bluuebunny/crossref_metadata_2025 huggingface dataset:
Immunohistochemical expression of tumor antigens MAGE‐A1, MAGE‐A3/4, and NY‐ESO‐1 in cancerous and benign prostatic tissue
Authors: Hudolin Tvrtko , Juretic Antonio , Spagnoli Giulio Cesare , Pasini Josip , Bandic Daniela , Heberer Michael , Kosicek Miljenko , Cacic Mirjana
Published: August 2005

OBJECTIVE

To investigate immunohistochemical expression of MAGE‐A and NY‐ESO‐1/LAGE‐1, cancer testis antigens in prostate tissues showing evidence of malignant transformation or benign hyperplasia.

METHODS

112 prostate samples from patients undergoing surgery at the Urology Clinic at the Zagreb Clinical Hospital Center from 1995 to 2003 were investigated in this study. Of these, 92 carcinoma samples were obtained by radical prostatectomy, and 20 benign prostatic hyperplasia samples by transvesical prostatectomy. Three monoclonal antibodies were used for immunohistochemical staining: 77B for MAGE‐A1, 57B for multi‐MAGE‐A and D8.38 for NY‐ESO‐1 expression.

RESULTS

Expression of MAGE‐A1 was observed in 10.8% of carcinoma samples, whereas multi‐MAGE‐A and NY‐ESO‐1/LAGE‐1 stained 85.9% and 84.8% of samples. Immunohistochemical staining was only detectable in the cytoplasm. A significant heterogeneity could be observed within a same tissue sample where areas with strong positivities coexisted with cancer testis antigens negative areas. Interestingly, a majority of 57B positive cases were also found to be D8.38 positive (correlation coefficient r = 0.727 (P < 0.01)). Cancer testis antigens expression was neither significantly correlated with PSA values nor with Gleason score. In benign prostatic hyperplasia tissues MAGE‐A1 expression was detected in 5%, while 57B and D8.38 staining was observed in 15% samples, and in all cases percentages of positive cells were always <10%.

CONCLUSION

Our data underline the peculiar relevance of cancer testis antigens expression in prostate cancers, with potential implications regarding both diagnosis and therapy. © 2005 Wiley‐Liss, Inc.
Differential attenuation of oxidative/nitrosative injuries in early prostatic neoplastic lesions in TRAMP mice by dietary antioxidants
Authors: Tam Neville N.C. , Nyska Abraham , Maronpot Robert R. , Kissling Grace , Lomnitski Liat , Suttie Andrew , Bakshi Shlomo , Bergman Margalit , Grossman Shlomo , Ho Shuk‐Mei
Published: August 2005

BACKGROUND

Dietary antioxidants with yet unproven efficacies in averting prostate cancer (PCa) are widely used in the United States as preventives. Experimental evidence establishing a causal relationship between oxidative and nitrosative stress (OS/NS) and PCa development and showing its modulation by dietary antioxidants would help justify their usage.

METHODS

The TRAMP (Transgenic Adenocarcinoma of the Mouse Prostate) mouse model was used to demonstrate the OS/NS‐associated damage, as evident by 8‐hydroxy‐2′‐deoxyguanosine (8‐OHdG), 4‐hydroxynonenal (4‐HNE)‐protein‐adducts and nitrotyrosine (Ntyr), in prostatic premalignant lesions, and to evaluate the antioxidant efficacy of various dietary supplements [natural antioxidant (NAO) from spinach extracts, ( − ) epigallocatechin‐3‐gallate (EGCG), or N‐acetylcystein (NAC)] during the early PCa development.

RESULT

We show, for the first time, that oxidative/nitrosative damages of genomic DNA and cellular proteins were discretely localized in premalignant lesions, but not in adjacent morphologically normal epithelia, of TRAMP prostates; these injuries were absent in age‐matched nontransgenic littermates. The extent of OS/NS‐related injuries correlated well with the tempo of development and prevalence of premalignant lesions in various prostatic lobes and exhibited a clear trend of increase from 12 to 20 weeks of age. Treatment of TRAMP mice with various antioxidants as dietary supplements resulted in differential alleviation of OS/NS‐related prostatic injuries. The antioxidant potencies of the dietary supplements did not fully correlate with their documented antiPCa actions, suggest that they may exert additional “nonantioxidant,” antitumor effects in this model.

CONCLUSIONS

Our data indicate that in TRAMP mice, OS/NS injuries are likely involved in early prostatic tumorigenesis and can be modulated by various antioxidants. © 2005 Wiley‐Liss, Inc.
E2F1 expression in LNCaP prostate cancer cells deregulates androgen dependent growth, suppresses differentiation, and enhances apoptosis
Authors: Libertini Stephen J. , Tepper Clifford G. , Guadalupe Moraima , Lu Ying , Asmuth David M. , Mudryj Maria
Published: August 2005

INTRODUCTION AND OBJECTIVES

To investigate the role of E2F/RB in androgen independent proliferation, differentiation, and sensitivity to apoptotic stimuli of LNCaP prostate cancer cells.

METHODS

The effects of E2F1 overexpression on androgen independent proliferation, differentiation, and apoptotic responses was assessed by flow cytometry, Western blot analysis and staining of nuclei.

RESULTS

Overexpression of E2F1 in LNCaP cells confers resistance to an androgen withdrawal‐mediated growth arrest, prevents differentiation, and modifies apoptotic responses. Androgen independent proliferation is associated with a dose dependent elevation of cyclin E. Cells expressing high levels of E2F1 continue to express androgen receptor and have a diminished expression of neuronal specific enolase when cultured in androgen‐depleted media. Additionally, E2F1‐expressing cells are more sensitive to etoposide‐induced apoptosis. Western blot analysis revealed that LNCaP‐E2F1 cells have elevated expression of p73, Apaf‐1, caspase‐3, caspase‐7, but expression of caspase‐8 and ‐9, p14(ARF), and Mcl‐1, is unaltered.

CONCLUSION

This is the first study that describes E2F1‐dependent modifications of androgen dependence, differentiation, and sensitivity to apoptotic stimuli in LNCaP cells. Our analysis also identifies a subset of E2F1 targets that are instrumental in altering proliferative, differentiation, and apoptotic properties. Deregulation of the E2F/RB pathway and subsequent modification of key regulatory proteins may promote the development of hormone‐refractory prostate tumors. Published 2005 Wiley‐Liss, Inc.
Plasma and prostate phytoestrogen concentrations in prostate cancer patients after oral phytoestogen supplementation
Authors: Rannikko Antti , Petas Anssi , Rannikko Sakari , Adlercreutz Herman
Published: August 2005

BACKGROUND

Phytoestrogens have been suggested to reduce the risk of prostate cancer (CaP), but no data exists on how oral phytoestrogen supplementation influences phytoestrogen concentrations in prostate tissue.

METHODS

Forty men with CaP, assigned for radical prostatectomy, received 240 mg of clover phytoestrogens or placebo daily for a 2‐week period before their operation in a prospective and randomized study. Phytoestrogens were measured in plasma and prostate tissue by time‐resolved fluoroimmunoassay (TR‐FIA).

RESULTS

All patients had low baseline phytoestrogen concentrations and only 35% had a detectable plasma concentration of equol. Oral supplementation with phytoestrogens induced a statistically significant (P < 0.001) 23‐ and 7‐fold increase in prostate tissue concentrations of the phytoestrogens genistein and daidzein, respectively. Supplemented patients demonstrated prostate tissue genistein and daidzein concentrations that were over twofold higher than their plasma. Interestingly, even though the placebo group did not receive phytoestrogen challenge, they also demonstrated twofold prostate tissue genistein and daidzein concentrations compared to their plasma values, suggesting that the prostate can concentrate available phytoestrogens. In addition, after the supplementation, 90% of the supplemented patients had a detectable plasma equol concentration.

CONCLUSIONS

We conclude that prostate tissue can concentrate genistein and daidzein. Significant elevation of intraprostatic genistein and daidzein concentrations can be achieved with a short‐term dietary phytoestrogen supplementation. © 2005 Wiley‐Liss, Inc.
Integrin‐dependent amplification of the G2 arrest induced by ionizing radiation
Authors: Kremer Celeste L. , Schmelz Monika , Cress Anne E.
Published: August 2005

The progressive loss of laminin 5 and the α6β4 integrin is a characteristic of the transition of prostatic intraepithelial neoplasia (PIN) to invasive human prostate cancer. Our objective was to determine if the loss of the interaction with laminin 5 would influence the ability of human epithelial cells to respond to DNA damage. Three cellular damage responses to ionizing radiation (IR) were analyzed including G2 progression, cdc2 phosphorylation, and cell survival. The adhesion of normal human prostate epithelial cells to laminin 5 amplified the G2 arrest induced by IR, and depends on a known cell binding domain of laminin 5. The alteration of G2 arrest was confirmed by an inhibition of phospho‐cdc2 nuclear translocation. In contrast, a prostate epithelial cancer cell line blocked in G2 independent of adhesion to laminin 5. The survival of these cell lines in response to IR was unaffected by adhesion to laminin 5. These results suggest that cell adhesion to laminin 5 in normal cells will amplify the IR induced G2 cell cycle progression block without altering cell survival. The loss of laminin 5 and the α6β4 integrin in PIN lesions may contribute to the selection and progression of genetically unstable cell types via attenuation of a DNA damage induced G2 arrest. © 2005 Wiley‐Liss, Inc.
Changes in gap junctional connexin isoforms during prostate cancer progression
Authors: Tate Amanda W. , Lung Tina , Radhakrishnan Anu , Lim So Dug , Lin Xi , Edlund Magnus
Published: August 2005

BACKGROUND

Connexins have their traditional function as part of gap junction (GJ) structures, but have recently been shown to have GJ‐independent roles. Although GJs and their connexin subunits are thought to be down‐regulated in cancer, depending on the connexin examined, many times the expression level is preserved or even increased. This is further apparent by the importance of GJs in “by‐stander effects” of radiation and viral targeting treatments.

METHODS

We surveyed connexin isoforms in prostate cancer cell lines and tissue with RT‐PCR and immunohistochemistry. Upon modulating GJ function, we observed prostate epithelial cell behaviors.

RESULTS

Advanced cells within PC‐3 and LNCaP prostate cancer progression models exhibit elevated connexin 26 (Cx26) levels—a trend validated in clinical samples. When GJs were inhibited, adhesion was not affected, but invasion and migration were strikingly decreased. A link between the expression of Cx26 and integrin adhesion‐linked functions are suggested by Cx26's direct interaction with focal adhesion kinase (FAK).

CONCLUSIONS

These results suggest a novel mechanism for adhesion regulation by a GJ‐independent Cx26 function that correlates with prostate disease progression. The increased Cx26 expression during prostate cancer progression plays a role in adhesion regulation possibly through its interaction with FAK. © 2005 Wiley‐Liss, Inc.
CXCL12/CXCR4 signaling activates Akt‐1 and MMP‐9 expression in prostate cancer cells: The role of bone microenvironment‐associated CXCL12
Authors: Chinni Sreenivasa R. , Sivalogan Sivasakthy , Dong Zhong , Filho J. Carlos Trindade , Deng Xiyun , Bonfil R. Daniel , Cher Michael L.
Published: August 2005

BACKGROUND

Hematopoietic cells home to bone by means of chemo‐attraction to marrow chemokines, and interaction of chemokines with their receptors leads to the expression/activation of adhesion molecules and proteases. Recent evidence suggests that similar mechanisms may be active in cancer metastasis. Previously, we showed that metalloproteases (MMPs), and in particular MMP‐9, play a role in prostate cancer (PC) expansion in bone.

METHODS

We used a variety of methods including RT‐PCR, immunohistochemistry, ELISA, gelatin zymography, cellular motility and invasion, and subcellular fractionation of PC cells applied to in vivo and in vitro models.

RESULTS

Here we showed that (a) CXCL12/CXCR4 axis is expressed in PC bone metastasis; (b) exogenous CXCL12 induced MMP‐9 expression by PC cells; (c) bone stromal cells and bone tissue conditioned media induced the migration of PC cells in a CXCR4‐dependent manner; (d) pharmacological inhibition of PI3 kinase and MAP kinase pathways abrogated CXCL12‐induced MMP‐9 expression and invasion of PC cells; (e) exogenous CXCL12 induced Akt1 phosphorylation is indispensable for proMMP‐9 secretion, migration, and invasion of PC cells; (f) CXCR4 was localized to lipid rafts in PC cells and initiated Akt phosphorylation.

CONCLUSIONS

These data suggest that chemoattractive mechanisms involve migration of cancer cells towards bone tissue, and that cell signaling induced by binding of the chemokine to its receptor leads to the activation of multiple signaling pathways and subsequent secretion of MMP‐9 into the local environment. These findings provide a link between chemoattractive mechanisms, growth of tumor cells in bone, and tumor‐enhanced bone matrix turnover. © 2005 Wiley‐Liss, Inc.
Association of hereditary prostate cancer gene polymorphic variants with sporadic aggressive prostate carcinoma
Authors: Noonan‐Wheeler Ferrin C. , Wu William , Roehl Kimberly A. , Klim Aleksandra , Haugen John , Suarez Brian K. , Kibel Adam S.
Published: August 2005

BACKGROUND

ELAC2, MSR1, and RNASEL are candidate genes for hereditary prostate carcinoma (HPC). While, studies have demonstrated that single nucleotide polymorphisms (SNPs) in these genes are associated with sporadic disease as well as HPC, these results are often not replicated in follow‐up studies. Given that the majority of patients studied had localized disease and up to 50% of localized prostate cancer is clinically insignificant, the inability to replicate the initial findings may reflect that some subjects had indolent tumors. Herein, we examine patients with metastatic disease to determine if an association exists between HPC SNPs and unambiguously significant prostate cancer.

METHODS

We examined polymorphisms within ELAC2 (S217L, A541T, E622V), MSR1 (P275A, R293X, aIVS5‐59c), and RNASEL (E265X, R462Q, D541E) in 150 European‐Americans with metastatic prostate cancer and 170 prostate cancer‐free controls using pyrosequencing assays.

RESULTS

Only ELAC2 217L (37% cases vs. 29% controls (P = 0.034)) and RNASEL 541E (61% cases vs. 53% controls (P = 0.045)) were over‐represented. Analysis of genotypes revealed that presence of the leucine ELAC2 allele (OR 1.54: 95% CI = 0.99–2.41, SS vs. SL, LL) and homozygosity for the glutamic acid RNASEL allele (OR 1.68: 95% CI = 1.04–2.70, EE vs. DE, DD) were associated with increased risk. Patients with both genotypes were of particularly high‐risk (OR 2.66: 95% CI = 1.36–5.19).

CONCLUSIONS

These results suggest that, in a European‐American population, ELAC2 217L and RNASEL 541E are associated with metastatic sporadic disease. ELAC2 and RNASEL SNP analysis may prove useful in determining which patients are at risk for developing clinically significant prostate carcinoma. © 2005 Wiley‐Liss, Inc.
Thermotherapy using magnetic nanoparticles combined with external radiation in an orthotopic rat model of prostate cancer
Authors: Johannsen Manfred , Thiesen Burghard , Gneveckow Uwe , Taymoorian Kasra , Waldöfner Norbert , Scholz Regina , Deger Serdar , Jung Klaus , Loening Stefan A. , Jordan Andreas
Published: August 2005

BACKGROUND

We evaluated the effects of thermotherapy using magnetic nanoparticles, also referred to as magnetic fluid hyperthermia (MFH), combined with external radiation, in the Dunning model of prostate cancer.

METHODS

Orthotopic tumors were induced in 96 male Copenhagen rats. Animals were randomly allocated to eight groups, including controls and groups for dose‐finding studies of external radiation. Treatment groups received two serial thermotherapy treatments following a single intratumoral injection of magnetic fluid or thermotherapy followed by external radiation (10 Gy). On day 20, after tumor induction, tumor weights in the treatment and control groups were compared and iron measurements in selected organs were carried out.

RESULTS

Mean maximal and minimal intratumoral temperatures obtained were 58.7°C (centrally) and 42.7°C (peripherally) during the first thermotherapy and 55.4°C and 42.3°C, respectively, during the second of two treatment sessions. Combined thermotherapy and radiation with 20 Gy was significantly more effective than radiation with 20 Gy alone and reduced tumor growth by 87.5–89.2% versus controls. Mean iron content in the prostates on day 20 was 87.5% of the injected dose of ferrites, whereas only 2.5% was found in the liver.

CONCLUSIONS

An additive effect was demonstrated for the combined treatment at a radiation dose of 20 Gy, which was equally effective in inhibiting tumor growth as radiation alone with 60 Gy. Serial heat treatments were possible without repeated injection of magnetic fluid. The optimal treatment schedules of this combination regarding temperatures, radiation dose, and fractionation need to be defined in further experimental studies. © 2005 Wiley‐Liss, Inc.
Effect of increasing ratio of estrogen: Androgen on proliferation of normal human prostate stromal and epithelial cells, and the malignant cell line LNCaP
Authors: King Keith J. , Nicholson Helen D. , Assinder Stephen J.
Published: August 2005

BACKGROUND

Changes in steroid ratios seen in the aging male are thought to promote prostate disease. The aims of this study were to compare the effects of varied ratios of steroids on growth of normal stromal and epithelial cell isolates, and the prostate cancer cell line, LNCaP.

METHODS

The effect of altered steroid ratios on cell proliferation of normal stromal (PrSC) and epithelial (PrEC) prostate cells, and the malignant cell line, LNCaP, were assessed.

RESULTS

Increasing the ratios of both estrogen:dihydrotestosterone (DHT) and DHT:estrogen, stimulated PrSC proliferation, with increasing estrogen:DHT having the greatest effect. LNCaP proliferation was increased significantly by both steroids, but altered ratios had no additional effect. PrEC proliferation was unaffected when cells were grown alone, despite presence of androgen receptors (AR) and estrogen receptors (ER). When grown in co‐culture PrEC cell proliferation was significantly increased by treatments.

CONCLUSIONS

PrSC proliferation is stimulated by an increasing ratio of estrogen:androgen. Proliferation of normal epithelial cells is stimulated as a result of an indirect action of steroids mediated by stromal cells. Malignant prostate cancer cells have an altered response in comparison. © 2005 Wiley‐Liss, Inc.
A Study on inhibitory effects of Sığla tree (Liquidambar orientalis Mill. var. orientalis) storax against several bacteria
Authors: Sağdıç Osman , Özkan Gülcan , Özcan Musa , Özçelik Sami
Published: August 2005

In this study, Sığla (Liquidambar orientalis Mill.) storax (styrax) was investigated for antibacterial activity against Aeromonas hydrophila, Bacillus amyloliquefaciens, B. brevis, B. cereus, B. megaterium, B. subtilis, Corynebacterium xerosis, Enterobacter aerogenes, Enterococcus faecalis, Escherichia coli, E. coli O157:H7, Klebsiella pneumoniae, Listeria monocytogenes, Micrococcus luteus, Mycobacterium smegmatis, Proteus vulgaris, Pseudomonas aeruginosa, P. fluorescens, Staphylococcus aureus and Yersinia enterocolitica. The storax was dissolved in absolute ethanol and was tested at concentrations of 10.0%, 1.0%, 0.4%, 0.2% and 0.1%. Pure ethanol was used for the control. The antibacterial activity of the Sığla storax was determined by using the agar diffusion method. The growths of A. hydrophila, B. amyloliquefaciens, B. megaterium, E. coli, E. coli O157:H7, L. monocytogenes and Y. enterocolitica were not inhibited by any of the concentrations of Sığla storax. The results showed that Sığla storax has antibacterial activity against many bacteria at concentrations of 10.0% and against some bacteria at concentrations of 1.0%, 0.4% and 0.2%. Copyright © 2005 John Wiley & Sons, Ltd.
Synthesis, Characterization, Molecular Structure, and Electrochemistry of a New Ferrocenoyl Derivative
Authors: Matesanz Ana I. , Cuadrado Isabel , Mosa Jadra , García Irene , Souza Pilar
Published: August 2005

A new organometallic compound containing a heterocyclic amine linked to the ferrocenoyl moiety was synthesized and characterized by elemental analysis (C, H, N), mass spectrometry, IR and 1HNMR spectroscopy. Its crystal and molecular structure was determined by X‐ray diffraction methods. This compound crystallizes in the monoclinic P21 space group, a = 5.80260(10), b = 9.24160(10), c = 12.3510(2) Å, β = 92.8200(10)° and Z = 2. An interesting feature of the crystal structure is the presence of an intermolecular non‐classical hydrogen bonding interaction between a cyclopentadienyl hydrogen atom and a carbonyl oxygen group. The electrochemical behaviour of this compound is characterized by the reversible one‐electron oxidation of the ferrocene moiety.
A First Principles Study of Hydrogen Storage in NaAlH4‐Related Complex Hydrides
Authors: Arroyo y de Dompablo M. E. , Ceder G.
Published: August 2005

We have applied first principles computations to predict the properties of complex hydrides related to the alanate NaAlH4, a very promising class of systems for reversible hydrogen storage. The effect of partial substitution on the Na site (by Li or K), and on the Al site (by B or Ga) on the thermodynamic stability of NaAlH4 and its decomposition product Na3AlH6 is investigated and evaluated by means of qualitative van't Hoff plots. From the calculated results we infer that the most promising improved hydrides are Na1−xLixAl1−yByH4, obtained by a double substitution on the Na and on the Al sites of NaAlH4.
Dinuclear Cobalt(III) Complexes Showing a Co2O2 Metallacycle
Authors: Fondo Matilde , Deibe Ana M. García , Ocampo Noelia , Bermejo Manuel R. , Sanmartín Jesús
Published: August 2005

The heptadentate Schiff base H3L reacts with cobalt(II) acetate in methanol to form the discrete dinuclear complex Co2L(OAc)2(OMe)(H2O)2 (1·2H2O). The reaction of 1·2H2O with NMe4OH·5H2O in methanol gives rise to displacement of the acetate by methanolate groups, yielding Co2L(OMe)3(H2O) (2·1H2O). Recrystallizations of the Schiff base, 1·2H2O and 2·H2O in different solvents, produce single crystals of H3L, 1·2.5H2O and 2·2MeOH, respectively. The crystal structures of 1·2.5H2O and 2·2MeOH show the cobalt atoms double bridged by and endogenous phenol oxygen atom and an exogenous methanolate oxygen donor, giving rise to Co2O2 cores with Co···Co distances of ca. 2.87 Å.
Copper(II), Cobalt(II), and Nickel(II) Complexes of two Novel Pyridine‐derived Macrocyclic Ligands bearing o‐ and pNitrobenzyl Pendant Groups
Authors: Martínez Jesús , Bastida Rufina , Macías Alejandro , Valencia Laura , Vicente Manuel
Published: August 2005

The pendant‐armed ligands L1 and L2 were synthesized by N‐alkylation of the four secondary amine groups of the macrocyclic precursor L using o‐nitrobenzylbromide (L1) and p‐nitrobenzylbromide (L2). Nitrates and perchlorates of CuII, NiII and CoII were used to synthesize the metal complexes of both ligands and the complexes were characterized by microanalysis, MS‐FAB, conductivity measurements, IR and UV‐Vis spectroscopy and magnetic studies. The crystal structures of L1, [CuL1](ClO4)2·CH3CN·H2O, [CuL2](ClO4)2·6CH3CN, [CuL2][Cu(NO3)4]·5CH3CN·0.5CH3OH and [NiL2](ClO4)2·3CH3CN·H2O were determined by single crystal X‐ray crystallography. These structural analysis reveal the free ligand L1, three mononuclear endomacrocyclic complexes {[CuL1](ClO4)2·CH3CN·H2O, [CuL2](ClO4)2·6CH3CN and [NiL2](ClO4)2·3CH3CN·H2O} and one binuclear complex {[CuL2][Cu(NO3)4]·5CH3CN·0.5CH3OH} in which one of the metals is in the macrocyclic framework and the other metal is outside the ligand cavity and coordinated to four nitrate ions.
Synthesis and Characterization of [(1,4‐diamine)dichloro]platinum(II) Compounds Preliminary Studies on their Biological Activity
Authors: de Mier‐Vinué Jordi , Montaña Ángel M. , Moreno Virtudes , Prieto María J.
Published: August 2005

Two 1,4‐diamine ligands were synthesized having 1,2‐bis(aminomethyl)‐cyclohexane and 1,2‐bis(aminomethyl)‐benzene structures. The two ligands have different electron density in the six‐membered ring: a cyclohexane versus a phenyl ring. The organic synthesis of the ligands was carried out by synthetic pathways of seven and four steps, respectively, starting from 1,2,3,6‐tetrahydrophthalic anhydride and diethyl phthalate. The coordination of platinum to these ligands afforded platinum(II) complexes which are analogue to the clinical drug cisplatin but form a seven‐membered chelate ring. The interaction of the platinum compounds with DNA was studied in order to know the relationship between the electron density of ligands and their capability to chelate DNA, by using three techniques: Circular Dichroism, Agarose Gel Electrophoresis and Atomic Force Microscopy. The degree of interaction of both compounds with DNA was slightly different, but both complexes showed a cisplatin‐like behaviour and are promising candidates to follow an extensive study of their cytotoxic activity.
Tetra(3‐methoxypropionato)diruthenium(II, III) Units: Supramolecular Organization in the Complex [Ru2(μ‐O2CCH2CH2OMe)4(H2O)2]BF4
Authors: Barral M. Carmen , González‐Prieto Rodrigo , Jiménez‐Aparicio Reyes , Priego J. Luis , Royer Elia C. , Torres M. Rosario , Urbanos Francisco A.
Published: August 2005

The synthesis and characterization of Ru2Cl(μ‐O2CCH2CH2OMe)4 (1), [Ru2(μ‐O2CCH2CH2OMe)4(H2O)2]BF4 (2), PPh4[Ru2Cl2(μ‐O2CCH2CH2OMe)4] (3), (PPh4)2[Ru2Br2(μ‐O2CCH2CH2OMe)4]NO3 (4), and (PPh4)2[Ru2I2(μ‐O2CCH2CH2OMe)4]I0.5(NO3)0.5 (5), are described. The structure of complexes 2–5 was established by single crystal X‐ray diffraction. All complexes show a diruthenium(II, III) unit bridged by four 3‐methoxypropionate ligands. The cationic complex 2 have two axially coordinated water molecules, with a Ru–Ru bond distance of 2.2681(12) Å. This complex shows a supramolecular two‐dimensional organization across hydrogen bonded between the axial water molecules and two methoxy groups of adjacent diruthenium units. The metal‐metal bond lengths, in the anionic complexes 3, 4, and 5, are 2.3039(5), 2.3077(6), and 2.3115(8) Å, respectively. These distances are longer than the observed in compound 2. In the anionic complexes, the axial positions of the diruthenium units are occupied by two halide ligands. Complexes 3–5 have PPh4+ cations as counterion, although 4 and 5 are double salts with PPh4NO3 and PPh4I0.5(NO3)0.5, respectively.

All compounds have been also characterized by elemental analysis, magnetic measurements, and spectroscopic techniques.
Mixed‐ligand Complexes with 2,6‐Pyridinedicarboxylato(2‐) and 4,7‐Diphenyl‐1,10‐Phenanthroline Ligands, [MII(pdc)(DPphen)(H2O)]·H2O (M = Co or Cu). Synthesis, Crystal Structures and Properties
Authors: Brandi‐Blanco María Pilar , Choquesillo‐Lazarte Duane , González‐Pérez Josefa María , Castiñeiras Alfonso , Niclós‐Gutiérrez Juan
Published: August 2005

Iso‐type [MII(pdc)(DPphen)(H2O]·H2O compounds (M = Co or Cu, pdc = 2,6‐pyridinedicarboxylato(2‐) ligand and DPphen = 4,7‐diphenyl‐1,10‐Phenanthroline) were synthesized and studied by X‐ray diffraction, thermal and spectral methods. The N,N′‐equatorial bidentate DPphen‐copper(II) chelation imposes a mer‐N(equatorial)+O2(apical) conformation to pdc in the coordination polyhedron (type 4+1+1). In the Co(II) derivative, the coordination is of type 1+2+2+1 because of a lesser Jahn‐Teller distortion. In the crystals, π,π‐interligand interactions between phen ligands connect the complex molecules in multi‐stacked chains. Aqua···O(carboxyl) H‐bonding interactions reinforce the stacked chains and build double chains in 1D supramolecular structures parallel to the a axis. Non coordinated water connect these structures by H‐bonds.
Electrochemical Synthesis and Characterization of Nickel(II) Complexes with N‐2‐Pyridyl‐sulfonamide Ligands
Authors: Beloso Inmaculada , Pérez‐Lourido Paulo , Castro Jesús , García‐Vázquez José A. , Romero Jaime
Published: August 2005

Heteroleptic nickel(II) complexes [NiL2L′] of a series of monoanionic and potentially bidentate N‐2‐pyridyl‐sulfonamide ligands [HL] and 2,2′‐bipyridine or 1,10‐Phenanthroline (L′) have been prepared by electrochemical oxidation of a nickel anode in an acetonitrile solution of the ligands. The complexes have been characterized by microanalysis, IR and electronic spectroscopy, magnetic measurements and LSI mass spectrometry. The crystal structure of [Ni(Ms6mepy)2(bipy)] has been determined by x‐ray diffraction and shows the metal in an octahedral NiN6 environment. Octahedral structures are also proposed for the other complexes with the N‐2‐pyridyl‐sulfonamide ligands acting as N,N′ or N, O bidentate systems, depending on the position of the methyl substituent on the pyridine ring.
Synthesis and Characterization of Spinel‐Type Gallia‐Alumina Solid Solutions
Authors: Areán C. Otero , Delgado M. Rodríguez , Montouillout V. , Massiot D.
Published: August 2005

By precipitation with ammonia of ethanolic solutions containing the appropriate proportions of gallium and aluminium nitrate, following by calcination of the resulting gels at 773 K, mixed Ga2O3/Al2O3 oxides having Ga:Al ratios of 9:1, 4:1, 1:1, 1:4 and 1:9 were obtained. Powder X‐ray diffraction showed that these mixed metal oxides form a series of solid solutions having the spinel‐type structure; also shown by γ‐Al2O3 and γ‐Ga2O3. The specific surface area (determined by nitrogen adsorption at 77 K) was found to range from 160 m2 g−1 for the mixed oxide having Ga:Al = 9:1 up to 370 m2 g−1 for that having Ga:Al = 1:9. High resolution MAS NMR showed that Ga3+ and Al3+ ions occur at both tetrahedral and octahedral sites in the spinel‐type structure of the mixed metal oxides, although there is a preferential occupation of tetrahedral sites by Ga3+ ions. A proportion of penta‐coordinated Al3+ ions was also found. IR spectra of carbon monoxide adsorbed at 77 K showed that the mixed metal oxides have a considerable Lewis acidity, related mainly to tetrahedrally coordinated metal ions exposed at crystal surfaces. The characteristic infrared absorption band of coordinated (adsorbed) CO appears in the range 2205–2190 cm−1, and its peak wavenumber is nearly independent of Ga:Al ratio in the mixed gallia‐alumina oxides.
Chromium(IV) Stabilisation in New Ceramic Matrices by Coprecipitation Method: Application as Ceramic Pigments
Authors: Monrós G. , Pinto H. , Badenes J. , Llusar M. , Tena M. A.
Published: August 2005

In this paper the stabilization of Cr4+ in new ceramic matrices as willemite Zn2SiO4 and galium‐gadolinium garnet GGG (Gd3Ga5O12) is studied and compared with the chromium‐sphene ceramic pigment using the traditional solid reaction and an unconventional coprecipitation method.The chromate amount etched from the powders using CrIII and CrVI precursors on ceramic and coprecipitation routes are analysed in order to evaluate the environmental impact on the waste water. Cr‐willemite and codoped Ca, Cr‐GGG produces solid solutions of Cr4+ ion occupying tetrahedral and dodecahedral sites, respectively, while Cr4+ into sphene lattice occupies octahedral sites. Cr‐willemite are stable when used as ceramic pigment in habitual tile glazes but Cr‐GGG unstabilses and produces green colour associated to Cr3+ solved in the glaze. Coprecipitate powders are more reactive than ceramic powders but in Cr‐GGG stabilizes the metastable Ca3Cr2O8 oxide. Chromate amount in washing hot water are not dependent of the chromium precursor but depends of the allowed reactivity level and the reaction media.
Synthesis and Electrochemical Study of Antifluorite‐type Phases in the Li‐M‐N‐O (M = Ti, V) Systems
Authors: Cabana J. , Mercier C. , Gautier D. , Palacín M. R.
Published: August 2005

Antifluorite‐type phases have been prepared in the Li‐M‐N‐O (M = Ti, V) systems by solid state reaction under nitrogen starting from mixtures of lithium nitride, different amounts of lithium oxide and the transition metal nitride. The two series of samples obtained can be formulated as Li5TiN3 · xLi2O and Li7VN4 · xLi2O solid solutions. X‐ray diffraction data indicate that, as the amount of oxygen increases, the superstructure peaks decrease in intensity without changing their position, whereas the peaks corresponding to the simple anti‐fluorite structure increase. Thus, samples with low oxygen content are a mixture of two phases: the corresponding ternary nitride (either Li5TiN3 or Li7VN4) and the quaternary oxinitride with a disordered antifluorite structure and hence structural disorder does not seem to be induced progressively, as previously believed. In agreement with previous studies, a decrease of the cell parameter with oxygen content is observed in both solid solutions. Even though no deintercalation/intercalation reactions were expected (no cationic vacancies exist in the sample and the transition metals are present in their highest oxidation states) an evaluation of the electrochemical performances of the samples vs. metallic lithium was done to test the possibility of conversion reactions taking place. However, none of them showed any electroactivity.
Mixed‐ligand Copper(II) Complexes with N‐isopropyl‐iminodiacetato(2‐) and C‐phenyl‐imidazole Ligands. Crystal Structures of H2iPIDA, [Cu(iPIDA)(H2ϕim)(H2O)]·3H2O and [Cu(iPIDA)(H5ϕim)]n
Authors: Rojas‐González Perla Xochitl , Brandi‐Blanco María Pilar , Castiñeiras Alfonso , Choquesillo‐Lazarte Duane , González‐Pérez Josefa María , Niclós‐Gutiérrez Juan
Published: August 2005

The crystal of the N‐isopropyl‐iminodiacetic acid (1) consists of a 3D H‐bonded framework where the zwitterion (H2iPIDA±) is intra‐stabilized by one N+‐H···O interaction and both carboxyl are half‐protonated and involved in linear O‐H···O inter‐molecular bridges of 2.46 Å. The mixed‐ligand complexes [Cu(iPIDA)(H2ϕim)(H2O)]·3H2O (2) and [Cu(iPIDA)(H5ϕim)]n (3) have also been synthesized and studied by thermal, spectral, magnetic and X‐ray diffraction methods. Both complexes exhibit a square base pyramidal coordination, type 4+1. Compound 3 is the less steric hindered 'remote' isomer, with H5ϕim instead of H4ϕim.
Interaction of Mn(acac)3 with Asymmetrical Schiff Base Ligands containing an Amido Group
Authors: González‐Noya Ana M. , Fernández M. Isabel , Maneiro Marcelino , Rodríguez M. Jesús , Pedrido Rosa , Vázquez Miguel , Bermejo Manuel R.
Published: August 2005

Interaction of asymmetrical Schiff base ligands H3Ln [where H3Ln are substituted 3–aza–4–(2–hydroxyphenyl)–N– (2–hydroxyphenyl)but–3–enamide] with Mn(acac)3 (acac = acetylacetonate) has been investigated. Two different type of manganese(III) complexes have been obtained depending on the nature of the substituents on the ligand. We have found that ligands containing donor substituents drives to the formation of two different kinds of complexes from the same reaction: Mn(Ln)(H2O)x (1a–5a) and [Mn(HLn)(acac)](H2O)y (1b–5b) (where Ln and HLn signify the ligand in its trianionic and dianionic form, respectively). However, when the substituents are electron withdrawing or poor donor only compounds of the type [Mn(HLn)(acac)](H2O)y (6–10) are obtained. All these compounds have been characterized by elemental analyses, IR and 1H NMR spectroscopy, FAB mass spectrometry, magnetic measurements and molar conductivities. The electrochemical behaviour of these complexes has also been studied.
Biological Activity of Flavonoids Copper Complexes
Authors: González‐Álvarez Marta , Alzuet Gloria , García‐Giménez José Luis , Macías Benigno , Borrás Joaquín
Published: August 2005

Three flavonoid copper(II) complexes Cu2(quercetin)(CH3COO)3(CH3OH) (1), Cu(anthrarufin)(CH3COO)·1/2H2O (2) and Cu(naringin)(OCH3)(CH3OH)2 (3) have been synthesized and characterized by elemental analysis, IR, electronic absorption and EPR (X‐band) spectroscopy. The complexes have a strong protective action over the Δsod1 mutant of S. cerevisiae against reactive oxygen radicals generated by an external source of free radicals (H2O2 or the superoxide‐generating, menadione). On the other hand, the complexes cleave DNA efficiently even in the absence of reducing agents. The main reactive oxygen species responsible for the DNA strand cleavage have been determined using radical scavengers. A probably mechanism of the DNA damage is proposed.
Study of Sb‐doped SnO2 Gray Ceramic Pigment with Cassiterite Structure
Authors: Tena M. A. , Sorlí S. , Llusar M. , Badenes J. A. , Forés A. , Monrós G.
Published: August 2005

In this study, SbxSn1−xO2 (0 ≤ x ≤ 0.5) compositions were synthesized by the ceramic method from Sb2O3‐SnO2 and Sb2O5‐SnO2 mixtures and characterized by Differential thermal analysis (DTA) and thermogravimetric analysis (TG), X‐ray diffraction, UV‐V‐NIR spectroscopy and CIE L*a*b* (Commission Internationale de l'Eclairage L*a*b*) parameters measurements. Solid solutions with cassiterite structure were obtained at 1300 °C. These solid solutions are stable into glazes. From Sb2O3, light gray coloured materials were obtained. From Sb2O5, bluish gray coloured materials were obtained at 1300 °C/6h when x ≥ 0.3. SbxSn1−xO2 with 0.3 ≤ x < 0.5, T = 1300 °C and Sb2O5 might be established as compositional range, fired temperature and antimony precursor to obtain gray ceramic pigments in this system.
Novel Cyclometallated Complexes Derived From a Halogenated Thiosemicarbazone. Crystal and Molecular Structures of 2‐FC6H4C(Me)=NN(H)C(=S)NHPh and[(Pd{2‐FC6H3C(Me)=NN=C(S)NHPh})2(μ‐PPh2(CH2)2PPh2)]
Authors: Adrio Luis A. , Amoedo Adriana , Antelo José M. , Fernández Jesús J. , Martínez Javier , Ortigueira Juan M. , Pereira M. Teresa , Vila José M.
Published: August 2005

Treatment of the thiosemicarbazone 2‐FC6H4C(Me)=NN(H)C(=S)NHPh, a, with palladium(II) acetate in acetic acid, or with lithium tetrachloropalladate(II) in methanol, gave the tetranuclear cyclometallated complex [Pd{2‐FC6H3C(Me)=NN=C(S)NHPh}]4 (1a). Reaction of 1a with the diphosphines Ph2P(CH2)2PPh2 (dppe), Ph2PCH=CHPPh2 (trans‐dpe) Ph2P(CH2)3Ph2 (dppp) or Ph2P(CH2)4Ph2 (dppb) in a 1:2 molar ratio gave the dinuclear cyclometallated complexes [(Pd{2‐FC6H3C(Me)=NN=C(S)NHPh})2(μ‐Ph2P(CH2)nPPh2)], (n = 2, 2a; 3, 4a; 4, 5a) and [(Pd{2‐FC6H3C(Me)=NN=C(S)NHPh})2(μ‐Ph2PCH=CHPPh2)], (3a). The X‐ray crystal structure of ligand a and of complex 2a are described. The structure of complex 2a shows the palladium atom is bonded to four different donor atoms: C, N, S and P.
Synthesis, Spectroscopic and EPR Results and Crystal Structure of Copper(II) Formato Derivatives with Pyrazine and Dimethylpyrazines
Authors: Barquín Montserrat , Garmendia María J. González , Larrínaga Liher , Pinilla Elena , Torres María R.
Published: August 2005

The complexes of copper formato with pyrazine and dimethylpyrazines: Cu(HCOO)2(pyrz) (1), Cu2(HCOO)4(pyrz) (2), Cu2(HCOO)4(2,3‐Me2pyrz) (3), Cu2(HCOO)4(2,5‐Me2pyrz) (4), and Cu2(HCOO)4(2,6‐Me2pyrz)2 (5) have been synthesized and characterized by chemical analysis and IR and electronic spectro scopies. The three‐dimensional structure of compound 1 consists of –Cu–pyrz–Cu–pyrz– chains joined by bridging formate groups coordinated, in configuration syn‐anti, to two copper atoms. The coordination around the copper atom is orthorhombic with two Cu–O distances of 2.374(1) Å, two Cu–O of 1.952 Å and two Cu–N of 2.080 Å. Compound 5 is formed by molecular dimers with the [Cu2(μ‐HCOO)4] unit, two copper atoms and four syn‐syn fomate groups, and two ligands coordinated to the copper atoms in the axial positions. In compounds 2 and 3 chains of [Cu2(μ‐HCOO)4] dimers with pyrz or 2,3‐Me2pyrz as bridging ligands are formed.

The EPR signal of 1 is orthorhombic (g = 2.23, 2.20 and 2.06). In the EPR spectra of 2 – 5 compounds the triplet (S = 1) signals are observed. The g⟂, g∥ and D values are been calculated.
Synthesis and Characterization of Monomeric Aryloxo Palladium Complexes of the Type [Pd(N–N)(OAr)(C6F5)].Crystal Structure of [Pd(tmeda)(C6F5)(OC6H4NO2‐p)]
Authors: Ruiz José , Martínez M. Teresa , Vicente Consuelo , Rodríguez Venancio , López Gregorio , Pérez José , Chaloner Penny A. , Hitchcock Peter B.
Published: August 2005

Mononuclear palladium‐hydroxo complexes of the type [Pd(N–N)(C6F5)(OH)][(N–N) = 2,2′‐bipyridine (bipy), 4,4′‐dimethyl‐2,2′‐bipyridine (Me2bipy), 1,10‐phenantroline (phen) or N,N,N′,N′‐tetramethylethylenediamine (tmeda) react with phenols ArOH in tetrahydrofuran giving the corresponding aryloxo complexes [Pd(N–N)(C6F5)(OAr)]. Elemental analyses and spectroscopic (IR, 1H and 19F) methods have been used to characterize the new complexes. The X‐ray crystal structure of [Pd(tmeda)(C6F5)(OC6H4NO2‐p)] has been determined. In the crystal packing the planes defined by two C6H4 rings show a parallel orientation. There are also intermolecular C–H···F and C‐H···O hydrogen bonds.
Cobalt Chalcogenide Clusters. Synthesis, Characterization and DFT Calculations of [Co4Se2(CO)10] and [Co4Te2(CO)11]. Crystal Structure of [Co8Se4(CO)16(μ‐dppa)2]
Authors: Sevillano Paloma , Koenig Sven , Himmel Daniel , Fuhr Olaf , Fenske Dieter
Published: August 2005

The reactions of [Co2(CO)8] with E(SiMe3)2 (E = Se, Te) in CH2Cl2 result in the formation of the compounds [Co4Se2(CO)10]> (1) and [Co4Te2(CO)11] (2), respectively. Both cluster complexes have similar molecular structures in which the cobalt atoms form four‐membered rings with μ4‐bridging chalcogen atoms (Se and Te) above and below the plane of the metal atoms and the carbonyl ligands as either terminal or μ2‐bridging ligands. DFT‐calculations for both compounds have been carried out in order to obtain some more information about their electronic distribution. In the presence of the phosphine Ph2PC≡CPPh2 (dppa), the reaction of [Co2(CO)8] with Se(SiMe3)2 leads to the formation of [Co8Se4(CO)16(μ‐dppa)2] (3). During the reaction two molecules of [Co2(CO)8] have been added to the acetylene groups of the dppa ligands, whilst the remaining cobalt atoms coordinate to the phosphorus atoms of the phosphine. In this compounds the selenium atoms act as μ3‐ligands, bridging the metal atoms bonded to the phosphorus with those bonded to the acetylene groups.
Selective Catalytic Reduction of Nitric Oxide by Ammonia over Ag and Zn‐Exchanged Cuban Natural Zeolites
Authors: Moreno‐Tost Ramón , Santamaría‐González José , Rodríguez‐Castellón Enrique , Jiménez‐López Antonio , Autié Miguel A. , Glacial Marisol Carreras , Castro Giselle Autié , Guerra Magali
Published: August 2005

The catalytic selective reduction of NO over metal‐exchanged (ZnII, AgI) natural zeolites (mordenite and clinoptilolite) from Cuba using NH3 as a reducing agent in the presence of excess oxygen was studied. Both transition metals slightly improve the catalytic performance for the NO reduction. ZnII‐exchanged zeolites exhibit a moderate catalytic activity, with conversions of NO of ≈58 % and high selectivity to N2 at high temperatures.
Increased left atrial volume index is an independent predictor of raised serum natriuretic peptide in patients with suspected heart failure but normal left ventricular ejection fraction: Implication for diagnosis of diastolic heart failure
Authors: Lim Tiong K. , Ashrafian Houman , Dwivedi Girish , Collinson Paul O. , Senior Roxy
Published: August 2005

Background:

Left atrial volume index (LAVI) is increasingly recognised as a relatively load‐independent marker of left ventricular (LV) filling pressures. We assessed the capacity of LAVI to predict LV diastolic dysfunction in comparison with N‐terminal pro B‐type natriuretic peptide (NTproBNP) in patients with suspected heart failure and a normal ejection fraction (EF).

Methods:

137 patients with suspected heart failure (HF), referred from the community for echocardiography, prospectively underwent Doppler echocardiography, LAVI and NTproBNP estimation. Raised LAVI and reduced LV systolic function were defined as >26 ml/m2 and LV EF <50% respectively.

Results:

Of 137 patients, 21 were excluded (2 with significant mitral valve disease and 19 with atrial fibrillation). Of the remaining 116 subjects, 92 showed normal LV systolic function. The univariate predictors of serum log NTproBNP were age (p<0.001), LA dimension (p=0.001), LAVI (p<0.001), A wave (p=0.001), E:A (p=0.07) and septal wall thickness (p=0.004). However on multivariate analysis, LAVI was found to be the most consistent and significant predictor of NTproBNP. The area under the curve of the receiver operating characteristic (ROC) curve for NTproBNP in detecting patients with LVEF ≥50percnt; and LAVI >26ml/m2 was 0.81 (p<0.0001) and for patients with LAVI >26ml/m2 with and without LVEF ≥50% was 0.82 (p<=0.0001).

Conclusion:

This data confirms that LAVI on resting echocardiography, specifically in patients with suspected HF and normal LV systolic function is a powerful independent predictor of LV diastolic dysfunction as predicted by serum NTproBNP. In a population with a high suspicion of diastolic heart failure, LAVI may significantly contribute to diagnostic precision.
Genome‐wide application of RNAi to the discovery of potential drug targets
Authors: Ito Masanori , Kawano Kenji , Miyagishi Makoto , Taira Kazunari
Published: August 2005

Progress is being made in the development of RNA interference‐based (RNAi‐based) strategies for the control of gene expression. It has been demonstrated that small interfering RNAs (siRNAs) can silence the expression of target genes in a sequence‐specific manner in mammalian cells. Various groups, including our own, have developed systems for vector‐mediated specific RNAi. Vector‐based siRNA‐ (or shRNA) expression libraries directed against the entire human genome and siRNA libraries based on chemically synthesized oligonucleotides now allow the rapid identification of functional genes and potential drug targets. Use of such libraries will enhance our understanding of numerous biological phenomena and contribute to the rational design of drugs against heritable, infectious and malignant diseases.
Industrial Location and Voter Participation in Europe
Authors: BUSCH MARC L. , REINHARDT ERIC
Published: August 2005

Does the geographic concentration of industry ‘matter’ outside the United States? Observers have long speculated that while geographically concentrated industries may be influential in American politics, this is probably not the case in countries where the electorate votes more as a national constituency. Others disagree, urging that clustered industries have an advantage regardless of how the political map is drawn. We sharpen the terms of debate and weigh in with empirical evidence from a cross-sectional analysis of intended voter turnout in eight member-states of the European Union and a multi-year study of voter turnout in the Netherlands. These tests uniformly show that, across different types of electoral systems, including those in which voters vote as a national constituency, thereby removing any effects of electoral geography per se, workers in traded industries that are physically concentrated are, in fact, substantially more likely to vote than employees in traded but geographically dispersed sectors.
Missing Intertexts: Hannah Crafts's The Bondwoman's Narrative and African American Literary History
Authors: BALLINGER GILL , LUSTIG TIM , TOWNSHEND DALE
Published: August 2005

I sit with Shakespeare and he winces not. Across the color line I move arm in arm with Balzac and Dumas, where smiling men and welcoming women glide in gilded halls. From out the caves of evening that swing between the strong-limbed earth and the tracery of the stars, I summon Aristotle and Aurelius and what soul I will, and they come all graciously with no scorn nor condescension. So, wed with Truth, I dwell above the Veil.