bluuebunny/crossref_metadata_2025 huggingface dataset:
Relationship of Hepatic Functional Imaging to Irinotecan Pharmacokinetics and Genetic Parameters of Drug Elimination
Authors: Michael Michael , Thompson Mick , Hicks Rod J. , Mitchell Paul L. , Ellis Andrew , Milner Alvin D. , Di Iulio Julia , Scott Andrew M. , Gurtler Volker , Hoskins Janelle M. , Clarke Stephen J. , Tebbut Niall C. , Foo Kian , Jefford Michael , Zalcberg John R.
Published: August 2006

Purpose

The marked variability of irinotecan (Ir) clearance warrants individualized dosing based on hepatic drug handling. The aims of this trial were to identify parameters from functional hepatic nuclear imaging (HNI) that correlate with (1) Ir pharmacology, and (2) single-nucleotide polymorphisms (SNPs) for the ABCB1 (P-glycoprotein) and UGT-1A1 genes, known to influence Ir handling.

Methods

Patients underwent genotyping for ABCB1 SNPs and UTUGT-1A1*28 carriage and HNI with99mTc-DIDA (acetanilidoiminodiacetic acid)/99mTc-DISIDA (disofenin) and MIBI (99mTc-sestamibi) scans, probes for biliary transport proteins ABCC1 and -2, and ABCB1 function. HNI data were analyzed by noncompartmental and deconvolutional analysis to provide hepatic extraction and biliary excretion parameters. Patients received Ir, fluorouracil, and folinic acid using a weekly ×2, every-3-weeks schedule. Plasma was taken for Ir and SN-38 analysis on day 1, cycle 1.

Results

Of the 21 patients accrued, Ir pharmacokinetics data were obtained from 16 patients.99mTc-DIDA/DISIDA percent retention at 1 hour (1-hour RET) correlated to baseline serum bilirubin (P = .008). Both99mTc-DIDA/DISIDA and MIBI 1-hour RET correlated with SN-38 area under the curve (AUC; P < .01). On multiple regression analysis, SN-38 AUC = −215 + 18.68 × bilirubin + 4.27 × MIBI 1-hour RET (P = .009, R2= 44.2%). HNI parameters did not correlate with Ir toxicity or UGT1A1*28 carriage. MIBI excretion was prolonged in patients with the ABCB1 exon 26 TT variant allele relative to wild-type (P = .015).

Conclusion

Functional imaging of hepatic uptake and excretory pathways may have potential to predict Ir pharmacokinetics. Evaluation of a larger cohort as well as polymorphisms in other biliary transporters and UGT1A1 alleles is warranted.
Phase II Trial of CHOP Plus Rituximab in Patients With HIV-Associated Non-Hodgkin's Lymphoma
Authors: Boué François , Gabarre Jean , Gisselbrecht Christian , Reynes Jacques , Cheret Antoine , Bonnet Fabrice , Billaud Eric , Raphael Martine , Lancar Remi , Costagliola Dominique
Published: August 2006

Purpose

To evaluate the safety and efficacy of rituximab adjunction to the cyclophosphamide, doxorubicin, vincristine, and prednisone (CHOP) regimen in patients with newly diagnosed AIDS-related non-Hodgkin's lymphoma.

Patients and Methods

HIV-seropositive patients with high-grade lymphoma of B-cell origin were eligible if they had no more than one of the following characteristics: CD4 cell count less than 100/μL, prior AIDS, or performance status less than 2. This multicenter phase II trial evaluated the response rate and disease-free survival after six courses of rituximab plus CHOP.

Results

Sixty-one patients were enrolled. All the patients were assessable for safety and 52 were assessable for the tumor response after treatment completion. Characteristics of patients were median age, 41 years; median CD4 cells, 172/μL; histology, diffuse large B-cell lymphoma (n = 42), immunoblastic (n = 2), Burkitt lymphoma (n = 16), and plasmablastic (n = 1); 42 patients with stage III to IV; International Prognostic Index 0 to 1 (n=31), and 2 to 3 (n = 27). Grade 3 or 4 toxicity consisted of febrile neutropenia in nine patients, anemia in 16 patients, and thrombocytopenia in five patients. Complete remission (CR) or unconfirmed CR was achieved in 40 of the 52 assessable patients, partial remission was achieved in five patients, and seven patients experienced progression. Forty-three patients were alive after a median follow-up of 33 months. The estimated 2-year overall survival rate was 75% (95% CI, 64% to 86%). Eighteen patients died: 16 as a result of lymphoma, one as a result of infection, and one as a result of encephalitis.

Conclusion

Rituximab adjunction to CHOP produced a CR rate of 77% and a 2-year survival rate of 75% in patients with AIDS-related non-Hodgkin's lymphoma, without increasing the risk of life-threatening infections.
Factors Associated With Outcomes in Allogeneic Hematopoietic Cell Transplantation With Nonmyeloablative Conditioning After Failed Myeloablative Hematopoietic Cell Transplantation
Authors: Baron Frédéric , Storb Rainer , Storer Barry E. , Maris Michael B. , Niederwieser Dietger , Shizuru Judith A. , Chauncey Thomas R. , Bruno Benedetto , Forman Stephen J. , McSweeney Peter A. , Maziarz Richard T. , Pulsipher Michael A. , Agura Edward D. , Wade James , Sorror Mohamed , Maloney David G. , Sandmaier Brenda M.
Published: August 2006

Purpose

Several studies have investigated the feasibility of allogeneic hematopoietic cell transplantations (HCTs) after reduced-intensity conditioning in patients who experienced relapse after myeloablative HCT. Although most studies showed relatively low nonrelapse mortality (NRM) rates and encouraging short-term results, it has yet to be defined which patients would benefit most from these approaches.

Patients and Methods

We analyzed data from 147 patients with hematologic malignancies who experienced treatment failure with conventional autologous (n = 135), allogeneic (n = 10), or syngeneic (n = 2) HCT and were treated with HLA-matched related (n = 62) or unrelated (n = 85) grafts after conditioning with 2 Gy of total-body irradiation with or without fludarabine.

Results

Three-year probabilities of NRM, relapse, and overall survival were 32%, 48%, and 27%, respectively, for related recipients, and 28%, 44%, and 44%, respectively, for unrelated recipients. The best outcomes were observed in patients with non-Hodgkin's lymphoma, whereas patients with multiple myeloma and Hodgkin's disease had worse outcomes as a result of high incidences of relapse and progression. Being in partial remission (PR) or complete remission (CR) at HCT (P = .002) and developing chronic graft-versus-host disease (GVHD; P = .03) resulted in lower risks of relapse and progression. Factors associated with better overall survival were PR or CR (P = .01) and lack of comorbidity (P = .03) at HCT and absence of acute GVHD after HCT (P = .06).

Conclusion

Encouraging outcomes were seen with allogeneic HCT after nonmyeloablative conditioning in selected patients who had experienced relapse after a high-dose HCT, particularly in patients with non-Hodgkin's lymphoma. Results with unrelated grafts were comparable with results with related grafts.
Androgen Therapy Induces Muscle Protein Anabolism in Older Women
Authors: Sheffield-Moore Melinda , Paddon-Jones Douglas , Casperson Shanon L. , Gilkison Charles , Volpi Elena , Wolf Steven E. , Jiang Jie , Rosenblatt Judah I. , Urban Randall J.
Published: August 2006

Context: Normal healthy men and women undergo a gradual loss of skeletal muscle mass and strength with advancing age. While androgens are protein anabolic in older men, the metabolic effects in older women are poorly understood.

Objective and Design: The objective of this study was to determine whether oral administration of a synthetic derivative of testosterone [oxandrolone, Oxandrin (OX)] (7.5 mg orally twice daily for 14 d) to five older women (age, 65 ± 2 yr) would enhance skeletal muscle anabolic biomarkers including mixed muscle fractional synthetic rate (FSR), net phenylalanine balance, androgen receptor, and IGF-I protein expression at d 0, 5, and 14 of treatment. As a positive control, seven older men were examined after 14 d of OX (10 mg orally twice daily).

Setting: The study was performed at the General Clinical Research Center.

Results: Fourteen days of OX significantly increased skeletal muscle FSR in older women (d 0, 0.073 ± 0.006 vs. d 5, 0.092 ± 0.006 vs. d 14, 0.115 ± 0.007%/h) (P < 0.05, d 0 vs. d 14). Conversely, OX stimulated FSR in older men after only 5 d (d 0, 0.061 ± 0.003 vs. d 5, 0.101 ± 0.01 vs. d 14, 0.084 ± 0.01%/h) (P < 0.05, d 0 vs. d 5). Androgen receptor expression was significantly increased in older men by d 14, but had not increased in older women. No change was noted in IGF-I expression in either group. We conclude that the skeletal muscle of older women and men responds to androgen administration, although the time course of anabolism appears to be gender specific.
Functional Significance of Polycystic-Size Ovaries in Healthy Adolescents
Authors: Mortensen Monica , Rosenfield Robert L. , Littlejohn Elizabeth
Published: August 2006

Context: The relevance of adult polycystic ovary criteria to adolescence is unclear.

Objective: The objective was to determine the functional significance of polycystic-size ovaries (PSO) in healthy adolescents.

Design/Setting/Participants/Interventions: Healthy 11- to 18-yr-old postmenarcheal volunteers (n = 22) were recruited and divided into groups with normal size ovaries (VNSO; n = 10) or a polycystic-size ovary (VPSO; n = 12). They were secondarily compared with adolescents with polycystic ovary syndrome (PCOS; n = 8) matched for gynecological age and a PSO. All underwent GnRH agonist (GnRHag), oral glucose tolerance, and ACTH1–24 testing in our General Clinical Research Center.

Results: VPSO had a higher peak 17-hydroxyprogesterone (17PROG) response to GnRHag than VNSO (146 ± 14 ng/dl, mean ± sem, vs. 85 ± 11; P = 0.008), as well as larger ovaries (13.3 ± 0.7 cc vs. 8.5 ± 0.8 cc). VPSO peak 17PROG was elevated (>137 ng/dl) in 42% (5 of 12). However, VPSO and VNSO androgen levels were similar, with the exception of one VPSO subject who had hyperandrogenemia and thus met criteria for PCOS. VPSO were similar to VNSO in LH, FSH, estradiol, and adrenal androgenic function. Although the VPSO group resembled the PCOS group in their 17PROG response to the GnRHag test, they differed in having significantly smaller ovaries and lower body mass index and in lacking evidence of peripheral androgen excess and of insulin resistance.

Conclusion: A PSO in asymptomatic adolescents seems typically to be a normal variant. However, about half have a subclinical PCOS type of ovarian dysfunction; it is unknown whether this indicates a genetic carrier state or a risk for anovulation.
Assessment of Adrenal Reserve in Pregnancy: Defining the Normal Response to the Adrenocorticotropin Stimulation Test
Authors: Suri Daesman , Moran Jill , Hibbard Judith U. , Kasza Kristen , Weiss Roy E.
Published: August 2006

Context: Normal pregnancy is a state of hypercortisolism, making adrenal insufficiency difficult to diagnose.

Objective: We sought to identify a normative, minimum-response threshold for the ACTH stimulation test in pregnancy. We hypothesized that salivary free cortisol (SaFC) would prove a more physiological and less variable measure of adrenal reserve in pregnancy than serum cortisol (SC).

Design: This is a prospective study of normal controls.

Setting: The study was conducted in an obstetrical clinic in a tertiary care hospital.

Patients: Patients included 36 healthy ambulatory pregnant women (aged 18–37 yr) with singleton pregnancies.

Intervention: The 250-μg ACTH stimulation test was performed in the healthy pregnant volunteers. Based on their gestational age at the time of recruitment, women were studied in one of the trimesters and were restudied at 11–14 wk postpartum.

Main Outcome Measures: Total SC, aldosterone, and SaFC concentrations were measured before and after ACTH. The response in pregnancy was compared with postpartum values.

Results: Basal SC (P = 0.01), aldosterone (P = 0.001), and SaFC (P = 0.01) values progressively increased during the trimesters of pregnancy and decreased postpartum, confirming that pregnant women have increased basal glucocorticoid and mineralocorticoid production. There was enhanced responsiveness of the maternal adrenal glands to ACTH stimulation as pregnancy progressed, as measured by peak stimulated SaFC (P = 0.009) and aldosterone (P = 0.01). In the milieu of altered binding globulins, SaFC is a more consistent, binding-globulin-independent measure of stimulated adrenal function than total SC. Minimum criteria for the normal SaFC response to ACTH stimulation in the second and third trimesters of pregnancy and postpartum have been generated based on a predominantly African-American group of subjects.

Conclusions: Reliable data are available for the evaluation of the adrenal axis in pregnancy with a noninvasive, outpatient measure of SaFC. Glucocorticoid therapy in pregnancy should take into account that adrenal reserve increases as pregnancy progresses.
Estradiol and Regulation of Anti-Müllerian Hormone, Inhibin-A, and Inhibin-B Secretion: Analysis of Small Antral and Preovulatory Human Follicles’ Fluid
Authors: Andersen Claus Yding , Byskov Anne Grete
Published: August 2006

Context: In ovaries surgically removed for fertility preservation, hormone concentrations in fluid from small antral follicles were determined. Levels were compared with those found in preovulatory follicular fluid.

Objective: The objective of this study is to measure intrafollicular concentrations of anti-Müllerian hormone (AMH), inhibin-A, inhibin-B, estradiol, and progesterone.

Setting: The study was set in a university hospital.

Patients: Patients were 22 women suffering from a cancer disease and 16 women undergoing assisted reproduction.

Interventions: Fluid from 35 follicles (diameter, 3–8 mm) was included and compared with that of 32 preovulatory follicles.

Main Outcome Measures: The main outcome measures were intrafollicular concentrations of the measured hormones and their possible correlation.

Results: Concentrations of AMH in small antral follicles were almost three orders of magnitude higher than in follicle fluid of preovulatory follicles, 790 ± 95 vs. 1.17 ± 0.14 ng/ml (mean ± sem), respectively. There was a significant negative correlation between estradiol and AMH in fluid from small antral follicles, whereas inhibin-A and inhibin-B were correlated positively with estradiol concentrations. Progesterone showed a similar correlation to levels of AMH but only in fluid of preovulatory follicles.

Conclusions: The high expression of AMH in granulosa cells of small antral follicles actually translates into very high follicle fluid AMH concentrations. This most likely explains the correlation between serum AMH levels and the number of small antral follicles as previously demonstrated. The negative correlation between estradiol and AMH suggests that FSH down-regulates AMH expression. Thus, the microenvironment of the follicle shows profound changes with developmental stage and highlights the importance of studies to understand the mechanisms that regulate follicular growth and development during antral stages of development.
Radioactive Iodine Therapy for Goitrous Hashimoto’s Thyroiditis
Authors: Tajiri Junichi
Published: August 2006

Context: Hashimoto’s thyroiditis is an autoimmune disease that can produce marked clinical symptoms when patients have large diffuse goiters.

Design: This retrospective cohort study was designed to evaluate whether radioactive iodine (RAI) is effective for Hashimoto’s thyroiditis with a large goiter. Starting in November 1999, 13 Hashimoto’s patients with large goiters, whose thyroiditis was refractory to TSH suppression therapy with thyroid hormone administration [two men and 11 women with a mean age of 61.2 ± 8.9 yr (50–79 yr)], were recruited for the present study. The duration of symptomatic goiter before undergoing RAI was 12.0 ± 7.9 yr (4–33 yr). Thirteen millicuries of 131I was administered two to six times, at an interval of 1–6 months on an outpatient basis. Thyroid weight was measured ultrasonographically, or by computed tomography if ultrasound was not possible due to the large size of the goiter.

Results: RAI was administered an average of 4.7 ± 1.4 times (two to six times), with a total dose of 59.8 ± 17.3 mCi (25.0–78.0 mCi). The observation period was 47.9 ± 13.4 months (26–66 months) after the first RAI. The average weight of the thyroid gland was 125.3 ± 57.7 g (42.9–269.4 g) before the first RAI, decreasing significantly to 49.7 ± 25.8 g (18.3–93.3 g) after the last RAI (P < 0.001, paired Student’s t test). The percent reduction from baseline was 58.7 ± 14.2% (35.7–84.0%). None of the patients showed an increase in goiter size or complained of a pressure sensation after any of the RAI treatments.

Conclusion: RAI is effective in Hashimoto’s thyroiditis with a large goiter.
Kinematic Viscosities of 1,2-Ethanediol/1,4-Dioxane Binary Mixtures from −10 to +80 °C
Authors: Corradini Fulvio , Marcheselli Luigi , Tassi Lorenzo , Tosi Giuseppe
Published: August 2006

Mixture kinematic viscosities (ν) were measured for the 1,2-ethanediol/1,4-dioxane binaries, covering the whole miscibility field (0 ≤ X1 ≤ 1), at 19 temperatures ranging from −10 to +80 °C. The experimental ν values were fitted by different equations, such as Grunberg–Nissan, McAllister, Auslander, Heric, and polynomial one, using pure component properties for the binaries studied. A comparison of the calculated and experimental data shows that all the selected equations can be safely employed to predict the dependence of ν on the composition and on the temperature of the system studied when no binary experimental data are available.
Multiple Pulse Excitation of Molecular Vibration in Resonant Pump-Probe Experiments. I. Perturbative Approach
Authors: Kawashima Hitoshi , Shida Tadamasa
Published: August 2006

The possibility of stepwise amplification of molecular vibration by resonant multiple pulse excitation is theoretically considered on the basis of perturbation theory. A grating experiment favorable to its observation is proposed. It has proved that the effective interval of the repetitive irradiation to attain large amplitude vibrations is equal to odd halves of the period of the vibrational cycle and that there is no gain with an interval equal to the integral multiples of the vibrational period while such an interval is effective in mode selective excitation. It has also proved that the dispersed signal shifts periodically over a range of energy and that the range is widened as the vibrational amplitude is increased.
Interaction of Sodium 4′-(Butylamino)azobenzene-4-sulfonate with 2-(Octylsulfinyl)ethanol in Adsorbed Film and Micelle
Authors: Tanaka Fudeko , Harada Yuzo , Todoroki Natsuko , Aratono Makoto , Motomura Kinsi
Published: August 2006

The surface tension of the aqueous solution of anionic dye and nonionic surfactant mixture was measured as a function of total concentration at various compositions and at 298.15 K under atmospheric pressure. The dye used is sodium 4′-(butylamino)azobenzene-4-sulfonate (SBAS) and the nonionic surfactant is 2-(octylsulfinyl)ethanol (OSE). By use of thermodynamic relations developed previously, the phase diagrams of adsorption and micelle formation were constructed. It was found that SBAS and OSE are completely miscible with each other in the adsorbed film and that the adsorbed film is enriched in OSE compared with the solution except for a composition close to pure OSE. It was concluded that SBAS and OSE interact attractively with each other in the adsorbed and micellar states and, furthermore, that the interaction is more attractive in the micelle than in the adsorbed film. The miscibility of dye and nonionic surfactant is suggested to play an important role in the working of nonionic surfactant as a levelling agent in dyeing process.
Enantiometric Separation with Use of Stationary Phase Coated with Micellar Bile Salt for Microcolumn Liquid Chromatography
Authors: Hu Wenzhi , Haraguchi Hiroki
Published: August 2006

A novel method for enantiometric separation using an ODS stationary phase coated with bile salt micelles in high-performance liquid chromatography has been developed, where bile salt surfactants such as sodium cholate and sodium deoxycholate were used for micelle formation. The present method was applied to the separation of the enantiomers of 1,1′-binaphthyl-2,2′-diyl hydrogenphosphate (BNDHP) and N-dansylphenylalanine by using acetonitrile–water solution as the mobile phase. The dependence of the capacity factors and separation factors on the acetonitrile concentration in the mobile phase was examined for BNDHP enantiomers. These factors decreased with increasing acetonitrile concentration, which resulted in the change of separation characteristics of BNDHP enantiomers. Although BNDHP and N-dansylphenylalanine enantiomers were separated, similar enantiomers such as 2,2′-dihydroxy-1,1′ -binaphthyl and other N-dansylamino acids were not separated in the present separation system.
Syntheses and Spectral Properties of Dinitrosylmolybdenum(0) and Dioxomolybdenum(VI) Complexes
Authors: Maurya Mannar R , Gopinathan Changaramponnath
Published: August 2006

Syntheses of dinitrosylmolybdenum(0) complexes of Schiff bases derived from salicylaldehyde, 5-chlorosalicylaldehyde, o-hydroxyacetophenone, and p-nitrobenzoylhydrazide have been carried out in one step by the reaction of [Mo(acac)2(NO)2] (acacH = acetylacetone) and the Schiff bases. The complexes are of the type [Mo(LH)2(NO)2] (LH2 = Schiff base) in which Schiff bases behave as monobasic bidentate ligands and coordinate to molybdenum through the azomethine nitrogen and enolic oxygen of the hydrazide moiety after deprotonation. Two geometrical isomers with nitrosyl groups trans to each other have been noticed in solution. Dioxomolybdenum(VI) complexes of the above Schiff bases have also been synthesized using [MoO2(acac)2] as precursor for comparison.
Syntheses and Structures of NiS2N2 Compounds. [N,N′-Bis(o-mercaptobenzyliden)ethylenediaminato]nickel(II), Ni(tsalen), and [N,N′-Bis(o-mercaptobenzyl)ethylenediaminato]nickel(II), Ni(ebmba)
Authors: Yamamura Takeshi , Tadokoro Makoto , Tanaka Koji , Kuroda Reiko
Published: August 2006

The syntheses, structures, absorption spectra, and redox potentials of Ni(tsalen), H2tsalen = N,N′-bis(o-mercaptobenzyliden)ethylenediamine, and Ni(ebmba), H2ebmba = N,N′-bis(o-mercaptobenzyl)ethylenediamine, are described. Ni(tsalen) was prepared directly from N,N′-bis(o-t-buthylthiobenzyliden)ethylenediamine, from which H2ebmba and, subsequently, Ni(ebmba) were also prepared. The crystal data for these two complexes are as follows: 1) Ni(tsalen); space group Pna21 with the unit-cell dimensions a = 8.929(1), b = 22.603(2), c = 7.484(1) Å, Z = 4, 2) Ni(ebmba); space group P21/c, a = 13.324(5), b = 7.9263(8), c = 15.262(3) Å, β = 101.23(2)°. Ni(tsalen) and Ni(ebmba) adopt squareplanar geometries with average Ni–S distances of 2.157 and 2.165 Å, respectively. The Ni–N distances of these complexes are 1.85(5) and 1.945 Å, respectively. These values, as well as the redox potentials and absorption maxima, ware compared with those of another type of NiS2N2 compound, [Ni(ebtsa)]2−; H4ebtsa = N,N′-bis(o-mercaptobenzoyl)ethlenediamide.
Epimerization-Crystallization Method in Optical Resolution of 2,2′-Dihydroxy-1,1′-binaphthyl, and Kinetic Study
Authors: Kawashima Masatoshi , Hirata Reiko
Published: August 2006

Optical resolution of 2,2′-dihydroxy-1,1′-binaphthyl (1) with (R,R)-1,2-cyclohexanediamine (2) in toluene yielded optically pure (R)-1 in a yield of 160% based on the theoretical amount of the enantiomer contained in the racemate by selective crystallization of a less soluble complex, (R)-1·(R,R)-2, and epimerization of more soluble complex, (S)-1·(R,R)-2. Also optically pure (S)-1 was obtained with the same enantiomer of the resolving agent, (R,R)-2, in a yield of 154%. (R,R)-1,2-Diphenyl-1,2-ethanediamine (3) was a suitable resolving agent for both 1 and 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl. Kinetic study indicated that the reversible first-order rate constants for the epimerizations of (S)-1·(R,R)-2 and (S)-1·(R,R)-3 were larger than that for the racemization of (S)-1. The activation energy and frequency factor for the epimerization of (S)-1·(R,R)-2 were 109 kJ mol−1 K−1 and 3 × 1010 s−1, respectively, and those for (S)-1·(R,R)-3 were 96 kJ mol−1 K−1 and 1 × 108 s−1, while those for the racemization of (S)-1 were 85 kJ mol−1 K−1 and 9 × 105 s−1, respectively.
Solid Acid and Base-Catalyzed Cyanosilylation of Carbonyl Compounds with Cyanotrimethylsilane
Authors: Higuchi Katsumi , Onaka Makoto , Izumi Yusuke
Published: August 2006

A new attempt was investigated to utilize inorganic solid acids and bases for the promotion of the reaction of cyanotrimethylsilane (Me3SiCN) with carbonyl compounds. Strongly acidic solids, such as Sn4+ ion-exchanged montmorillonite (Sn-Mont) and Fe3+ ion-exchanged montmorillonite (Fe-Mont), as well as basic solids, such as calcium fluoride (CaF2), hydroxyapatite (HAp), calcium oxide (CaO), and magnesium oxide (MgO), catalyzed the reaction of Me3SiCN with aldehydes and ketones to afford the corresponding 2-(trimethylsiloxy)alkanenitriles in good yields. The reactions of dimethyl acetals with Me3SiCN in the presence of solid acids afforded 2-methoxyalkanenitriles. In cyanosilylations of α,β-unsaturated ketones two kinds of adducts were produced selectively, depending on the use of a solid acid or a solid base: 1,4-Adducts (trimethylsilyl enol ether forms) were selectively obtained in the presence of strong solid acids, such as Fe-Mont and Sn-Mont, while 1,2-adducts (trimethylsilyl ether forms) were predominantly formed in the presence of solid bases, such as HAp, CaO, and MgO. The solid acids and bases realized higher activities and selectivities in the cyanosilylation than did conventional homogeneous catalysts.
A Base-Catalyzed H/D Exchange Reaction in the 6-(1-Pyridinio)-6-deoxy Derivatives of Cyclodextrins
Authors: Mu Ping , Fujie Masahiko , Matsui Yoshihisa
Published: August 2006

Mono[6-(1-pyridinio)-6-deoxy]-α-cyclodextrin and its analogs exchanged the α-hydrogens of their pyridinio moieties with the deuteriums of solvent D2O in an alkaline buffer solution via the formation of the pyridinium ylide intermediates. The H/D exchange reaction was facilitated by the hydrophobic cavity of cyclodextrin, as well as by a substitution of the additional pyridinio group for the primary OH group, especially in the adjacent glucopyranose moiety of the cyclodextrin residue. On the other hand, the reaction was moderately retarded by an increase in the ionic strength of the solution, and markedly retarded by inorganic anions, such as I−, SCN−, and ClO4−, which were strongly bound to the cavity of cyclodextrin.
Syntheses and Structures of 1,1-Dimethyl-1,2,6,10b-tetrahydro-6,10b-o-benzenoaceanthrylenes: Sterically Congested Triptycenes Carrying Five-Membered Ring
Authors: Toyota Shinji , Endo Masahiko , Teruhi Mitsuru , Noda Yoshiyuki , Oki Michinori , Yamasaki Mikio , Shibahara Takashi
Published: August 2006

Sterically compressed title compounds which carry a five-membered ring condensed to the triptycene skeleton were synthesized by the Diels-Alder reaction of 1,1-dimethyl-1,2-dihydroaceanthrylene with a benzyne. The structures of three compounds were determined by X-ray crystallography. The molecules have several abnormal bond lengths and angles in addition to significant deformation of the benzene rings as well as the triptycene skeleton to avoid the eclipsed conformation about C(1)–C(10b) and C(1)–C(2) bonds. The effects of the substituents at the 7—10 positions are rather small, but an interesting bond angle deformation is found on comparison of the C(10a)–C(10)–substituent bond angles. Molecular mechanics calculation was performed for the dimethoxy compound to compare the calculated structure with the X-ray structure. Molecular flexibility of the unsubstituted compound was discussed on the basis of MM2 calculation.
Archaebacterial Lipids: Stable Anionic Membranes from 1,2-Bis(dihydrophytyl)glycero-3-phosphate
Authors: Yamauchi Kiyoshi , Togawa Katsuya , Kinoshita Masayoshi
Published: August 2006

1,2-Bis(dihydrophytyl)glycero-3-phosphate (DPhyPA) was synthesized as an analog of archaebacterial lipids. Upon sonicating in amine-containing buffers like 0.05 M Tris–HCl (pH 7.8), the lipid gave rise to the stable liposomal assemblies, which could store 5(6)-carboxyfluorescein at high temperature as high as 70 °C in the interior. The assembly also had a large negative zeta-potential and showed an absence of gel-to-liquid crystalline phase transition from −20 to 80 °C. A Langmuir monolayer at an air/water interface suggested that the maximum molecular area of the lipid was 0.9—1.0 nm2. These properties were compared with the assemblies prepared from conventional 1,2-dipalmitoyl-sn-glycero-3-phosphate and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine.
Crystal Structure and Conformation of N-(t-Butoxycarbonyl)-l-valine N-Hydroxysuccinimide Ester
Authors: Sukumar N , Ponnuswamy M N , Jayakumar R
Published: August 2006

An X-ray crystal structure analysis of the title compound (C14H22N2O6) was carried out. There are two molecules (A & B) in the asymmetric unit. In both molecules valine side chains exist in a staggered conformation. The molecules in the crystalline state are stabilized by N–H···O and C–H···O hydrogen bonding.
Enantioselective Esterification of Cyclic Dicarboxylic Anhydrides Using Chiral Amino Alcohols as Auxiliaries
Authors: Shimizu Makoto , Matsukawa Kohzoh , Fujisawa Tamotsu
Published: August 2006

Cyclic dicarboxylic anhydrides were enantioselectively esterified with the complex formed from cinchonidine, diethylzinc, and methanol, and the half-esters obtained were readily transformed into lactones via reduction and dehydration.
Liquid-Phase Hydration of Acrylonitrile on Skeletal Copper Catalysts Prepared from Cu–Ti and Cu–Zr Amorphous Alloys
Authors: Funabiki Takuzo , Yamashita Hiromi , Yase Makoto , Omatsu Toshihiro , Yoshida Satohiro
Published: August 2006

Liquid-phase hydration of acrylonitrile has been carried out on the skeletal copper catalysts which were prepared by treating pulverized amorphous Cu–Ti and Cu–Zr alloys with an HF solution. The catalysts from amorphous alloys were more effective to produce acrylamide selectively than those from crystalline alloys. This high activity was brought about by the highly homogeneous structure of the amorphous alloys.
Synthesis of Formaldehyde Acetals by Phase Transfer Catalysis
Authors: Wang Maw-Ling , Chang Shahng-Wern
Published: August 2006

By employing phase transfer catalysis, formaldehyde acetals were synthesized from the reaction of alcohols and dibromomethane at moderate temperatures. Using a high alkaline concentration, the reaction could be improved to obtain a 100% yield by reacting dibromomethane and 1-alcohol employing tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. Six kinds of alcohols with various structures, four sorts of solvents with various dielectric constants and seven types of catalysts were examined to test their reactivities to the reactions. Only one unique product with two alkoxides substituents was observed which indicated the presence of a rather fast reaction rate during the second reaction of the organic phase. The reaction was dramatically enhanced by adding a small amount of quaternary ammonium salt (QX) to obtain a 100% yield utilizing the alcohols with nonbonding electron pairs within a short period of reaction time. The conversion was also observed to be strongly dependent upon the structure of the quaternary ammonium salts. The reaction rate and the product yield were satisfactorily accounted for the chemical reaction equilibrium of alcohols and KOH in the aqueous phase, the hydration of the active catalyst (QOR) in the organic phase and the distribution of QOR between two phases.
The β-Type Structures of Very Simple N-Octanoyl-l-glutamic Acid Oligomers (Residue Number, N = 2—6) and Their β1→β2-Type Transition
Authors: Uehara Toshiyuki , Okabayashi Hirofumi , Taga Keijiro , Yoshida Tadayoshi , Kojima Hiroshi , Nishio Etuso
Published: August 2006

N-Octanoyl-l-glutamic acid oligomers (residue number, N = 2—6) have been synthesized in order to study their molecular conformations in the solid state. The X-ray powder diffraction patterns and vibrational spectra of these oligomers have been investigated and compared with those of the α-helical and β-sheet conformations of poly-l-glutamic acid. For fresh samples of these oligomers, the tetramer, pentamer, and hexamer take up a conformation similar to the β1-form of poly-l-glutamic acid. However, the β1-type conformation of these oligomers is rapidly transformed to a β2-type conformation with time at room temperature, indicating that a transition similar to the β1→β2 transition of poly-l-glutamic acid occurs, even in the tetramer, pentamer, and hexamer. For fresh samples of the dimer and trimer, these molecules take up the β2-type structure. This means that the critical size of the oligomer for the formation of the β1→β2-type transition is the tetramer.
Vibrational Spectra of N-Octanoyl-l-glutamic Acid Oligomer Barium Salts and Their Conformations
Authors: Uehara Toshiyuki , Okabayashi Hirofumi , Taga Keijiro , Yoshida Tadayoshi , Kojima Hiroshi , Nishio Etsuo
Published: August 2006

Barium salts of N-octanoyl-l-glutamic acid oligomers (oct-oligomer salts, residue number, N = 2—6, 8, 10, 12, 14, 16, 18, 20, and 22) have been prepared. The vibrational spectra of these molecules were measured and compared with those of β-Ca-poly(l-glutamic acid). For the vibrational spectra of these oligomer salts, the very broad amide I bands at 1644—1655 cm−1 (IR), amide III bands at 1240—1256 cm−1 (Raman) and at 1240—1250 cm−1 (IR) are due to a disordered structure. The Raman bands at 840—855 cm−1 and their counter part at 835—848 cm−1 in the IR spectra may also come from disordered structures. In the CαC stretching-mode region, which strongly reflects the skeletal backbone structure, the Raman bands at 941—944 cm−1 were observed in common for those oligomer salts having residue numbers of N = 4—22, and correspond well to the 943 cm−1 band characteristic of the extended helical conformation of charged poly(l-glutamic acid). We may conclude that the oligomer salts (N = 2—22) have disordered structures. However, the oligomer chains having at least residue numbers above N = 4 are locally relatively regular and may take up an extended helical structure.
Optical Resolution on Regioselectively Carbamoylated Cellulose and Amylose with 3,5-Dimethylphenyl and 3,5-Dichlorophenyl Isocyanates
Authors: Kaida Yuriko , Okamoto Yoshio
Published: August 2006

The optical resolving ability of two types of regioselectively carbamoylated cellulose and amylose with 3,5-dimethylphenyl and 3,5-dichlorophenyl isocyanates was evaluated. One had 3,5-dimethylphenylcarbamate groups at the 2 and 3 positions and a 3,5-dichlorophenylcarbamate group at the 6 position; the other had 3,5-dichlorophenylcarbamate groups at the 2 and 3 positions and a 3,5-dimethylphenylcarbamate group at the 6 position. In cellulose derivatives, the side chains at the 2,3, and 6 positions seem to interact complicatedly with racemates. On the other hand, in the amylose derivatives, the side chains at the 2 and 3 positions may mainly influence the chiral recognition ability. The optical resolving abilities of the cellulose and amylose derivatives having irregularly either 3,5-dimethylphenyl- or 3,5-dichlorophenylcarbamate groups at the 2,3, and 6 positions were also examined.
Role of 3-Morpholino-1-propanesulfonic Acid as Energy Transferor in Chemiluminescence Reaction of Fluorescein Catalyzed by Horseradish Peroxidase
Authors: Segawa Tadashi , Kamidate Tamio , Watanabe Hiroto
Published: August 2006

The horseradish peroxidase (HRP)-catalyzed chemiluminescence (CL) reaction of fluorescein (FL) with hydrogen peroxide (H2O2) was carried out in aqueous media buffered by citrate, phosphate, imidazole, and 3-morpholino-1-propanesulfonic acid (MOPS) at pH 7.0. When the H2O2 concentration was below 2 × 10−5 M, one peak was observed in a CL response curve in each buffer component tested. In contrast, only MOPS gave two peaks in the response curve at a concentration higher than 2 × 10−5 M H2O2. The CL emission of the second peak was attributable to formation from an excited FL dianion. The total photon amounts of CL emission of the second peak were dependent on the MOPS concentration. Dissolved oxygen was consumed during the occurence of the second peak. These results could be explained by taking into account the role of MOPS as an energy transferor. That is, MOPS reacted successively with the FL radical, produced from the catalytic cycle of HRP, and the dissolved oxygen to form an excited MOPS compound. An energy transfer occurred from the excited MOPS compound to the FL dianion, resulting in the emission of light.
C-2 Epimerization of Aldoses by Calcium Ion in Basic Solutions. A Simple System to Transform d-Glucose and d-Xylose into d-Mannose and d-Lyxose
Authors: Yanagihara Ryoji , Soeda Kaori , Shiina Sumito , Osanai Shuichi , Yoshikawa Sadao
Published: August 2006

Aldoses were epimerized at C-2 by Ca2+ in aqueous or alcoholic basic solutions through a stereospecific [1-2] rearrangement of the carbon skeletons of the aldose. The skeletal rearrangement was confirmed by 13C NMR analysis of the reaction products. The reaction of [1-13C]- and [2-13C]-d-glucose afforded [2-13C]- and [1-13C]-d-mannose, respectively, as major products. The effects of metal ions, bases, and solvents were examined, and it was found that a high concentration of Ca2+ and a base (>pH 12.3) were especially effective for the present rearrangement. Separation of the reaction products was also effected by using Ca2+ cation-exchange chromatography. Thus, under the optimized conditions, d-mannose and d-lyxose, which are rare in nature and expensive, were easily obtained in high isolated yields from d-glucose and d-xylose, respectively.
Ring-Enlarged Dibenzo-Crown-6 Ethers. Cation Binding and X-Ray Crystal Structure of Dibenzo-22-Crown-6
Authors: Ouchi Mikio , Araki Takashi , Hakushi Tadao , Sobhia M Elizabeth , Chacko Kizakkekoikkal K , Skobridis Konstantinos , Weber Edwin
Published: August 2006

The cation binding of dibenzo-20-crown-6 (2) and dibenzo-22-crown-6 (3) are determined by quantitative solvent extraction study. Compound 3 shows high Tl+/K+ and Tl+/Rb+ selectivity. The crystal structure of 3 is reported. Crystal data: monoclinic (P21/c), a = 7.328(1), b = 17.395(4), c = 8.939(1) Å, β = 102.78(1)°, Z = 2, R = 0.049 for 2122 reflections. The macrocycle shows a crystallographic center of symmetry with elliptical arrangement of the heteroatoms stabilized by possible C–H···O dipolar attractions.
Effect of Potassium-Treated Zirconia on the Oxidative Coupling of Methane
Authors: Sugiyama Shigeru , Shimodan Kazuaki , Ookubo Akira , Shigemoto Naoya , Hayashi Hiromu , Moffat John B
Published: August 2006

Various zirconia were prepared from ZrOCl2·8H2O by the addition of aqueous ammonia and potassium hydroxide; the effect of the catalyst preparation on the oxidative coupling of methane over zirconia was studied. The selectivity to such C2 compounds as ethylene and ethane was strongly influenced by the pH of the preparative solution of ZrOCl2·8H2O, NH3 aq, and KOH, as well as the sequence of the addition of each hydroxide during the preparation of the catalyst.
Further Study on Trapping Sites of Hydrogen Atoms in Solid Hydrogen at 4.2 K Analyzed by the ESR Linewidths
Authors: Miyazaki Tetsuo , Morikita Hiroyuki
Published: August 2006

The ESR linewidths of H(D) atoms, produced in γ-irradiated solid hydrogen, depend significantly upon the matrices of the hydrogen isotopes. The ESR linewidth has been calculated by considering the dipole interactions of the electron spin magnetic moments of a trapped hydrogen atom with the nuclear magnetic moments of the surrounding hydrogen nuclei in addition to the Fermi interactions. It is concluded from a comparison of the experimental ESR linewidths with the theoretical ones that the H atoms in solid H2 are trapped at substitutional sites, while the H(D) atoms in solid HD and D2 are trapped at interstitial octahedral sites.
Organic Synthesis Using Sodium Bromate. II. A Facile Synthesis of N-Bromo Imides and Amides Using Sodium Bromate and Hydrobromic Acid (or Sodium Bromide) in the Presence of Sulfuric Acid
Authors: Fujisaki Shizuo , Hamura Satoshi , Eguchi Hisao , Nishida Akiko
Published: August 2006

The reaction of imides and amides in water (or aqueous acetic acid) with sodium bromate and hydrobromic acid (or sodium bromide) in the presence of sulfuric acid under mild conditions gave the corresponding N-bromides in high yields.
Effect of Temperature on the Color Developed by Near Ultraviolet Light for 4,4′-Bipyridinium Salts (Viologens) Embedded in Poly(1-vinyl-2-pyrrolidone) Matrix
Authors: Kamogawa Hiroyoshi , Nanasawa Masato
Published: August 2006

Thermal stability of the colors developed by UV light for 4,4′-bipyridinium salts (viologens) embedded in the glass-sandwiched poly(1-vinyl-2-pyrrolidone) is dominated by the kind of counter anion. Temperature increase resulted in either no or slight changes of the colors developed for the major viologens, whereas it resulted in bleaching for some viologen sulfonates.
Ni(0)-Triphenylphosphine Complex-Catalyzed Homo-Coupling of 1-Alkenyl Halides with Zinc Powder
Authors: Sasaki Ken , Nakao Kikuji , Kobayashi Yoshihiko , Sakai Mutsuji , Uchino Norito , Sakakibara Yasumasa , Takagi Kentaro
Published: August 2006

The homo-coupling of 1-alkenyl halides was examined in the presence of NiBr2(PPh3)2, PPh3, and excess zinc. The reactions proceed under very mild conditions to give high yields of conjugated dienes. The addition of KI or thiourea was unnecessary for a successful reaction, in contrast with systems without an external phosphine ligand.
Sintered-Tantalum Electrode Modified with Polypyrrole by Electropolymerization
Authors: Park Young-Seo , Ohta Tomoyuki , Takeoka Shinji , Yamamoto Kimihisa , Tsuchida Eishun
Published: August 2006

Polypyrrole (PPy) formation in the interior of a porous electrode by electropolymerization was considered to be impossible. When a concentrated pyrrole solution was soaked into a sintered-Ta electrode and electrolyzed in a pyrrole-free solution, PPy was formed in the interior. PPy occupied 70% of the inner space, and no defect was observed by SEM.
Synthesis of Pentafluoroethyl Trifluoroacetate by Low-Temperature Direct Fluorination
Authors: Arimura Takashi , Shibakami Motonari , Tamura Masanori , Kurosawa Shigeru , Sekiya Akira
Published: August 2006

Ethyl acetate was perfluorinated by direct fluorination in the presence of cesium fluoride, affording pentafluoroethyl trifluoroacetate in excellent yield. In the reaction pathway, the dimerization of trifluoroacetyl fluoride with cesium fluoride gives pentafluoroethyl trifluoroacetate.
Effects of alcohol on the processing of social threat‐related stimuli in socially phobic women
Authors: Gerlach Alexander L. , Schiller Anke , Wild Cornelia , Rist Fred
Published: August 2006

Background. Social phobics are at a higher risk of developing alcohol problems. The mechanism promoting this association is not clear. According to Sayette (1993b), alcohol attenuates anxiety responses by disrupting initial appraisal of threatening stimuli. We used the emotional Stroop test and an implicit memory test to investigate whether alcohol hinders appraisal of social threat words in patients diagnosed with social phobia.

Procedure. Thirty‐two women with social phobia (DSM‐IV) and 32 female controls performed an emotional Stroop test either after drinking alcohol resulting in a blood alcohol levels (BAL) of 0.6‰ or after drinking a non‐alcoholic beverage. The emotional Stroop test contained social anxiety‐related and neutral stimuli. Implicit memory for the words presented was tested with a word‐stem completion test.

Results. Without alcohol, both controls and socially‐phobic participants took longer to name the colour of socially‐threatening stimuli than of neutral stimuli. Alcohol levelled response latencies to the two stimulus categories only in controls. Socially‐phobic participants responded more slowly to social anxiety‐related stimuli than to neutral stimuli, irrespective of their BAL. In contrast to controls, social phobics showed an implicit memory bias for social threat words. This bias was attenuated by alcohol.

Discussion. Alcohol disrupts appraisal of social anxiety‐related stimuli in controls but not in social phobics; in these it hinders the consolidation of memory. This also suggests that social phobics experience similar anxiety with and without alcohol, but remember this experienced anxiety less precisely. This effect might act as a reinforcer for the use of alcohol for the purpose of self‐medication in future situations.
Father‐daughter relationship and eating psychopathology: The mediating role of core beliefs
Authors: Jones Ceri J. , Leung Newman , Harris Gillian
Published: August 2006

Objective. The study aimed to establish the relationships between recalled paternal rearing behaviours, core beliefs and eating symptomatology and to test whether core beliefs play a mediating role between the father‐daughter relationship and eating psychopathology.

Design. Associations between eating psychopathology, core beliefs and recalled parental rearing behaviours were examined in women with and without eating disorders. Regression analyses were used to test whether core beliefs played a mediating role in the relationship between paternal rearing behaviours and eating psychopathology.

Method. Sixty‐six eating‐disordered women and fifty female controls completed three self‐report questionnaires measuring parental rearing behaviours, core beliefs and eating psychopathology.

Results. In eating‐disordered women, paternal rejection and overprotection were found to predict aspects of eating psychopathology via the mediating role of abandonment, defectiveness/shame and vulnerability to harm core beliefs.

Discussion. Core beliefs relating to feelings of abandonment and inherent defectiveness appear to be important in the relationship between unhealthy father‐daughter relationships and eating disorder symptoms.
Written emotional disclosure following first‐episode psychosis: Effects on symptoms of post‐traumatic stress disorder
Authors: Bernard Mark , Jackson Chris , Jones Chris
Published: August 2006

Objective.This paper examined whether written emotional disclosure reduces psychosis‐related post‐traumatic stress disorder symptoms in a small clinical sample recovering from a first episode of psychosis.

Method.Approximately 2.5 years after their first episode of psychosis, 22 people completed measures of traumatic symptoms, recovery style, insight, anxiety and depression. Participants then wrote about the most stressful aspects of their illness (N=12) or about emotionally neutral topics (N=10) for 15 minutes on three separate occasions. Approximately 5 weeks later, participants re‐completed the same dependent measures.

Results.Participants who wrote about their psychotic experiences showed less overall severity and avoidance of traumatic symptoms compared with participants who did not write about their psychotic experiences. There were no effects on the other dependent measures.

Conclusions.Preliminary evidence with a small clinical sample suggests that providing people who are recovering from a psychotic episode with an opportunity to disclose the most stressful aspects of their illness and treatment may lessen the traumatic impact of these experiences. However, this finding requires replication with a larger sample.