bluuebunny/crossref_metadata_2025 huggingface dataset:
Distribution of Corticotropin-Releasing Factor and Urocortin 1 in the Vole Brain
Authors: Lim Miranda M. , Tsivkovskaia Natalia O. , Bai Yaohui , Young Larry J. , Ryabinin Andrey E.
Published: July 2006

Brain receptor patterns for the corticotropin-releasing factor (CRF) receptors, CRF1 and CRF2, are dramatically different between monogamous and promiscuous vole species, and CRF physiologically regulates pair bonding behavior in the monogamous prairie vole. However, it is uncertain whether species differences also exist in the neuroanatomical distribution of the endogenous ligands for the CRF1 and CRF2 receptors, such as CRF and urocortin-1 (Ucn1). We compared the expression of CRF and Ucn1 in four vole species, monogamous prairie and pine voles, and promiscuous meadow and montane voles, using in situ hybridization of CRF and Ucn1 mRNA. Our results reveal that CRF mRNA expression patterns in all four vole species appear highly conserved throughout the brain, including the olfactory bulb, nucleus accumbens, bed nucleus of the stria terminalis, medial preoptic area, central amygdala, hippocampus, posterior thalamus, and cerebellum. Similarly, Ucn1 mRNA primarily localized to the Edinger-Westphal nucleus in all four vole species. Immunocytochemistry in prairie and meadow voles confirmed localization of CRF and Ucn1 protein to these previously identified brain regions. These data demonstrate a striking dichotomy between the extraordinary species diversity of brain receptor patterns when compared to the highly conserved brain distributions of their respective ligands. Our findings generate novel hypotheses regarding the evolutionary mechanisms underlying the neural circuitry of species-typical social behaviors.
Nutritional Assessment: Predictive Variables at Hospital Admission Related with Length of Stay
Authors: De Luis Daniel A. , Izaola Olatz , Cuellar Luis , Terroba MaConcepcion , Cabezas Gloria , Rojo S. , Aller Rocio , Sagrado M. Gonzalez
Published: July 2006

Background: Studies indicate that 40–50% of hospitalized patients show malnutrition, a variable that is associated with length of stay and morbidity. The aim of our study was to detect nutritional parameters, which could have an influence on length of stay in hospitalized patients. Material and Methods: All patients with a nutritional evaluation at hospital admission were elegible for inclusion. A total of 1,088 patients were studied from January 1999 to December 2003. Length of stay (LOS) data was obtained from the patient hospital record after the patient was discharged. All patients received instruction in 24-hour written food record keeping. Albumin, prealbumin, transferrin, glucose levels and total lymphocytes, were measured in all patients. Weight, body mass index, tricipital skinfold, midarm muscle circumference and midarm muscle area were assessed in a standard way. Weight loss in the previous 3 months was recorded. Results: A total of 1,088 patients were enrolled, mean age 61.8 ± 17 years, weight 64.2 ± 15 kg and BMI 23.9 ± 4.6, with a weight loss 4.15 ± 9.6 kg. The sex distribution of patients was 65.2% male and 34.8% females. Distribution of diagnosis showed leukemia and lymphoma (11.5%), solid cancer (37.4%), infections (3.5%), neurological disease (13.6%), respiratory tract disease (8.8%), and miscellaneous group (25.3%). Length of stay was 29.45 ± 25.13 days. In whole group, the correlation analysis among length of stay (days) and predictive parameters showed a positive association between albumin and length of stay (r = –0.2; p < 0.05). In the multivariant analysis with a dependent variable (length of stay (days)) and independent variables with an association in univariant analysis adjusted by age and sex, only albumin remained as an independent predictor in the model (F = 8.8; p < 0.05), with an increase of 6.2 days (95% CI: 3.5–8.9) with each decrease of 1 g/dl of albumin. Conclusion: The serum albumin levels are a good marker of LOS, a decrease in admission levels produces an increase in LOS.
The “Value Added” of Neurocognitive Testing after Sports-Related Concussion
Authors: Van Kampen Derk A. , Lovell Mark R. , Pardini Jamie E. , Collins Michael W. , Fu Freddie H.
Published: July 2006

Background

Neurocognitive testing has been endorsed as a “cornerstone’ of concussion management by recent Vienna and Prague meetings of the Concussion in Sport Group. Neurocognitive testing is important given the potential unreliability of athlete self-report after injury. Relying only on athletes'ormalities after injury.

Study Design

Case control study; Level of evidence, 3.

Methods

High school and college athletes with a diagnosed concussion were tested 2 days after injury. Postinjury neurocognitive performance (Immediate Postconcussion Assessment and Cognitive Testing) and symptom (postconcussion symptom) scores were compared with preinjury (baseline) scores and with those of an agex and education-matched noninjured athlete control group. “Abnormal” test performance was determined statistically with Reliable Change Index scores.

Results

Sixty-four percent of concussed athletes reported a significant increase in symptoms, as judged by postconcussion symptom scores, compared with preinjury baseline at 2 days after injury. Eighty-three percent of the concussed sample demonstrated significantly poorer neurocognitive test results relative to their own baseline performance. The addition of neurocognitive testing resulted in a net increase in sensitivity of 19%. Ninety-three percent of the sample had either abnormal neurocognitive test results or a significant increase in symptoms, relative to their own baseline; 30% of a control group demonstrated either abnormalities in neurocognitive testing or elevated symptoms, as judged by postconcussion symptom scores. For the concussed group, use of symptom and neurocognitive test results resulted in an increased yield of 29% overreliance on symptoms alone. In contrast, 0% of the control group had both symptoms and abnormal neurocognitive testing.

Conclusion

Reliance on patients’ self-reported symptoms after concussion is likely to result in underdiagnosis of concussion and may result in premature return to play. Neurocognitive testing increases diagnostic accuracy when used in conjunction with self-reported symptoms.
Pronociceptive and Antinociceptive Neuromediators in Patellar Tendinopathy
Authors: Lian Øystein , Dahl Johan , Ackermann Paul W. , Frihagen Frede , Engebretsen Lars , Bahr Roald
Published: July 2006

Background

The occurrence of nerve ingrowth and its relation to chronic tendon pain (tendinopathy) are still largely unknown. In healthy tendons, the innervation is confined to the paratenon, whereas the tendon proper is devoid of nerve fibers. In this study on the pathogenesis of tendinopathy, the authors examined sensory and sympathetic nerve fiber occurrence in the patellar tendon.

Hypothesis

Nerve ingrowth and altered expression of sensory and sympathetic neuromediators play a major role in the pathophysiology of pain in patellar tendinopathy.

Study Design

Case control study; Level of evidence, 3.

Methods

Biopsies from the patellar tendon in patients with patellar tendinopathy (n = 10) were compared with biopsies from a control group (n = 10) without any previous or current knee symptoms compatible with patellar tendinopathy. The biopsies were stained immunohistochemically for sensory and autonomic nerve markers. The biopsies from the 2 groups were compared using subjective and semiquantitative methods.

Results

Chronic painful patellar tendons exhibited increased occurrence of sprouting nonvascular sensory, substance P–positive nerve fibers and a decreased occurrence of vascular sympathetic nerve fibers, positive to tyroxin hydroxylase, a marker for noradrenaline.

Conclusion

The altered sensory-sympathetic innervation suggests a role in the pathophysiology of tendinopathy. Ingrowth of sprouting substance P fibers presumably reflects a nociceptive and maybe a proliferative role, possibly as reactions to repeated microtraumata, whereas the decreased occurrence of tyroxin hydroxylase may represent a reduced antinociceptive role. These findings could be used to develop targeted pharmacotherapy for the specific treatment of tendinopathy.
Analytic Autoethnography
Authors: Anderson Leon
Published: July 2006

Autoethnography has recently become a popular form of qualitative research. The current discourse on this genre of research refers almost exclusively to “evocative autoethnography” that draws upon postmodern sensibilities and whose advocates distance themselves from realist and analytic ethnographic traditions. The dominance of evocative autoethnography has obscured recognition of the compatibility of autoethnographic research with more traditional ethnographic practices. The author proposes the term analytic autoethnography to refer to research in which the researcher is (1) a full member in the research group or setting, (2) visible as such a member in published texts, and (3) committed to developing theoretical understandings of broader social phenomena. After briefly tracing the history of proto-autoethnographic research among realist ethnographers, the author proposes five key features of analytic autoethnography. He concludes with a consideration of the advantages and limitations of this genre of qualitative research.
What, We Worry?
Authors: Best Joel
Published: July 2006

Inevitably, more is forgotten than is remembered; what is lost to memory may be viewed as collective amnesia. This article considers the development of qualitative sociology as a distinct social world within the discipline; its emergence reflects sociology's growth and shifts in publishing practices that encouraged sociology's division into separate specialties. However, these developments have costs: ethnography is increasingly divorced from its historical context, and despite receiving considerable lip service, synthetic grounded theory is uncommon. Ethnographers need to consider both the benefits and the costs of these developments.
Love in the Time of Neo-Liberalism
Authors: Mannon Susan E.
Published: July 2006

Households around the world have shifted structurally from a breadwinner/homemaker model to dual-income earning arrangements. What this trend means for marital power has been a contested issue among scholars. Most studies suggest that household power is determined by a complex interplay between each spouse's economic contributions to the household and existing gender norms. Few scholars, however, have examined how this interplay is worked out under particular political-economic conditions. Responding to the dearth of research on the developing world in this area, the author examines a community in Costa Rica where neo-liberal economic restructuring has led to an increase in women's informal work and a decrease in men's income-earning power. Drawing from ethnographic and interview data on married life in Costa Rica, the author analyzes the effect that these trends have on marital power and the division of household labor. The author argues that changing economic circumstances may blur the traditional gender boundaries in Costa Rican households but they do not necessarily erase them.
Just One of the Guys?
Authors: Schilt Kristen
Published: July 2006

This article examines the reproduction of gendered workplace inequalities through in-depth interviews with female-to-male transsexuals (FTMs). Many FTMs enter the workforce as women and then transition to become men, an experience that can provide them with an “outsider-within” perspective on the “patriarchal dividend”—the advantages men in general gain from the subordination of women. Many of the respondents in this article find themselves, as men, receiving more authority, reward, and respect in the workplace than they received as women, even when they remain in the same jobs. The author argues that their experiences can make the underpinnings of gendered workplace disparities visible and help illuminate how structural disadvantages for women are reproduced in workplace interactions. As tall, white FTMs see more advantages than short FTMs and FTMs of color, these experiences also illustrate how men's gender advantages at work vary with characteristics such as race/ethnicity and body structure.
Inequality Regimes
Authors: Acker Joan
Published: July 2006

In this article, the author addresses two feminist issues: first, how to conceptualize intersectionality, the mutual reproduction of class, gender, and racial relations of inequality, and second, how to identify barriers to creating equality in work organizations. She develops one answer to both issues, suggesting the idea of “inequality regimes” as an analytic approach to understanding the creation of inequalities in work organizations. Inequality regimes are the interlocked practices and processes that result in continuing inequalities in all work organizations. Work organizations are critical locations for the investigation of the continuous creation of complex inequalities because much societal inequality originates in such organizations. Work organizations are also the target for many attempts to alter patterns of inequality: The study of change efforts and the oppositions they engender are often opportunities to observe frequently invisible aspects of the reproduction of inequalities. The concept of inequality regimes may be useful in analyzing organizational change projects to better understand why these projects so often fail and why they succeed when this occurs.
A Typological Analysis of Behavioral Profiles of Sexually Abused Children
Authors: Hébert Martine , Parent Nathalie , Daignault Isabelle V. , Tourigny Marc
Published: July 2006

A cluster analysis is used to explore differential outcomes in 123 French Canadian children reporting sexual abuse contrasted with 123 control children. Mothers' reports of behavioral problems on the Child Behavior Checklist, abuse-related variables, personal factors, and family characteristics are used as potential variables discriminating clusters. Results reveal four clusters: (a) anxiety constellation group refers to children displaying behavior problems on a subset of scales, (b) the severe distress group refers to children showing a broader array of behavior problems, (c) victims of less severe sexual abuse (SA) group consists of children disclosing mostly extrafamilial SA, and (d) resilient children refers to children who, while disclosing severe abuse, rely less on avoidance coping. Findings underscore the need to go beyond abuse-related variables to orient treatment for children disclosing sexual abuse and for tailoring interventions to distinct subgroups.
The Potential for Child Neglect: The Case of Adolescent Mothers and Their Children
Authors: Lounds Julie J. , Borkowski John G. , Whitman Thomas L.
Published: July 2006

The present study examines the role of neglect potential in adolescent mother-child dyads, both in terms of antecedents and its consequences for children's development. Participants were 100 adolescent mother-child dyads who were part of a larger, longitudinal study. Data were collected from the third trimester of pregnancy until the children's 10th year. Histories of maternal neglect and the quality of mother-child interactions during early childhood were found to predict neglect potential during middle childhood. Mothers with high neglect potential had children who exhibited more externalizing problems and fewer adaptive behaviors, with neglect potential mediating the effects of both early abuse potential and the quality of parenting on children's later externalizing behaviors. Results suggest that neglect potential may be a mechanism through which early potential for child abuse and insensitive maternal interactions affect later externalizing problems in children of adolescent mothers.
Expression of angiogenic growth factors by uterine natural killer cells during early pregnancy
Authors: Lash Gendie E , Schiessl Barbara , Kirkley Maureen , Innes Barbara A , Cooper Alix , Searle Roger F , Robson Stephen C , Bulmer Judith N
Published: July 2006

Remodeling of uterine spiral arteries is critical for the continuation of a successful pregnancy. Uterine natural killer (uNK) cells are the predominant leukocyte population in the early pregnant decidua, and a role for these cells in spiral artery remodeling in pregnancy has been suggested. Angiogenic growth factors were measured in isolated uNK and total (unseparated) decidual cells (8–10 or 12–14 weeks gestation, n=5 each gestational age) after culture for 48 h. Angiopoietin (Ang)1, placental growth factor, transforming growth factor-β1 (TGF-β1), and vascular endothelial growth factor (VEGF)-C were measured by enzyme-linked immunosorbent assay. Angiogenin, Ang2, fibroblast growth factor basic, intercellular adhesion molecule (ICAM)-1, keratinocyte growth factor (KGF), platelet-derived growth factor-BB, and VEGF-A were measured using a FASTQuant angiogenic growth factor multiplex protein assay. Levels of Ang2, ICAM-1, and KGF, secreted by the total decidual fraction, decreased with increasing gestational age. uNK levels of Ang2 and VEGF-C also decreased with increasing gestational age. At 8–10 weeks gestation, there was no difference in the level of Ang1, Ang2, TGF-β1, and VEGF-C secreted by uNK cells and the total decidual fraction. At 12–14 weeks, uNK cells secreted significantly lower levels of VEGF-C than the total decidual fraction. Early pregnancy decidua is a major source of angiogenic growth factors whose levels decrease with increasing gestational age, suggesting that they may play a role in spiral artery remodeling. uNK cells appear to be a prominent source of Ang1, Ang2, TGF-β1, and VEGF-C within the placental bed.
Prospective 12-month course of bipolar disorder in out-patients with and without comorbid anxiety disorders
Authors: Otto Michael W. , Simon Naomi M. , Wisniewski Stephen R. , Miklowitz David J. , Kogan Jane N. , Reilly-Harrington Noreen A. , Frank Ellen , Nierenberg Andrew A. , Marangell Lauren B. , Sagduyu Kemal , Weiss Roger D. , Miyahara Sachiko , Thase Michael E. , Sachs Gary S. , Pollack Mark H.
Published: July 2006

Background

The impact of anxiety disorders has not been well delineated in prospective studies of bipolar disorder.

Aims

To examine the association between anxiety and course of bipolar disorder, as defined by mood episodes, quality of life and role functioning.

Method

A thousand out-patients with bipolar disorder were followed prospectively for 1 year.

Results

A current comorbid anxiety disorder (present in 31.9% of participants) was associated with fewer days well, a lower likelihood of timely recovery from depression, risk of earlier relapse, lower quality of life and diminished role function over 1 year of prospective study. The negative impact was greater with multiple anxiety disorders.

Conclusions

Anxiety disorders, including those present during relative euthymia, predicted a poorer bipolar course. The detrimental effects of anxiety were not simply a feature of mood state. Treatment studies targeting anxiety disorders will help to clarify the nature of the impact of anxiety on bipolar course.
Effects of a mutual support group for families of Chinese people with schizophrenia: 18-month follow-up
Authors: Chien Wai-Tong , Chan Sally W. C. , Thompson David R.
Published: July 2006

Background

Family intervention in schizophrenia can reduce patient relapse and improve medication adherence, but few studies on this have involved a Chinese population.

Aims

To examine the effects of a mutual support group for Chinese families of people with schizophrenia, compared with psychoeducation and standard care.

Method

Randomised controlled trial in Hong Kong with 96 families of out-patients with schizophrenia, of whom 32 received mutual support, 33 psychoeducation and 31 standard care. The psychoeducation group included patients in all the sessions, the mutual support group did not. Intervention was provided over 6 months, and patient- and family-related psychosocial outcomes were compared over an 18-month follow-up.

Results

Mutual support consistently produced greater improvement in patient and family functioning and caregiver burden over the intervention and follow-up periods, compared with the other two conditions. The number of readmissions did not decrease significantly, but their duration did.

Conclusions

Mutual support for families of Chinese people with schizophrenia can substantially benefit family and patient functioning and caregiver burden.
Exposure to obstetric complications and subsequent development of bipolar disorder
Authors: Scott Jan , McNeill Yvonne , Cavanagh Jonathan , Cannon Mary , Murray Robin
Published: July 2006

Background

Research has suggested an association between obstetric complications and bipolar disorder. However, no quantitative evaluation has been made of the pooled data from existing studies.

Aims

To systematically review studies comparing exposure to obstetric complications in cases of bipolar disorderv.non-psychiatric controls, and in cases of bipolar disorderv.cases of other mental disorders.

Method

Publications were identified by computer searches of seven databases, by hand searches of reference lists and from raw data received from researchers.

Results

Forty-six studies were identified, of which 22 met the inclusion criteria. The pooled odds ratio for exposure to obstetric complications and subsequent development of bipolar disorder was 1.01 (95% Cl 0.76–1.35) compared with healthy controls, 1.13 (95% Cl 0.64–1.99) compared with cases of unipolar disorder and 0.61 (95% Cl 0.39–0.95) compared with those who developed schizophrenia.

Conclusions

There is no robust evidence that exposure to obstetric complications increases the risk of developing bipolar disorder. However, the range of events regarded as obstetric complications and methodological inadequacies make definitive conclusions difficult.
Recent Progress in High-Resolution Spectroscopic Studies on Transient Molecules
Authors: Hirota Eizi
Published: July 2006

The microwave and/or infrared spectra of alkali monoxides and NO3 were observed in order to characterize these molecules in detail, which play significant roles in atmospheric chemistry. Similar studies were carried out on a few inorganic molecules, including SinHm neutrals and ions with n = 1, 2 and m = 1, 2, 3, in view of their important roles in electronic-device processing. Recent innovations in high-resolution spectroscopic methods are briefly discussed.
Synergy between the CoMoS Phase and Supported or Unsupported Cobalt Sulfide. Existence of a Remote Control Effect
Authors: Karroua Mohamed , Matralis Haris , Sham Edgardo , Grange Paul , Delmon Bernard
Published: July 2006

Unsupported Co9S8, MoS2, and CoMoS sulfides (prepared by the HSP method) as well as supported MoS2/Al2O3 and CoSx/C (prepared by impregnation) were used to prepare a series of binary mechanical mixtures of various compositions. A variety of physicochemical techniques (temperature programmed decomposition and sulfidation, both followed by subsequent TPO, XRD, TPR, microelectrophoresis, XPS and AEM) were used to study the samples, verify the formation of the “CoMoS phase” in the mixed CoMo sulfide and investigate the existence of interactions between the sulfides forming the mechanical mixtures. The catalytic activity of the supported and unsupported HSP sulfides as well as that of the mechanical mixtures was tested in the hydrodesulfurization of thiophene (HDS) and the hydrogenation of cyclohexene (HYD) at 573 K and 3 MPa. The mechanical mixtures exhibit a synergy in HDS and HYD. This shows that cobalt sulfide (supported or unsupported HSP) can promote the activity not only of molybdenum sulfide, but also of the unsupported HSP “CoMoS phase”. In addition, XRD and AEM (performed before and after catalytic tests) were used to study the evolution of the unsupported “CoMoS phase” during the catalytic reaction. It was found that this phase is unstable; cobalt segregates from the CoMoS association to form Co9S8, even after a relatively short period in the reactor. These results provide more evidence that the remote control mechanism plays a major role in the synergetic behavior of the CoMo hydrotreating catalysts.
Ab Initio Study of the Molecular Structure and NMR Carbon–Lithium Coupling Constant for Trichloromethyllithium
Authors: Koizumi Terutake , Kikuchi Osamu
Published: July 2006

Ab initio calculations of the molecular structure and NMR C–Li coupling constant for trichloromethyllithium have indicated that the classical C3v form is favorable for trichloromethyllithium observed by NMR spectroscopy.
Raman Noncoincidence Effect and Intermolecular Interactions in Liquid Dimethyl Sulfoxide: Simulations Based on the Transition Dipole Coupling Mechanism and Liquid Structures Derived by Monte Carlo Method
Authors: Torii Hajime , Tasumi Mitsuo
Published: July 2006

Model calculations are performed on the Raman noncoincidence effect (frequency difference between the isotropic and anisotropic components) observed in the region of the S=O stretching band of liquid dimethyl sulfoxide (DMSO). Liquid structures are obtained by Monte Carlo simulations, by using potential functions without specific interactions involving the hydrogen atoms of the methyl groups. Intermolecular coupling between the S=O stretches is evaluated by the transition dipole coupling mechanism. The magnitude and the direction of the transition dipole are calculated by ab initio molecular orbital calculations at the second-order Møller–Plesset perturbation level with a basis set extended from 6-31G(2d,p). The calculated sign and magnitude of the Raman noncoincidence are in reasonable agreement with the observed, indicating that the observed large Raman noncoincidence can be mostly explained by the liquid structures obtained without specific interactions involving the hydrogen atoms of the methyl groups. The pair distribution function of liquid DMSO is also calculated to the second order in the orientation correlation of molecules. The origin of the Raman noncoincidence effect is discussed by comparing the cases of liquid DMSO, acetone, and methanol.
Microviscosity and Micellar Phase Diagrams Determined with Fluorescence Probes
Authors: Miyagishi Shigeyoshi , Kurimoto Hirotaka , Asakawa Tsuyoshi
Published: July 2006

The dependence of microviscosity on salt and surfactant concentrations was determined in micellar solutions of alkyltrimethylammonium bromides by using two fluorescent probes, auramine and 1,3-dipyrenylpropane (P3P). The microviscosity increased with the growth of the micelles, it changed at the sphere to rodlike micelles transition point, and it became constant above the overlap threshold point of rod micelles, that is, the overlapping of micelles did not influence the microviscosity. The transition points of the micellar solutions (the critical micelle concentrations, the sphere-rod transition point, and the micelle overlapping point) determined by the present method were in good agreement with those in the literature. Phase diagrams of the micellar solutions were determined from the above data.
Internal Rotation of the Methyl Groups in the t-Butyl Radical as Studied by ESR
Authors: Kubota Souichi , Matsushita Michio , Shida Tadamasa , Abu-Raqabah Atieh , Symons Martyn C R , Wyatt Jane L
Published: July 2006

The ESR spectrum of the t-butyl radical in a rigid matrix is observed at temperatures between 6.6 and 70 K. At temperatures below about 50 K equally spaced nineteen lines are observed which is associated with the tunneling rotation of the three methyl groups. By the analysis of the spectral pattern at a low temperature of 6.6 K the pairwise interaction potential of the internal rotation, if any, is deduced to be proportional to cos θi cos θj where θi and θj are the internal rotation angles of two methyl groups. By the simulation of the spectral change with temperature the thermal activation energy for the internal rotation is estimated to be 6 ± 2 kJ mol−1.
The Aggregated Higher-Structure of 1,3 : 2,4-Di-O-benzylidene-d-sorbitol in Organic Gels
Authors: Yamasaki Seiji , Ohashi Yukihiro , Tsutsumi Hisao , Tsujii Kaoru
Published: July 2006

1,3 : 2,4-Di-O-benzylidene-d-sorbitol (d-DBS) can cause gelation of organic solvents of a wide range of polarity into a gel state. The aggregated structures of d-DBS/organic solvent systems were studied, mainly by using IR, UV, and circular dichroism (CD) spectroscopy. In the case of the racemate Dl-DBS, no gel state was formed. In IR spectra of d-DBS and Dl-DBS in the solid state, the intensities of νOH and νCO absorption in d-DBS were found to be larger than those in Dl-DBS. It is assumed that the hydrogen bonding formed between an acetal oxygen and a hydroxyl group in the aggregation of d-DBS. From the changes in the IR spectra from solution into a gel state, we can conclude that the chirality and the hydrogen bonding of DBS molecules are essential for the formation of the gel. Comparing the gel-forming ability of d-DBS with its derivatives, 5- or 6-hydroxyl-group-blocked compounds by methyl group, the 6-hydroxyl group seems to be important in the formation of d-DBS aggregates. The results of UV spectra suggest that the benzene rings are ordered in a side by side arrangement. The molar ellipticities in CD spectra increased about 500 times during the change from the solution to the gel state. From these results, it is concluded that d-DBS forms a helical structure of thin fibrous crystals in the gel state.
Synthesis of Electroactive Protein Hybrid, Fec-BSA-Dig, and Its Application to a Novel Homogeneous Electrochemical Immunoassay
Authors: Suzawa Toshiyuki , Ikariyama Yoshihito , Aizawa Masuo
Published: July 2006

A novel homogeneous electrochemical immunoassay using ferrocene- (Fec-), digoxin- (Dig-) doubleconjugated protein, has been developed. The system is based on the principle that electrochemical activity of the conjugate is suppressed in the presence of an antibody, and restored in the presence of free digoxin. Hence, a new homogeneous immunoassay can be carried out when the electroactivity of the conjugate is determined. Here, we synthesize the conjugate by controlling the numbers of ferrocene and digoxin on individual carrier proteins simultaneously. Bovine serum albumin (BSA) is selected as a carrier protein to which the electrochemical labels and the several hapten molecule are bound by Schiff’s base formation. Since the conjugate synthesized here behaves as a multivalent antigen, and is capable of binding to antidigoxin antibody, therefore the antigen having electrochemical activity loses its activity depending on antibody concentration. When the conjugate, in which 39 molecules of ferrocene and 8 molecules of digoxin are bound, is used for the inhibition experiment of electrochemical reaction before and after the immunoreaction, peak height currents, responsible for the redox reactions of the bound ferrocene, decreased depending on the added antibody in a dose-dependent fashion. This system is feasible as a homogeneous electrochemical immunoassay, since the method may provide a simple and a rapid approach toward a homogeneous assay of bioactive substances.
C,N-Chelated (2-Pyridylmethyl)rhodium(III) Complexes and a Novel Dinuclear Rhodium(III) Complex Containing a 2,6-Dimethylpyridine-α,α′-diyl Group as an η2(C,N) : η3(C,C′,N)-Bridging Ligand
Authors: Shinkawa Nobuyuki , Sato Aya , Shinya Junko , Nakamura Yukio , Okeya Seichi
Published: July 2006

Oxidative-addition reactions of excess 2-(chloromethyl) and 2,6-bis(chloromethyl)pyridines with [RhCl(PPh3)3] in toluene at room temperature afforded (2-pyridylmethyl)- and {2-(6-chloromethyl)pyridylmethyl}rhodium(III) complexes, cis(PP)-[RhCl2{C5H3(6-R)N-2-CH2}(PPh3)2] (R = H, 1-cis; R = CH2Cl, 2-cis), respectively, which isomerized to the corresponding trans(PP) complexes at elevated temperature. In refluxing toluene, the reactions thus resulted in the trans(PP) complexes (R = H, 1-trans; R = CH2Cl, 2-trans) exclusively. A novel dinuclear rhodium(III) complex [Rh2Cl4{C5H3N-2,6-(CH2)2}(PPh3)2], in which the 2,6-dimethylpyridine-α,α′-diyl ligand is C,N-chelated to one rhodium atom and bound to the second one in an η3-pseudo-1-azaallylic fashion, was obtained by reactions of 2,6-bis(chloromethyl)pyridine with [RhCl(PPh3)3] (1 : 2 in mole) and of the 2-cis with [RhCl(PPh3)3] (1 : 1 in mole), both in refluxing toluene. These were characterized by 1H, 13C, and 31P NMR spectroscopy and mass spectrometry as well as an elemental analysis and a molecular-weight determination.
Studies of the Hydrous Titanium Oxide Ion Exchanger. IV. Rate of the Isotopic Exchange of Sodium Ions between the Exchanger in the Na+ Form and Aqueous Solution
Authors: Inoue Yasushi , Yamazaki Hiromichi , Kasuga Fuminori
Published: July 2006

The isotopic exchange rate of Na+ between hydrous titanium(IV) oxides, precipitated at pH 6 and 13, in the Na+ form and aqueous solution of sodium salt was determined radiochemically. The rate in the exchanger precipitated at pH 6 is controlled by the diffusion of Na+ in the exchanger particles (particle diffusion). The diffusion coefficient and its activation energy are 1.9 × 10−11 m2 s−1 (pH 12, 5.0 °C) and 29 kJ mol−1 (pH 12), respectively. The rate in the exchanger precipitated at pH 13 is also controlled by the particle diffusion. The rate is much slower than that in the other; this can be explained by assuming the existence of two kinds of independently diffusing ions (fast and slow species) in the exchanger. The diffusion coefficients are of the order of 10−12 and 10−13 m2 s−1 for the fast and the slow species, respectively. Their activation energies are 48—60 kJ mol−1 at pH 12. The marked difference in kinetics between two exchanges was interpreted in terms of the difference in the acid-base property and in the microstructure of the matrix.
Effects of ortho-Methyl Substituents on the Rate of Dissociation of Imidazole Ligands in Tetraarylporphyrinatocobalt(III) Complexes
Authors: Nakamura Mikio
Published: July 2006

Dissociation rates of the imidazoles in [Co(tpp)(L)2]+ and [Co(tmp)(L)2]+, where L is an unhindered imidazole such as 1-methylimidazole or a hindered imidazole such as 2-alkylimidazole, have been determined in chloroform-d solution by the 1H NMR saturation transfer method. The rate constants in the tmp complexes were smaller than those of the corresponding tpp complexes in every imidazole ligand examined. The largest difference between these two systems was observed in bis(1,2-dimethylimidazole) complexes and the ratio of the rate constants, k(tpp)/k(tmp), reached as much as 2500 at 90 °C. While the rate constants greatly increased in the tpp system on going from the unhindered imidazole to the hindered one, the increase was rather small in the tmp system. These results were interpreted in tems of the deformation of the porphyrinatocobalt core: Since the two hidered ligands in the tmp complexes are fixed perpendicularly in the cavities created by the deformed porphyrin ring, the distance between the 2-alkyl and the deformed porphyrinatocobalt core would increase, which results in weakening the steric repulsion and slowing down the dissociation rate. The attractive interaction between the ortho-methyls and the imidazole π system would also contribute to the stability of the tmp complexes.
Formation of 2,6-Naphthalenedicarboxylic Acid by the Co–Mn–Br-Catalyzed Autoxidation of 2,6-Diethylnaphthalene in Acetic Acid
Authors: Kamiya Yoshio , Hama Takashi , Kijima Ichiro
Published: July 2006

In order to elucidate the reaction mechanism and the optimum reaction conditions for the formation of 2,6-naphthalenedicarboxylic acid (NDCA), the Co(OAc)2–Mn(OAc)2–NaBr-catalyzed oxidation of 2,6-diethylnaphthalene by molecular oxygen was carried out in acetic acid. The oxidation of the ethyl groups to carboxyl groups proceeded mainly via acetyl groups and partly via 1-hydroxyethyl and 1-acetoxyethyl groups. A synergistic catalytic effect due to Co and Mn acetates was observed not only on the rate of oxidation but also on the selective formation of NDCA. The rate of oxidation was strongly retarded at higher concentrations of the substrate, showing that the naphthalene nucleus terminates the chain reaction step of the oxidation. A high concentration of metal catalyst resulted in an increase of acetoxyethylnaphthoic acid. At the optimum reaction conditions, a nearly 90% yield of NDCA was obtained along with small amounts of substituted naphthoic and trimellitic acids. The differences in the yield of NDCA from 2,6-dimethyl, 2,6-diethyl, and 2,6-diisopropylnaphthalenes were compared under similar reaction conditions and are discussed.
Preparation of 2-Hydroxymethylated Aldose by the Stereospecific Rearrangement of Ketose
Authors: Yanagihara Ryoji , Egashira Jun , Yoshikawa Sadao , Osanai Shuichi
Published: July 2006

A simple one-stage reaction system which yields 2-C hydroxymethylated aldopentose has been investigated. Four different 2-C branched aldopentoses (2-C hydroxymethylated d-arabinose, d-ribose (Hamamelose), l-lyxose, and d-xylose) were prepared from the corresponding ketoses (d-psicose, d-fructose, l-sorbose, and d-tagatose, respectively). These branched sugars were synthesized by a similar mechanism to the 2-C epimerization of aldose using a nickel complex. It was confirmed that the isomerization of ketose to the side-branched sugar proceeded in the ternary nickel complex through a sequence of stereospecific rearrangements in the sugar. The yields were dependent upon the structure of the substrate ketose and the nickel-ethylenediamine complex. N,N′-Dialkylated cyclohexanediamines were the most suitable ligands for preparing the 2-C hydroxymethylated branched chain sugar.
Attempts at Direct Detection of Reactive Species in Selective Excitation of the Contact Charge Transfer Pairs of Hexamethylbenzene and Oxygen
Authors: Komatsu Toshiki , Tsuchiya Masahiro , Furusawa Gen-ichi , Kuriyama Yasunao , Sakuragi Hirochika , Nakanishi Fusae , Tokumaru Katsumi
Published: July 2006

Pulsed laser excitation of contact charge transfer pairs of hexamethylbenzene (HMB) and oxygen in methanol-acetonitrile gave no evidence for intermediacy of reactive species such as HMB radical cations and pentamethylbenzyl cations (ArCH2+), though stationary irradiation of the pair in hydroxylic solvents afforded distinct products arising from the cationic species. The mechanism of reactions was discussed in comparison with 9,10-dicyanoanthracene-sensitized oxygenation of HMB.
Reduction of Arylcarbonyl Using Zinc Dust in Acetic Acid
Authors: Rani B Radha , Ubukata Makoto , Osada Hiroyuki
Published: July 2006

Zinc dust in acetic acid has been found to be a versatile and chemoselective reagent for the reduction of various arylcarbonyls to the corresponding alcohols or their acetates in fair yields.
Stereochemical Control in Microbial Reduction. XXV. Additives Controlling Diastereoselectivity in a Microbial Reduction of Ethyl 2-Methyl-3-oxobutanoate
Authors: Kawai Yasushi , Takanobe Kousuke , Ohno Atsuyoshi
Published: July 2006

Stereoselectivity of microbe-catalyzed reduction of ethyl 2-methyl-3-oxobutanoate to optically active 3-hydroxy-2-methylbutanoate can be controlled by the addition of methyl vinyl ketone to the reaction system. The reduction by Geotrichum candidum, Endmyces magnusii, and Mucor javanicus with an appropriate additive affords the corresponding anti-(2S,3S)-hydroxy ester selectively, whereas the reduction by bakers’ yeast and Candidatropicalis with an additive gives the corresponding syn-(2R,3S)-hydroxy ester selectively.
Practical and Safe Sulfonylation of 2-Alkynyl and 2-Alkenyl Alcohols Using the Combined Bases of a Catalytic Amount of Tertiary Amine and Potassium Carbonate
Authors: Tanabe Yoo , Yamamoto Hitomi , Yoshida Yoshihiro , Miyawaki Takashi , Utsumi Naoka
Published: July 2006

Several 2-alkynyl and 2-alkenyl alcohols were effectively sulfonylated with methanesulfonyl chloride or p-toluenesulfonyl chloride using the combined bases of a catalytic amount of tertiary amine and potassium carbonate. The reaction was conducted with reliable safety and while avoiding the disposal of wasted amines. The mesylation of 2-propyn-1-ol proceeded on a large scale (more than 20 kg) without a substantial production of explosive 3-chloro-1-propyne. The choice of the catalysts was important, and sterically unhindered tertiary amines, such as trimethylamine, N,N-dimethylbenzylamine, and triethylamine, were effective. Without these catalysts the reactions were significantly retarded. The reaction was so mild that it could be applied to complex and optically active 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopenten-1-one, which is an important alcohol moiety of synthetic pyrethroids.
Thermolysis of Dicyclopentadienylmethyl Alcohols. A Novel Synthesis of Fulvenes
Authors: Kumagai Takashi , Ohno Mayumi , Mitani Kooji , Yamamoto Ken-ichi , Oda Masaji
Published: July 2006

Thermolyses of isomeric mixtures of dicyclopentadienylmethyl alcohols were obtained by reactions of the corresponding isomeric mixture of metallodicyclopentadiene with aldehydes and ketones at 300 °C by a flow method. These thermolyses give by cycloreversion the corresponding isomeric mixtures of cyclopentadienylmethyl alcohols. These mixtures in turn furnish the corresponding fulvenes upon treatment with bases. At higher temperatures, the thermolyses regenerate starting ketones, probably by retro-ene reaction of the cycloreversed alcohols.
Efficient Preparation of Alkoxymethyl Carbonates by Using Potassium Carbonate, Chloromethyl Alkyl Ethers, and Alcohols
Authors: Teranishi Katsunori , Komoda Atsuko , Hisamatsu Makoto , Yamada Tetsuya
Published: July 2006

A synthesis of new “alkoxymethyl carbonate” is presented starting with alcohol. In the presence of potassium carbonate, primary alcohols react with chloromethyl alkyl ethers in N,N-dimethylformamide under mild conditions to give the corresponding alkoxymethyl carbonates in good yields without giving the alkoxymethyl ethers. The yield of alkoxymethyl carbonate is seriously effected by reaction solvent and the present method is not applicable for tertiary alcohol. Methoxymethyl carbonate can be removed readily under mild basic or acidic conditions, and undergoes selective alkoxide interchange of methoxymethoxide group under basic conditions.
Studies on Synthetic Ionophores. X. Transport Behavior of Na+ and K+ with an ω-Hydroxy Carboxylic Acid Containing Octaether Linkages as a Synthetic Analog of Natural Carboxylic Acid Ionophores through an Organic Liquid Membrane
Authors: Yamaguchi Kazuo , Kuboniwa Hitoshi , Nagami Satoru , Bando Toru , Hirao Akira , Nakahama Seiichi , Yamazaki Noboru
Published: July 2006

2-[[2-[2-[2-[2-[2-[2-[2-(2-Hydroxyethoxy)phenoxy]ethoxy]phenoxy]ethoxy]phenoxy]ethoxy]phenoxy]methyl]benzoic acid (1) was employed as a carrier to transport alkali metal ions. The transport selectivity sequence through 1,2-dichloroethane membrane was K+ ≥ Rb+ > Cs+ > Na+ ≥ Li+. The high preference of K+ to Na+ in competitive transport through 1,2-dichloroethane–toluene was consistent with the difference of solubility between the potassium and sodium salts of 1. However, the separate transport rates of K+ and Na+ through 1,2-dichloroethane were comparable. The amount of water incorporated from aqueous to organic layer by the sodium salt was much more than by the potassium salt, and the amounts were dependent on the stirring rates of the two layers. The sodium salt lowered the interfacial tension between the aqueous and organic layers, while the potassium salt did not change it. Emulsion-like aggregates of the sodium salt in the organic layer were observed by dynamic light scattering. The above experiments showed that K+ was transported as the potassium salt of 1, while Na+ was incorporated into the organic layer and transported as an aggregate of the sodium salt containing water.
Stereo- and Chemo-Selectivity in Reduction of α-[Phenyl(or Methyl)seleno]alkyl Aryl Ketones with Metal Hydrides
Authors: Aoki Ikuo , Nishibayashi Yoshiaki , Uemura Sakae
Published: July 2006

Metal hydride reduction of a variety of α-[phenyl(or methyl)seleno]alkyl aryl ketones gives a mixture of threo- and erythro-β-aryl-β-hydroxyalkyl phenyl(or methyl)selenides by carbonyl reduction and 1-aryl-1-alkanol by the substitution of a phenyl(or methyl)seleno group with hydrogen. With all metal hydrides examined the formation of the threo-isomer always predominated. The addition of various metal chlorides in the reduction system did not affect the diastereoselectivity much, in a sharp contrast to the so-far known reduction of various α-heteroatom (N, P, O, S)-substituted ketones.
Stereoselective Reduction of β,δ-Diketo Esters. A Novel Strategy for the Synthesis of Artificial HMG-CoA Reductase Inhibitors
Authors: Hiyama Tamejiro , Reddy Guntoori Bhaskar , Minami Tatsuya , Hanamoto Takeshi
Published: July 2006

Condensation of N-methoxy-N-methyl amides with the dianions of acetoacetates gives in good yields β,δ-diketo esters, which are reduced with Et2BOMe–NaBH4 in tetrahydrofuran–methanol highly selectively to give syn-β,δ-dihydroxy esters in one step. Similarly, the β,δ-diketo esters of the Taber’s chiral alcohol or its enantiomer respectively are reduced to give syn-β,δ-dihydroxy esters of moderate enantiomeric excess. Higher diastereo- and enantioselectivity were achieved by reduction of the β,δ-diketo esters of the Taber’s chiral alcohol or its enantiomer successively with diisobutylalane and with Et2BOMe–NaBH4. The resulting syn-diol esters were hydrolyzed and lactonized to give various types of β-hydroxy-δ-lactones commonly found in artificial HMG-CoA reductase inhibitors.
Polymerization of Sulfur-Containing Aromatic Disubstituted Acetylenes and Polymer Characterization
Authors: Watase Takanori , Tachimori Hiroshi , Masuda Toshio
Published: July 2006

1-Phenylthio-1-alkynes (PhS–C≡C–R; R = Me, n-Bu, n-C6H13, n-C8H17, n-C10H21, and n-C12H25) polymerized in 40—80% yields in toluene at 80 °C in the presence of MoCl5–Ph3SiH (1 : 2) catalyst, but did not polymerize with the corresponding W catalyst. The produced polymers with R = n–C8H17 and longer were soluble in toluene, chloroform, etc., whose weight-average molecular weights (Mw) reached 2 × 104. 1-Alkylthio-2-phenylacetylenes (RS–C≡C–Ph; R = Me, Et, n-Bu) polymerized in 10—20% yields with a WCl6–Ph3SiH (1 : 2) catalyst, while they did not produce any polymer with Mo catalysts. Only the polymer with R = n–Bu was soluble in several organic solvents, whose Mw was ca. 1 × 104. Although 1-phenylthio-2-phenylacetylene (PhS–C≡C–Ph) polymerized with both MoCl5–Ph3SiH and WCl6–Ph3SiH, the produced polymers were insoluble in all solvents. Poly(1-phenylthio-1-dodecyne) and poly(1-butylthio-2-phenylacetylene) were yellow solids with absorption maxima at around 280 m; their weight loss in a thermogravimetric analysis started at around 200 °C.
Enzymatic Ring-Opening Polymerization of Lactones to Polyesters by Lipase Catalyst: Unusually High Reactivity of Macrolides
Authors: Uyama Hiroshi , Takeya Kazuhiro , Kobayashi Shiro
Published: July 2006

Enzymatic ring-opening polymerization of macrolides was carried out by using various lipases as catalysts. The monomers used in this study were 11-undecanolide (12-membered, UDL) and 15-pentadecanolide (16-membered, PDL). Among the enzymes examined, lipases derived from Pseudomonas fluorescens (lipase P) and from Candida cylindracea (lipase B) gave polyUDL with high molecular weight in a high yield. From 1H and 13C NMR analysis, the polymer was found to possess the terminal structure of a carboxylic acid group at one end and a hydroxyl group at the other. The rate of the UDL polymerization using lipase P was larger than that using lipase B, whereas the polymerization of UDL using lipase B produced the polymer of higher molecular weight in comparison with that obtained by using lipase P. Lipases from Pseudomonas sp. and porcine pancreas showed a catalytic activity for the polymerization of UDL. PDL was also polymerized by lipase catalyst to give the corresponding polyester. The enzymatic polymerizations of UDL and PDL have been compared with that of 6-hexanolide (ε-caprolactone, ε-CL). The polymerization of the macrolides using lipase P proceeded much faster than that of ε-CL. This is probably due to the strong recognition of the macrolides by the lipase catalyst.