bluuebunny/crossref_metadata_2025 huggingface dataset:
Linkage and Association Between Distinct Variants of the
APOA1/C3/A4/A5
Gene Cluster and Familial Combined Hyperlipidemia
Authors: Eichenbaum-Voline Sophie , Olivier Michael , Jones Emma L. , Naoumova Rossitza P. , Jones Bethan , Gau Brian , Patel Hetal N. , Seed Mary , Betteridge D. John , Galton David J. , Rubin Edward M. , Scott James , Shoulders Carol C. , Pennacchio Len A.
Published: October 2003

Objective—

Combined hyperlipidemia is a common disorder, characterized by a highly atherogenic lipoprotein profile and a substantially increased risk of coronary heart disease. The purpose of this study was to establish whether variations of apolipoprotein A5 (
APOA5
), a newly discovered gene of lipid metabolism located 30 kbp downstream of the
APOA1/C3/A4
gene cluster, contributes to the transmission of familial combined hyperlipidemia (FCHL).

Methods and Results—

We performed linkage and association tests on 128 families. Two independent alleles,

APOA5
c.56G

and
APOC3

c.386G

, of the
APOA1/C3/A4/A5
gene cluster were overtransmitted in FCHL (
P
=0.004 and 0.007, respectively). This was paired with reduced transmission of the common
APOA1/C3/A4/A5
haplotype (frequency 0.4461) to affected subjects (
P
=0.012). The
APOA5

c.56G

genotype accounted for 7.3% to 13.8% of the variance in plasma triglyceride levels in probands (
P
<0.004). The
APOC3

c.386G

genotypes accounted for 4.4% to 5.1% of the variance in triglyceride levels in FCHL spouses (
P
<0.007), suggesting that this allele marks a FCHL quantitative trait as well as representing a susceptibility locus for the condition.

Conclusions—

A combined linkage and association analysis establishes that variation at the
APOA1/C3/A4/A5
gene cluster contributes to FCHL transmission in a substantial proportion of northern European families.
Dynamics of the Pulmonary Venous Flow in the Fetus and Its Association With Vascular Diameter
Authors: Zielinsky Paulo , Piccoli Antônio , Gus Eduardo , Manica João Luiz , Satler Fabíola , Nicoloso Luiz Henrique , Luchese Stelamaris , Marcantonio Silvana , Scheid Marlui , Hatém Domingos
Published: October 2003

Background—

The usual positioning of the Doppler sample volume to assess fetal pulmonary vein flow is in the distal portion of the vein, where the vessel diameter is maximal. This study was performed to test the association of the pulmonary vein pulsatility index (PVPI) with the vessel diameter.

Methods and Results—

Twenty-three normal fetuses (mean gestational age, 28.6±5.3 weeks) were studied by Doppler echocardiography. Pulmonary right upper vein flow was assessed adjacent to the venoatrial junction (“distal” position) and in the middle of the vein (“proximal” position). The vessel diameter was measured by 2D echocardiography with power Doppler, and the PVPI was obtained by the ratio (maximal velocity [systolic or diastolic peak]−minimal velocity [presystolic peak])/mean velocity. The statistical analysis used
t
test and exponential correlation studies. Mean distal diameter was 0.33±0.10 cm (0.11 to 0.57 cm), and mean proximal diameter was 0.16±0.08 cm (0.11 to 0.25 cm) (
P
<0.0001). Mean distal PVPI was 0.84±0.21 (0.59 to 1.38), and mean proximal PVPI was 2.09±0.59 (1.23 to 3.11) (
P
<0.0001). Exponential inverse correlation between pulmonary vein diameter and pulsatility index was highly significant (
P
<0.0001), with a determination coefficient of 0.439.

Conclusions—

In the normal fetus, the pulmonary venous flow pulsatility decreases from the lung to the heart, and this parameter is inversely correlated to the diameter of the pulmonary vein, which increases from its proximal to its distal portion. This study emphasizes the importance of the correct positioning of the Doppler sample volume, adjacent to the venoatrial junction, to assess pulmonary venous flow dynamics.
Joint Effects of C-Reactive Protein and Glycated Hemoglobin in Predicting Future Cardiovascular Events of Patients With Advanced Atherosclerosis
Authors: Schillinger Martin , Exner Markus , Amighi Jasmin , Mlekusch Wolfgang , Sabeti Schila , Rumpold Helmut , Wagner Oswald , Minar Erich
Published: October 2003

Background—

C-reactive protein (CRP) and glycohemoglobin (HbA1c) are established risk factors for the development of cardiovascular disease. We investigated the joint effects of these parameters on cardiovascular outcome of patients with advanced atherosclerosis.

Methods and Results—

We studied 454 patients with advanced atherosclerosis (median age, 69 years; 264 male). Cardiovascular risk profile, high-sensitivity CRP (hs-CRP), and HbA1c were obtained at baseline, and patients were followed for a median of 21 months (interquartile range, 13 to 26) for the occurrence of major adverse cardiovascular events (MACE) (myocardial infarction, percutaneous coronary interventions, coronary artery bypass graft, carotid revascularization, stroke, and death). We observed 166 MACE in 128 patients (28%). Cumulative event-free survival rates at 6, 12, and 24 months were 91%, 85%, and 73%, respectively. Adjusted hazard ratios for the occurrence of MACE according to increasing quartiles of hs-CRP and HbA1c were 1.35 (
P
=0.31), 1.90 (
P
=0.026) and 2.13 (
P
=0.007), and 1.40 (
P
=0.26), 1.81 (
P
=0.059), and 2.36 (
P
=0.023), respectively, compared with the lowest quartiles. Considering both parameters jointly, we found that patients with hs-CRP >0.44 mg/dL and HbA1c >6.2% (upper quartiles) were at highest risk for MACE, with each parameter adding to the prognostic information of the other.

Conclusions—

Inflammation, indicated by hs-CRP, and hyperglycemia, indicated by HbA1c, jointly contribute to the cardiovascular risk of patients with advanced atherosclerosis. Patients with both hs-CRP and HbA1c in the upper quartiles (>0.44 mg/dL and >6.2%, respectively) are at particularly high risk for poor cardiovascular outcome.
Effect of Shear Stress on Asymmetric Dimethylarginine Release From Vascular Endothelial Cells
Authors: Osanai Tomohiro , Saitoh Masayuki , Sasaki Satoko , Tomita Hirofumi , Matsunaga Toshiro , Okumura Ken
Published: October 2003

We demonstrated recently that plasma concentrations of asymmetric dimethylarginine (ADMA), an endogenous inhibitor of nitric oxide (NO) synthase, are increased by high salt intake concomitantly with a decrease in plasma levels of NO in human hypertension. We investigated the effect of shear stress on ADMA release in 2 types of cells: transformed human umbilical vein endothelial cells (HUVECs; cell line ECV-304) and HUVECs. Exposure of ECV-304 cells and HUVECs to shear stress with the use of a cone-plate viscometer enhanced gene expression of protein arginine methyltransferase (PRMT-1), ADMA synthase. In HUVECs, the ratio of PRMT-1 to glyceraldehyde 3-phosphate dehydrogenase mRNA was increased by 2-fold by a shear stress of ≥15 dyne/cm
2
. A dominant-negative mutant of IκB kinase α and troglitazone at 8 μmol/L, an activator of peroxisome proliferator–activated receptor γ, abolished the shear stress–induced increase in PRMT-1 gene expression in parallel with the blockade of nuclear factor (NF)-κB translocation into the nucleus. The activity of dimethylarginine dimethylaminohydrolase, the degradation enzyme of ADMA, was unchanged after shear stress ≤15 dyne/cm
2
and was enhanced by 1.48±0.06-fold (
P
<0.05) by shear stress at 25 dyne/cm
2
. The release of ADMA was increased by 1.64±0.10-fold (
P
<0.05) by shear stress at 15 dyne/cm
2
but was not affected by shear stress at 25 dyne/cm
2
. These results indicate that shear stress enhances gene expression of PRMT-1 and ADMA release via activation of the NF-κB pathway. Shear stress at higher magnitudes facilitates the degradation of ADMA, thus returning ADMA release levels to baseline.
Decisions of the World Court Relevant to the UN Convention on the Law of the Sea — A Reference Guide by Barbara Kwiatkowska (Book Review)
Authors:   Lauterpacht
Published: October 2003

No Abstract
Clofarabine, a novel nucleoside analog, is active in pediatric patients with advanced leukemia
Authors: Jeha Sima , Gandhi Varsha , Chan Ka Wah , McDonald Lisa , Ramirez Irma , Madden Renee , Rytting Michael , Brandt Mark , Keating Michael , Plunkett William , Kantarjian Hagop
Published: October 2003

Despite progress in leukemia therapy, most children who experience relapse have a dismal prognosis. New, effective approaches are needed. We conducted a phase 1 study of a novel nucleoside analog, clofarabine, in pediatric patients with refractory and relapsed leukemia. Clofarabine was infused intravenously over 1 hour each day for 5 days. Six dose levels, between 11.25 and 70 mg/m2 per day for 5 days, were studied in 25 patients. A modified 3 + 3 phase 1 design was followed with 30% dose escalation until the dose-limiting toxicity (DLT) was defined. The maximum tolerated dose (MTD) was 52 mg/m2 per day for 5 days. At the end of infusion at MTD, clofarabine triphosphate levels in leukemia blasts varied between 6 μM and 19 μM, which resulted in complete and sustained inhibition of DNA synthesis. The DLT was reversible hepatotoxicity and skin rash at 70 mg/m2 per day for 5 days. Twenty-five patients were treated. Five patients achieved complete remission (CR), and 3 achieved partial remission (PR), for an overall response rate of 32%. Clofarabine is well tolerated and shows significant antileukemic activity in heavily pretreated children. Multicenter phase 2 trials in pediatric acute lymphoblastic leukemia (ALL) and acute myeloid leukemia (AML) are ongoing.
The pathogenic roles of tumor necrosis factor receptor p55 in acetaminophen-induced liver injury in mice
Authors: Ishida Yuko , Kondo Toshikazu , Tsuneyama Koichi , Lu Peirong , Takayasu Tatsunori , Mukaida Naofumi
Published: October 2003

Acetaminophen (APAP) causes a massive production of intrahepatic tumor necrosis factor α (TNF-α). However, it still remains elusive regarding the roles of TNF-α in APAP-induced liver injury. Hence, we examined pathogenic roles of the TNF-α–TNF receptor with a molecular weight of 55 kDa (TNF-Rp55) axis in APAP-induced hepatotoxicity using TNF-Rp55-deficient [TNF-Rp55-knockout (KO)] mice. When wild-type (WT) BALB/c and TNF-Rp55-KO mice were intraperitoneally injected with a lethal dose of APAP (750 mg/kg), the mortality of TNF-Rp55-KO mice was marginally but significantly reduced compared with WT mice. Upon treatment with a nonlethal dose (600 mg/kg), WT mice exhibited an increase in serum transaminase levels. Histopathologically, centrilobular hepatic necrosis with leukocyte infiltration was evident at 10 and 24 h after APAP challenge. Moreover, mRNA expression of adhesion molecules, several chemokines, interferon-γ (IFN-γ), and inducible nitric oxide synthase (iNOS) was enhanced in the liver. On the contrary, serum transaminase elevation and histopathological changes were attenuated in TNF-Rp55-KO mice injected with APAP (600 mg/kg). The gene expression of all molecules except for IFN-γ and iNOS was significantly attenuated in TNF-Rp55-KO mice. Moreover, anti-TNF-α neutralizing antibodies alleviated liver injury when administered at 2 or 8 h after but not at 1 h before APAP challenge to WT mice. Collectively, the TNF-α–TNF-Rp55 axis has pathogenic roles in APAP-induced liver failure.
The chronic consequences of severe sepsis
Authors: Benjamim Claudia F , Hogaboam Cory M , Kunkel Steven L
Published: October 2003

The early events of severe sepsis set in motion a cascade of events that significantly contributes to the morbidity and mortality observed during the first few days of this syndrome. Although sepsis is a deadly, acute disease, survivors also suffer long-term consequences. Clinical data underscore subsequent high mortality rates associated with patients who are long-term survivors of the acute septic episode. Within 1 year of surviving severe sepsis, there is a 26% predicted mortality rate, and many patients succumb to lung complications. In this review, we focus on the cellular and molecular mechanisms that dictate the longer-term sequela of sepsis and related lung injury. We have established a murine model of experimental sepsis [cecal ligation and puncture (CLP)], which results in an approximate 60% survival rate. Our studies have demonstrated that these survivors are susceptible to a fungal infection with 100% mortality when challenged 3 days or 15 days post-recovery from the initial CLP. This increased mortality correlates with changes in cytokines and Toll-like receptor expression and alterations in lung leukocyte populations. We hypothesize that the lung becomes predisposed to nosocomial infections for extended periods of time after severe sepsis via mechanisms that include alterations in inflammatory cytokines and an increase in immunomodulatory chemokines, such as monocyte chemoattractant protein-1 and C10. These mediators may alter the innate-immune response by affecting dendritic cells and macrophages, which could provide a mechanism for the immunosuppression observed following sepsis.
Generation of a Phenotypic Array of Hypothalamic Neuronal Cell Models to Study Complex Neuroendocrine Disorders
Authors: Belsham Denise D. , Cai Fang , Cui Hong , Smukler Simon R. , Salapatek Anne Marie F. , Shkreta Lulzim
Published: October 2003

Knowledge of how the brain achieves its diverse central control of basic physiology is severely limited by the virtual absence of appropriate cell models. Isolation of clonal populations of unique peptidergic neurons from the hypothalamus will facilitate these studies. Herein we describe the mass immortalization of mouse primary hypothalamic cells in monolayer culture, resulting in the generation of a vast representation of hypothalamic cell types. Subcloning of the heterogeneous cell populations resulted in the establishment of 38 representative clonal neuronal cell lines, of which 16 have been further characterized by analysis of 28 neuroendocrine markers. These cell lines represent the first available models to study the regulation of neuropeptides associated with the control of feeding behavior, including neuropeptide Y, ghrelin, urocortin, proopiomelanocortin, melanin-concentrating hormone, neurotensin, proglucagon, and GHRH. Importantly, a representative cell line responds appropriately to leptin stimulation and results in the repression of neuropeptide Y gene expression. These cell models can be used for detailed molecular analysis of neuropeptide gene regulation and signal transduction events involved in the direct hormonal control of unique hypothalamic neurons, not yet possible in the whole brain. Such studies may contribute information necessary for the strategic design of therapeutic interventions for complex neuroendocrine disorders, such as obesity.
Novel Activation Step Required for Transcriptional Competence of Progesterone Receptor on Chromatin Templates
Authors: Thackray Varykina G. , Toft David O. , Nordeen Steven K.
Published: October 2003

To elucidate the earliest molecular steps in the activation of transcription by the progesterone receptor (PR), we investigated its activity in a cell-free transcription system utilizing chromatin templates. PR prepared as a ligand-free, recombinant protein failed to induce transcription on chromatin templates. However, transcriptional competence could be restored by coincubation with rabbit reticulocyte lysate (RRL). The interaction of PR with chaperones results in a receptor conformation competent to bind ligand and RRL contains abundant chaperone-mediated protein folding activity. Blocking this activity with the specific inhibitor geldanamycin inhibited receptor-dependent transcriptional activity. However, recombinant chaperones could not replace RRL in the restoration of transcriptional activity on chromatin templates, suggesting the presence of an additional activity in the lysate. Under chromatin assembly conditions, PR could bind naked DNA and RRL did not increase that binding. In contrast, PR bound to a chromatin template only poorly. Interestingly, RRL stimulated sequence-specific binding by PR to target sites in chromatin and the concomitant recruitment of the steroid receptor coactivator 1 to the promoter. Thus, our results indicate that a novel protein-mediated activity in RRL is involved in an additional, heretofore unrecognized, activation step required for PR to become transcriptionally competent on chromatin templates.
Stepwise formation of a SMAD activity gradient during dorsal-ventral patterning of theDrosophilaembryo
Authors: Sutherland David J. , Li Mingfa , Liu Xiao-qing , Stefancsik Raymund , Raftery Laurel A.
Published: October 2003

Genetic evidence suggests that the Drosophila ectoderm is patterned by a spatial gradient of bone morphogenetic protein (BMP). Here we compare patterns of two related cellular responses, both signal-dependent phosphorylation of the BMP-regulated R-SMAD, MAD, and signal-dependent changes in levels and sub-cellular distribution of the co-SMAD Medea. Our data demonstrate that nuclear accumulation of the co-SMAD Medea requires a BMP signal during blastoderm and gastrula stages. During this period, nuclear co-SMAD responses occur in three distinct patterns. At the end of blastoderm,a broad dorsal domain of weak SMAD response is detected. During early gastrulation, this domain narrows to a thin stripe of strong SMAD response at the dorsal midline. SMAD response levels continue to rise in the dorsal midline region during gastrulation, and flanking plateaus of weak responses are detected in dorsolateral cells. Thus, the thresholds for gene expression responses are implicit in the levels of SMAD responses during gastrulation. Both BMP ligands, DPP and Screw, are required for nuclear co-SMAD responses during these stages. The BMP antagonist Short gastrulation (SOG) is required to elevate peak responses at the dorsal midline as well as to depress responses in dorsolateral cells. The midline SMAD response gradient can form in embryos with reduced dpp gene dosage, but the peak level is reduced. These data support a model in which weak BMP activity during blastoderm defines the boundary between ventral neurogenic ectoderm and dorsal ectoderm. Subsequently, BMP activity creates a step gradient of SMAD responses that patterns the amnioserosa and dorsomedial ectoderm.
Nkx6.1 controls migration and axon pathfinding of cranial branchio-motoneurons
Authors: Müller Myriam , Jabs Normund , Lork Dietrich E. , Fritzsch Bernd , Sander Maike
Published: October 2003

As many studies have focused on the mechanisms of motoneuron specification,little is known about the factors that control the subsequent development of postmitotic motoneurons. Previously, we showed that the transcription factor Nkx6.1 is required for the early specification of somatic motoneuron progenitors in the spinal cord. Our present analysis of hindbrain motoneuron development in Nkx6.1-deficient mouse embryos reveals that the early specification of branchio-motoneurons is independent of Nkx6.1 function, but that it is required for their subsequent development. In Nkx6.1mutant mice, we observed defects in the migration, as well as in the axon projections of branchio-motoneurons. A detailed analysis of the migratory defect in facial branchio-motoneurons reveals ectopic expression of the cell surface receptors Ret and Unc5h3 in premigratory neurons,but no changes in the rhombomeric environment. Taken together, our findings demonstrate a requirement for Nkx6.1 in the development of postmitotic motoneurons, and suggest a cell-autonomous function in the control of branchio-motoneuron migration.
Wavelet‐based estimation of a discriminant function
Authors: Chang Woojin , Kim Seong‐Hee , Vidakovic Brani
Published: October 2003

In this paper, we consider wavelet‐based binary linear classifiers. Both consistency results and implementational issues are addressed. We show that under mild assumptions on the design density wavelet discrimination rules are L2‐consistent. The proposed method is illustrated on synthetic data sets in which the ‘truth’ is known and on an applied discrimination problem from the industrial field. Copyright © 2003 John Wiley & Sons, Ltd.
Catalysis of Oxo Transfer to Prochiral Sulfides by Oxovanadium(V) Compounds That Model the Active Center of Haloperoxidases
Authors: Santoni Gabriella , Licini Giulia , Rehder Dieter
Published: October 2003

The catalytic properties of a new class of chiral vanadium compounds—[(S,S,S)‐VO(OMe)L1] (5), [(S,S)‐VO(OMe)L2] (6), [(S,S)‐VO(OMe)L3] (7), and [(R,R,R)‐VO(OMe)L4] (8), as well as the system VO(OiPr)3/(R,R,R)‐H2L4 [H2L1=(S,S)‐bis(2‐hydroxypropyl)‐(S)‐1‐phenylethylamine, 1; H2L2=(S,S)‐bis(2‐hydroxypropyl)benzylamine, 2; H2L3=(S,S)‐bis(2‐hydroxypropyl)isopropylamine), 3; (H2L4)=(R,R)‐bis(2‐phenylethanol)‐(R)‐1‐phenylethylamine, 4]—in the asymmetric oxidation of prochiral sulfides by organic hydroperoxides have been investigated. Particular attention has been paid to the factors that guide the discrimination between the two prochiral faces of the sulfides (methyl p‐tolyl sulfide and benzyl phenyl sulfide), to steric implications stemming from the oxidant (cumyl hydroperoxide and tert‐butyl hydroperoxide), and to the specific complex used. As an example, (S)‐methyl p‐tolyl sulfoxide was obtained in a 31 % enantiomeric excess by use of cumyl hydroperoxide as oxidant and complex 5 as the catalyst, after 150 min at 0 °C and with 100 % conversion of the sulfide. The crystal and molecular structures of 5 and 6 reveal the close relationship between these complexes and the active center of vanadate‐dependent haloperoxidases: the vanadium is in a slightly distorted trigonal‐bipyramidal environment with the nitrogen and the methoxy group in the axial positions, and the oxo and alkoxide functions of L2 and L3 are the plane. The presence and equilibrium situation of isomers of the catalysts in solution has been investigated by 51V EXSY and variable‐temperature multinuclear NMR spectroscopy. An intermediately formed peroxo (ROO−) vanadium complex was detected by 51V NMR spectroscopy.
Pyrrole‐Appended Derivatives of O‐Confused Oxaporphyrins and Their Complexes with Nickel(II), Palladium(II), and Silver(III)
Authors: Pawlicki Miłosz , Latos‐Grażyński Lechosław
Published: October 2003

Condensation of 2,4‐bis(phenylhydroxymethyl)furan with pyrrole and p‐toluylaldehyde formed, instead of the expected 5,20‐diphenyl‐10,15‐di(p‐tolyl)‐2‐oxa‐21‐carbaporphyrin, a pyrrole addition product [(H,pyr)OCPH]H2; this product can formally be considered as an effect of hydrogenation of 3‐(2′‐pyrrolyl)‐5,20‐diphenyl‐10,15‐di(p‐tolyl)‐2‐oxa‐21‐carbaporphyrin ([(pyr)OCPH]H). The new oxacarbaporphyrinoid presents the 1H NMR spectroscopy features of an aromatic molecule, including the upfield shift of the inner H21 atom. Insertion of NiCl2 or PdCl2 into [(H,pyr)OCPH]H2 gave two structurally related organometallic complexes, [(pyr)OCP]NiII] and [(pyr)OCP]PdII], in which the metal ions are bound by three pyrrolic nitrogens and the trigonally hybridized C21 atom of the inverted furan. The reaction of [(H,pyr)OCPH]H2 with silver(I) acetate yields a stable AgIII complex [(C2H5O,pyr)OCP]AgIII] substituted at the C3 position by the ethoxy and pyrrole moieties. The macrocyclic frame of [(H,pyr)OCPH]H2 is conserved. Addition of trifluoroacetic acid to [(C2H5O,pyr)OCP]AgIII] yielded a new aromatic complex [(pyr)OCP]AgIII]+. The structures of [(pyr)OCP]NiII] and [(C2H5O,pyr)OCP]AgIII] have been determined by X‐ray crystallography. In both molecules the macrocycles are only slightly distorted from planarity and the nickel(II) and silver(III) are located in the NNNC plane. The dihedral angle between the macrocyclic and appended‐pyrrole planes of [(pyr)OCP]NiII] reflects the biphenyl‐like arrangement with the NH group pointing out toward the adjacent phenyl ring on the C5 position. Tetrahedral geometry around the C3 atom was detected for [(C2H5O,pyr)OCP]AgIII]. The NiC and AgC bond lengths are similar to other nickel(II) or silver(III) carbaporphyrinoids where the trigonal carbon atom coordinates the metal ion. The trend detected in the 13C chemical shifts for the appended‐pyrrole resonances has been rationalized by the extent of effective conjugation between the macrocycle and the appended pyrrole moiety controlled by the hybridization of the C3 atom and the metal ion oxidation state. The dianionic or trianionic macrocyclic core of the pyrrole‐appended derivatives is favored to match the oxidation state of nickel(II), palladium(II), or silver(III), respectively.
Electronically Tuned Chiral Ruthenium Porphyrins: Extremely Stable and Selective Catalysts for Asymmetric Epoxidation and Cyclopropanation
Authors: Berkessel Albrecht , Kaiser Patrick , Lex Johann
Published: October 2003

We report the use of three enantiomerically pure and electronically tuned ruthenium carbonyl porphyrin catalysts for the asymmetric cyclopropanation and epoxidation of a variety of olefinic substrates. The D4‐symmetric ligands carry a methoxy, a methyl or a trifluoromethyl group at the 10‐position of each of the 9‐[anti‐(1,2,3,4,5,6,7,8‐octahydro‐1,4:5,8‐dimethanoanthracene)]‐substituents at the meso‐positions of the porphyrin. Introduction of a CF3‐substituent in this remote position resulted in greatly improved catalyst stability, and turnover numbers of up to 7 500 were achieved for cyclopropanation, and up to 14 200 for epoxidation, with ee values typically >90 % and ≈80 %, respectively. In one example, the axial CO ligand at the ruthenium was exchanged for PF3, resulting in the first chiral ruthenium porphyrin with a PF3 ligand reported to date. In cyclopropanations with ethyl diazoacetate, the latter catalyst performed exceedingly well, and gave a 95 % ee in the case of 1,1‐diphenylethylene as substrate.
Chiral Arene Ruthenium Complexes: Synthesis and Molecular Structure of the Enantiopure Cluster Cation (S)‐[H3Ru3{C6H5[CH(CH3)CH2OH]}(C6Me6)2(O)]+
Authors: Vieille‐Petit Ludovic , Therrien Bruno , Süss‐Fink Georg
Published: October 2003

The reaction of enantiopure (R)‐(2‐cyclohexa‐1,4‐dienyl)propan‐1‐ol with ruthenium chloride hydrate yields, without racemisation of the chiral ligand, the chloro‐bridged dinuclear complex (S,S)‐[RuCl2{C6H5[CH(CH3)CH2OH]}]2 (1). The dimer 1 reacts with triphenylphosphane to give the mononuclear complex (S)‐[RuCl2{C6H5[CH(CH3)CH2OH]}(PPh3)] (2). A single‐crystal X‐ray structure analysis of 2 reveals the absolute configuration of the asymmetric carbon atom to have remained, the change from (R) to (S) being due to the priority change caused by coordination; in the solid state, onedimensional hydrogen‐bonded chains are formed between the hydroxy functions and chloro ligands of neighbouring molecules. The mononuclear cationic complex (S)‐[Ru{C6H5[CH(CH3)CH2OH]}(H2O)3]2+, formed in situ from 1 in aqueous solution, reacts with the dinuclear complex [H3Ru2(C6Me6)2]+ to give a chiral trinuclear arene‐ruthenium cluster, the cation (S)‐[H3Ru3{C6H5[CH(CH3)CH2OH]} (C6Me6)2(O)]+ (3). This enantiopure cation has been isolated and characterised as its tetrafluoroborate salt. The single‐crystal X‐ray structure analysis of (S)‐[3][BF4] shows a strong intramolecular hydrogen bond between the μ3‐oxo cap and the hydroxy function, which also persists in acetone solvent, as demonstrated by NMR spectroscopy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
New Tris(pyrazolyl)triazine and Pyrazolylpyridine Gold(I) and Palladium(II) Derivatives Based on the 3,5‐Bis(4‐butoxyphenyl)pyrazole Group − Architectures with Different Types of Bonding Interactions
Authors: Claramunt Rosa M. , Cornago Pilar , Cano Mercedes , Heras José V. , Gallego M. Luz , Pinilla Elena , Torres M. Rosario
Published: October 2003

The 3,5‐bis(4‐butoxyphenyl)pyrazolyl group (Pzbp2) has been used as a building block for mono‐ and polymetallic derivatives of 2,4,6‐tris[3,5‐bis(4‐butoxyphenyl)pyrazol‐1‐yl]‐1,3,5‐triazine (TPzbp2Tz, 1), 2‐[3,5‐bis(4‐butoxyphenyl)pyrazol‐1‐yl]pyridine (Pzbp2Py, 2), and 3,5‐bis(4‐butoxyphenyl)pyrazole (HPzbp2, 3) ligands. The synthesis and characterisation of the new hexadentate ligand 1 are described, together with the chemistry of its metal complexes containing [Pd(η3‐C3H5)]+ and [Au(PPh3)]+ fragments. The related complexes containing Pzbp2Py (2) were also studied and their structural characteristics were compared to those of the TPzbp2Tz species. The role of the counter‐ion on the supramolecular assembly of complexes containing the HPzbp2 ligand 3 was made clear by the X‐ray structures of [Pd(η3‐C3H5)(HPzbp2)2](BF4) and [Au(HPzbp2)(PPh3)](NO3). Hydrogen bonds and/or bonding interactions are responsible for pseudohelical one‐dimensional polymers or supramolecular columnar arrays, respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Empowerment psychotherapy with adolescent females of color
Authors: Querimit Dara S. , Conner Latoya C.
Published: October 2003

We present an empowerment model that fosters strengths and promotes positive identity development among adolescent females of color. Race, ethnicity, gender, and socioeconomic status are integrated in an African American context. A case study illustrates a strength‐based approach to conceptualizing and treating a young, Black adolescent female in her cultural context. We conclude with clinical implications for using an empowerment‐based approach in psychotherapy with culturally diverse adolescent females. © 2003 Wiley Periodicals, Inc. J Clin Psychol/In Session.
Age‐related differences in MAP kinase activity in VSMC in response to glucose or TNF‐α
Authors: Li Muyao , Mossman Brooke T. , Kolpa Emily , Timblin Cynthia R. , Shukla Arti , Taatjes Douglas J. , Fukagawa Naomi K.
Published: October 2003

Aortic vascular smooth muscle cells (VSMC) were used to study the effect of age on responses to high glucose concentrations or the cytokine, tumor necrosis factor‐alpha (TNF‐α). Activator protein‐1 (AP‐1) binding to DNA increased more in VSMC from old versus young rats (P < 0.02) and was related to increased expression of its components, c‐Fos, Fra‐1, and JunD. The relationship to upstream signals, i.e., activities of mitogen‐activated protein kinases (MAPK), was studied using antibodies to total and phosphorylated forms of extracellular signal‐regulated kinases (ERK), c‐Jun N‐terminal kinases (JNK) and p38. High glucose and TNF‐α increased ERK phosphorylation more in old (P < 0.05); whereas only TNF‐α induced JNK activation in young (P < 0.04). PD98059, a MEK inhibitor, attenuated AP‐1 activation, lowered c‐Fos and Fra‐1 protein levels and reduced cell number and cells positive for proliferating cell nuclear antigen in old. We concluded that age differentially influenced activation of signaling pathways in VSMC exposed to high glucose or TNF‐α. This may contribute to the increased risk for vascular disease associated with aging and diabetes mellitus (DM). J. Cell. Physiol. 197: 418–425, 2003© 2003 Wiley‐Liss, Inc.
Irrigation with plant extracts in ecofarming increases biomass production and mineral and organic nitrogen content of plants
Authors: Gramss Gerhard , Voigt Klaus‐Dieter , Bergmann Hans
Published: October 2003

Seedlings of alfalfa, rape, spinach, and wheat, potted on sandy soil, were irrigated with an aqueous extract of pea shoot (PE, 9.84 g dry weight l–1) or a solution of Ca, K, Mg, P, and NO3‐N salts (SS) in a concentration similar to that in PE, for 31–48 days. In comparison to water‐irrigated controls, both SS and PE treated plants showed nearly equal increases in shoot dry weight (29–40 %), whereas PE‐treated plants had higher fresh weights (38–84 %) due to increased succulence. Treatment with SS did not enhance, but sometimes even reduce, the concentrations of Ca, K, Mg, and several trace elements in shoot tissues. In contrast, PE‐treated plants had higher Ca, K, Mg, and organic N, but lower As and Ni contents and were thus of higher nutritive value. Reduced contents of metals in plant tissue correlated with their reduced solubility in the soil solution, which was not due to changes in pH. Fertilizer components such as K and Mg (metals of lower exchange intensity) were incorporated into the soil to release Ca, Sr, and Ba (metals of higher exchange intensity) and reduce the solubility of most trace elements and metal‐complexing humic substances. In addition, application of Ca precipitated heavy metals and humic complexes directly from the soil solution. This effect was partially overcome by PE. Its carboxylic acids could act as phytochelators of metal ions and as mobilizers of the highly diffusible humic substances which carry metals to roots. It is concluded that continuous PE application replaces the quantities of Ca, K, Mg, P, and organic N, but not of NO3‐N consumed during plant growth. Using PE does not add any relevant quantities of toxic metals to the plant‐soil system.
Effect of crop type and crop growth on atmospheric nitrogen deposition
Authors: Böhme Frank , Merbach Ines , Weigel Annett , Russow Rolf
Published: October 2003

Varying atmospheric nitrogen (N) depositions for different crops were observed at Bad Lauchstädt (Saxony‐Anhalt, Germany) when using the ITNI system (ITNI = Integrated Total Nitrogen Input), which is based on the 15N isotope dilution method. These differences were only partly explained by climatic influences. The effects of crops on the atmospheric N deposition measured by the ITNI system are discussed. For this purpose, data of six different plant species recorded in 1998 were re‐analyzed. It was found that the airborne N input is closely correlated with the morphology and metabolism of crops. Daily atmospheric N depositions of 129.0–360.8 g per hectare were measured for the plant species used. The nutritional supply of plants, especially with N, is another factor of influence on the N input from the atmosphere which should be considered. To investigate this aspect, a pot experiment was conducted with the grass Lolium perenne at three different N levels. An increase in the airborne N uptake (corresponding to N fertilization) was observed as biomass production rose.
Repräsentanz und Vergleichbarkeit von Daten und Flächen der Bodendauerbeobachtung
Authors: Schröder Winfried , Schmidt Gunther , Pesch Roland
Published: October 2003

Es wird ein Verfahren für die Prüfung der Eignung der Daten von Bodendauerbeobachtungsflächen (BDF) der Länder für Bodenschutzaufgaben sowie die Umweltbeobachtung und ‐berichterstattung des Bundes vorgestellt. Grundlage für die Eignungsprüfung der BDF‐Daten sind die Kriterien Landschaftsrepräsentanz sowie Vergleichbarkeit und räumliche Verallgemeinerbarkeit der Messdaten. Die Erfüllung dieser Eignungskriterien wird in einem dreistufigen Ansatz geprüft:

1. Erhebung von Informationen über die Vergleichbarkeit der Daten von BDF anhand der Messmethoden und ‐größen einschließlich ihrer Qualitätssicherung;

2. statistische Analyse der Repräsentanz von BDF der Länder in Bezug auf flächendeckend verfügbare Daten über bodenschutzrelevante Landschaftsmerkmale sowie

3. geostatistische Analyse der räumlichen Verallgemeinerbarkeit der BDF‐Messdaten.

Dafür verwendete Daten und Statistik‐Software werden in einem Geographischen Informationssystem (GIS) verknüpft. Die Metadatenanalyse belegt, dass die Bodendauerbeobachtung ökosystemar angelegt ist, einen beachtlichen Grad methodischer Harmonisierung aufweist und deshalb eine besonders wichtige Form des Länder übergreifenden Umweltmonitorings darstellt. Die Repräsentanzanalyse zeigt, dass zur Beurteilung der Effizienz und Suffizienz eines Umweltmessnetzes nicht nur die Landschaftsrepräsentanz seiner Standorte, sondern zusätzlich die geostatistische Repräsentanz der dort erhobenen Daten analysiert werden muss. Hierbei liefert die geostatistische Auswertung Hinweise auf die erforderliche Anzahl der Messstellen, deren räumliche Anordnung an der Landschaftsstruktur orientiert werden sollte.
Effect of sodium chloride on denitrification in glucose amended soil treated with ammonium and nitrate nitrogen
Authors: Azam F. , Müller C.
Published: October 2003

Laboratory incubations were conducted to study the effect of sodium chloride (NaCl) on denitrification and respiratory gases (CO2, O2) from soil treated with ammonium or nitrate and incubated at 20 % moisture. The same samples were assayed for denitrifying enzyme activity (DEA) after incubation at 40 % moisture with glucose and NO3–. Under aerobic conditions (20 % water content), a flush of activity was observed at 6 hours after start of incubation and subsided to negligible levels at 12 hours. Sodium chloride significantly depressed N2O and CO2 emissions and O2 consumption. Significantly more loss of N2O occurred from NH4+‐ than NO3–‐treated soil at all NaCl levels and was attributed to higher microbial activity. A highly significant positive correlation was obtained between N2O emission and respiratory gases. The respiratory quotient (CO2 evolved/O2) was higher for NH4+‐treated soil and decreased with the amount of NaCl. At 40 % moisture, N2O emissions were higher than at 20 % and peaked at 37 hours followed by a sharp decrease. Short‐term incubations of soil with NH4+ or NO3– did not have an effect on denitrifying enzyme activity (DEA) while NaCl had a positive effect, particularly in previously NO3–‐treated soil.
Solvent effects on sunscreen active ingredients using Raman spectroscopy
Authors: Beyere L. , Yarasi S. , Loppnow G. R.
Published: October 2003

We present Raman spectra of five sunscreen active ingredients in 10 solvents. Shifts in the UV absorption maxima and the CO Raman mode wavenumber are observed for some of the sunscreens as a function of solvent. Correlations between the observed wavenumber shifts and solvent properties indicate that hydrogen bonding is a key interaction between sunscreen active ingredients and solvent. Interestingly, the relative Raman intensities are also sensitive to the hydrogen‐bonding and polarizability properties of the solvent, reflecting differential stabilization of the sunscreen's resonance structures. These results suggest an ‘expanded polarizability’ view of the solvent's effect on the solute. The observed wavenumber and relative intensity changes were also utilized to identify the active agents present in commercial sunscreen preparations from their in situ Raman spectra. Copyright © 2003 John Wiley & Sons, Ltd.
Application of FT‐Raman and FTIR measurements using a novel spectral reconstruction algorithm
Authors: Sin Su Ying , Widjaja Effendi , Yu Liya E. , Garland Marc
Published: October 2003

Recently, an advanced spectral reconstruction algorithm based on information entropy was developed to identify individual compounds contained in mixture spectra without recourse to any library or any a priori knowledge. In this study, standard mixtures containing various polycyclic aromatic hydrocarbons (PAHs) and α,ω‐dicarboxylic acids were measured by solid‐state FT‐Raman and FTIR spectroscopy, and this was followed by the application of the aforementioned algorithm to recover all pure component spectra contained therein. The results demonstrate that the developed algorithm successfully recovered the spectra of individual species even though only a very limited number of mixture spectral measurements were made. FT‐Raman measurements coupled with chemometric analysis provides satisfactory pure spectral results for both PAHs and α,ω‐dicarboxylic acids. Additionally, FT‐Raman measurements together with FTIR measurements provided even better spectral recovery for some of the α,ω‐dicarboxylic acids when using band‐target entropy minimization (BTEM). This study demonstrates that chemometric analysis without a priori information provides a promising solution and simplified approach to identify individual components from samples containing a complex composition. In particular, this is desired for a better understanding of environmental samples. Copyright © 2003 John Wiley & Sons, Ltd.
Use of Hydroxyl Functionalized (Meth)acrylic Cross‐Linked Polymer Microparticles as Chain Transfer Agent in Cationic Photopolymerization of Cycloaliphatic Epoxy Monomer, 1
Authors: Valette Ludovic , Pascault Jean‐Pierre , Magny Benoît
Published: October 2003

In the case of cationic‐type photopolymerized epoxy networks, a new type of chain transfer agent based on hydroxyl functional acrylic cross‐linked polymer microparticles (CPM, also called microgels) has been tested. The CPM functionality was obtained through hydroxyethyl acrylate (HEA) monomer, used as comonomer with butyl acrylate (BA) and hexane diol diacrylate (HDDA). Stabilizing monomers were also required for the synthesis of CPM. In order to compare their particular effects, 4 sets of CPM were synthesized with 4 different stabilizing agents, either hydroxyl functional or not. Consequently, two types of OH groups were present in the particles: primary groups coming from HEA and preferentially located in the particles, and optional hydroxyl groups due to the hydroxyl functional stabilizing agents which were mainly placed onto the particles' surface. The viscoelastic properties of the photopolymerized films have been used to obtain information about the chain transfer reaction and the network microstructure. In all cases, the rubber modulus, $E'_{\rm r}$ was improved because of the decrease of the number of dangling epoxy chains in the epoxy network. When hydroxyl groups were only present in the particles, the mobility of the linkages was assumed to be low, and the mechanical relaxation temperature, Tα, strongly increased. However, CPM aggregation occurred at high CPM concentrations, lowering $E'_{\rm r}$ and Tα. On the contrary, when OH groups were located both on the surface as well as inside the particles, no large CPM aggregation took place, even with [CPM] = 40 wt.‐%. Nevertheless, the presumably higher mobility of the linkages on the particles' surface prevented any Tα increase. The water absorption of all systems based on CPM was very low, around 2% whatever the concentration of chain transfer agent.

Schematic description of the transfer reaction between a propagating cationic‐type epoxy chain and a hydroxyl functional CPM.

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Schematic description of the transfer reaction between a propagating cationic‐type epoxy chain and a hydroxyl functional CPM.
The Effect of Transreactions on the Structure and Dynamic Mechanical Properties of 1:1 Poly(ethylene terephthalate)/Poly(ethylene 2,6‐naphthalate) Blends Produced by Cryogenic Mechanical Alloying
Authors: Mano João F. , Denchev Zlatan , Nogales Aurora , Bruix Marta , Ezquerra Tiberio A.
Published: October 2003

Cryogenically alloyed poly(ethylene terephthalate) (PET)/poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) blends (1:1 w/w) were subjected to melt pressing at 300 °C for various times. The binary polymer systems so obtained were studied by means of atomic force microscopy (AFM), dynamic mechanical analysis (DMA) and proton NMR. A high level of homogenization at the nanometer scale was achieved. By changing the time of melt pressing in the range of 1–35 min, PET‐PEN block copolymers with average block lengths decreasing between 10 and 2 repeat units were produced. This copolymer formation was accompanied by significant changes in the dynamic mechanical properties as revealed by the variations in the temperature dependence of the loss factor, tan δ, in the region of the glass transition. Particularly, with the increase of annealing time a transition from double to single alpha‐relaxation was observed. The traditional two‐phase Takayanagi model applied to these alpha‐relaxation data did not provide an adequate description of the viscoelastic behavior as a function of annealing time. The results were discussed in terms of the Adam‐Gibbs theory of the cooperatively rearranging regions.

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A refrigeration facility for milk cooling powered by photovoltaic solar energy
Authors: De Blas M. , Appelbaum J. , Torres J. L. , García A. , Prieto E. , Illanes R.
Published: October 2003

The use of renewable energy sources is usually a reliable alternative in rural areas and developing countries, where the grid line does not exist or is at a great distance. In this work, the characteristics and working conditions of a refrigeration facility designed for cooling down an expected daily production of 150 l of milk are analyzed. The facility is a stand‐alone, direct‐coupled system where 20 photovoltaic modules, 120 Wp each, power two permanent magnet, direct current motors of 24 V, 650 W. Each motor drives a separate cooling system compressor, which provides the flexibility to operate the equipment with one or two motors and with various interconnections of the PV modules, depending on the available irradiance level and the thermodynamic state of the system. The photovoltaic energy obtained during daylight hours is stored in the form of sensible and latent heat of frozen water in a tank surrounding a milk container.

Thermodynamic analysis of the system shows that the autonomy of the system is 2·5 consecutive cloudy days if the available stored ice energy is 80% of the nominal capacity of the water/ice tank. Results of the refrigeration efficiency are similar to those obtained by other commercial refrigeration facilities powered by a photovoltaic array, including batteries. Copyright © 2003 John Wiley & Sons, Ltd.
Functionalization of polyethylene based on metallocene catalysis and its application to syntheses of new graft copolymers possessing polar polymer segments
Authors: Kashiwa Norio , Matsugi Tomoaki , Kojoh Shin‐Ichi , Kaneko Hideyuki , Kawahara Nobuo , Matsuo Shingo , Nobori Tadahito , Imuta Jun‐Ichi
Published: October 2003

The control of hydroxylated polyethylene (PE) structures was investigated in the copolymerization of ethylene with allyl alcohol or 10‐undecen‐1‐ol with a specific metallocene, methylaluminoxane, and trialkyl aluminum catalyst system through changes in the copolymerization conditions. The incorporation of allyl alcohol into the PE backbones was controllable through changes in the trialkyl aluminum, leading to terminally hydroxylated PE or a copolymer possessing hydroxyalkyl side chains. The copolymerization of ethylene with 10‐undecen‐1‐ol gave copolymers with hydroxyalkyl side chains of various contents with a variety of molecular weights through changes in the copolymerization conditions. The obtained copolymers were useful as macroinitiators that allowed polar polymer segments to grow on the PE backbones, leading to the creation of graft copolymers that possessed PE and polar polymer segments. In this way, polyethylene‐g‐poly(propylene glycol) (PE‐g‐PPG) and polyethylene‐g‐poly(ϵ‐caprolactone) (PE‐g‐PCL) were synthesized. The 13C NMR analysis of PE‐g‐PPG suggested that all the hydroxyl groups were consumed for propylene oxide polymerization, and transmission electron microscopy demonstrated nanoorder phase separation and indistinct phase boundaries. 13C NMR and gel permeation chromatography analyses indicated the formation of PE‐g‐PCL, in which 36–80 mol % of the hydroxyl groups worked as initiators for ϵ‐caprolactone polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3657–3666, 2003
Dielectric assembly of a collagen‐model polypeptide in a triple helix
Authors: Imanishi Yukio , Kawazoe Naoki , Ichizawa Kensuke
Published: October 2003

In expectation of the formation of a thermally stable, dielectric supramolecular assembly of a polypeptide with an amino acid sequence similar to that of type‐2 collagen, a sequential polypeptide consisting of the repetition of the Pro‐Pro‐Gly tripeptide was synthesized by solid‐phase synthesis. Column chromatography of an ethanol solution of (Pro‐Pro‐Gly)10NH2 showed the presence of a double helix or triple helix of the polypeptide. The pattern of a circular dichroism (CD) spectrum of an ethanol solution of (Pro‐Pro‐Gly)10NH2 was very similar to that of an aqueous solution of (Pro‐Pro‐Gly)10OH, strongly suggesting the presence of a triple helix of the polypeptide in ethanol. An oriented monolayer assembly of (Pro‐Pro‐Gly)10NH2 was formed on a thin gold film. The distribution of surface unevenness and the surface potential were investigated with Kelvin force microscopy. The rising spots carried an electric potential from room temperature to 150 °C. The correspondence showed the usefulness of the oriented monolayer of the sequential polypeptide materials for thermally stable, dielectric nanodevices. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3632–3639, 2003