bluuebunny/crossref_metadata_2025 huggingface dataset:
Postoperative Nomogram for Disease-Specific Survival After an R0 Resection for Gastric Carcinoma
Authors: Kattan Michael W. , Karpeh Martin S. , Mazumdar Madhu , Brennan Murray F.
Published: September 2003

Purpose: Few published studies have addressed individual patient risk after R0 resection for gastric cancer. We developed and internally validated a nomogram that combines these factors to predict the probability of 5-year gastric cancer–specific survival on the basis of 1,039 patients treated at a single institution.

Methods: Nomogram predictor variables included age, sex, primary site (distal one-third, middle one-third, gastroesophageal junction, and proximal one-third), Lauren histotype (diffuse, intestinal, mixed), number of positive lymph nodes resected, number of negative lymph nodes resected, and depth of invasion. Death as a result of gastric cancer was the predicted end point. The concordance index was used as an accuracy measure, with bootstrapping to correct for optimistic bias. Calibration plots were constructed.

Results: Gastric cancer–specific survival at 5 years was 50%. A nomogram was constructed on the basis of a Cox regression model. The bootstrap-corrected concordance index was 0.80. When compared with the predictive ability of American Joint Committee on Cancer stage, the nomogram discrimination was superior (P < .001). Nomogram calibration appeared to be excellent.

Conclusion: A nomogram was developed to predict 5-year disease-specific survival after R0 resection for gastric cancer. This tool should be useful for patient counseling, follow-up scheduling, and clinical trial eligibility determination.
High p27Kip1 Expression Predicts Superior Relapse-Free and Overall Survival for Premenopausal Women With Early-Stage Breast Cancer Receiving Adjuvant Treatment With Tamoxifen Plus Goserelin
Authors: Pohl Gudrun , Rudas Margaretha , Dietze Otto , Lax Sigurd , Markis Eva , Pirker Robert , Zielinski Christoph C. , Hausmaninger Hubert , Kubista Ernst , Samonigg Hellmut , Jakesz Raimund , Filipits Martin
Published: September 2003

Purpose: To determine the predictive value of p27Kip1 in premenopausal women with early-stage hormone receptor–positive breast cancer.

Patients and Methods: We retrospectively examined tumor specimens from 512 patients with breast cancer who were enrolled onto Austrian Breast and Colorectal Cancer Study Group (ABCSG) Trial 5. In this trial, premenopausal, hormone receptor–positive breast cancer patients with stage I and II disease were randomly assigned to receive either 5 years of tamoxifen plus 3 years of goserelin or six cycles of cyclophosphamide, methotrexate, and fluorouracil. p27Kip1 expression was assessed by immunohistochemistry, and its association with clinical outcome was determined. Statistical analyses were performed to test for interaction between p27Kip1 status and treatment.

Results: High p27Kip1 expression (nuclear p27Kip1 staining in ≥ 50% of tumor cells) independently predicted superior relapse-free survival (RFS) and overall survival (OS) in both the total study population (RFS: relative risk [RR], 0.53; 95% CI, 0.34 to 0.82; P = .004; OS: RR, 0.29; 95% CI, 0.15 to 0.58; P < .001) and patients treated with combination endocrine therapy (RFS: RR, 0.32; 95% CI, 0.16 to 0.63; P = .001; OS: RR, 0.16; 95% CI, 0.05 to 0.53; P = .003). The interaction between p27Kip1 expression and treatment was statistically significant for RFS (P = .04) but not for OS (P = .27).

Conclusion: High p27Kip1 expression was an independent predictor of responsiveness to hormonal therapy and thus may be useful for the selection of premenopausal women with early-stage hormone receptor–positive breast cancer for adjuvant combination endocrine therapy.
Analysis of Surgical Salvage After Failure of Primary Therapy in Rectal Cancer: Results From Intergroup Study 0114
Authors: Tepper J.E. , O’Connell M. , Hollis D. , Niedzwiecki D. , Cooke E. , Mayer R.J.
Published: September 2003

Purpose: Intergroup Study 0114 was designed to study the effect of various chemotherapy regimens delivered after potentially curative surgical resection of T3, T4, and/or node-positive rectal cancer. A subset analysis was undertaken to investigate the prevalence and influence of salvage therapy among patients with recurrent disease.

Patients and Methods: Adjuvant therapy consisted of two cycles of fluorouracil (FU)-based chemotherapy followed by pelvic irradiation with chemotherapy and two more cycles of chemotherapy after radiation therapy. A total of 1,792 patients were entered onto the study and 1,696 were assessable. After a median of 8.9 years of follow-up, 715 patients (42%) had disease recurrence, and an additional 10% died without evidence of disease. Five hundred patients with follow-up information available had a single organ or single site of first recurrence (73.5% of all recurrences).

Results: A total of 171 patients (34% of those with a single organ or single site of recurrence) had a potentially curative resection of the metastatic or locally recurrent disease. Single-site first recurrences in the liver, lung, or pelvis occurred in 448 patients (90% of the single-site recurrences), with 159 (35%) of these undergoing surgical resection for attempted cure. Overall survival differed significantly between the resected and nonresected groups (P < .0001), with overall 5-year probabilities of .27 and .06, respectively. Controlling for worst performance status at the time of recurrence does not alter this relationship. Patients who underwent salvage surgery had significantly increased survival (P < .001) for each site.

Conclusion: Attempted surgical salvage of rectal cancer recurrence is performed commonly in the United States. The chance of a long-term cure with such intervention is approximately 27%.
Altered Expression of MLH1, MSH2, and MSH6 in Predisposition to Hereditary Nonpolyposis Colorectal Cancer
Authors: Renkonen Elise , Zhang Yange , Lohi Hannes , Salovaara Reijo , Abdel-Rahman Wael M. , Nilbert Mef , Aittomäki Kristiina , Järvinen Heikki J. , Mecklin Jukka-Pekka , Lindblom Annika , Peltomäki Päivi
Published: September 2003

Purpose: A considerable fraction (30% to 70%) of families with verified or putative hereditary nonpolyposis colorectal cancer fails to show mutations in DNA mismatch repair (MMR) genes. Our purpose was to address the genetic etiology of such families.

Materials and Methods: We scrutinized a population-based cohort of 26 families from Finland that had screened mutation-negative by previous techniques. Blood was tested for allelic messenger RNA (mRNA) expression of MLH1, MSH2, and MSH6 by single nucleotide primer extension (SNuPE), and tumor tissue for MMR protein expression by immunohistochemistry (IHC) as well as for microsatellite instability (MSI). Full-length cDNAs of genes implicated by SNuPE or IHC were cloned and sequenced.

Results: Unbalanced mRNA expression of MLH1 alleles was evident in two families. An inherited nonsense mutation was subsequently identified in one family, and complete silencing of the mutated allele was identified in the other family. Extinct protein expression by IHC implicated MLH1 in these two and in four other families, MSH2 in four families, and MSH6 in one family. Although no unequivocal genomic mutations were detected in the latter families, haplotype and other findings provided support for heritable defects. With one exception, all tumors with IHC alterations showed MSI, in contrast to the remaining families, which showed neither IHC changes nor MSI.

Conclusion: Our expression-based strategy stratified the present “mutation-negative” cohort into two discrete categories: families linked to the major MMR genes MLH1, MSH2, and MSH6 (11 [42%] of 26) and those likely to be associated with other, as yet unknown susceptibility genes (15 [58%] of 26).
Quality of Life in Women With Breast Cancer During the First Year After Random Assignment to Adjuvant Treatment With Marrow-Supported High-Dose Chemotherapy With Cyclophosphamide, Thiotepa, and Carboplatin or Tailored Therapy With Fluorouracil, Epirubicin, and Cyclophosphamide: Scandinavian Breast Group Study 9401
Authors: Brandberg Yvonne , Michelson Helena , Nilsson Bo , Bolund Christina , Erikstein Bjørn , Hietanen Päivi , Kaasa Stein , Nilsson Jonas , Wiklund Tom , Wilking Nils , Bergh Jonas
Published: September 2003

Purpose: To compare, in high-risk breast cancer patients, the effects on health-related quality of life (HRQoL) of two adjuvant treatments. Treatments were compared at eight points during the first year after random assignment to treatment with tailored fluorouracil, epirubicin, and cyclophosphamide (FEC) therapy for nine courses versus induction FEC therapy for three courses followed by high-dose chemotherapy with cyclophosphamide, thiotepa, and carboplatin (CTCb) supported by peripheral-blood stem cells.

Patients and Methods: From March 1994 to March 1998, 525 breast cancer patients (estimated relapse risk > 70% within 5 years with standard therapy) were included in the Scandinavian Breast Group 9401 study. HRQoL evaluation, using the European Organization for Research and Treatment of Cancer Quality of Life Questionnaire (EORTC QLQ)-C30 and EORTC Breast Cancer Module–23, included 408 of 446 eligible patients in Finland, Norway, and Sweden.

Results: Eighty-four percent to 95% of the patients completed questionnaires at eight points of assessment. Nostatistically significant overall differences were found between the tailored FEC group and the CTCb group for any of the HRQoL variables. Statistically significant differences over time were found for all HRQoL variables. HRQoL in the CTCb group demonstrated a steeper decrease, but a faster recovery than in the tailored FEC group. Emotional functioning improved with increased time from randomization. Higher levels of problems in body image and arm symptoms were reported in the tailored FEC group compared with the CTCb group. Sexual functioning and satisfaction were impaired during the study period.

Conclusion: Both treatments had a negative influence on HRQoL during the treatment period. Despite the aggressive therapies, the patient’s HRQoL returned to levels found at inclusion on most variables.
Venous Thromboembolism Associated With Long-Term Use of Central Venous Catheters in Cancer Patients
Authors: Verso Melina , Agnelli Giancarlo
Published: September 2003

Long-term central venous catheters (CVCs) have considerably improved the management of cancer patients because they facilitate chemotherapy, transfusions, parenteral nutrition, and blood sampling. However, the use of long-term CVCs, especially for chemotherapy, has been associated with the occurrence of upper-limb deep venous thrombosis (UL-DVT). The incidence of clinically overt UL-DVT related to CVCs has been reported to vary between 0.3% and 28.3%. The incidence of CVC-related UL-DVT screened by venography reportedly varies between 27% and 66%. The incidence of clinically overt pulmonary embolism (PE) in patients with CVC-related UL-DVT ranges from 15% to 25%, but an autopsy-proven PE rate of up to 50% has been reported. Vessel injury caused by the procedure of CVC insertion, venous stasis caused by the indwelling CVC, and cancer-related hypercoagulability are the main pathogenetic factors for CVC-related venous thromboembolism (VTE). Several studies have assessed the benefit of the prophylaxis of UL-DVT after CVC insertion in cancer patients. According to the results of these studies, prophylaxis with low molecular weight heparin or a low fixed dose of warfarin has been recently proposed. However, the limitations of the experimental design of the prophylactic studies do not allow definitive recommendations. The recommended therapy for UL-DVT associated with CVC is based on anticoagulant therapy with or without catheter removal. This review focuses on the epidemiology, pathogenesis, diagnosis, prevention, and treatment of VTE in cancer patients with long-term CVC.
Effect of Arsenic Trioxide on QT Interval in Patients With Advanced Malignancies
Authors: Barbey Jean T. , Pezzullo John C. , Soignet Steven L.
Published: September 2003

Purpose: Arsenic trioxide is an effective treatment for patients with acute promyelocytic leukemia (APL) who have relapsed from or are refractory to all-trans-retinoic acid and anthracycline chemotherapy. Since arsenic can prolong the QT interval and lead to torsade de pointes, a life-threatening ventricular arrhythmia, this retrospective analysis was conducted to determine the degree of QT prolongation in patients treated with arsenic trioxide.

Patients and Methods: Clinical data and serial ECGs from 99 patients with advanced malignancies who received 170 courses of arsenic trioxide in either a phase I or phase II investigational study were reviewed.

Results: Prolonged QT intervals developed in 38 patients (26 patients had intervals ≥ 500 milliseconds). Compared with baseline, the heart rate—corrected (QTc) interval was prolonged by 30 to 60 milliseconds in 36.6% of treatment courses, and by more than 60 milliseconds in 35.4% of patients. The degree of prolongation was higher in men than in women during the first course of therapy, and in patients with hypokalemia. In patients receiving multiple courses, QTc intervals returned to pretreatment levels before the second course, signifying that arsenic trioxide does not permanently prolong the QTc interval. One hypokalemic, arsenic trioxide–treated patient with relapsed APL developed asymptomatic torsade de pointes, which resolved spontaneously and did not recur after electrolyte replacement. There were no sudden or arrhythmia-related deaths.

Conclusion: This analysis shows that arsenic trioxide can prolong the QTc interval. However, with appropriate ECG monitoring and management of electrolytes and concomitant medications, arsenic trioxide can be safely administered in patients with relapsed APL.
Inherited and Acquired Risk Factors for Venous Thromboembolic Disease Among Women Taking Tamoxifen to Prevent Breast Cancer
Authors: Duggan Catherine , Marriott Kevin , Edwards Rob , Cuzick Jack
Published: September 2003

Purpose: Venous thromboembolism (VTE) is of particular concern in women receiving tamoxifen in a chemopreventive setting. We investigate the association between acquired and inherited risk factors for VTE in the International Breast Cancer Intervention Study (IBIS-I) trial of tamoxifen prophylaxis for women at increased risk of breast cancer.

Methods: We used a nested case-control study design to investigate the role of tamoxifen and acquired risk factors in the risk of developing a VTE.

Results: Tamoxifen was associated with a significantly increased risk of developing a major VTE (odds ratio [OR], 2.1; 95% CI, 1.1 to 4.1). Women who had surgery, immobilization, or fracture in the previous month had a greatly increased risk of developing a major VTE (OR, 4.7; 95% CI, 2.2 to 10.1). Prothrombin and factor V Leiden mutations were found exclusively among control women: factor V Leiden in eight of 159 control women (5.0%) and the prothrombin mutation in three control women (1.9%). Thirty-five women with a VTE and a blood sample were negative for these mutations. The upper one-sided 97.5% CI for the OR of having either mutation was 1.87. Being overweight, smoking, or taking hormone replacement therapy was not associated with VTE in this study, but the CIs were wide.

Conclusion: Tamoxifen and prior surgery, fracture, or immobilization were associated with a significantly increased risk of developing a VTE. Factor V Leiden and prothrombin mutations were not associated with thrombosis in this population.
Childhood T-Cell Acute Lymphoblastic Leukemia: The Dana-Farber Cancer Institute Acute Lymphoblastic Leukemia Consortium Experience
Authors: Goldberg John M. , Silverman Lewis B. , Levy Donna E. , Dalton Virginia Kimball , Gelber Richard D. , Lehmann Leslie , Cohen Harvey J. , Sallan Stephen E. , Asselin Barbara L.
Published: September 2003

Purpose: T-cell acute lymphoblastic leukemia (T-ALL) accounts for 10% to 15% of newly diagnosed cases of childhood acute lymphoblastic leukemia (ALL). Historically, T-ALL patients have had a worse prognosis than other ALL patients.

Patients and Methods: We reviewed the outcomes of 125 patients with T-ALL treated on Dana-Farber Cancer Institute (DFCI) ALL Consortium trials between 1981 and 1995. Therapy included four- or five-agent remission induction; consolidation therapy with doxorubicin, vincristine, corticosteroid, mercaptopurine, and weekly high-dose asparaginase; and cranial radiation. T-ALL patients were treated the same as high-risk B-progenitor ALL patients. Fifteen patients with T-cell lymphoblastic lymphoma were also treated with the same high-risk regimen between 1981 and 2000.

Results: The 5-year event-free survival (EFS) rate for T-ALL patients was 75% ± 4%. Fourteen of 15 patients with T-cell lymphoblastic lymphoma were long-term survivors. There was no significant difference in EFS comparing patients with T-ALL and B-progenitor ALL (P = .56), although T-ALL patients had significantly higher rates of induction failure (P < .0001), and central nervous system (CNS) relapse (P = .02). The median time to relapse in T-ALL patients was 1.2 years versus 2.5 years in B-progenitor ALL patients (P = .001). There were no pretreatment characteristics associated with worse prognosis in patients with T-ALL.

Conclusion: T-ALL patients fared as well as B-progenitor patients on DFCI ALL Consortium protocols. Patients with T-ALL remain at increased risk for induction failure, early relapse, and isolated CNS relapse. Future studies should focus on the identification of and treatment for T-ALL patients at high risk for treatment failure.
The Impact of a Physician Awareness Group and the First Year of Training on Hematology-Oncology Fellows
Authors: Sekeres Mikkael A. , Chernoff Miriam , Lynch Thomas J. , Kasendorf Eydie I. , Lasser Daniel H. , Greenberg Donna B.
Published: September 2003

Purpose: To assess the impact of a Balint-like physician awareness group on hematology-oncology fellows’ attitudes and measure changes in attitudes during the first fellowship year.

Patients and Methods: We used a modified crossover design in which one half of a fellowship class at a time was exposed to the group intervention over a 2-year period (2000 to 2002). Two 14-fellow classes were followed for 1 year each and were given three “attitudes” questionnaires, at the beginning, middle, and end of the academic year.

Results: Forty Balint group sessions were held during the 2-year study period; 82 questionnaires of the 84 administered (98%) were recovered. Instrument content and criterion validity were demonstrated, as was topic domain reliability. Overall, mean attitude scores increased following the group intervention, from 3.6 (95% CI, 3.5 to 3.7) to 3.7 (95% CI, 3.6 to 3.8; P = .09). Within domains, scores increased in a “fellow’s views of him/herself as a physician,” from 3.8 (95% CI, 3.6 to 3.9) to 4.1 (95% CI, 3.9 to 4.2; P = .008) and “comfort dealing with emotional patient/clinical situations,” from 3.5 (95% CI, 3.3 to 3.7) to 3.7 (95% CI, 3.6 to 3.9; P = .11). Changes in responses to individual questions included: an increase in fellows’ comfort with the technical aspects of being an oncologist (P < .03); an increase in fellows’ comfort with discussing the stress of home at work (P < .023); and an increase among fellows in feeling pressed for time to discuss psychosocial issues with patients (P = .035).

Conclusion: A physician awareness group was feasible and enhanced fellows’ development as physicians. Further research is needed to determine how to incorporate such groups into oncology fellowships.
Expression of CEACAM6 in Resectable Colorectal Cancer: A Factor of Independent Prognostic Significance
Authors: Jantscheff Peter , Terracciano Luigi , Lowy Adam , Glatz-Krieger Katharina , Grunert Fritz , Micheel Burkhard , Brümmer Jens , Laffer Urs , Metzger Urs , Herrmann Richard , Rochlitz Christoph
Published: September 2003

Purpose: CEACAM6, CEACAM1, and human carcinoembryonic antigen (CEA) are coexpressed in normal colorectal epithelia, but show deregulated expression in colorectal cancers (CRC). Upregulation of CEACAM6 expression in hyperplastic polyps and early adenomas represents one of the earliest observable molecular events leading to colorectal tumors. The aim of our study was to evaluate the prognostic relevance of CEACAM6, CEACAM1, and CEA tissue expression in patients with CRC.

Patients and Methods: Immunohistochemical analysis was carried out on tissue microarrays from 243 paraffin-embedded biopsies from a randomized controlled clinical trial (Swiss Group for Clinical Cancer Research [SAKK] 40/81) of adjuvant fluorouracil-based chemotherapy with CEACAM-specific monoclonal antibodies. The median follow-up was 8 years. Overall survival (OS) and disease-free survival (DFS) were calculated using Kaplan-Meier estimates and hazard ratios (HRs) estimated using Cox proportional hazards models.

Results: Tissue expression of CEACAM6, CEACAM1, and CEA was enhanced in 55%, 58%, and 94% of patients, respectively. Multivariate Cox analysis including sex, age, tumor site, stage, differentiation grade, treatment, and nodal status as covariates showed that CEACAM6 overexpression independently predicted poor OS (HR, 1.86; P = .0100) and DFS (HR, 2.00; P = .0028), whereas CEACAM1 or CEA were not significantly related to these outcomes. The data did not provide evidence for or against the hypothesis that the CEACAM6 effect on survival differs according to treatment.

Conclusion: Expression of the cell adhesion molecule CEACAM6 in CRC is an independent prognostic factor allowing subdivision of patients into low- and high-risk groups. Whether CEACAM6 or CEA and CEACAM1 might be useful as predictive markers of chemotherapy benefit remains unclear.
Events at the end of mitosis in the budding and fission yeasts
Authors: Simanis Viesturs
Published: September 2003

The mitotic exit network (MEN) and the septation initiation network (SIN) control events at the end of mitosis in S. cerevisiae and S. pombe, respectively. SIN initiates contraction of the actin ring and synthesis of the division septum, thereby bringing about cytokinesis. The MEN is also required for cytokinesis, but its main role is to control inactivation of mitotic cyclin-dependent kinases (CDKs) at the end of mitosis, and thereby regulate mitotic exit. Each revolves around a Ras-family GTPase and involves several protein kinases, and SIN and MEN proteins are localised to the spindle pole body. In S. cerevisiae, a second network, known as FEAR, cooperates with the MEN to bring about mitotic exit, and a third, AMEN, contributes to switching the MEN off. Some of the central components of the FEAR, SIN and MEN have been conserved through evolution, which suggests that aspects of their function in controlling events at the end of mitosis might be conserved in higher eukaryotes.
Model Study for Preparation of Asymmetric N,N′-Disubstituted Piperazine Library: Efficient Synthesis of Aryl Piperazine and Benzyl Piperazine Derivatives on the Solid Support
Authors: Yamamoto Yasuo , Ajito Keiichi , Ohtsuka Yasuo
Published: September 2003

Several classes of asymmetrical N,N′-disubstituted aryl piperazine and benzyl piperazine derivatives were successfully synthesized by the solid phase method from the same intermediate.
Synthesis of Copolymers Containing C60, Cyclododecyl, and Sulfonate Groups: Photophysical Behavior of C60 in Highly Constrained Microenvironments
Authors: Higashida Suguru , Nishiyama Katsura , Yusa Shin-ichi , Morishima Yotaro , Janot Jean-Marc , Seta Patrick , Imahori Hiroshi , Kaneda Takahiro , Sakata Yoshiteru
Published: September 2003

C60 was covalently incorporated into hydrophobic cluster of amphiphilic polysulfonates. In this cluster C60 chromophores showed extremely blue-shifted fluorescence and no thermally activated delayed fluorescence.
Polymerization of 6-Amino-6-deoxy-D-glucose Involving Amadori Rearrangement: A New Method for Synthesis of Aminopolysaccharide
Authors: Kadokawa Jun-ichi , Hino Daisuke , Karasu Masa , Tagaya Hideyuki , Chiba Koji
Published: September 2003

This paper describes synthesis of a new aminopolysaccharide by thermal polymerization of 6-amino-6-deoxy-D-glucose in the presence of acetic acid. The polymerization proceeded via Amadori rearrangement to give the aminopolysaccharide having aminoketose structure in the main chain. The molecular weight was determined by GPC analysis after acetylation of the product polysaccharide.
Crystallization of (Pro-Hyp-Gly)10 and Its Triple-Helical Structure Deduced from Cylindrical Patterson Map
Authors: Okuyama Kenji , Nagarajan Venugopalan , Kamitori Shigehiro , Noguchi Keiichi
Published: September 2003

Two morphologically different crystals of a collagen model peptide(Pro-Hyp-Gly)10 were obtained using PEG 200 as the precipitating agent. Both the crystals belonged to a monoclinic system with the space group P21 and diffracted to a resolution of 1.8 Å. Although the crystal data were quite different from those of homologous model peptide, (Pro-Pro-Gly)10, the cylindrical Patterson map showed that the main chain conformation of this compound is exactly the same as that of (Pro-Pro-Gly)10. This result supports the Okuyama model for collagen structure.
Photocatalytic Activity of RuS2/SiO2 for Water Decomposition
Authors: Hara Kohjiro , Sayama Kazuhiro , Arakawa Hironori
Published: September 2003

Hydrogen and oxygen were produced, respectively, from water in the presence of sacrificial reagents by photocatalytic reaction using RuS2 powder catalyst under UV light irradiation for the first time. Photocatalytic activity of RuS2 significantly improved by support on SiO2.
A Superoxodicopper(II) Complex Oxidatively Generated by a Reaction of Di-μ-hydroxodicopper(II) Complex with Hydrogen Peroxide
Authors: Kodera Masahito , Tachi Yoshimitsu , Hirota Shun , Katayama Kou , Shimakoshi Hisashi , Kano Koji , Fujisawa Kiyoshi , Moro-oka Yoshihiko , Naruta Yoshinori , Kitagawa Teizo
Published: September 2003

Di-μ-hydroxodicopper(II) complex with a hexapyridine dinucleating ligand, [Cu2(OH)2(hexpy)](CF3SO3)2 (hexpy=1,2-bis[2-(bis(2-pyridyl)methyl)-6-pyridyl]ethane), reacts with H2O2 in MeCN/CH2Cl2 to give a superoxodicopper(II) complex.
Electrochemical Reduction of NO on ZnO and In2O3 Semiconductor Electrodes in Aqueous K2SO4 Solutions
Authors: Kudo Akihiko , Watanabe Karoi , Minakata Yuji , Mine Akiyo
Published: September 2003

NO was efficiently reduced on ZnO and In2O3 of n-type semiconductor electrodes in aqueous solutions. Harmless N2 was obtained as a main reduction product. Current-potential curves on the ZnO and In2O3 electrodes under NO were quite similar to those under N2O. It is proposed that the NO reduction on the ZnO and In2O3 electrodes proceeds via the redox mechanism in which oxygen vacancies formed by the electrochemical reduction on the electrode surface play an important role.
Preparation of m-Acylaniline Derivatives by the Reaction of Tricarbonyl(cyclohexadienone O-benzyloxime)iron Complex and Higher Order Cuprates
Authors: Ban Soo Ho , Hayashi Yujiro , Narasaka Koichi
Published: September 2003

Reaction of tricarbonyl[(2,3,4,5-η)-2,4-cyclohexadien-1-one O-benzyloxime]iron and organocuprates, followed by the treatment with acetic anhydride and carbon monoxide, affords [(1,2,3,4-η)-1-(N-acetoxy-N-benzyloxyamino)-5-endo-acyl-1,3-cyclohexadiene]tricarbonylirons, which are converted to m-acylaniline derivatives by treating with potassium carbonate.
Regioselective Acylation of (5-Alkylidene-1,3-cyclohexadiene)tricarbonyliron Complexes by the Reaction with Organometallic Reagents
Authors: Iwakoshi Mitsuhiko , Ban Soo Ho , Hayashi Yujiro , Narasaka Koichi
Published: September 2003

Reaction of [(1,2,3,4-η)-5-alkylidene-1,3-cyclohexadiene]tricarbonylirons and organometallic reagents generates acyl[(1,2,3,4,5-η)-1-alkylcyclohexadienyl]dicarbonylirons. The acyl group in these complexes migrates to the cyclohexadienyl moiety under carbon monoxide atmosphere, providing [(1,2,3,4-η)-6-acyl-2-alkyl-1,3-cyclohexadiene]tricarbonylirons, which are further transformed to m-alkylphenyl ketones by the oxidation with trimethylamine N-oxide.
Asymmetric Direct α,β-Functionalization of Allenes via Asymmetric Carbopalladation
Authors: Hiroi Kunio , Kato Fumiko , Yamagata Akiko
Published: September 2003

Asymmetric direct α,β-functionalization of allenes with chiral phosphine ligands was successfully achieved with extremely high enantioselectivity via asymmetric carbopalladation to the racemic allenes. The same palladium-catalyzed alkylation of a chiral allene was executed with complete enantiospecificity. The stereochemistry of this reaction was determined and the mechanism of this asymmetric induction is proposed.
Selective Bindings of a Lectin for Phase-separated Glycolipid Monolayers
Authors: Hashizume Mineo , Sato Toshinori , Okahata Yoshio
Published: September 2003

Phase separation was observed by measuring surface pressure (π)-area (A) isotherms of the mixed monolayer of lactosylceramide (LacCer) and dioleoylphosphatidylcholine (DOPC). Bindings of Allomyrina dichotoma (allo A) lectin to LacCer in mixed monolayers were measured by means of quartz-crystal microbalance (QCM) that was attached horizontally to the monolayers. Allo A showed the high binding affinity for the LacCer phase-separated in the DOPC monolayer, but showed the low binding affinity for the LacCer homogeneously mixed with dipalmitoylphosphatidylcholine (DPPC) matrix.
Discrimination among Amino Acids Using an Amperometric Biosensor Based on Electrochemical Nonlinearity
Authors: Nakata Satoshi , Hirata Yoko , Takitani Rie , Yoshikawa Kenichi
Published: September 2003

We propose a novel sensing system based on the multidimensional information contained in a dynamic nonlinear response. A sinusoidal potential was applied to an amperometric L-amino acid sensor, and the resulting current of the sensor was analyzed by fast Fourier transformation (FFT). The amplitudes of the higher harmonics of the FFT characterize the nonlinear properties of the response. The amplitudes of the higher harmonics of the FFT exhibit characteristic changes which depend on the concentration and the chemical structure of amino acids at the sensor surface.
Selective Conjugate Alkylation of Alkyllithium Nucleophiles to α,β,γ,δ-Unsaturated Aldehydes with Functionalized Lewis Acid Receptors
Authors: Ooi Takashi , Kondo Yuichiro , Kon-i Kana , Maruoka Keiji
Published: September 2003

Selective 1,4- and 1,6-addition of alkyllithium reagents to α,β,γ,δ-unsaturated aldehydes has been successfully realized with fluorinated aluminum tris(2,6-diphenylphenoxide) (ATPH) derivatives as functionalized Lewis acid receptors.
Self-Assembly Process of Organosulfur Molecular Layers on Gold Electrode: An in situ Ellipsometric and Electrochemical Study
Authors: Eu Seunghun , Paik Woon-kie
Published: September 2003

Electrochemical and ellipsometric measurements were made on gold surface while alkanethiols and organic disulfides were adsorbed. Anodic oxidation was observed to occur with molecular layer formation from thiols. Disulfide molecules appeared to oxidatively adsorb after reductive dissociation.
Electron Transfer Reaction of Cytochrome c at Poly(ethylene oxide)-Thiolate-Modified Gold Electrode
Authors: Ohno Hiroyuki , Kato Ken-ichi
Published: September 2003

Gold electrode was modified with poly(ethylene oxide)s having thiol end (PEO-SH). The electron transfer reaction of cytochrome c was evaluated by the gold electrode modified with PEO-SH, having PEO molecular weight of 150, where the adsorption of proteins and resulting denaturation were restrained. The increase of PEO molecular weight conducted suppression of the redox responses at the modified gold electrode.
The Substituent Effect on Stereoselective Reductive Lithiation of 4,5-Disubstituted 2-Phenylthiooxolane
Authors: Amano Seiji , Fujiwara Kenshu , Murai Akio
Published: September 2003

In the reductive lithiation of 2-phenylthiooxolane system, the coexistence of the substituents at C2 and C3 with cis-configuration was found to increase the ratio of 2,5-trans-2-lithiooxolane at 2,5-cis derivative.
Mixed Monolayers of a Calix[4]resorcinarene with a Nematic Liquid Crystal and Their Bilayered Structuring
Authors: Matsuzawa Yoko , Seki Takahiro , Ichimura Kunihiro
Published: September 2003

Perpendicular orientation of nematic liquid crystalline azobenzene (C6Azo) on a water surface was demonstrated by spreading a mixture of C6Azo with O-octacarboxymethylated calix[4]resorcinarene (CRA-CM) as a host. A host-guest mixed monolayer of C6Azo with CRA-CM formed a double-layered structure by further compression.
Formation of CO(d3Δi, a′3Σ+) by Dissociative Ion-Ion Neutralization Reaction of CO2+ with C6F6− in the Helium Flowing Afterglow
Authors: Tsuji Masaharu , Oda Erika , Nakamura Masafumi , Nishimura Yukio
Published: September 2003

The ion-ion neutralization reaction of CO2+ with C6F6− has been spectroscopically studied in a He flowing afterglow. The CO(d3Δ1-a3Πr) transition from v′=0-3 and the CO(a′3Σ+-a3Πr) transition from v′=3-7 were observed with a CO(a′-a)/CO(d-a) ratio of 3.9. The vibrational distributions of CO(d,a′) indicated that 43 and 62 % of the total excess energies are deposited into vibrational modes of CO(d) and CO(a′), respectively.
Microscopic Solvation Effects on Si-Si Bond Cleavage Reactions of Cluster Cation Radicals of (p-Cyanophenyl)pentamethyldisilane with Hydroxylic Molecules
Authors: Tajima Yuko , Ishikawa Haruki , Shimanuki Yoichi , Miyazawa Takashi , Mikami Naohiko , Kira Mitsuo
Published: September 2003

Facile Si-Si bond cleavage reactions of cation radicals of jet-cooled clusters of (p-cyanophenyl)pentamethyldisilane with H2O or CH3OH were found to occur via intracluster nucleophilic attack of a solvent molecule by means of resonance-enhanced two photon ionization mass spectrometry.
Coating of POPC Giant Liposomes with Hydrophobized Polysaccharide
Authors: Ueda Takehiko , Lee Stephen J , Nakatani Yoichi , Ourisson Guy , Sunamoto Junzo
Published: September 2003

POPC giant liposomes were incubated with pullulan that was hydrophobized by cholesteryl groups and labelled by a fluorescent marker (FITC). Confocal laser microscopy clearly showed coating of the outer surface of the liposomes with the polymer. This is the first and direct observation of the supramolecular assembly of an artificial cell wall onto cell-sized liposomes.
Concerning the Basicity of Ozone
Authors: Cacace Fulvio , Speranza Maurizio
Published: September 2003

A comprehensive view on the basicity order of simple molecules, including ozone, is reported and contrasted with recent estimates in heterogeneous systems.
Mixed-valence Hexanuclear Cobalt(II, III) Complex Made Up of Two Defective Cubane Cores
Authors: Mikuriya Masahiro , Fukuya Mika
Published: September 2003

A mixed-valence cobalt(II, III) complex, [Co6L2(CH3COO)2(CH3O)6L′]·2CH3OH(H3L=2,6-bis(saliclylideneaminomethyl)-4-methylphenol and H2L′=salicylazine), has been isolated and characterized by X-ray crystallography, which reveals a unique hexanuclear structure consisting of two defective cubane-cores.
Fluoranthocyanine: A New Member of the Phthalocyanine Family
Authors: Kobayashi Nagao , Yoshikawa Yuko , Ito Osamu , Goodbrand H Bruce , Mayo Jim
Published: September 2003

Fluoranthocyanine, a phthalocyanine analog fused by four five-membered rings and four 1,8-naphthalene units, has been synthesized and characterized by electronic absorption, magnetic circular dichroism, and fluorescence spectroscopy.
Biphasic Cyanation of Aryl Halides with Counter Phase Transfer Catalysts
Authors: Okano Tamon , Kiji Jitsuo , Toyooka Yoshiharu
Published: September 2003

The cyanation of aryl iodides with NaCN under heptane-water two-phase conditions is efficiently catalyzed by PdCl2{PPh2(m-C6H4SO3Na)}2 in the presence of zinc chloride and NaBH4, and gave the corresponding aryl nitriles in high yields. The biphasic cyanation had an advantage in that the aryl nitriles are easily separated from the mixtures of catalyst and reagents.
Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene
Authors: Hoshi Takashi , Shimada Ryusaku , Kabuto Chizuko , Sanji Takanobu , Sakurai Hideki
Published: September 2003

(Trimethylsilylmethyl)trimethyldisilene was generated photochemically from 1-phenyl-7-trimethylsilylmethyl-7,8,8-trimethyl-7,8-disilabicyclo[2.2.2]octa-2,5-diene (masked disilene). UV spectrum and regioselectivity of the addition reaction of phenols to the disilene were discussed. The molecular structure of the masked disilene was also determined by single-crystal X-ray diffraction.
Catalytic Activities of CoAl2O4 for Key Reactions Related to Selective Reduction of Nitrogen Monoxide with Ethene in Excess Oxygen
Authors: Okazaki Noriyasu , Tsuda Shinya , Shiina Yoshikazu , Tada Akio , Iwamoto Masakazu
Published: September 2003

The synthesis of Co3O4-free CoAl2O4 was successfully achieved, and its was revealed that this oxide (CoAl2O4) was more active than Al2O3 for NO+O2 reaction, the initiation step of the selective reduction of NO over cobalt-loaded aluminas, but was less active than Co3O4-containing CoAl2O4 for C2H4+O2 reaction, a side reaction.
Ruthenium-Catalyzed Addition Reaction of Diphenylphosphinic Acid to Terminal Alkynes: Regioselective Synthersis of Alkenyl Diphenylphosphinates
Authors: Hua Ruimao , Tanaka Masato
Published: September 2003

Diphenylphosphinic acid adds across the triple bond of terminal alkynes in the presence of Ru3(CO)12, leading to regioselective formation of alkenyl diphenylphosphinates CH2=C(R)[OP(O)Ph2].
Chemoselective Synthesis of Diamines with Cationically Polymerizable Groups and Polyimides Synthesis
Authors: Tojo Hitoshi , Kameyama Atsushi , Nishikubo Tadatomi
Published: September 2003

Functional diamines with cationically polymerizable groups were successfully prepared in one-step by the chemoselective reaction of 4,4′-diamino-3,3′-dicarboxydiphenylmethane (1) using 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU). The reaction of 1 with propargyl bromide (2a), 2-chloroethyl vinyl ether (2b), and 2-bromomethyl-1,4,6-trioxa-spiro[4.4]nonane (2c) using DBU proceeded chemoselectively under mild conditions without any protection of the amino group to produce the corresponding diamines (3a-3c) in high yields.
Structure and Properties of (DTM-TTP)(TCNQ)(TCE) and the Related Complex
Authors: Mori Takehiko , Murata Kyoji , Misaki Yohji , Tanaka Kazuyoshi
Published: September 2003

DTM-TTP (2-(4,5-bisthiomethyl-1,3-dithiol-2-ylidene)-5-(1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene) and TCNQ (tetracyanoquinodimethane) form the title 1:1 complex including 1,1,2-trichloroethane (TCE). The crystal structure is composed of segregated stacks. This complex undergoes a metal-insulator transition around 100 K. Thermoelectric power takes small positive values, and the magnetic susceptibility is paramagnetic down to low temperatures.
Regioselective Synthesis of 8-Hydroxytetrahydroquinolines by the Cyclization of m-Hydroxyphenethyl Ketone O-2,4-Dinitrophenyloximes
Authors: Ono Ayako , Uchiyama Katsuya , Hayashi Yujiro , Narasaka Koichi
Published: September 2003

8-Hydroxy-1,2,3,4-tetrahydroquinolines are synthesized from m-hydroxyphenethyl ketone O-2,4-dinitrophenyloximes by the cyclization on the sp2 nitrogen atom of the oxime derivatives using sodium hydride and sodium cyanoborohydride.
Growth of Layered Perovskite-Type Na2Ca2Nb4O13 Crystals by the Na2SO4 Flux Method
Authors: Oishi Shuji , Nagai Yoshiteru , Chiba Koji , Ishizawa Nobuo
Published: September 2003

Rectangular thin plate-shaped crystals of layered perovskite-type Na2Ca2Nb4O13 were grown from a Na2SO4 flux by a slow cooling method. The crystals of sizes up to 0.8 mm × 0.8 mm × 0.05 mm were grown. The obtained crystals were colorless and transparent. The most suitable solute content was 6 mol%. The structure had a pseudotetragonal symmetry.
Efficient Oxidation of Various Phenols Catalyzed by Di-μ-hydroxodicopper(II) Complexes of a Hexapyridine Dinucleating Ligand
Authors: Kodera Masahito , Shimakoshi Hisashi , Tachi Yoshimitsu , Katayama Kou , Kano Koji
Published: September 2003

The di-μ-hydroxodicopper(II) complexes [Cu2(OH)2(hexpy)](X)2[X=ClO4 and CF3SO3, hexpy: 1,2-bis[2-di-(2-pyridyl)methyl-6-pyridyl]ethane] efficiently catalyze the oxidation of various phenols with H2O2.
RhCl(PPh3)3/NaI Catalyst System for Hydrosilylation of 1-Alkynes: Stereodivergent Syntheses of E- and Z-Alkenylsilanes with Heteroatom Substituents on Silicon
Authors: Mori Atsunori , Takahisa Eisuke , Kajiro Hiroshi , Hirabayashi Kazunori , Nishihara Yasushi , Hiyama Tamejiro
Published: September 2003

Both (E)- and (Z)-alkenylsilanes are synthesized by the reaction of hydrosilanes and 1-alkynes catalyzed by RhCl(PPh3)3/NaI or RhI(PPh3)3 highly selectively.
Diastereoselective π-Complexation: Reaction of Planar-chiral Cyclopentadienyl-Ruthenium Complexes with Prochiral Arenes
Authors: Komatsuzaki Nobuko , Kikuchi Hidetoshi , Yamamoto Mari , Uno Mitsunari , Takahashi Shigetoshi
Published: September 2003

The reaction of (trisubstituted cyclopentadienyl)tris(acetonitrile)ruthenium complexes, [Cp′Ru(CH3CN)3][PF6], with prochiral trisubstituted arenes gave planar-chiral [Cp′Ru(arene)][PF6] complexes with a diastereoselectivity up to 46% d.e.
Model Study for the Total Synthesis of Antifungal Australifungin: Construction of α-Diketone and β-Ketoaldehyde Moieties
Authors: Takao Ken-ichi , Nagata Seigo , Kobayashi Susumu , Ito Hisanaka , Taguchi Takeo
Published: September 2003

A model study for the total synthesis of australifungin was performed. Olefinic aldehyde was successfully converted to the target molecule having both α-diketone and β-ketoaldehyde moieties.
One-electron Oxidation of N-Benzylphenothiazine by Nitric Acid in the Presence of β-Cyclodextrin
Authors: Zhang Hai-Ming , Ruan Xiu-Qin , Guo Qing-Xiang , Liu You-Cheng
Published: September 2003

Oxidation of N-benzylphenothiazine with nitric acid in aqueous solution was investigated in the presence of β-cyclodextrin by means of UV-vis and ESR spectroscopy. The N-benzylphenothiazine radical cation generated in β-cyclodextrin cavity is much more stable than that outside of β-cyclodextrin cavity and that in organic solvent.
A Nonresonated Orthogonally Twisted Amide
Authors: Yamada Shinji , Nunami Noriko , Hori Kayako
Published: September 2003

The structure of N-pivaloylphthalimide was studied by IR, 13C NMR and UV spectroscopies, and X-ray analysis. The C(O)-N bond is orthogonally twisted, and the bond length is as long as that of C-N single bond.
Dioxygen Insertion into the Axial Si-C Bonds of Organosilicon Porphyrins
Authors: Zheng Jian-Yu , Konishi Katsuaki , Aida Takuzo
Published: September 2003

A dialkylsilicon porphyrin Si(TPP)(CH2CH3)2 (1) (TPP=5,10,15,20-tetraphenylporphinato) reacted with dioxygen in the dark to give a bis(ethylperoxide) complex (5), from which a dihydroxysilicon porphyrin (Si(TPP)(OH)2, (6) was obtained upon reduction and hydrolysis. In contrast with the phosphorous analogue [P(TPP)(OH)2]OH, the crystal structure of 6 showed an almost planar conformation of the porphyrin ligand.
Controlled Synthesis of C/D-Ring Components of Phycobilin Derivatives Bearing a Photoreactive Group at D-Ring
Authors: Masukawa Takanori , Kato Hirohide , Kakiuchi Takashi , Jayasundera Krishanthi Padmarani , Kinoshita Hideki , Inomata Katsuhiko
Published: September 2003

C/D-Ring components of phycobilin derivatives bearing a photoreactive group at D-ring were regioselectively synthesized by applying our original synthetic reactions such as acid-catalyzed rearrangement of 2-tosyl group of 3,4-disubstituted 2-tosylpyrroles to 5-position, regioselective preparation of 3,4-disubstituted 5-tosylpyrrolinones, and their Wittig-type new coupling reaction with 2-formyl pyrrole.
Physical Properties of 3-Ethylsydnone and the Alkyl Substituents
Authors: Handa Minoru , Suzuki Takami , Fukuda Hiroki , Sasaki Yukio
Published: September 2003

3-Ethyl-4-ethylsydnone was newly synthesized, and the physical properties of 3-ethylsydnone, 3-ethyl-4-methylsydnone and 3-ethyl-4-ethylsydnone at various temperatures were investigated. The highest dielectric constant was for 3-ethylsydnone. The alkyl substituent effect at the 4-position of the sydnone ring on the dielectric constant can be explained by the 13C NMR spectra.
Propagating Waves and Pattern Formation in a Reaction-Diffusion System with Pyrogallol as Substrate
Authors: Sridevi Venkatachalam , Ramaswamy Renganathan
Published: September 2003

The striking similarity between the nonlinear dynamical phenomena in chemical systems and those in biological systems, has enhanced the interest in the search of new reaction-diffusion systems. Here we report an oscillatory chemical system, which exhibits different types of chemical waves and patterns when kept unstirred. The reaction constituents are 1,2,3-trihydroxybenzene (pyrogallol), ferroin, sulphuric acid and potassium bromate. The system has a significant advantage of being gas-free.
A Study of Photooxygenation of Cycloalkenes under 2,4,6-Triphenylpyrylium Tetrafluoroborate Sensitization
Authors: Sridhar Madabhushi , Kumar Butty Ashok
Published: September 2003

2,4,6-Triphenylpyrylium tetrafluoroborate sensitized oxygenation of cycloalkenes to allylic hydroperoxides is described. This reaction appears to involve unusual electron transfer mechanism in the formation of observed products.
Stabilization of Cobalt Complexes by Functionalized Silanes in Inorganic-Organic Hybrid Materials
Authors: Kuraki Jun , Iwasaki Mitsunobu , Ito Seishiro
Published: September 2003

The surrounding fields around cobalt ions in the pore-free inorganic-organic hybrid materials were controlled through coordination bonds by various functional groups directly bonded to the silica framework. Tetrachloro cobalt (II) ion [CoCl4]2− was also stabilized for a period of over one month in the pore-free materials, whereas it was gradually transformed to [Co(H2O)6]2+ in the porous ones. The pore volume of the hybrid materials was changed against the methyltrimethoxysilane to total silane ratio.
Novel Water-soluble Hexa(sulfobutyl)fullerenes as Potent Free Radical Scavengers
Authors: Chi Yu , Bhonsle JB , Canteenwala Taizoon , Huang Jen-Pang , Shiea Jentaie , Chen Bo-Ji , Chiang Long Y
Published: September 2003

Novel highly water-soluble hexa(sulfobutyl)fullerenes were synthesized via electron reductions of C60. It showed an enhanced superoxide radical (O2−·) scavenging activity at a dose level of 100 μM.
Stereocontrol in the Addition of Allyl Metal Reagents to an Optically Active Imine Derived from Malic Acid, Leading to a Formal Synthesis of (+)-Negamycin
Authors: Shimizu Makoto , Morita Asato , Fujisawa Tamotsu
Published: September 2003

Complete anti-stereoselection has been achieved on the addition of allyl metal reagents to an optically active imine derived from malic acid. The homoallyl amine thus obtained was converted into the known intermediate for the synthesis of (+)-Negamycin in enantiomerically pure form.
Synthesis and Crystal Structure of a New 3D Scaffold-Like Compound [Mn(4,4′-bipy)(N3)2]n
Authors: Shen Hao-Yu , Liao Dai-Zheng , Jiang Zong-Hui , Yan Shi-Ping , Sun Bai-Wan , Wang Geng-Lin , Xin-Kan Yao , Wang Hong-Gen
Published: September 2003

A new 3D scaffold-like compound [Mn(4,4′-bipy)(N3)2]n has been synthesized and its structure determined by single-crystal X-ray analysis. The molecular structure consists of a three-dimensional network in which Mn2+ are linked by EE bridged azido ligands and 4,4′-bipy ligands. Magnetic measurement indicates that the overall magnetic behavior is weakly antiferromagnetic.
Benzo[1,2:4,5]bis(1,1,2,2-tetraisopropyldisilacyclobutene)
Authors: Kyushin Soichiro , Kitahara Tsukasa , Matsumoto Hideyuki
Published: September 2003

Benzo[1,2:4,5]bis(1,1,2,2-tetraisopropyldisilacyclobutene) (1) was synthesized. The X-ray crystal analysis shows that the benzene ring is deformed from the D6h symmetry. Compound 1 shows an intense 1Lb absorption band in the UV spectrum. In the emission spectrum, intense phosphorescence (Φp = 0.72) was observed at 77 K.