleanup of gold surfaces was also developed. The proposed method was tested for certified samples and employed for lead analysis in rainwater samples in São Paulo City.