bluuebunny/crossref_metadata_2025 huggingface dataset:
Preadministration of High-Dose Salicylates, Suppressors of NF-κB Activation, May Increase the Chemosensitivity of Many Cancers: An Example of Proapoptotic Signal Modulation Therapy
Authors: McCarty Mark F. , Block Keith I.
Published: August 2006

NF-κB activity is elevated in a high proportion of cancers, particularly advanced cancers that have been treated previously. Cytotoxic treatment selects for such up-regulation inasmuch as NF-κB promotes transcription of a large number of proteins that inhibit both the intrinsic and extrinsic pathways of apoptosis; NF-κB also boosts expression of mdr1, which expels many drugs from cells. Indeed, high NF-κB activity appears to be largely responsible for the chemo- and radioresistance of many cancers. Thus, agents that suppress NF-κB activity should be useful as adjuvants to cytotoxic cancer therapy. Of the compounds that are known to be NF-κB antagonists, the most practical for current use may be the nonsteroidal anti-inflammatory drugs aspirin, salicylic acid, and sulindac, each of which binds to and inhibits Iκ kinase- β, a central mediator of NF-κ activation; the low millimolar plasma concentrations of salicylate required for effective inhibition of this kinase in vivo can be achieved with high-dose regimens traditionally used to manage rheumatic disorders. The gastrointestinal toxicity of such regimens could be minimized by using salsalate or enteric-coated sodium salicy-late or by administering misoprostol in conjunction with aspirin therapy. Presumably, best results would be seen if these agents were administered for several days prior to a course of chemo- or radiotherapy, continuing throughout the course. This concept should first be tested in nude mice bearing xenografts of chemoresistant human tumors known to have elevated NF-κ activity. Ultimately, more complex adjuvant regimens can be envisioned in which salicylates are used in conjunction with other NF-κ antagonists and/or agents that target other mediators of down-regulated apoptosis in cancer, such as Stat3; coadministration of salicylate and organic selenium may have intriguing potential in this regard. These strategies may also have potential as adjuvants to metronomic chemotherapy, which seeks to suppress angio-genesis by targeting cycling endothelial cells in tumors.
Tai Chi Chuan: Mind-Body Practice or Exercise Intervention? Studying the Benefit for Cancer Survivors
Authors: Mansky Patrick , Sannes Tim , Wallerstedt Dawn , Ge Adeline , Ryan Mary , Johnson Laura Lee , Chesney Margaret , Gerber Lynn
Published: August 2006

Tai chi chuan (TCC) has been used as a mind-body practice in Asian culture for centuries to improve wellness and reduce stress and has recently received attention by researchers as an exercise intervention. A review of the English literature on research in TCC published from 1989 to 2006 identified 20 prospective, randomized, controlled clinical trials in a number of populations, including elderly participants (7 studies), patients with cardiovascular complications (3 studies), patients with chronic disease (6 studies), and patients who might gain psychological benefit from TCC practice (2 studies). However, only the studies of TCC in the elderly and 2 studies of TCC for cardiovascular disease had adequate designs and size to allow conclusions about the efficacy of TCC. Most (11 studies) were small and provided limited information on the benefit of TCC in the settings tested. There is growing awareness that cancer survivors represent a population with multiple needs related to physical deconditioning, cardiovascular disease risk, and psychological stress. TCC as an intervention may provide benefit to cancer survivors in these multiple areas of need based on its characteristics of combining aspects of meditation and aerobic exercise. However, little research has been conducted to date to determine the benefit of TCC in this population. We propose a model to study the unique characteristics of TCC compared to physical exercise that may highlight characteristic features of this mind-body intervention in cancer survivors.
The Autoimmune Disease Database: a dynamically compiled literature-derived database
Authors: Karopka Thomas , Fluck Juliane , Mevissen Heinz-Theodor , Glass Änne
Published: August 2006

Background

Autoimmune diseases are disorders caused by an immune response directed against the body's own organs, tissues and cells. In practice more than 80 clinically distinct diseases, among them systemic lupus erythematosus and rheumatoid arthritis, are classified as autoimmune diseases. Although their etiology is unclear these diseases share certain similarities at the molecular level i.e. susceptibility regions on the chromosomes or the involvement of common genes. To gain an overview of these related diseases it is not feasible to do a literary review but it requires methods of automated analyses of the more than 500,000 Medline documents related to autoimmune disorders.

Results

In this paper we present the first version of the Autoimmune Disease Database which to our knowledge is the first comprehensive literature-based database covering all known or suspected autoimmune diseases. This dynamically compiled database allows researchers to link autoimmune diseases to the candidate genes or proteins through the use of named entity recognition which identifies genes/proteins in the corresponding Medline abstracts. The Autoimmune Disease Database covers 103 autoimmune disease concepts. This list was expanded to include synonyms and spelling variants yielding a list of over 1,200 disease names. The current version of the database provides links to 541,690 abstracts and over 5,000 unique genes/proteins.

Conclusion

The Autoimmune Disease Database provides the researcher with a tool to navigate potential gene-disease relationships in Medline abstracts in the context of autoimmune diseases.
Comparative analysis and integrative classification of NCI60 cell lines and primary tumors using gene expression profiling data
Authors: Wang Huixia , Huang Shuguang , Shou Jianyong , Su Eric W , Onyia Jude E , Liao Birong , Li Shuyu
Published: August 2006

Background

NCI60 cell lines are derived from cancers of 9 tissue origins and have been invaluable in vitro models for cancer research and anti-cancer drug screen. Although extensive studies have been carried out to assess the molecular features of NCI60 cell lines related to cancer and their sensitivities to more than 100,000 chemical compounds, it remains unclear if and how well these cell lines represent or model their tumor tissues of origin. Identification and confirmation of correct origins of NCI60 cell lines are critical to their usage as model systems and to translate in vitro studies into clinical potentials. Here we report a direct comparison between NCI60 cell lines and primary tumors by analyzing global gene expression profiles.

Results

Comparative analysis suggested that 51 of 59 cell lines we analyzed represent their presumed tumors of origin. Taking advantage of available clinical information of primary tumor samples used to generate gene expression profiling data, we further classified those cell lines with the correct origins into different subtypes of cancer or different stages in cancer development. For example, 6 of 7 non-small cell lung cancer cell lines were classified as lung adenocarcinomas and all of them were classified into late stages in tumor progression.

Conclusion

Taken together, we developed and applied a novel approach for systematic comparative analysis and integrative classification of NCI60 cell lines and primary tumors. Our results could provide guidance to the selection of appropriate cell lines for cancer research and pharmaceutical compound screenings. Moreover, this gene expression profile based approach can be generally applied to evaluate experimental model systems such as cell lines and animal models for human diseases.
Plasma levels of soluble tumor necrosis factor-α receptors are related to total and LDL-cholesterol in lean, but not in obese subjects
Authors: Straczkowski Marek , Kowalska Irina , Nikolajuk Agnieszka , Adamska Agnieszka , Karolczuk-Zarachowicz Malgorzata , Karczewska-Kupczewska Monika , Kozlowska Agnieszka , Gorska Maria
Published: August 2006

Background

Tumor necrosis factor-α (TNFα) is a mediator of insulin resistance. Plasma levels of soluble TNFα receptors (sTNFR1 and sTNFR2) probably reflect paracrine action of the cytokine. TNFα is also a regulator of lipid metabolism, however, data about impact of obesity on the relationships between TNFα and plasma lipids remain controversial.

Aim

The purpose of the present study was to examine the associations of TNFα system with plasma lipids in lean and obese subjects with normal glucose metabolism.

Methods

We examined 63 subjects, 33 lean (BMI<25 kg × m-2) and 30 with marked overweight or obesity (BMI>27.8 kg × m-2). Anthropometric and biochemical parameters were measured. Oral glucose tolerance test and euglycemic hyperinsulinemic clamp were also performed.

Results

Obese subjects were markedly more insulin resistant and had higher levels of both TNFα receptors. Total (TC) and LDL-cholesterol (LDL-C), triglycerides (TG) and non-esterified fatty acids (NEFA) were also higher in the obese group. In obese subjects, both receptors were significantly related to TG and HDL-cholesterol (HDL-C), while sTNFR2 was also associated with NEFA. All those correlations disappeared after controlling for insulin sensitivity. In lean subjects, both receptors were related to TC, HDL-C and LDL-C. In that group, sTNFR1 predicted values of all those parameters independently of BMI, plasma glucose and insulin, and insulin sensitivity.

Conclusion

We conclude that TNFα receptors are associated with plasma lipids in different way in lean and in obese subjects. TNFα system is probably important in determining cholesterol levels in lean subjects, while in obese this effect might be masked by other metabolic abnormalities.
A novel system for gene silencing using siRNAs in rice leaf and stem-derived protoplasts
Authors: Bart Rebecca , Chern Mawsheng , Park Chang-Jin , Bartley Laura , Ronald Pamela C
Published: August 2006

Background

Transient assays using protoplasts are ideal for processing large quantities of genetic data coming out of hi-throughput assays. Previously, protoplasts have routinely been prepared from dicot tissue or cell suspension cultures and yet a good system for rice protoplast isolation and manipulation is lacking.

Results

We have established a rice seedling protoplast system designed for the rapid characterization of large numbers of genes. We report optimized methods for protoplast isolation from 7–14 day old etiolated rice seedlings. We show that the reporter genes luciferase GL2 and GUS are maximally expressed approximately 20 h after polyethylene glycol (PEG)-mediated transformation into protoplasts. In addition we found that transformation efficiency varied significantly with plasmid size. Five micrograms of a 4.5 kb plasmid resulted in 60–70% transformation efficiency. In contrast, using 50 μg of a 12 kb plasmid we obtained a maximum of 25–30% efficiency. We also show that short interfering RNAs (siRNAs) can be used to silence exogenous genes quickly and efficiently. An siRNA targeting luciferase resulted in a significant level of silencing after only 3 hours and up to an 83% decrease in expression. We have also isolated protoplasts from cells prepared from fully green tissue. These green tissue-derived protoplasts can be transformed to express high levels of luciferase activity and should be useful for assaying light sensitive cellular processes.

Conclusion

We report a system for isolation, transformation and gene silencing of etiolated rice leaf and stem-derived protoplasts. Additionally, we have extended the technology to protoplasts isolated from fully green tissue. The protoplast system will bridge the gap between hi-throughput assays and functional biology as it can be used to quickly study large number of genes for which the function is unknown.
Rapid detection of pneumothorax by ultrasonography in patients with multiple trauma
Authors: Zhang Mao , Liu Zhi-Hai , Yang Jian-Xin , Gan Jian-Xin , Xu Shao-Wen , You Xiang-Dong , Jiang Guan-Yu
Published: August 2006

Introduction

Early detection of pneumothorax in multiple trauma patients is critically important. It can be argued that the efficacy of ultrasonography (US) for detection of pneumothorax is enhanced if it is performed and interpreted directly by the clinician in charge of the patients. The aim of this study was to assess the ability of emergency department clinicians to perform bedside US to detect and assess the size of the pneumothorax in patients with multiple trauma.

Methods

Over a 14 month period, patients with multiple trauma treated in the emergency department were enrolled in this prospective study. Bedside US was performed by emergency department clinicians in charge of the patients. Portable supine chest radiography (CXR) and computed tomography (CT) were obtained within an interval of three hours. Using CT and chest drain as the gold standard, the diagnostic efficacy of US and CXR for the detection of pneumothorax, defined as rapidity and accuracy (sensitivity, specificity, positive predictive value, negative predictive value), were compared. The size of the pneumothorax (small, medium and large) determined by US was also compared to that determined by CT.

Results

Of 135 patients (injury severity score = 29.1 ± 12.4) included in the study, 83 received mechanical ventilation. The time needed for diagnosis of pneumothorax was significantly shorter with US compared to CXR (2.3 ± 2.9 versus 19.9 ± 10.3 minutes, p < 0.001). CT and chest drain confirmed 29 cases of pneumothorax (21.5%). The diagnostic sensitivity, specificity, positive and negative predictive values and accuracy for US and radiography were 86.2% versus 27.6% (p < 0.001), 97.2% versus 100% (not significant), 89.3% versus 100% (not significant), 96.3% versus 83.5% (p = 0.002), and 94.8% versus 84.4% (p = 0.005), respectively. US was highly consistent with CT in determining the size of pneumothorax (Kappa = 0.669, p < 0.001).

Conclusion

Bedside clinician-performed US provides a reliable tool and has the advantages of being simple and rapid and having higher sensitivity and accuracy compared to chest radiography for the detection of pneumothorax in patients with multiple trauma.
Screening for smoking and substance misuse in pregnant women with mental illness
Authors: Shah Nisha , Howard Louise
Published: August 2006

Aims and Method

Smoking and substance misuse adversely affect the outcome of pregnancy and psychiatric patients are known to smoke more than other patients. Data collected at the time of routine antenatal booking were analysed to investigate whether pregnant women with mental health problems smoke more than other pregnant women.

Results

Data were collected from 156 women. Those with a psychiatric diagnosis (n=76) were significantly more likely to smoke (P<0.001). Associations were also found with illicit drug use and previous termination of pregnancy. The most common psychiatric diagnosis was depression (62%). A diagnosis of schizophrenia was not recorded for any of the women.

Clinical Implications

The strong association between smoking and psychiatric diagnosis results in an increased risk of obstetric complications in psychiatric patients. Anti-smoking interventions might be delivered by adequately trained midwives and opportunistically during contact with mental health professionals.
Visual acuity and reported eye problems among psychiatric in-patients
Authors: Punukollu Bhaskar , Phelan Michael
Published: August 2006

Aims and Method

The aim of this study was to examine visual problems among patients admitted to an inner city acute mental health unit. We measured visual acuity using a Snellen chart. Patients were also asked about perceived eye problems and access to services.

Results

Of 55 in-patients on five acute general adult wards at an inner city mental health unit over a 3-day period, 31 agreed to participate in the study. Twenty (65%) had impaired visual acuity and 19 (61%) had not been to an optician for 5 or more years. Seventeen patients (55%) reported experiencing difficulty with their eyesight. The main problems reported were blurring of vision and periorbital pain. Of these 17 patients, 15 (88%) had impaired visual acuity on Snellen testing. Half of those who had previously been prescribed glasses or contact lenses reported that they had been lost.

Clinical Implications

Visual impairment appears to be another area of physical health which is underrecognised and undertreated in people with severe mental health problems. Although there are numerous issues that must be addressed by mental health staff, patients should be asked about eye problems and supported in accessing opticians.
Drug-related movement disorders: training experiences of psychiatrists
Authors: Kuruvilla Kompancariel , Sedano-Ruiz Jose Antonio , Ley Ann
Published: August 2006

Aims and Method

A questionnaire was sent by post to 185 psychiatrists in Devon and Cornwall to investigate training in the assessment and management of drug-related movement disorders and current training needs.

Results

Responses were obtained from 143 psychiatrists (77%). Formal training was reported by 67 out of 140 (48%). Only 26 out of 142 (18%) had received formal training in the use of rating scales, which were rarely used. The mean level of satisfaction with training received was below the mid-point on a 5-point scale at 2.76 (s.d.=1.23). Mean levels of confidence in the assessment and management of drug-related movement disorders were just above mid-point at 3.25 (s.d.=1.04) and 3.16 (s.d.=0.99) respectively. Specific training was thought to be necessary by 135 out of 141 psychiatrists (96%) and there were high levels of interest in further training, particularly from those below consultant grade.

Clinical Implications

Drug-related movement disorders affect patients' adherence to medication and their quality of life. Psychiatrists need more structured clinical training in assessing and managing these disorders in order to provide the best clinical care.
Developing a regional specialist registrar day
Authors: Ogden David J.
Published: August 2006

Higher specialist training in psychiatry requires the development of a broad range of knowledge and skills in a short space of time. However, a brief national survey of programme directors confirms reports from peers that structured, targeted teaching tends not to continue beyond completion of College Membership examinations. Exceptions to this rule are child and adolescent psychiatry and to a lesser extent psychotherapy, which reflects requirements laid out in the Higher Specialist Training Handbook (Royal College of Psychiatrists, 1998). Specialist registrars must therefore, using limited study time and funding, attempt to acquire knowledge from local and national courses. These, however, are usually aimed at more generic groups: for example, all health service specialist registrars or at consultants for fulfilment of continuing professional development.
Results of Genoidentical Hemopoietic Stem Cell Transplantation With Reduced Intensity Conditioning for Acute Myelocytic Leukemia: Higher Doses of Stem Cells Infused Benefit Patients Receiving Transplants in Second Remission or Beyond—The Acute Leukemia Working Party of the European Cooperative Group for Blood and Marrow Transplantation
Authors: Gorin Norbert-Claude , Labopin Myriam , Boiron Jean-Michel , Theorin Niklas , Littlewood Tim , Slavin Shimon , Greinix Hildegard , Cahn Jean Yves , Alessandrino E. Paolo , Rambaldi Alessandro , Nagler Arnon , Polge Emmanuelle , Rocha Vanderson
Published: August 2006

Purpose

Nucleated cell dose is an important and modifiable factor in hematopoietic stem cell transplantation (HSCT), however its association with outcomes in the context of reduced intensity conditioning regimen (RIC) HSCT for adults with acute myelocytic leukemia (AML) is not known.

Patients and Methods

From 1998 to 2003, 253 patients with de novo AML, received transplants with RIC and peripheral blood from a genoidentical donor. Median age was 55 years (range, 18 to 72) and the median follow-up was 17 months (range, 2 to 67). One hundred forty one patients received transplants in first remission (CR1), 47 received transplants in second remission (CR2), and 65 patients received transplants in a more advanced phase. Fludarabin-based RIC was used in 91% of patients and low-dose (< 4 Gy) total-body radiation in 23% of patients. The median nucleated and CD34 cell dose infused were 9.1× 108/kg and 5.8× 106/kg, respectively.

Results

Overall, 2-year leukemia-free survival (LFS) was 41% ± 4% and it was 46% ± 5% for patients receiving a higher cell dose (> 9.1× 108/kg) and 37% ± 5% for the remainders (P = .03). Higher cell doses exclusively benefited patients who received transplantations in CR2 or beyond, with LFS of 47 ± 8 versus 20 ± 8, with no detectable effect for patients who received transplants in CR1. In a multivariate analysis of the overall patient population, higher nucleated cell dose cells were associated with higher LFS (P = .04), higher incidence of chronic graft-versus-host disease (P = .01), and there was a trend towards a lower relapse incidence (P = .06). Interestingly, CD34+ cell dose was not associated with any outcomes.

Conclusion

Nucleated cell dose is an important factor that can be modified to improve results of RIC for patients with AML transplanted later than in CR1.
Infrared Spectroscopic Studies of the Formation and Catalytic Activity of Nd2O3
Authors: Hussein Gamal Abdel-Halim Mohamed , Ismail Hamdy Mahmoud
Published: August 2006

Nd2O3 catalyst was obtained as a final product of the thermal decomposition of Nd(CH3COO)3·2H2O. The decomposition processes up to 800 °C were characterized by means of TG, DTA, XRD, and IR spectroscopy of the gas and solid phase products. The activation energy values were determined non-isothermally for thermal events involved in the decomposition course. The results indicate that Nd(AcO)3 is completely decomposed to Nd2O3 at 670 °C through five different intermediates; Nd(OH)(CH3COO)2 at 310 °C, NdO(CH3COO) at 320 °C, Nd2(CO3)3 at 350 °C, Nd2O(CO3)2 at 385 °C, and Nd2O2(CO3) at 410 °C. The oxide, Nd2O3, obtained at 800 °C possesses higher surface area (30 m2 g−1) than that obtained at 1000 °C (10 m2 g−1).

Thus, the oxide obtained at 800 °C was tested qualitatively and quantitatively as a catalyst towards the decomposition of 2-propanol at 100—400 °C by IR-spectroscopy. The results indicate that Nd2O3 catalyses 2-propanol dehydrogenation (forming acetone) at < 300 °C and dehydration (forming propene) at > 250 °C. At > 350°C, acetone was involved in a secondary surface reaction, presumably with the surface hydroxyl groups, to give CH4 and CO2 in the gas phase.
Monte Carlo Simulation of Liquid Ammonia and an Evaluation of the Thermodynamic Properties. The Comparative Study of NH3, H2O, and HF
Authors: Honda Kazuhiko , Kitaura Kazuo , Nishimoto Kichisuke
Published: August 2006

Monte Carlo (MC) simulation was done for liquid ammonia using the potential function expressed by the intermolecular overlap integrals and fractional point charges on the atoms. Thermodynamic properties were estimated using a partition function whose parameters are obtained by referring the results of the MC simulation. The calculated thermodynamic properties were examined by the physically meaningful interaction terms. A comparative study with NH3, H2O, and HF was done and a new index proposed to characterize the liquid with hydrogen bondings.
Study of Hydration and Ionization of Nitric Acid in Benzene
Authors: Naganawa Hirochika , Tachimori Shoichi
Published: August 2006

The hydration and ionization of nitric acid in benzene were examined at 298 K. The distribution of nitric acid and of water between aqueous solutions and benzene were determined as functions of water activity in the aqueous phase. Two hydrates, mono- and decahydrate, were found in addition to the anhydride in the organic phase by analyzing the distribution data on the basis of the stoichiometry of the acid hydration. The mono- and decahydrate were ascribed to molecular and ionized nitric acid, respectively, by means of spectrophotometry of the organic phase. By the analyses of the absorption spectra and the distribution data, the ionization of nitric acid by water in benzene was clarified and the equilibrium constant was determined.
Effect of Some d-Transition Metal Complexes of Salen-Type Ligands and Acetylacetone on Fluorescence of Europium(III) and Terbium(III)
Authors: Sakamoto Masatomi , Yamamoto Koji , Matsumoto Akira , Nishida Yuzo , Okawa Hisashi
Published: August 2006

Fluorescence spectra of europium(III) and terbium(III) have been measured in methanolic solutions containing various amounts of [M(salen)] (M = Cu(II), Ni(II)), [Cr(salen)(H2O)2]Cl, [M(saltn)] (M = Cu(II), Ni(II)), [Cu(acacen)], [M(acac)2] (M = Cu(II), VIVO), [M(acac)3] (M = Cr(III), Co(III)), or [Ni(acac)2(H2O)2]. Our purpose was to investigate the influence of these metal complexes on the fluorescence of Eu(III) and Tb(III), where H2salen, H2saltn, H2acacen, and Hacac stand for N,N′ -bis(salicylidene)ethylenediamine, N,N′-bis(salicylidene)-1,3-propanediamine, N,N′ -bis(1-methyl-3-oxobutylidene)ethylenediamine, and acetylacetone, respectively. The fluorescence intensities of both Eu(III) and Tb(III) decreased with increasing the concentration of [M(salen)] (M = Cu, Ni), [Cr(salen)(H2O)2]Cl, [M(saltn)] (M = Cu, Ni), [Cu(acacen)], and [M(acac)3] (M = Cr, Co), whereas it was little affected by simple metal salts. The intensity of Tb(III) increased up to the addition of a given amount of [M(acac)2] (M = Cu, VO) or [Ni(acac)2(H2O)2] and then decreased on further addition, whereas the intensity of Eu(III) decreased gradually by the addition of these acetylacetonate complexes. These results are explained by the formation of heteronuclear complex species and by the stabilities of acetylacetonate complexes.
Fluorescence Spectroscopic Study of Subtilisins as Relevant to Their Catalytic Activity in Aqueous–Organic Media
Authors: Kijima Tatsuro , Yamamoto Shinji , Kise Hideo
Published: August 2006

The fluorescence spectra of subtilisin Carlsberg (STC) and subtilisin BPN′ (STB) were measured in aqueous–organic mixed solvents over a wide range of solvent composition. The tryptophan fluorophores were used as probes of the environmental polarity, and the structural changes of the enzymes were detected as changes of the difference in the emission wavelength between the enzymes and N-acetyl-l-tryptophan ethyl ester (Δλem). It was found that Δλem was well correlated with the catalytic activity of the enzymes, as expressed by the hydrolysis rate of N-acetyl-l-tyrosine ethyl ester. For example, the characteristic dependency of the activity of STC on the solvent composition in acetonitrile–water was closely related to the change in Δλem. Similar correlations between Δλem and the catalytic activity were observed for subtilisins in aqueous 1,4-dioxane, THF, DMF, DMA, and DMSO solutions with high correlation coefficients, except for STB in water–DMF and –DMA. The results are discussed in terms of the structural modification of the enzymes in these aqueous–organic media.
Convenient Synthesis of 4-Methylene-2-oxazolidinones and 4-Methylenetetrahydro-1,3-oxazin-2-ones via Transition-Metal Catalyzed Intramolecular Addition of Nitrogen Atom to Acetylenic Triple Bond
Authors: Tamaru Yoshinao , Kimura Masanari , Tanaka Shuji , Kure Sigeru , Yoshida Zen-ichi
Published: August 2006

2-Propynyl tosylcarbamates 1 undergo cyclization smoothly by the catalysis of CuCl/Et3N or AgNCO/Et3N to furnish 4-methylene-2-oxazolidinones 2 in good yields. The similar cyclization of the N-acyl derivatives of 1 (PhCO, MeCO, EtOCO, etc.) is catalyzed effectively by AgNCO/t-BuOK. These reactions accommodate a variety of substituents at C1 and C3 of 2-propyn-1-ol and provide (Z)-2 as single stereoisomers. The scope of the cyclization of 3-butynyl carbamates is rather limited, and in general only N-tosyl derivatives of terminally unsubstituted 3-butyn-1-ols undergo cyclization to give 4-methylenetetrahydro-1,3-oxazin-2-ones in synthetically useful yields by the catalysis of AgNCO/Et3N or AgNCO/t-BuOK.
Ultrasonic Relaxation Associated with Solute–Solvent Interaction in an Aqueous Solution of 5-Methoxy-1-pentanol
Authors: Nishikawa Sadakatsu , Kuramoto Naoki , Uchiyama Tomoko
Published: August 2006

After 5-methoxy-1-pentanol was synthesized, the sound velocity, density, and ultrasonic absorption coefficients in the frequency range from 7.5 to 220 MHz were measured in aqueous solutions at 25 °C. The sound velocity and density were reported in terms of the polynomials as a function of the analytical concentration. The absorption could be described approximately by a single Debye-type relaxational equation in the 2.00 and 5.00 mol dm−3 range. The cause of the relaxation was attributed to a perturbation of an equilibrium associated with an interaction between the solute and the solvent; the rate and thermodynamic constants were determined. The results are discussed by comparing them with those previously reported in relation to the water structure.
The Change of Diamagnetic Susceptibility and the Thermodynamic Data due to Hydrogen Bonding between 2-Propanol and Various Hydrogen Acceptors
Authors: Takahashi Fujio , Sakai Yasuzo , Nakazawa Yoshinori , Mizutani Yohsuke
Published: August 2006

The diamagnetic susceptibility and the equilibrium constants were determined for systems of 2-propanol and various kinds of hydrogen acceptors. Acetone, methyl ethyl ketone, tetrahydrofuran, dimethyl sulfoxide, and N, N-dimethylacetamide were used as hydrogen acceptors. The diamagnetic susceptibility of 2-propanol without self-association was estimated to be −41.7 × 10−6 cm3 mol−1 from the results for mixtures of 2-propanol and carbon tetrachloride. Then the sum of the diamagnetic susceptibilities of both a hydrogen acceptor and 2-propanol without self-association was calculated. From the differences between experimental results and calculated values, the changes of diamagnetic susceptibility (ΔχM) due to hydrogen bonding were estimated to be in the region of 9.0—13.5 × 10−6 cm3 mol−1. ΔH, ΔS, and ΔG due to hydrogen bonding were determined. ΔχM seemed to be related to ΔS and ΔG. On the other hand, ΔH was −17.9—18.7 kJ mol−1, and it seemed not to be related to ΔχM.
μ-Peroxo Dicobalt Complexes Containing an Unsymmetrical Dinucleating Ligand : Synthesis, Characterization, and Oxygen Affinity
Authors: Kayatani Takayuki , Hayashi Yoshihito , Suzuki Masatatsu , Uehara Akira
Published: August 2006

A new unsymmetric dinucleating ligand, Htpdb (Htpdb = 1,4-bis[bis(2-pyridylmethyl)amino]-2-butanol), was synthesized. This is a hybrid of Htpdp (1,3-bis[bis(2-pyridylmethyl)amino]-2-propanol) and Htmdp (1,5-bis[bis(2-pyridylmethyl)amino]-3-pentanol). Its dinuclear cobalt(II,II) complexes, [Co2(tpdb)(RCOO)](ClO4)2·nH2O (RCOO = CH3COO (1) and C6H5COO (2)), were prepared. Their electronic spectra indicate that 1 and 2 have a five-coordinate structure with a bridging carboxylato group. The complexes reacted reversibly with molecular oxygen in acetonitrile to form dioxygen complexes [Co2(tpdb)(RCOO)(O2)]2+. The structure of a dioxygen complex [Co2(tpdb)(CH3COO)(O2)](PF6)2·CH3CN·0.5H2O (3) was determined by X-ray crystallography. 3 cystallizes in orthorhombic space group Pmn21 with a = 23.034 (6), b = 17.352 (2), c = 10.355 (2) Å, and Z = 4. Two cobalt atoms are triply bridged by dioxygen, acetato, and alkoxo groups. Two cobalt atoms are triply bridged by dioxygen, acetato, and alkoxo groups. P(O2)1/2 of 1 is 720 Torr in acetonitrile at 20 °C; this value is in between those of the corresponding tpdp and tmdp complexes. The bridging skeleton of the dinucleating ligands contributes significantly to the oxygen affinities of the complexes. The complex 2, [Co2(tpdb)(C6H5COO)]2+, underwent an oxidative degradation in methanol–water mixture (1 : 1) in the presence of C6H5COONa to produce a dinuclear mixed valence complex [Co2(tpdb)(C6H5COO)2](ClO4)2·H2O (4).
Thermodynamic Study of Formation Reactions of Mercury(II) Complexes with Polyamino Polycarboxylic Macrocycles
Authors: Kodama Mutsuo
Published: August 2006

We have investigated the equilibria of complex formation reactions of mercury(II) ions with polyamino polycarboxylic macrocycles: DOTA (H4dota, H4L), TETA (H4teta, H4L), PEPA (H5pepa, H5L), and HEHA (H6heha, H6L) by employing a polarographic method. Under the experimental conditions employed, tetra-, penta-, and hexa-amine macrocycles: TETA, PEPA, and HEHA, were found to form 1 : 1 ratio protonated complexes as well as normal complexes, while the other tetra-amine macrocycle, DOTA, forms solely a 1 : 1 ratio normal complex, HgL2−. Measurement of thermodynamic parameters, ΔH and ΔS, showed that the introduction of acetate groups into the polyaza frame gives rise to a greater increase in the entropy of reaction, but produces a less exothermic effect.
Synthesis and Stereochemistry of Homoleptic Cobalt(III) Complexes Containing Pyrimidine-2-thionate and Its Derivatives
Authors: Yamanari Kazuaki , Dogi Shozo , Okusako Kensen , Fujihara Takashi , Fuyuhiro Akira , Kaizaki Sumio
Published: August 2006

A room-temperature reaction of Co(CH3CO2)2·4H2O with pyrimidine-2-thione (Hpymt), or eight kinds of their derivatives (mole ratio = 1 : 2.8—3.0) in methanol, was carried out in air. It was found that the substituent group at a 4-position in the pymt skeleton governs the product. The pymt and its derivatives, having an alkyl or an amino group as the 4-substituent, gave tris-type cobalt(III) complexes mer-[Co(N-S)3] in good yields. On the other hand, the 2-thiouracil derivatives, having an oxygen or a sulfur atom as the 4-substituent, produced only bis-type cobalt(II) complexes [Co(N-S)2]. Such different ligand behavior concerns the different electronic structures of the pyrimidine rings. The presence of three linkage isomers in mer-[Co(4-methyl-pymt)3] has been confirmed by 59Co NMR spectroscopy, and an important role of the CH···π attractive interaction has been found.
Effects of Substrate Structure on Lipase-Catalyzed Transesterification of ω-Substituted 1-Alkanols in Organic Solvents
Authors: Nakamura Kaoru , Kawasaki Masashi , Ohno Atsuyoshi
Published: August 2006

Lipase-catalyzed transesterifications of ω-phenyl-1-alkanols with vinyl acetate in organic solvents have been investigated. Benzyl alcohol is the most reactive substrate among those studied. It is proposed that a lipase form Pseudomonas cepacia (PCL) has a domain to attract an aromatic moiety of a substrate.
A Manganese(III) Complex with 1-[(2-Hydroxyethyl)amino]-2-(salicylideneamino)ethane
Authors: Mikuriya Masahiro , Takebayashi Haruyuki , Matsunami Ken
Published: August 2006

A meridional manganese(III) complex with tridentate 1-[(2-hydroxyethyl)amino]-2-(salicylideneamino)ethane (H2L6-5-5), [Mn(HL6-5-5)2]Br, has been synthesized and characterized by X-ray crystal structure analysis, electronic absorption spectroscopy, and variable temperature magnetic susceptibility. The manganese atom is coordinated in an elongated octahedral environment.
The Role of Surfactants in Achieving Highly Loaded Aqueous Suspensions of Organic Particles
Authors: Ogura Tsugitoshi , Tanoura Masazumi , Tatsuhara Kiyoshi , Hiraki Akio
Published: August 2006

The behaviors and roles of anionic surfactants in highly loaded aqueous suspensions of carbon black were investigated in order to clarify how they increase the achievable concentration while maintaining the apparent viscosity of a suspension. In a suspension, organic particles and the water bound to them define the effective volume of the solid particles, which determines the relative viscosity, as formulated by the Brinkman equation. The surfactant was found to be adsorbed on the organic particles, decreasing the amount of bound water, as measured by 1H NMR. The result of the study was that a surfactant in a highly-loaded aqueous suspension plays the following three roles at the same time: (Role-1) The decrease in the bound water due to the surfactant allows an increase in the achievable solid concentration at a fixed viscosity by decreasing the effective volume fraction of solids in a suspension. (Role-2) The adsorption of the surfactant was also found to be necessary to inhibit the aggregation of dispersed particles; if, however, the amount of surfactant is insufficient, aggregation can occur even with mechanical stirring, owing to a hydrophobic interaction among the particles. (Role-3) The surfactant influences the viscosity of the suspension through the “k” factor of the Brinkman equation. Surfactants with larger molecules were found to give a larger k value, thus increasing the viscosity, probably because of their effects on the interactions between the dispersed particles.
Effects of Pressure and Solvent on the Thermal Isomerization of Mercury and Silver Dithizonates
Authors: Sueishi Yoshimi , Mukai Tatsuhiko , Matsumoto Kazumi , Yamamoto Shunzo , Nishimura Norio
Published: August 2006

The thermal isomerizations of mercury and silver dithizonates (Hg(HDz)2 and Ag(HDz)) were followed spectrophotometrically at high pressures and in various solvents. From the pressure dependence of the rate, the activation volumes for the isomerization of Hg(HDz)2 in aprotic solvents were estimated to be about 6 cm3 mol−1, and were compared with those for Ag(HDz). The observed positive values of the activation volumes have been explained in terms of the increase in the intrinsic volume accompanying the isomerization of dithizone. Based on these results, a possible structure of the transition state for the thermal isomerization of Hg(HDz)2 in aprotic solvents was proposed. Moreover, we have followed the thermal isomerization of Hg(HDz)2 in various types of alcohols at low temperatures. The results in alcohols are discussed in terms of solvent hydrogen-bonding ability, and a reaction mechanism is proposed.
Structure and Physical Properties of (EP-TTP)2Au(CN)2
Authors: Mori Takehiko , Misaki Yohji , Yamabe Tokio
Published: August 2006

The title organic charge transfer salt, where EP-TTP is 2-(4,5-ethylenedithio-1,3-dithiol-2-ylidene)-5(4,5-trimethylenedithio-1,3-dithiol-2-ylidene)-1,3,4,6-tetrathiapentalene, has so-called β-type donor arrangement, but the Fermi surface is basically one-dimensional. This salt exhibits metallic conductivity down to 0.7 K. The thermoelectric power and ESR show simple metal-like behavior.
Mechanism of Propene–Deuterium Addition and Exchange Reaction over Silica-Supported ZrO2
Authors: Naito Shuichi , Tanimoto Mitsutoshi
Published: August 2006

The mechanism of propene–deuterium reaction over unsupported and silica-supported ZrO2 catalysts was studied with kinetic investigation as well as microwave spectroscopic analysis of monodeuteriopropene. Unsupported ZrO2 exhibited the identical catalytic behavior for C3H6–D2 reaction with other oxide catalysts previously reported: Only propane-d2 was selectively formed in the addition process, with no hydrogen exchange in propene. By supporting on silica, the rate of C3H6–D2 reaction increased considerably, with the decrease of activation energy. Hydrogen exchange in propene proceeded simultaneously with addition via associative mechanism through propyl and isopropyl intermediates. Small particles of ZrO2 were proposed as active sites of this characteristic catalytic behavior.
Preparation, Characterization, and Solid State Thermal Studies of Nickel(II) Iodide Complexes of Ethane-1,2-diamine and Its Derivatives
Authors: Das Debasis , Ghosh Ashutosh , Chaudhuri Nirmalendu Ray
Published: August 2006

[NiL3]I2·2H2O [L = N–methylethane–1,2–diamine (meen) and 2-methylpropane-1,2-diamine (ibn)], [NiL3]I2 [L = ethane–1,2–diamine (en), N-ethylethane-1,2-diamine (eten), N-propylethane-1,2-diamine (pren), and propane-1,2-diamine (pn)], [NiL2(H2O)2]I2 (L = meen and eten), and [Ni2L2]I2 [L = N-isopropylethane-1,2-diamine (ipren) and ibn] have been synthesized from solution and characterized. [NiL2I2] (L = en, meen, eten, and pren] and [Ni(ibn)2]I2 have been isolated in the solid state from their corresponding parent tris(diamine) complex by temperature arrest technique. [NiL2(H2O)2]I2 (L = meen and eten) upon heating undergo deaquation-anation reaction. All the diamine species excepting [Ni(ipren)2]I2 and [Ni(ibn)2]I2 which possess square-planar geometry, are octahedral and both the diaqua and diiodobis(diamine) species possess trans-octahedral geometry showing variation only in [Ni(en)2I2], which is having cis-octahedral geometry. [Ni(meen)2I2] and [Ni(eten)2I2] show irreversible endothermic phase transitions (160—190 °C; ΔH = 5.65 kJ mol−1 and 204—225 °C; ΔH = 4.23 kJ mol−1, respectively) without any visual color change with retention of trans-octahedral configuration. In case of [Ni(eten)2I2] the post phase species reverts to the original diaqua species, [Ni(eten)2(H2O)2]I2 on keeping in open atmosphere whereas the rehydrated species of its meen analogue, [Ni(meen)2(H2O)2]I2 after deaquation does not show the phase transition. On the other hand, corresponding pren analogue shows reversible endothermic phase transition (68—111 °C; ΔH = 2.42 kJ mol−1 for heating and 98—77 °C; ΔH = −1.4 kJ mol−1 for cooling). The occurrence of this type of phase transition is due to the conformational changes in the diamine chelate rings. The square-planar [Ni(ibn)2]I2 undergoes time dependent reversible phase transition (232—248 °C; ΔH = 5.99 kJ mol−1) without any visual color change retaining the original geometry. Here also conformational changes in chelate rings are assumed to be responsible for this transition.
Regioselective Preparation of Diethyl 3,4-Disubstituted 1,5-Dihydro-5-oxo-2H-pyrrol-2-ylphosphonates and Their Coupling with Aldehydes. Application to the Synthesis of C/D-Rings Component of Phycocyanobilin
Authors: Ngwe Hla , Kinoshita Hideki , Inomata Katsuhiko
Published: August 2006

Diethyl 3,4-disubstituted 1,5-dihydro-5-oxo-2H-pyrrol-2-ylphosphonates were regioselectively prepared by acidic hydrolysis of diethyl 3,4-disubstituted 5-bromo-2-pyrrolylphosphonates. The resulting 1,5-dihydro-2H-pyrrol-2-ones readily underwent the coupling reaction with various aldehydes to afford the corresponding 1,5-dihydro-5-methylene-2H-pyrrol-2-ones including pyrromethenone derivatives in good yields. A series of these reactions was successfully applied to the synthesis of C/D-rings component of phycocyanobilin.
Visible Spectra of Methyl Red in Benzene–Water Microemulsions
Authors: Barman Tapash K , Paul Babul C , Ismail Kochi
Published: August 2006

Visible absorption spectra of Methyl Red in buffered benzene–water microemulsions (MEs) stabilized by sodium dodecyl sulfate and 1-butanol were recorded at 25 °C and at various pH values. Three compositions of the ME were used with R = 24, 32, and 48 where R is the water (aqueous buffer)-to-surfactant molar ratio. pKaof Methyl Red is found to be 6.12, 6.38, and 6.6 in MEs of R = 24, 32, and 48, respectively. The effective dielectric constant of the ME is estimated to be about 45 ± 3.
Formation of Intercalation Compounds of a Layered Sodium Octosilicate with n-Alkyltrimethylammonium Ions and the Application to Organic Derivatization
Authors: Endo Kimiharu , Sugahara Yoshiyuki , Kuroda Kazuyuki
Published: August 2006

In this study, n-alkyltrimethylammonium ions ([CnH2n+1N(CH3)3]+; n = 12,14,16,18) were intercalated in the interlayer space of layered sodium octosilicate (Na2Si8O17·nH2O) via an ion-exchange reaction. The interlayer space was further modified by grafting of the trimethylsilyl groups via a reaction between a dodecyltrimethylammonium–octosilicate intercalation compound and chlorotrimethylsilane.
Anaesthesia for elective inguinal hernia repair in rural Ghana - appeal for local anaesthesia in resource-poor countries
Authors: Wilhelm T J , Anemana S , Kyamanywa P , Rennie J , Post S , Freudenberg S
Published: August 2006

Local anaesthesia has been identified as the most favourable anaesthesia for elective inguinal hernia repair with respect to complication rate, cost-effectiveness, and overall patient satisfaction.

Operation theatre notes in all seven hospitals in the Northern Region in Ghana over the period of 1 year were reviewed. Only 22.4% out of 1038 repairs were performed under local anaesthesia while predominantly spinal and general anaesthesia were used (48.0 and 29.6%, respectively). African surgeons chose local anaesthesia far less frequently than visiting overseas surgeons (15.6 versus 27.7%, respectively).

All surgeons in resource-poor countries should be encouraged to use local anaesthesia more frequently for elective inguinal hernia repair. Valuable resources in sub-Saharan African hospitals could be saved, especially if used in combination with outpatient surgery.

The technique should be taught in teaching institutions. A simple step-by-step technique is described.
International health links: an evaluation of partnerships between health-care organizations in the UK and developing countries
Authors: Baguley Dave , Killeen Tim , Wright John
Published: August 2006

Increasingly, international health links are evolving between UK health-care institutions and those in developing countries, the core aims of which are to seek the transfer of ideas, knowledge, skills and training. This study aimed to evaluate established health links, what constitutes them and how they are supported. Benefits and challenges associated with the links, as perceived both by link coordinators in the UK and their overseas partners, were explored. Fourteen links between health-care organizations in the UK and those in developing countries were identified and interviews were successfully conducted with 22 link coordinators: 13 in the UK and nine in developing countries.

The interviews indicated that health links offer mutual benefits to both partners in terms of shared skills and the promotion of global awareness. Links can act as important catalysts; stimulating increases in institutional capacity for research and training.

They provide opportunities for personal and professional development of staff and promote the development of friendships and supportive networks between diverse communities. Many of the health links showed signs of evolving from uniprofessional links between individual institutions into broader, multidisciplinary community partnerships.

The main challenges facing health links arise from cultural differences, funding problems, communication difficulties and bureaucracy. There was broad agreement that greater recognition of the value and importance of health links by the NHS and closer collaboration between government departments to provide support and resources could promote wider and more effective link partnerships.
A randomized controlled trial of an interactive Web-based intervention for reducing alcohol consumption
Authors: Wallace P , Linke S , Murray E , Mccambridge J , Thompson S
Published: August 2006

In an uncontrolled pilot study of an interactive, Web-based treatment programme for people with alcohol problems, the mean number of units consumed decreased from 33 per week to 23. A two-arm online randomized controlled trial will be conducted to determine the effectiveness of an interactive Web-based intervention for reducing alcohol consumption. Participants will be randomized to intervention (access to an interactive Web-based intervention plus information) or control (access to an information Website only) groups, and followed up for six months. The primary outcome measure will be reduction in units of alcohol consumed in the previous seven days; secondary outcome measures will determine effects on alcohol dependence, alcohol-related harm and social disruption and quality of life. Recruitment, consent, randomization, intervention and follow-up will all be delivered online.