bluuebunny/crossref_metadata_2025 huggingface dataset:
Nickel(II) Chloride‐Catalyzed Regioselective Hydrothiolation of Alkynes
Authors: Ananikov Valentine P. , Malyshev Denis A. , Beletskaya Irina P. , Aleksandrov Grigory G. , Eremenko Igor L.
Published: December 2005

Regioselective Markovnikov‐type addition of PhSH to alkynes (HC≡C‐R) has been performed using easily available nickel complexes. The non‐catalytic side reaction leading to anti‐Markovnikov products was suppressed by addition of γ‐terpinene to the catalytic system. The other side reaction leading to the bis(phenylthio)alkene was avoided by excluding phosphine and phosphite ligands from the catalytic system. It was found that catalytic amounts of Et3N significantly increased the yield and selectivity of the catalytic reaction. Under optimized conditions high product yields of 60–85% were obtained for various alkynes [R=n‐C5H11, CH2NMe2, CH2OMe, CH2SPh, C6H11(OH), (CH2)3CN]. The X‐ray structure of one of the synthesized products is reported.
Highly Efficient and Metal‐Free Aerobic Hydrocarbons Oxidation Process by an o‐Phenanthroline‐Mediated Organocatalytic System
Authors: Tong Xinli , Xu Jie , Miao Hong
Published: December 2005

A highly efficient o‐phenanthroline‐mediated, metal‐free catalytic system has been developed for oxidation of hydrocarbons with dioxygen in the presence of N‐hydroxyphthalimide; various hydrocarbons were efficiently and high selectively oxidized, e.g., ethylbenzene to acetophenone in 97% selectivity and 76% conversion, under mild conditions.
Nanocrystalline Magnesium Oxide‐Stabilized Palladium(0): An Efficient and Reusable Catalyst for Suzuki and Stille Cross‐Coupling of Aryl Halides
Authors: Lakshmi Kantam M. , Roy Sarabindu , Roy Moumita , Sreedhar B. , Choudary B. M.
Published: December 2005

A nanocrystalline magnesium oxide‐stabilized palladium(0) catalyst is prepared by counterion stabilization of PdCl42− with nanocrystalline MgO followed by reduction. This ligand‐free heterogeneous nanocrystalline MgO‐stabilized nanopalladium [NAPMgPd(0)] catalyst using the basic MgO in place of basic ligands exhibits excellent activity in Suzuki and Stille cross‐coupling of haloarenes (chloro, bromo and iodo) to afford the unsymmetrical biaryls. The catalyst is quantitatively recovered by simple filtration and reused for four cycles with almost consistent activity.
Highly Air‐ and Water‐Stable Fluorinated Ferrocenylphosphine‐Aminophosphine Ligands and their Applications in Asymmetric Hydrogenations
Authors: Li Xingshu , Jia Xian , Xu Lijin , Kok Stanton H. L. , Yip C. W. , Chan Albert S. C.
Published: December 2005

Air‐ and water‐stable fluorinated ferrocenylphosphine‐aminophosphine ligands have been synthesized and applied to the Rh‐catalyzed asymmetric hydrogenation of enamides and α‐dehydroamino acid derivatives. These reactions afforded the corresponding products in good to excellent ees (up to 99.7% ee) and nearly quantitative yields. The combination of the remarkable air‐ and water‐stability with excellent catalytic performance makes these catalysts excellent choices for practical applications.
Cyanation of N‐Acylhydrazones with Trimethylsilyl Cyanide Promoted by a Brønsted Base and a Lewis Acid
Authors: Konishi Hideyuki , Ogawa Chikako , Sugiura Masaharu , Kobayashi Shū
Published: December 2005

Cyanation of N‐acylhydrazones using trimethylsilyl cyanide (TMSCN) proceeded well in the presence of an amine to afford the corresponding α‐hydrazinonitriles in high yields. For less reactive substrates, the combined use of an amine and a catalytic amount of scandium triflate [Sc(OTf)3] was effective to promote the reactions. The mechanistic study suggested that the amine worked as a Brønsted base.
Nevo syndrome with an NSD1 deletion: A variant of Sotos syndrome?
Authors: Kanemoto Nobuko , Kanemoto Katsuyoshi , Nishimura Gen , Kamoda Tomohiro , Visser Remco , Shimokawa Osamu , Matsumoto Naomichi
Published: December 2005

A 17‐month‐old girl with clinical manifestations of Nevo syndrome and NSD1 (nuclear receptor binding SET domain protein 1) deletion is described. Nevo syndrome is a rare overgrowth syndrome showing considerable phenotypic overlap with Sotos syndrome—another, more frequent overgrowth syndrome caused by NSD1 mutations or deletions. About a half of Japanese Sotos syndrome patients carry a 2.2‐Mb common deletion encompassing NSD1 and present with frequent brain, cardiovascular, or urinary tract anomalies. The girl we described had the common deletion and showed patent ductus arteriosus, atrial septal defect, vesicoureteral reflux, and bilateral hydronephrosis. It was thus concluded that the clinical manifestations, including the Nevo syndrome phenotype, were caused by the microdeletion. © 2005 Wiley‐Liss, Inc.
Syntheses and supramolecular structures of two 5‐nitrosalicylate titanocene complexes
Authors: Gao Ziwei , Zhang Caiyun , Dong Mingyuan , Gao Lingxiang , Zhang Guofang , Liu Zhaotie , Wang Gaofeng , Wu Denghui
Published: December 2005

Two 4‐coordinated titanocene complexes, [(η5‐C5H5)2Ti(O,O′)(5‐NO2‐OCC6H3)] (I) and [(η5‐C5H5)2Ti(2‐OH‐5‐NO2‐O2CC6H3)2] (II), have been synthesized by reaction of Cp2TiCl2and 5‐nitrosalicylic acid in aqueous media. Single‐crystal X‐ray analyses of I and II display the mononuclear forms of TiIV, and geometries at titanium atoms are distorted tetrahedrons, while the coordination environment at TiIVin complex I is different from that in complex II. Crystallographic characterization revealed that each of the complexes exhibits a three‐dimensional framework constructed through weak interactions, which are H‐bonding, π–π stacking and C–H·π interactions, but they differ greatly when forming the three‐dimensional network structure in both complexes. The results show that the dramatic change of conditions has great effect on the molecular structure of 5‐nitrosalicylate titanocene, thereby significantly influencing the weak interactions and the specific framework structure. Copyright © 2005 John Wiley & Sons, Ltd.
Prevention and reversal of lupus in NZB/NZW mice by costimulatory blockade with adeno‐associated virus–mediated gene transfer
Authors: Ye Xiaojing , Zhu Tong , Bastacky Sheldon , McHale Teresa , Li Juan , Xiao Xiao
Published: December 2005

Objective

To investigate the potency of costimulatory blockade with adeno‐associated virus (AAV)–mediated gene transfer in the prevention and reversal of lupus in a murine model.

Methods

AAV vectors expressing CTLA‐4Ig or CD40Ig were injected into NZB/NZW mice. Serum levels of transgene expression and autoantibody titers were determined by enzyme‐linked immunosorbent assay. The therapeutic effects on proteinuria, renal pathologic features, and survival rate were evaluated. Splenic T cell phenotypes were analyzed by flow cytometry. The humoral immune response to a foreign antigen was also examined in treated mice.

Results

A single injection of AAV serotype 8 (AAV8)–CTLA‐4Ig in neonatal NZB/NZW mice before the onset of lupus effectively delayed and inhibited autoantibody production, proteinuria, and kidney damage and prolonged their lifespan. In addition, coinjection of AAV8‐CTLA‐4Ig and AAV8‐CD40Ig vectors into neonatal mice achieved a synergistic effect and the best efficacy. The preventive effects were attributed to suppression of CD4+ T cell activation and the transition from naive to memory T cells. Moreover, coinjection of these 2 vectors in adult mice reversed the existing autoantibody levels, suppressed the development of proteinuria, and prolonged their lifespan. The therapeutic effects were found to be dependent on the vector dose. In addition, AAV‐mediated long‐term gene expression did not severely suppress the host humoral response to foreign antigen.

Conclusion

Our findings show that delivery of costimulatory inhibitor transgenes by AAV vectors could prevent and reverse lupus in this murine model, suggesting the potential of AAV‐mediated gene transfer as an alternative treatment for lupus.
Immunomodulatory effects of etanercept on peripheral joint synovitis in the spondylarthropathies
Authors: Kruithof Elli , Rycke Leen De , Roth Johannes , Mielants Herman , Bosch Filip Van Den , Keyser Filip De , Veys Eric M. , Baeten Dominique
Published: December 2005

Objective

Because different tumor necrosis factor α (TNFα) blockers may have distinct immunomodulatory effects on specific disease manifestations, the present study was carried out to investigate the immunomodulating effects of etanercept on peripheral synovitis in the spondylarthropathies (SpA).

Methods

Peripheral joint disease was assessed clinically, histologically, and radiologically in a prospective 2‐year study of 20 patients with SpA treated with etanercept. Synovial tissue biopsy samples obtained at weeks 0, 12, and 52 were analyzed by histology and immunohistochemistry for the extent of inflammation, changes to tissue architecture, and matrix degradation. Serum levels of myeloid‐related protein 8 (MRP‐8)/MRP‐14, matrix metalloproteinase 3 (MMP‐3), and cartilage oligomeric matrix protein (COMP) were determined by enzyme‐linked immunosorbent assay.

Results

Etanercept induced a rapid and sustained clinical improvement of peripheral joint disease. Histologic synovitis was down‐regulated, with a profound reduction in global cellular infiltration and T lymphocytes, but not B lymphocytes. The most prominent change in markers of inflammation was a reduction in the different macrophage subsets (CD68, CD163, MRP‐8, and MRP‐14), but this was not paralleled by a decrease in serum MRP‐8/MRP‐14. Structural changes included normalization of lining layer hyperplasia and a moderate reduction in vascularity. However, no effect on the microarchitecture of lymphoid aggregates was observed. In terms of an effect on matrix degradation, the synovial expression of MMP‐3 and MMP‐9 was down‐modulated in correlation with a rapid and profound decrease in serum MMP‐3. At week 52, serum COMP levels were also reduced. No significant radiologic disease progression was observed in these patients over a 2‐year period.

Conclusion

Use of etanercept effectively down‐modulated the immunopathologic processes of SpA synovitis, both in the short term and in the long term.
Immune modulation of collagen‐induced arthritis by intranasal cytokine gene delivery: A model for the therapy of rheumatoid arthritis
Authors: Woods Andrew M. , Thompson Stephen J. , Wooley Paul H. , Panayi Gabriel , Klavinskis Linda S.
Published: December 2005

Objective

To develop a passively targeted, patient‐compliant, intranasal interleukin‐10 (IL‐10) gene therapy delivery system and to investigate its therapeutic benefit in experimental collagen‐induced arthritis, a model of rheumatoid arthritis.

Methods

Arthritis was induced in DBA/1 mice and monitored following intranasal administration of an IL‐10 plasmid (pG‐IL‐10) or the empty vector 2 days (days −2 and 19) prior to collagen injection (prophylactic group, as a single dose after collagen boost on day 21 (early therapy group, or as a single dose upon acquisition of a disease score of 3 (late therapy group. IL‐10–induced alterations in cytokine secretion and proliferation by spleen and lymph node cells were assessed on days 31 and 65 and correlated with histologic changes and bone erosions assessed on day 65.

Results

Intranasal delivery of pG‐IL‐10 significantly delayed arthritis onset and reduced disease severity in the prophylactic group and early therapy group, reduced cellular infiltration and bone loss in the early therapy group, and reduced T cell proliferation in response to collagen on days 31 and 65 in these two groups, with a significant reduction in tumor necrosis factor α production on day 65. Within the late therapy group, disease progression was arrested for the rest of the study. The intranasally administered pG‐IL‐10 targeted monocytes and macrophages and showed dissemination to inflamed joints and draining lymph nodes in vivo. Importantly, systemic levels of IL‐10 (in serum) were transient (peaking on day 2) and undetectable by day 4.

Conclusion

Intranasal IL‐10 gene delivery significantly reduces bone destruction, shows evidence of reducing joint inflammation, and may be mediated by high local levels of IL‐10 produced by transfected monocytes trafficking to inflamed joints and draining lymph nodes.
Meta-analysis of sentinel lymph node biopsy after preoperative chemotherapy in patients with breast cancer
Authors: Xing Y , Foy M , Cox D D , Kuerer H M , Hunt K K , Cormier J N
Published: December 2005

Background

Women with breast cancer are more frequently being treated with preoperative neoadjuvant chemotherapy. The reliability of sentinel lymph node biopsy (SLNB) following chemotherapy has not been determined. This was a meta-analysis of studies that examined the results of SLNB after preoperative chemotherapy.

Methods

Included articles had to meet two criteria. First, patients had to have had operable breast cancer and to have undergone SLNB after preoperative chemotherapy and, second, patients had to have undergone subsequent axillary lymph node dissection. Meta-analyses were performed in which Bayesian hierarchical models were created to estimate the identification rate (IR) and sensitivity of SLNB in this setting.

Results

Twenty-one studies were identified that included a total of 1273 patients. The IRs reported ranged from 72 to 100 per cent, with a pooled estimate of 90 per cent. The sensitivity of SLNB ranged from 67 to 100 per cent, with a pooled estimate of 88 (95 per cent confidence interval 85 to 90) per cent. Meta-analyses performed using Bayesian modelling resulted in (posterior) estimates for IR and sensitivity of 91 (95 per cent credible interval 88 to 94) and 88 (95 per cent credible interval 84 to 91) per cent respectively.

Conclusion

SLNB is a reliable tool for planning treatment after preoperative chemotherapy.
Randomized clinical trial of Lichtenstein patch or Prolene Hernia System® for inguinal hernia repair
Authors: Vironen J , Nieminen J , Eklund A , Paavolainen P
Published: December 2005

Background

In this randomized prospective study the short- and long-term outcomes of patients undergoing inguinal hernia repair with either Lichtenstein mesh or the Prolene Hernia System® (PHS) were evaluated.

Methods

Postoperative pain and time to return to work, driving and sporting hobbies were recorded after 300 inguinal hernia repairs done by one of the two methods. Long-term sequelae and complications were assessed at follow-up visits 1 week, 1 month and 1 year after the operation.

Results

The median duration of operation for unilateral primary hernia was 37 min for the Lichtenstein operation and 27 min for the PHS procedure (P < 0·001). Postoperative pain was similar after both operations. Median sick leave was 7 days in both groups. Time to driving a car was 4 versus 3 days, and time to return to sporting hobbies 13 versus 11 days, in the Lichtenstein and PHS groups, respectively. Apart from a residual femoral hernia after Lichtenstein repair, no recurrent inguinal hernias were detected.

Conclusion

Both Lichtenstein and PHS methods resulted in rapid recovery and low recurrence rates. The PHS operation was significantly quicker.
Randomized clinical trial of day-care versus overnight-stay laparoscopic cholecystectomy
Authors: Johansson M , Thune A , Nelvin L , Lundell L
Published: December 2005

Background

Laparoscopic cholecystectomy has been performed as a day-care procedure for many years. Few studies have been conducted with primary focus on patient acceptance and preferences in terms of quality of life for this practice compared with overnight stay.

Methods

Data from 100 patients with symptomatic gallstones randomized to laparoscopic cholecystectomy performed either as a day-care procedure or with overnight stay were analysed. Complications, admissions and readmissions, quality of life and health economic aspects were assessed. Two instruments were used to assess quality of life, the Hospital Anxiety and Depression Scale (HADS) and the Psychological General Well-Being Index (PGWB).

Results

Forty-eight (92 per cent) of 52 patients in day-care group were discharged 4–8 h after the operation. Forty-two (88 per cent) of 48 in the overnight group went home on the first day after surgery. The overall conversion rate was 2 per cent. Two patients had complications after surgery, both in the day-care group. No patient in either group was readmitted. There was no significant difference in total quality of life score between the two groups. The mean direct medical cost per patient in the day-care group (€3085) was lower than that in the overnight group (€3394).

Conclusion

Laparoscopic cholecystectomy can be performed as a day-case procedure with a low rate of complications and admissions/readmissions. Patient acceptance in terms of quality of life variables is similar to that for cholecystectomy with an overnight stay. The day-care strategy is associated with a reduction in cost.
Guanine Oxidation by Electron Transfer: One‐ versus Two‐Electron Oxidation Mechanism
Authors: Kupan Adam , Saulière Aude , Broussy Sylvain , Seguy Christel , Pratviel Geneviève , Meunier Bernard
Published: December 2005

The degeneracy of the guanine radical cation, which is formed in DNA by oxidation of guanine by electron transfer, was studied by a detailed analysis of the oxidation products of guanine on oligonucleotide duplexes and by labeling experiments. It was shown that imidazolone, the major product of guanine oxidation, is formed through a one‐electron oxidation process and incorporates one oxygen atom from O2. The formation of 8‐oxo‐7,8‐dihydroguanine by a two‐electron oxidation process was a minor pathway. The two‐electron oxidation mechanism was also evidenced by the formation of a tris(hydroxymethyl)aminomethane adduct.
Extended Electrochemical Windows Made Accessible by Room Temperature Ionic Liquid/Organic Solvent Electrolyte Systems
Authors: Buzzeo Marisa C. , Hardacre Christopher , Compton Richard G.
Published: December 2005

The electrochemical windows of acetonitrile solutions doped with 0.1 M concentrations of several ionic liquids were examined by cyclic voltammetry at gold and platinum microelectrodes. These results were compared with those observed in the commonly used 0.1 M tetrabutylammonium perchlorate/acetonitrile system as well as with neat ionic liquids. The use of a trifluorotris(pentafluoroethyl)phosphate‐based ionic liquid, specifically, as supporting electrolyte in acetonitrile solutions affords a wider anodic window, which is attributed to the high stability of the anionic component of these intrinsically conductive and thermally robust compounds.
Role of the monomeric GTPase Rho in hematopoietic progenitor cell migration and transplantation
Authors: Göttig Stephan , Möbest Dietrich , Rüster Brigitte , Grace Bithiah , Winter Sylvia , Seifried Erhard , Gille Jens , Wieland Thomas , Henschler Reinhard
Published: December 2005

To investigate the role of the monomeric guanosine triphosphatase (GTPase) Rho on migration of hematopoietic progenitor cells (HPC), we employed different clostridial toxins which inhibit the Rho family of GTPases. Pretreatment with C2I‐C3, a cell‐accessible C3 transferase fusion protein that targets Rho, increased chemokinetic migration of the factor‐dependent multipotent cell line Factor Dependent Cell Paterson with mixed lineage differentiation potential (FDCP‐mix) and of primary lineage marker‐depleted HPC in vitro. In contrast, treatment with lethal toxin (LT) from Clostridium sordellii, which predominantly inactivates Rac, and with toxin B from C. difficile, which inactivates Rho, Rac and Cdc42, decreased in vitro migration. When HPC pretreated with LT or toxin B were transplanted into mice, homing to the bone marrow was impaired, whereas C2I‐C3 treatment did not alter HPC homing. However, in a competitive hematopoietic repopulation experiment in C57BL/6 mice, pretreatment of bone marrow cells with any of the inhibitors, including the Rho inhibitor C2I‐C3, resulted in suppressed donor‐type hematopoiesis. Our data indicate that whereas Rac supports HPC cell cycling, migration, short‐term homing and hematopoietic regeneration, Rho coordinates down‐regulation of HPC migration and is required for hematopoietic regeneration.
A mutant human IgG molecule with only one C1q binding site can activate complement and induce lysis of target cells
Authors: Michaelsen Terje E. , Thommesen John E. , Ihle Oistein , Gregers Tone F. , Sandin Randi H. , Brekke Ole Henrik , Sandlie Inger
Published: December 2005

There are potentially two binding sites for C1q on IgG, one on each CH2 domain of the gamma heavy chains, close to the lower hinge region. It is not clear whether the presence and involvement of both the C1q binding sites is necessary to induce the activation signal of human IgG. In order to clarify this issue, we made a hybrid mutant IgG1/IgG3 molecule where the IgG1 half of the molecule was made unable to activate complement through the introduction of a P329A mutation. The IgG3 half of the molecule was mutated to harbor a hinge region identical to that of IgG1, and for detection a peptide tag derived from p21ras was introduced into the FG loop of the CH1 domain. The hybrid IgG1P329A/IgG3h1‐ras molecules were isolated by Protein A affinity chromatography and shown to activate complement and induce complement‐mediated lysis at the same levels as wild‐type IgG1 and IgG3h1‐ras molecules. Thus, one C1q binding site per IgG is sufficient to induce activation. Wild‐type human IgG molecules might also normally expose only one C1q binding site as already shown for interaction with FcγR, were IgG expose one binding site per molecule.
Influenza H2 haemagglutinin activates B cells via a MyD88‐dependent pathway
Authors: Marshall‐Clarke Stuart , Tasker Lynn , Buchatska Olena , Downes Joan , Pennock Joanne , Wharton Steve , Borrow Persephone , Wiseman David Z.
Published: December 2005

Influenza viruses are serious respiratory pathogens, responsible for half a million deaths each year. The viral surface haemagglutinin (HA) protein has been shown to be an important determinant of viral pathogenicity. HA is the virion attachment and fusion protein, and the major target for neutralizing antibodies; however, it is also involved in triggering innate responses that may have an important impact on the disease course. We have examined the role of the toll‐like receptor (TLR) family in innate responses to influenza virus and influenza HA. TLR7 has recently been found to mediate recognition of influenza RNA. Here, we show for the first time that influenza HA of the H2 subtype induces innate responses in murine B lymphocytes via a MyD88‐dependent pathway distinct from that involved in sensing viral RNA. We also show that inactivated influenza virus induces activation of human B cells. Our findings suggest that the molecule mediating these responses may be a novel member of the TLR family.
A transmembrane‐anchored rat RAE‐1‐like transcript as a ligand for NKR‐P2, the rat ortholog of human and mouse NKG2D
Authors: Savithri Balasubramanian , Khar Ashok
Published: December 2005

NKG2D is a potent activating immunoreceptor that has been extensively characterized in NK cells and shown to lend costimulatory functions in CD8+ T cells under certain conditions. The list is growing of ligands for NKG2D, which are distantly related to MHC class I molecule and are often up‐regulated during cellular distress. Here, we describe the cloning of a novel (and incidentally the first) ligand for NKR‐P2, the rat ortholog of human and mouse NKG2D, termed as rat RAE‐1‐like transcript (RRLT). The newly identified ligand is homologous to mouse RAE‐1 family of proteins, but differs from them in being transmembrane anchored. The protein localizes to cell surface, and is expressed in a variety of tumor cell lines and tissues. Ectopic expression of the ligand induces NK cell activation, and renders the target cells susceptible to NK cell killing. In addition, the role of RRLT‐NKR‐P2 interaction in tumor killing has been demonstrated.
Crystal structure of HLA‐A*2402 complexed with a telomerase peptide
Authors: Cole David K. , Rizkallah Pierre J. , Gao Feng , Watson Neil I. , Boulter Jonathan M. , Bell John I. , Sami Malkit , Gao George F. , Jakobsen Bent K.
Published: December 2005

HLA‐A*2402 is the most commonly expressed HLA allele in oriental populations. It is also widely expressed in the Caucasian population, making it one of, if not the most abundant HLA I types. In order to study its structure in terms of overall fold and peptide presentation, a soluble form of this HLA I (α1, α2, α3 and β2m domains) has been expressed, refolded and crystallized in complex with a cancer‐related telomerase peptide (VYGFVRACL), and its structure has been solved to 2.8 Å resolution. The overall structure of HLA‐A*2402 is virtually identical to other reported peptide‐HLA I structures. However, there are distinct features observable from this structure at the HLA I peptide binding pockets. The size and depth of pocket B makes it highly suitable for binding to large aromatic side chains, which explains the high prevalence of tyrosine at peptide position 2. Also, for HLA binding at peptide position 5, there is an additional anchor point, which allows the proximal amino acids to protrude out, providing a prominent feature for TCR interaction. Finally, pocket F allows the anchor residue at position 9 to be bound unusually deeply within the HLA structure.
Structural Relationships in High‐Nuclearity Heterobimetallic Bismuth‐Oxo Clusters (Eur. J. Inorg. Chem. 24/2005)
Authors: Mehring Michael , Paalasmaa Sanna , Schürmann Markus
Published: December 2005

The cover picture shows three heterobimetallic sodium‐bismuth‐oxo silanolates: [Bi10Na5O7(OH)6(OSiMe3)15] (2), [Bi15‐Na3O18(OSiMe3)12] (3) and [Bi14Na8O18(OSiMe3)14(thf)4] (4). These novel polynuclear metal‐oxo clusters were obtained in addition to the hexanuclear oxygen‐centred complex [Bi2Na4O(OSiMe3)8] (1), which represents a well‐known structural motif found in several heterometallic group 15/group 1 compounds. As result of the similar ionic radii of sodium and bismuth and the flexible coordination chemistry of these main group metals, the formation of a large variety of heterobimetallic molecular structures is conceivable. Structural relationships between the metal‐oxo silanolates are described and a comparison with other polynuclear bismuth‐oxo compounds is given in order to identify basic building blocks. The approach is envisaged to develop rational design strategies towards molecular bismuth‐containing precursors for heterometallic materials. Details are discussed in the article by M. Mehring et al. on p. 4891 ff.
Sulfite Determination at In Situ Plated Copper Modified Gold Ultramicroelectrode Arrays
Authors: Ordeig Olga , Banks Craig E. , del Campo F. Javier , Muñoz Francesc Xavier , Davis James , Compton Richard G.
Published: December 2005

The electroanalytical detection of sulfite has been explored at an in situ formed copper ultramicroelectrode array. The protocol is based upon the in situ deposition of copper at a gold ultramicroelectrode array of cubic geometry which consists of 256 ultramicroelectrodes which are 5 microns in radius and are separated from their nearest neighbor by 100 microns. The immobilized copper array is electrocatalytic for the electrochemical reduction of sulfur dioxide which is formed after protonation of sulfite at low pH values (<pH 2). A sensitivity and detection limit of 0.35 nA μM−1 and 6 μM respectively is shown to be possible in pH 2.5 using linear sweep voltammetry with a linear range observed from 20–500 μM.
Carotid intima‐media thickness in late‐onset major depressive disorder
Authors: Chen Cheng‐Sheng , Chen Cheng‐Chung , Kuo Yu‐Ting , Chiang I‐Chan , Ko Chih‐Hung , Lin Hsiu‐Fen
Published: December 2005

Background

This study explored whether patients with late‐onset major depressive disorder showed higher carotid artery intima‐medium thickness (IMT) and investigated the relationship between the IMT and white matter hyperintensities on magnetic resonance imaging (MRI) among patients.

Methods

Fourteen elderly patients with late‐onset major depressive disorder from a psychiatric outpatient clinic and 11 non‐depressed controls received a comprehensive psychiatric assessment, ultrasound IMT measurements of the carotid arteries, and cerebral MRI.

Results

The carotid IMT was higher in the patient group vs the control group (1.26 ± 0.30 vs 1.00 ± 0.20 mm; t = 2.40, p < 0.03). The difference was more apparent in the common carotid artery (1.20 ± 0.32 vs 0.97 ± 0.13 mm; t = 2.31, p < 0.04). There was a high correlation (r = 0.55, p < 0.05) between the carotid IMT and white matter hyperintensities among patients with late‐onset major depressive disorder.

Conclusion

Results of this study suggest that atherosclerosis represented by the carotid IMT contributes to the development of late‐onset major depressive disorder. The findings support the vascular depression hypothesis. Copyright © 2005 John Wiley & Sons, Ltd.
Late‐life depression: the differences between early‐ and late‐onset illness in a community‐based sample
Authors: Janssen Joost , Beekman Aartjan T. F. , Comijs Hannie C. , Deeg Dorly J. H. , Heeren Thea J.
Published: December 2005

Background

Several studies have described etiological and clinical differences between elderly depressed patients with early onset of their illness compared to late onset. While most studies have been carried out in clinical samples it is unclear whether the findings can be generalized to the elderly population as a whole. The aim of this study was to compare early‐onset (EOD) and late‐onset (LOD) depressive illness in a community‐based sample.

Methods

Large (n = 3107) representative sample of older persons (55–85 years) in the Netherlands. Two‐stage screen procedure to identify elderly with MDD. The Center for Epidemiologic Studies Depression scale (CES‐D) was used as a screen and the Diagnostic Interview Schedule (DIS) to diagnose MDD. Data on 90 older persons with early‐onset depression and 39 with late‐onset depression were available.

Results

Those with LOD were older, and more often widowed. Family psychiatric history, vascular pathology, and stressful early and late life events did not differ between groups. EOD subjects had more often double depression and more anxiety.

Conclusions

In a community‐based sample we did not detect clear differences in etiology and phenomenology between EOD and LOD. This discrepancy with reports from clinical samples could be due to selection bias in clinical studies. Consequently, all patients with late‐life depression deserve a diagnostic work‐up of both psychosocial and somatic risk factors and treatment interventions should be focused accordingly. Copyright © 2005 John Wiley & Sons, Ltd.
Epigenetic regulation of metallothionein‐i gene expression: Differential regulation of methylated and unmethylated promoters by DNA methyltransferases and methyl CpG binding proteins
Authors: Majumder Sarmila , Kutay Huban , Datta Jharna , Summers Dennis , Jacob Samson T. , Ghoshal Kalpana
Published: December 2005

Metallothioneins (MTs) are a group of cysteine‐rich stress response proteins that scavenge reactive oxygen species and heavy metals. Recently, we have shown that MT‐I promoter is methylated and suppressed in some solid and liquid tumors and can be robustly activated following treatment with inhibitors of DNA methyltransferase (DNMT) and histone deacetylase (HDAC). Here, we have analyzed MT‐I chromatin structure in active, unmethylated (Hepa cells) and in repressed, methylated state (lymphosarcoma cells). Restriction enzyme accessibility assay showed that the MT‐I promoter has an open conformation in unmethylated state as opposed to refractory chromatin structure in methylated state. Positioning of nucleosomal arrays on the methylated promoter further confirmed the closed chromatin structure of the methylated promoter. Chromatin immunoprecipitation (ChIP) assay demonstrated that the unmethylated promoter is associated with K9‐acetyl, K4‐methyl, and S10‐phospho histone H3 whereas the methylated promoter is predominantly associated with K9‐methyl H3. HP1α that recognizes K9‐methyl H3 inhibited methylated MT‐1 promoter activity whereas closely related HP1γ repressed the promoter irrespective of its methylation status. Ubiquitously expressed DNA methyltransferase 1 (DNMT1) suppressed MT‐I promoter activity irrespective of its methylation status that does not require its catalytic activity. The DNMT1‐mediated repression of MT‐I promoter was relieved by trichostatin A, an HDAC inhibitor. Among the methyl CpG binding proteins, MBD2 and MBD4 specifically associated with the methylated promoter and inhibited its activity. In contrast, MBD1 and MeCP2 interacted with both promoters and suppressed the promoter activity irrespective of its methylation status. These results demonstrate that the methylated and unmethylated MT‐I promoter are differentially regulated by DNA methyltransferase and methyl‐CpG binding proteins, and DNMT1 could suppress MT promoter by a transcriptional mechanism independent of its enzymatic function. These studies suggest that the components of epigenetic machinery differentially regulate methylated and unmethylated MT‐I gene expression. J. Cell. Biochem. 97: 1300–1316, 2006. © 2005 Wiley‐Liss, Inc.
Ultrastructural and cytochemical aspects of the female gonad of Geoplana burmeisteri (Platyhelminthes, Tricladida, Terricola)
Authors: Falleni Alessandra , Lucchesi Paolo , Ghezzani Claudio , Silveira Marina , Gremigni Vittorio
Published: December 2005

The ultrastructure of the female gonad of the land planarian Geoplana burmeisteri was investigated by means of electron microscopy and cytochemical techniques. It consists of two small germaria located ventral to the intestine and of two irregular, lateral rows of vitelline follicles, both enveloped by a tunica composed of an extracellular lamina and an inner sheath of accessory cells. Accessory cell projections completely surround developing oocytes and vitellocytes. The main feature of oocyte maturation is the appearance of chromatoid bodies and the development of the rough endoplasmic reticulum (RER) and Golgi complexes. These organelles appear to be correlated with the production of egg inclusions of medium electron density, about 1.5–1.8 μm in diameter, which remain scattered in the ooplasm of mature oocytes. On the basis of cytochemical tests demonstrating their glycoprotein composition, these inclusions were interpreted as residual yolk globules. Vitellocytes are typical secretory cells with well‐developed RER and Golgi complexes that are mainly involved in the production of yolk globules and eggshell globules, respectively. Eggshell globules appear to arise from repeated coalescence of small Golgi‐derived vesicles and, at an intermediate stage of maturation, show a multigranular pattern. Later, after vesicle fusion, they reach a diameter of 1.3–1.6 μm when completely mature and show a meandering/concentric pattern, as is typical of the situation seen in most Proseriata and Tricladida. The content of yolk globules is completely digested by pronase, while the content of eggshell globules is unaffected. Mature vitellocytes contain, in addition, a large quantity of glycogen and lipid droplets as further reserve material. On the basis of the ultrastructural characteristics of the female gonad described above and in relation to the current literature, we conclude that G. burmeisteri appears to be more closely related to the freshwater triclads, in particular to members of the Dugesiidae, than to the marine triclads. J. Morphol. © 2005 Wiley‐Liss, Inc.
Molecular activity of sirolimus and its possible application in tuberous sclerosis treatment
Authors: Jozwiak Jaroslaw , Jozwiak Sergiusz , Oldak Monika
Published: December 2005

Sirolimus is one of the intensively investigated drugs with pluripotent activities. It binds to its intracellular receptor FKBP12 (FK506‐binding protein 12), a member of the family of FK506‐binding proteins, and inhibits the activity of mTOR, a serine/threonine kinase involved in numerous cell processes linked to cell growth control. The drug is currently registered for the prophylaxis of organ rejection and for use in coronary stents. However, unique characteristics of sirolimus make it a good candidate for anti‐cancer therapy. Indeed, phase II and III clinical studies in humans with several types of neoplasms are already under way. The review describes molecular activity of sirolimus and its analogs, characteristic for specific applications, in view of very recent advances involving tuberous sclerosis complex (TSC)‐mediated signaling pathways. Current studies with sirolimus performed in tuberous sclerosis animal models are presented. Possible application of sirolimus for treating tuberous sclerosis, disease caused by mutations of TSC proteins, is discussed. © 2005 Wiley Periodicals, Inc. Med Res Rev
Incorporation of selective population transfer and homo‐spin decoupling into selective one‐dimensional experiments
Authors: Uzawa Jun , Fujimoto Yasuo , Yoshida Shigeo
Published: December 2005

The incorporation of selective population transfer (SPT) and homo‐spin decoupling (HSD) into selective one‐dimensional (1D) experiments has been shown to be very useful in obtaining information on the elucidation of the structure of organic compounds. To demonstrate this, the determination of the relative configuration of the sugar moiety of Mi‐saponins has been presented. Copyright © 2006 John Wiley & Sons, Ltd.
Synthesis and properties of organosoluble polynaphthalimides based on 1,4,5,8‐naphthalene tetracarboxylic dianhydride, 3,3‐bis[4‐(4‐aminophenoxy)phenyl]phthalide, and various aromatic diamines
Authors: Yang Chin‐Ping , Su Yu‐Yang , Wang Je‐Min
Published: December 2005

Two series of polynaphthalimides (PNIs), II and III, were prepared from 1,4,5,8‐naphthalene tetracarboxylic dianhydride with the usual aromatic diamines (Ia–Ih) or Ia, which was used as a soluble modifying agent, and Ib–Ih via a one‐stage process with high‐temperature condensation. Series II and III had inherent viscosities of 0.57–1.34 and 1.15–1.63 dL/g, respectively. IIa and most of the III series were soluble in 1‐methy‐2‐pyrrolidone and m‐cresol at 5–10 wt % and afforded transparent and tough films by m‐cresol solvent casting with a tensile strength in the range of 75–99 MPa. The glass‐transition temperature and softening temperature of these PNIs were in the ranges of 360–404 and 188–241 °C, respectively, and the 10% weight loss temperatures were above 495 °C, with more than a 44% char yield at 800 °C in nitrogen. These PNI films had dielectric constants of 4.14–6.46 (1 MHz), with moisture absorption in the range of 0.87–1.91 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 940–948, 2006
Exchange coupling across quasi‐amorphous Zr–Fe spacer
Authors: Smardz L. , Smardz K. , Niedoba H.
Published: December 2005

Fe/Zr/Fe trilayers with wedge‐shaped Zr interlayer were prepared using UHV (5 × 10–10 mbar) DC/RF magnetron sputtering. The planar growth and interface alloying of the Fe and Zr layers was confirmed in‐situ by X‐ray photoelectron spectroscopy. For a Zr layer thickness (d Zr) from 1 to 3 nm we have observed patch domains characteristic for antiferromagnetic interlayer exchange coupling. Results showed that the Fe sublayers are very weakly exchange coupled or decoupled for d Zr > 3 nm. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Temperature effects in a spin‐orbital model for manganites
Authors: Daghofer M. , Neuber D. R. , Oleś Andrzej M. , von der Linden Wolfgang
Published: December 2005

We study a two‐dimensional effective orbital superexchange model derived for strongly correlated eg electrons coupled to t 2g core spins in layered manganites. One finds that the ferromagnetic (FM) and antiferromagnetic (AF) correlations closely compete, and small changes of parameters can switch the type of magnetic order. For the same reason, spin order is easily destroyed with rising temperature, while alternating orbital correlations can persist to temperatures where FM order has already melted. A scenario for the AF phase observed in LaSrMnO4 is presented. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Transversal and longitudinal diffusion in polar disordered organic materials
Authors: Novikov Sergey V. , Malliaras George G.
Published: December 2005

Longitudinal and transversal diffusion of charge carriers in disordered polar organic materials has been studied using Monte Carlo simulation. It was found that the simple Einstein relation is valid for the transversal diffusion coefficient, while neither the simple nor the modified Einstein relation is valid for the longitudinal diffusion coefficient. Effect of the field dependence of the transversal diffusion coefficient on the ultimate resolution of organic devices has been discussed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Conductance fluctuations and corrections to the localization length in two‐dimensional localized systems
Authors: Prior J. , Somoza A. M. , Ortuño M.
Published: December 2005

We have studied numerically the average and the fluctuations of the conductance in two‐dimensional disordered non‐interacting systems in the localized regime. We have calculated the zero temperature conductance from the Green functions, which can be efficiently obtained propagating strip by strip. We have studied the finite size corrections to the average of the logarithm of the conductance and they turn out to be crucial in the numerical calculation of the localization length. We found that the third moment of the logarithm of the conductance ln g is proportional to 〈ln g〉 for large systems. As the variance goes as 〈ln g〉2/3, we conclude that the distribution of ln g does not tend to a log normal distribution, but to an asymmetric distribution that keeps a constant shape in the limit of large sizes. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Quantitative non‐destructive determination of trace elements in archaeological pottery using a portable beam stability‐controlled XRF spectrometer
Authors: Romano F. P. , Pappalardo G. , Pappalardo L. , Garraffo S. , Gigli R. , Pautasso A.
Published: December 2005

A portable beam stability‐controlled XRF spectrometer developed at the LNS/INFN laboratories at Catania (Italy) was used for the non‐destructive determination of some trace elements (Rb, Sr, Y, Zr and Nb) in fine pottery artefacts. The XRF system and the method developed to control the energy and intensity stability of the excitation beam are briefly discussed. Concentrations of Rb, Sr, Y, Zr and Nb were determined in 50 fine potsherds from the votive deposit of San Francesco in Catania by using a multi‐linear regression method. Additionally, in order to test the homogeneity of the material composing the fine pottery samples, a small portion of a few potsherds was powdered and analysed using the XRF system and the multilinear regression method. A comparison between non‐destructive and destructive approaches is presented and discussed. Finally, quantitative XRF data were compared with those obtained by chemical analysis of the powdered samples. The results allowed the testing of a non‐destructive methodology to be used for the identification and grouping of the different typological classes of fine pottery mainly represented in the San Francesco sanctuary. Copyright © 2005 John Wiley & Sons, Ltd.
Promiscuity in the part‐phosphorylative Entner–Doudoroff pathway of the archaeon Sulfolobus solfataricus
Authors: Lamble Henry J. , Theodossis Alex , Milburn Christine C. , Taylor Garry L. , Bull Steven D. , Hough David W. , Danson Michael J.
Published: December 2005

The hyperthermophilic archaeon Sulfolobus solfataricus metabolises glucose and galactose by a ‘promiscuous’ non‐phosphorylative variant of the Entner–Doudoroff pathway, in which a series of enzymes have sufficient substrate promiscuity to permit the metabolism of both sugars. Recently, it has been proposed that the part‐phosphorylative Entner–Doudoroff pathway occurs in parallel in S. solfataricus as an alternative route for glucose metabolism. In this report we demonstrate, by in vitro kinetic studies of d‐2‐keto‐3‐deoxygluconate (KDG) kinase and KDG aldolase, that the part‐phosphorylative pathway in S. solfataricus is also promiscuous for the metabolism of both glucose and galactose.
The biological clock of an hematophagous insect: Locomotor activity rhythms, circadian expression and downregulation after a blood meal
Authors: Meireles-Filho Antonio C.A. , da S. Rivas Gustavo B. , Gesto João S.M. , Machado Ricardo C. , Britto Constança , de Souza Nataly A. , Peixoto Alexandre A.
Published: December 2005

Despite the importance of circadian rhythms in vector‐borne disease transmission, very little is known about its molecular control in hematophagous insect vectors. In Drosophila melanogaster, a negative feedback loop of gene expression has been shown to contribute to the clock mechanism. Here, we describe some features of the circadian clock of the sandfly Lutzomyia longipalpis, a vector of visceral leishmaniasis. Compared to D. melanogaster, sandfly period and timeless, two negative elements of the feedback loop, show similar peaks of mRNA abundance. On the other hand, the expression of Clock (a positive transcription factor) differs between the two species, raising the possibility that the different phases of Clock expression could be associated with the observed differences in circadian activity rhythms. In addition, we show a reduction in locomotor activity after a blood meal, which is correlated with downregulation of period and timeless expression levels. Our results suggest that the circadian pacemaker and its control over the activity rhythms in this hematophagous insect are modulated by blood intake.
Free radicals‐mediated damage in transmitochondrial cells harboring the T14487C mutation in the ND6 gene of mtDNA
Authors: Gonzalo Ricardo , Garcia-Arumi Elena , Llige David , Marti Ramon , Solano Abelardo , Montoya Julio , Arenas Joaquín , Andreu Antonio L.
Published: December 2005

We have studied the production of reactive oxygen species (ROS) in transmitochondrial cells, harboring homoplasmic levels of the T14487C mtDNA mutation in the ND6 gene of mitochondrial DNA (mtDNA). Previous work has shown that this mutation causes complex I deficiency. Here, we show that this mutation causes an overproduction of ROS leading to an increase in the oxidation of lipids and mtDNA without modification of antioxidant enzyme activities. We suggest that mutations in mtDNA affecting complex I activity may result in oxidative cellular damage, and reinforce the possible role of ROS‐mediated mechanisms participating in some mtDNA‐related disorders.
Membrane topology of human ABC proteins
Authors: Tusnády Gábor E. , Sarkadi Balázs , Simon István , Váradi András
Published: December 2005

In this review, we summarize the currently available information on the membrane topology of some key members of the human ABC protein subfamilies, and present the predicted domain arrangements. In the lack of high‐resolution structures for eukaryotic ABC transporters this topology is based only on prediction algorithms and biochemical data for the location of various segments of the polypeptide chain, relative to the membrane. We suggest that topology models generated by the available prediction methods should only be used as guidelines to provide a basis of experimental strategies for the elucidation of the membrane topology.