bluuebunny/crossref_metadata_2025 huggingface dataset:
The crossover of burnout and work engagement among working couples
Authors: Bakker Arnold B. , Demerouti Evangelia , Schaufeli Wilmar B.
Published: August 2005

The present study tested the hypothesis that burnout and work engagement may crossover from husbands to wives and vice versa. Data were collected among 323 couples working in a variety of occupations. The Job Demands-Resources model was used to simultaneously examine possible correlates of burnout and engagement for each partner separately. The results of a series of hierarchical regression analyses provide evidence for the crossover of burnout (exhaustion and cynicism) and work engagement (vigor and dedication) among partners. The crossover relationships were significant and about equally strong for both partners, after controlling for some important characteristics of the work and home environment. These findings expand previous crossover research, particularly by showing that positive experiences at work may be transferred to the home domain. We argue that the crossover of positive feelings among partners should be placed more prominently on the research agenda.
Maintaining the Coalition: Class Coalitions and Policy Trajectories
Authors: Winders Bill
Published: August 2005

The author compares the trajectories of three U.S. policies from 1935 to 1952: the Agricultural Adjustment Act (AAA), the National Labor Relations Act (NLRA), and the Social Security Act (SSA). Agricultural policy expanded beyond the New Deal, labor policy was severely weakened, and social security saw only minor changes. Why? Class coalitions strongly influenced the trajectories of these policies. The coalition supporting the AAA largely maintained, but the coalition supporting the NLRA collapsed. Support from southern planters was particularly important for each policy. Focusing on trajectories rather than merely policy formation more clearly demonstrates the influence of class coalitions over state policy.
Guerrilla Workfare: Migrant Renovators, State Power, and Informal Work in Urban China
Authors: Guang Lei
Published: August 2005

The article explores Chinese rural migrants’ perspective on work and their relations with each other and with the Chinese state by drawing upon the ethnographical study of a group of rural home renovators in Beijing in the 1990s. The rural renovators were dubbed “guerrilla” workers because of their physical mobility, irregular employment, and unregistered status. After considering the novelty of guerrilla workfare in China, the article demonstrates the bifurcation of migrants’ social networks along the lines of work and everyday association, locates the politics of worker-state interaction at the place of their everyday living, and explores their understanding of work that is remarkably devoid of nostalgia for state socialism.
Managerial Trust-Building Through the Use of Legitimating Formal and Informal Control Mechanisms
Authors: Sitkin Sim B. , George Elizabeth
Published: August 2005

This article examines formal and informal decision criteria used by organizational decision-makers when making potentially controversial, legitimacy-relating decisions that could damage trust. Two experimental studies found consistent patterns of persistent use of formal controls and reduced use of informal controls under higher levels of perceived threat to trust. Institutional theory is consistent with the proposition that increased use of legitimated control uniformly enhances trust. In contrast, this article posits and finds support for an attenuated legalistic institutional proposition that increased use of even legitimated control can predictably foster, or undermine, trust - but such predictions can be made only if we systematically distinguish formal and informal control. Results suggest institutional pressures manifest at the individual level provide a complementary focus to macro-organizational institutionalization.
The Evolution of Intra-Organizational Trust Networks
Authors: van de Bunt Gerhard G. , Wittek Rafael P.M. , de Klepper Maurits C.
Published: August 2005

Based on the distinction between expressive and instrumental motives, six theoretical mechanisms for the formation of trust relationships are elaborated and empirically tested. When expressive motives drive tie formation, individuals primarily attach emotional value to social relationships. Three mechanisms have been tested: the homophily, the balancing, and the gossiping effect. When instrumental, control-related, motives drive tie formation, actors strategically establish relationships because of their potential use for the realization of material benefits or the avoidance of material losses. Again, three mechanisms have been tested: the signalling, the sharing group and the structural hole effect. Longitudinal data come from a sociometric panel study of 17 members of the management team of a German paper factory. Actor-oriented statistical modelling shows that all effects significantly affect trust formation separately. In a simultaneous test incorporating all six mechanisms, the pattern of structural holes turns out to be the major predictor of network evolution. The implications of structural hole theory for modelling the evolution of intra-organizational networks are discussed. keywords: balance, control, gossip, homophily, relational signalling, sharing groups, structural holes
Are Preferences for Equality a Matter of Perspective?
Authors: Schwappach David L.B.
Published: August 2005

Background . Many subjects attach equal value to different health care programs in surveys eliciting preferences for resource allocation. It has been suggested that subjects may be prepared to attach different priority if they were asked to evaluate someone else’s decision instead of adopting the role of a social decision maker. This study investigated whether the perspective individuals are asked to adopt affects their priority setting decisions and the likelihood of assigning equal value to health care programs. Methods . 1253 members of an Internet panel were presented a set of clinical vignettes describing preventive health care initiatives and were asked to prioritize among these. They choose between “discrimination,” that is, allocating all resources on the better program, and “equality,” that is, dividing the resources equally between programs while reducing efficiency. Respondents were randomized to either of 4 survey versions that differed in terms of perspective (evaluator vs. decision maker) and expert status (expert vs. layperson) of the role to be adopted. Results . Subjects in the evaluator perspectives were more likely to choose equality over discrimination between patients as compared to those in the social decision-maker perspectives, regardless of expert status (odds ratios 2.09 and 2.03, P < 0.0001). Excess rates of equality choices in the evaluator frames resulted from passive acceptance of equality decisions and active revision of prioritization decisions. Conclusion . Preferences for an equal allocation of resources are strongly affected by decision-making perspective but stable across expert status of the adopted role.
Systematic Review of Economic Evaluations of Smoking Cessation: Standardizing the Cost-Effectiveness
Authors: Ronckers E. T. , Groot W. , Ament A.J.H.A.
Published: August 2005

Objectives . This study was performed to render cost-effectiveness studies on smoking cessation therapies, utilized until now, more comparable and more useful for medical decision making. Methods . The cost-effectiveness ratios reported by the studies were recalculated using a societal perspective and guidelines for economic evaluation. Results . The costs of individual interventions generally increased as a result of the standardization procedure, whereas the effect size decreased. This resulted in increases in the cost-effectiveness ratios for individual studies ranging from 120% to 5600%. Conclusions . The variation between studies in the percentage increase in cost-effectiveness ratios is huge. This means that not following guidelines when calculating cost-effectiveness ratios can result in large errors. Despite the fact that the standardized cost-effectiveness ratios of smoking interventions were higher than the unstandardized cost-effectiveness ratios, interventions aimed at reducing the prevalence of smoking are cost-effective.
Perioperative Management of Patients on Oral Anticoagulants: A Decision Analysis
Authors: Dunn Andrew S. , Wisnivesky Juan , Ho Warren , Moore Carlton , McGinn Thomas , Sacks Henry S.
Published: August 2005

Background . To better inform clinicians on the optimal management of patients on oral anticoagulation who need to undergo surgery or invasive procedures, the authors performed a decision analysis examining whether a perioperative aggressive or minimalist strategy results in greater quality-adjusted survival. Methods . A decision analysis model was created comparing withholding warfarin (minimalist strategy) to withholding warfarin and administering treatment-dose subcutaneous low-molecular-weight heparin (LMWH) or intravenous heparin perioperatively (aggressive strategy). The base-case analysis examined a hypothetical 60-year-old hypertensive individual with mechanical aortic valve replacement undergoing major abdominal surgery. A probabilistic sensitivity analysis was performed using a Monte Carlo simulation with quality-adjusted life expectancy (QALE) as the outcome. Secondary analyses examined patients with a mechanical mitral valve and atrial fibrillation. Sensitivity analyses were performed for each variable. Results . Under the base-case scenario, the minimalist strategy was preferred for 78% of trials in the Monte Carlo simulation, with a mean benefit of 0.003 years (95% confidence interval, -0.005 years to 0.011 years). Sensitivity analyses based on point estimates indicate that the aggressive strategy is preferred when the annual stroke rate is >5.6% or the increase in postoperative major bleeding induced by heparin is <2.0%; however, the benefit is small over the range of plausible values. Conclusions . For most patients with a mechanical aortic valve or atrial fibrillation undergoing major surgery, a minimalist strategy of simply withholding oral anticoagulation provides similar QALE as an aggressive strategy of administering perioperative subcutaneous LMWH or intravenous heparin. The aggressive therapy provides greater QALE for patients at higher risk of stroke (e.g., mechanical mitral valves), although the benefit is small.
Pain experiences and non-pharmacological strategies for pain management after tonsillectomy: a qualitative interview study of children and parents
Authors: Idvall Ewa , Holm Charlotta , Runeson Ingrid
Published: August 2005

Tonsillectomy is one of the most common paediatric surgical procedures. This study aimed to investigate children’s experience of pain and the nonpharmacological strategies that they used to manage pain after tonsillectomy. A further aim was to investigate parental views on these same phenomena. Six children (aged seven to 18 years) and their parents (four mothers and two fathers) were interviewed separately on the day after tonsillectomy. The data were analysed using a qualitative approach. Pain experiences were divided into the categories of physiological pain and psychological pain. Children rated their ‘worst pain’ during the past 24 hours between 6 and 10 (visual analogue scale, 0-10). The non-pharmacological strategies used most frequently to manage pain were thermal regulation (physical method) and distraction (cognitive-behavioural method) according to the framework used. Specific non-pharmacological strategies for pain management relative to different surgical procedures need to be considered.
Queer Genealogies
Authors: Hicks Stephen
Published: August 2005

This article analyses claims about ‘family’ status made within narratives by and about lesbian and gay foster carers and adopters. The author asks how such claims work in order to challenge the view that lesbian and gay families are inherently conservative or radical. Instead this article analyses the uses to which conformity or rebellion claims are put, demonstrating that they are attempts to challenge homo-phobic practices, to assert the legitimacy of gay parenting, or to ask questions about standard kinship models. For social work, there is a need to recognize and work with these queer genealogies, and to develop reflexivity about the ways that ‘sexuality’ is theorized in and through practice.
Polypropylene Materials for Biaxially Oriented Film
Authors: Kimy Sehyun
Published: August 2005

Some relationships among polymer characteristics, processability, and properties of biaxially oriented film have been obtained in this study. For a balance between processability on a tenter frame and the film properties, an optimum level of xylene soluble fractions is preferred. Based on these results, a polypropylene material having a higher crystallinity and good processability has been developed. In addition, a beta-crystalline polypropylene that can be converted to microporous opaque film is reported.
Health system outcomes and determinants amenable to public health in industrialized countries: a pooled, cross-sectional time series analysis
Authors: Arah Onyebuchi A , Westert Gert P , Delnoij Diana M , Klazinga Niek S
Published: August 2005

Background

Few studies have tried to assess the combined cross-sectional and temporal contributions of a more comprehensive set of amenable factors to population health outcomes for wealthy countries during the last 30 years of the 20thcentury. We assessed the overall ecological associations between mortality and factors amenable to public health. These amenable factors included addictive and nutritional lifestyle, air quality, public health spending, healthcare coverage, and immunizations.

Methods

We used a pooled cross-sectional, time series analysis with corrected fixed effects regression models in an ecological design involving eighteen member countries of the Organisation for Economic Cooperation and Development during the period 1970 to 1999.

Results

Alcohol, tobacco, and fat consumption, and sometimes, air pollution were significantly associated with higher all-cause mortality and premature death. Immunizations, health care coverage, fruit/vegetable and protein consumption, and collective health expenditure had negative effects on mortality and premature death, even after controlling for the elderly, density of practicing physicians, doctor visits and per capita GDP. However, tobacco, air pollution, and fruit/vegetable intake were sometimes sensitive to adjustments.

Conclusion

Mortality and premature deaths could be improved by focusing on factors that are amenable to public health policies. Tackling these issues should be reflected in the ongoing assessments of health system performance.
Runx-dependent expression of PKC is critical for cell survival in the sea urchin embryo
Authors: Dickey-Sims Carrie , Robertson Anthony J , Rupp Dawn E , McCarthy John J , Coffman James A
Published: August 2005

Background

Runx transcription factors play critical roles in the developmental control of cell fate and contribute variously as oncoproteins and tumor suppressors to leukemia and other cancers. To discover fundamental Runx functions in the cell biology of animal development, we have employed morpholino antisense-mediated knockdown of the sea urchin Runx protein SpRunt-1. Previously we showed that embryos depleted of SpRunt-1 arrest development at early gastrula stage and underexpress the conventional protein kinase C SpPKC1.

Results

We report here that SpRunt-1 deficiency leads to ectopic cell proliferation and extensive apoptosis. Suppression of the apoptosis by pharmacological inhibition of caspase-3 prevents the ectopic proliferation and rescues gastrulation, indicating that many of the overt defects obtained by knockdown of SpRunt-1 are secondary to the apoptosis. Inhibition or knockdown of SpPKC1 also causes apoptosis, while cell survival is rescued in SpRunt-1 morphant embryos coinjected with SpPKC1 mRNA, suggesting that the apoptosis associated with SpRunt-1 deficiency is caused by the deficit in SpPKC1 expression. Chromatin immunoprecipitation indicates that SpRunt-1 interacts physically with SpPKC1 in vivo, and cis-regulatory analysis shows that this interaction activates SpPKC1 transcription.

Conclusions

Our results show that Runx-dependent activation of SpPKC1 is essential for maintaining protein kinase C activity at levels conducive to cell survival during embryogenesis.
Effect of gait speed on gait rhythmicity in Parkinson's disease: variability of stride time and swing time respond differently
Authors: Frenkel-Toledo Silvi , Giladi Nir , Peretz Chava , Herman Talia , Gruendlinger Leor , Hausdorff Jeffrey M
Published: August 2005

Background

The ability to maintain a steady gait rhythm is impaired in patients with Parkinson's disease (PD). This aspect of locomotor dyscontrol, which likely reflects impaired automaticity in PD, can be quantified by measuring the stride-to-stride variability of gait timing. Previous work has shown an increase in both the variability of the stride time and swing time in PD, but the origins of these changes are not fully understood. Patients with PD also generally walk with a reduced gait speed, a potential confounder of the observed changes in variability. The purpose of the present study was to examine the relationship between walking speed and gait variability.

Methods

Stride time variability and swing time variability were measured in 36 patients with PD (Hoehn and Yahr stage 2–2.5) and 30 healthy controls who walked on a treadmill at four different speeds: 1) Comfortable walking speed (CWS), 2) 80% of CWS 3) 90% of CWS, and 4) 110% of CWS. In addition, we studied the effects of walking slowly on level ground, both with and without a walker.

Results

Consistent with previous findings, increased variability of stride time and swing time was observed in the patients with PD in CWS, compared to controls. In both groups, there was a small but significant association between treadmill gait speed and stride time variability such that higher speeds were associated with lower (better) values of stride time variability (p = 0.0002). In contrast, swing time variability did not change in response to changes in gait speed. Similar results were observed with walking on level ground.

Conclusion

The present results demonstrate that swing time variability is independent of gait speed, at least over the range studied, and therefore, that it may be used as a speed-independent marker of rhythmicity and gait steadiness. Since walking speed did not affect stride time variability and swing time variability in the same way, it appears that these two aspects of gait rhythmicity are not entirely controlled by the same mechanisms. The present findings also suggest that the increased gait variability in PD is disease-related, and not simply a consequence of bradykinesia.
Evidence for a second class of S-adenosylmethionine riboswitches and other regulatory RNA motifs in alpha-proteobacteria
Authors: Corbino Keith A , Barrick Jeffrey E , Lim Jinsoo , Welz Rüdiger , Tucker Brian J , Puskarz Izabela , Mandal Maumita , Rudnick Noam D , Breaker Ronald R
Published: August 2005

Background

Riboswitches are RNA elements in the 5' untranslated leaders of bacterial mRNAs that directly sense the levels of specific metabolites with a structurally conserved aptamer domain to regulate expression of downstream genes. Riboswitches are most common in the genomes of low GC Gram-positive bacteria (for example, Bacillus subtilis contains examples of all known riboswitches), and some riboswitch classes seem to be restricted to this group.

Results

We used comparative sequence analysis and structural probing to identify five RNA elements (serC, speF, suhB, ybhL, and metA) that reside in the intergenic regions of Agrobacterium tumefaciens and many other α-proteobacteria. One of these, the metA motif, is found upstream of methionine biosynthesis genes and binds S-adenosylmethionine (SAM). This natural aptamer most likely functions as a SAM riboswitch (SAM-II) with a consensus sequence and structure that is distinct from the class of SAM riboswitches (SAM-I) predominantly found in Gram-positive bacteria. The minimal functional SAM-II aptamer consists of fewer than 70 nucleotides, which form a single stem and a pseudoknot. Despite its simple architecture and lower affinity for SAM, the SAM-II aptamer strongly discriminates against related compounds.

Conclusion

SAM-II is the only metabolite-binding riboswitch class identified so far that is not found in Gram-positive bacteria, and its existence demonstrates that biological systems can use multiple RNA structures to sense a single chemical compound. The two SAM riboswitches might be 'RNA World' relics that were selectively retained in certain bacterial lineages or new motifs that have emerged since the divergence of the major bacterial groups.
Genome-wide promoter extraction and analysis in human, mouse, and rat
Authors: Xuan Zhenyu , Zhao Fang , Wang Jinhua , Chen Gengxin , Zhang Michael Q
Published: August 2005

Large-scale and high-throughput genomics research needs reliable and comprehensive genome-wide promoter annotation resources. We have conducted a systematic investigation on how to improve mammalian promoter prediction by incorporating both transcript and conservation information. This enabled us to build a better multispecies promoter annotation pipeline and hence to create CSHLmpd (Cold Spring Harbor Laboratory Mammalian Promoter Database) for the biomedical research community, which can act as a starting reference system for more refined functional annotations.
Matrix-Isolation Spectroscopy Using Solid Parahydrogen as the Matrix: Application to High-Resolution Spectroscopy, Photochemistry, and Cryochemistry
Authors: Momose Takamasa , Shida Tadamasa
Published: August 2005

Solid parahydrogen is an excellent matrix for matrix-isolation spectroscopy. First, spectroscopic resolution exceeds the resolution attainable in conventional matrices so that detailed analysis of rotational structure of molecules in the solid phase may be performed in favorable cases. Secondly, in situ photolysis is feasible on account of the subduction of the cage effect in solid parahydrogen, which is in sharp contrast to the system in rare gas matrices. In this Account we describe 1) relevant properties of solid parahydrogen in connection with its use as the matrix, 2) outlines of experimental procedures using solid parahydrogen as the matrix, 3) examples of high-resolution spectroscopic studies, and 4) examples of studies on photochemistry and cryochemistry.
Structure and Magnetic Properties of a Chain Complex with Alternating Ru(II,III) Dimer and Nitroxide Radical Arrangement [Ru2(O2CCMe3)4(nitph)]n(BF4)n, nitph = 2-Phenyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-N-Oxide
Authors: Handa Makoto , Sayama Yasuyoshi , Mikuriya Masahiro , Nukada Ryoji , Hiromitsu Ichiro , Kasuga Kuninobu
Published: August 2005

A chain complex of diruthenium(II,III) cation dimer linked by a nitroxide radical, [Ru2(O2CCMe3)4(nitph)]n(BF4)n (nitph = 2-phenyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-N-oxide), has been prepared and characterized. The structure with an alternating alignment of Ru(II,III) core and nitph has been confirmed by the X-ray crystal analysis. The magnetic moment decreased steadily with decrease of temperature, against the expectation of ferrimagnetic behavior based on the alternated alignment of S1 = 3/2 (for Ru(II,III) core) and S2 = 1/2 (for nitph). It has been found that the zero-field splitting plays an important role in the magnetic behavior in addition to the interaction between the Ru(II,III) core and nitph.
Spectral Properties of Cytochrome c553 and a Membrane-Bound Cytochrome b from Alcaligenes xylosoxidans GIFU 1051
Authors: Sakurai Nobuhiko , Kumita Hideyuki , Sakurai Takeshi , Masuda Hideki
Published: August 2005

Cytochrome c553 and cytochrome b were isolated from soluble and membrane fractions of Alcaligenes xylosoxidans GIFU 1051, respectively, and their spectroscopic characterizations have been performed. Cytochrome c553 has been shown to be in the low spin state both in the oxidized and reduced forms at room temperature by the absorption and magnetic circular dichroism (MCD) spectra, while the high spin heme has been also observed in the cryogenic electron paramagnetic resonance (EPR) spectra. Exogenous small ligands such as NO and CO bind to cytochrome c553 by expelling the axial His ligand. The membrane-bound cytochrome b has two heme b centers in a protein molecule which are the active centers of NO reductase, the cytochrome bc complex, although the enzyme activity was rather low. The absorption, MCD, and EPR spectra of the membrane-bound cytochrome b showed that two heme b centers are in the different electronic states, the high and low spin states. Cytochrome c553 is the natural electron donor to the membrane-bound NO reductase, although the interprotein electron-transfer could not been studied because of the low enzyme activity of the cytochrome b subunit.
Intercalation of Dendritic Polyamines by α- and γ-Zirconium Phosphates
Authors: Kijima Tsuyoshi , Ohe Kaoru , Sasaki Fumie , Yada Mitsunori , Machida Masato
Published: August 2005

Tridentate polyamines, N(CH2CH2NH2)3 and N(RNH2)3 (R = CH2CH2CONHCH2CH2), react with both α- and γ-zirconium phosphates to give an intercalated phase in which the amine molecules are fully loaded as an interdigitating monolayer with their flatted molecular planes highly titles relative to the inorganic layers. On the other hand, although hexadentate polyamine, N(RN(RNH2)2)3, forms a more expanded intercalate from its dilute solution, the longer chain amine can not be intercalated from its concentrated solution, due to the entanglement of dissolved molecules.
Oxidation Chemistry of 1,3-Dimethylxanthine at Stationary Pyrolytic Graphite Electrode
Authors: Goyal Rajendra N , Singhal Naveen K
Published: August 2005

The electrochemical oxidation of 1,3-dimethylxanthine has been studied in the pH range 2.3—10.3 at a pyrolytic graphite electrode. The conjugate base has been found as the electroactive species oxidized over the entire pH range. The 4e, 4H+ charge transfer step is followed by competitive irreversible chemical reactions. The decomposition of UV-absorbing intermediate generated during the electrooxidation has been found to follow first-order kinetics. The products of the EC reaction have been separated by HPLC and gel-permeation chromatography and characterized by mp, 1H NMR, and mass spectra. The presence of methyl groups at positions 1 and 3 has been found to affect the course of mechanism, because the positive charge developed on nitrogen does not permit ring contraction. A tentative mechanism has also been suggested.
Mass-Spectrometric Study on Ion-Molecule Reactions of CH5+, C2H5+, and C3H5+ with Monosubstituted Benzenes Carrying a Carbonyl Group
Authors: Tsuji Masaharu , Nishimura Yukio
Published: August 2005

The gas-phase ion-molecule reactions of CH5+, C2H5+, and C3H5+ with five monosubstituted benzenes carrying a carbonyl group (PhCOX: X = H, CH3, C2H5, Ph, COPh) have been studied using an ion-trap type of GC/MS at a low CH4 pressure. The major product channels are proton transfer to the O-atom in a substituent, with or without further decomposition due to the elimination of CO, PhH, or (PhH + CO). Small amounts of initial adduct ions and their decomposition products are found in some reactions with C3H5+. The reaction mechanism is discussed, based on product ion distributions and semi-empirical calculations of the energies of intermediates and products.
Formation of Sodalite-Like Zincophosphate Framework from Zn/Al-Layered Double Hydroxide as a Starting Material
Authors: Fuda Kiyoshi , Shindo Osamu , Murakami Kenji , Matsunaga Toshiaki
Published: August 2005

The reaction between Zn/Al-layered double hydroxide (LDH) carbonate and Na2HPO4 in a suspension system was investigated under mild hydrothermal conditions. A sodalite-type sodium zincophosphate which incorporated a small amount of Al atoms was obtained at pH = 10.0, T = 358 K, under atmospheric pressure. The reaction was found to be sensitive to the reaction conditions. The obtained sodalite-like compound was characterized with FT-IR, powder XRD with Rietveld Refinement and thermal analyses. The product has a quite similar structure to that of the pure sodalite-like sodium zincophosphate, but showed an improved thermal stability compared to that of the pure one without Al.
Copper(II)–Lanthanide(III) Complexes of Symmetric Dinucleating Macrocycle with Two Phenolate Bridges
Authors: Manseki Kazuhiro , Kumagai Motoko , Sakamoto Masatomi , Sakiyama Hiroshi , Nishida Yuzo , Matsumoto Akira , Sadaoka Yoshihiko , Ohba Masaaki , Okawa Hisashi
Published: August 2005

The first heteronuclear copper(II)–lanthanide(III) complexes, CuLn(fsal-2,2)(NO3)3(H2O)n (n = 2 for Ln = Nd and n = 1 for Ln = Eu and Gd), of a symmetric macrocyclic dinucleating Schiff base ligand, H2fsal-2,2, which is a condensation product of two molecules of 2,6-diformyl-4-methylphenol and two molecules of ethylenediamine, were synthesized by the reaction of [N,N′-bis(3-formyl-5-methylsalicylidene)ethylenediaminato]copper(II) and ethylenediamine in the presence of lanthanide(III) ion as a template, where fsal-2,2 denotes the dianion formed by the deprotonation of two phenolic hydroxyl groups in H2fsal-2,2. The absorption spectra suggested that substrates possessing N- and O-donor groups, such as amino alcohols, are specifically bound at the Cu–Ln center through nitrogen-coordination to the copper site and through oxygen-coordination to the lanthanide site. The fluorescence intensity of Eu(III) decreased drastically upon forming the Cu–Eu complex. A cryomagnetic susceptibility measurement indicated a ferromagnetic spin-spin interaction between Cu(II) and Gd(III) ions.
Ultrasonic Effects on Electroorganic Processes. Part 9. Current Efficiency and Product Selectivity in the Electroreduction of Alkyl Halides to Alkyl Stannanes at a Reactive Tin Cathode
Authors: Atobe Mahito , Nonaka Tsutomu
Published: August 2005

The ultrasonic effects on the electroreduction of methyl and allyl halides (RX) to the corresponding stannanes (R3SnSnR3 and R4Sn) at a reactive (consumable) tin cathode were examined. The current efficiency and product selectivity for the reduction were found to be greatly affected by ultrasonic irradiation. For instance, the selectivity for (CH3)3SnSn(CH3)3 to (CH3)4Sn from CH3I was significantly increased under irradiation. This fact is rationalized as being due to because the intermediate species [(CH3)3Sn·] formed by the primary one-electron reduction of CH3I are activated for their coupling by mobilization on/from the cathode surface under irradiation. On the other hand, the ultrasonic effects on the reduction of CH3Br and C3H5Br seemed to be slightly different from those in the reduction of CH3I.
The One-Electron Transfer Induced Photocycloreversion of Stilbazolium Cyclodimers
Authors: Nakamura Tomotaka , Takagi Katsuhiko , Sawaki Yasuhiko
Published: August 2005

The irradiation of iodide salts of stereo isomeric stilbazolium cyclodimers in their CT bands (ca. 355 nm) resulted in a one-electron transfer induced photocycloreversion, which led to the formation of stilbazolium ions; the quantum yields (Φ) being highly sensitive to their structures, i.e., the Φ for syn-Head-to-Head (syn-HH) was found to be 0.35, for syn-Head-to-Tail (syn-HT) 0.0026, and for anti-Head-to-Head (anti-HH) 0.00095, respectively. This reaction shows a distinct contrast to photocycloreversion by irradiation at 255 nm, which resulted in a highly efficient, but nonselective, splitting, the Φ’s being in the range of 0.3—0.8. In the photosensitized cycloreversion of methyl sulfate salts of dimers using 9,10-dimethoxyanthracene (DMA) as a sensitizer, the quantum efficiencies show a structural dependence similar to the above case of irradiation at their CT bands. Cosensitization with DMA and 1-cyanonaphthalene as an electron mediator resulted in relative quantum yields showing a close coincidence to the yields in the irradiation of the CT band, i.e., 254 : 2.6 : 1 for syn-HH, syn-HT, and anti-HH, respectively. This implies that the one-electron transfer mechanism can be initiated both by CT band irradiation as well as DMA sensitization. It can be concluded that the structural dependence of the quantum efficiencies is attributed to the through-bond interaction of two pyridinium rings, which facilitates the splitting of the C–C bond in the cyclobutane ring.
Mechanistic Studies on Cyclopalladation of the Solvated Palladium(II) Complexes with N-Benzyl Triamine Ligands in Various Solvents. Crystal Structures of [Pd(Sol)(Bn2Medptn)](BF4)2 (Sol = Acetonitrile and N,N-Dimethylformamide; Bn2Medptn = N,N′-Dibenzyl-4-methyl-4-azaheptane-1,7-diamine) and [Pd(H−1Bn2Medptn-C,N,N′,N″)]CF3SO3
Authors: Yagyu Takeyoshi , Aizawa Sen-ichi , Funahashi Shigenobu
Published: August 2005

Several solvated palladium(II) complexes with the potentially cyclopalladating dibenzyl ligand have been synthesized. These include [Pd(CH3CN)(Bn2Medptn)](BF4)2 (1) (Bn2Medptn = N, N′-dibenzyl-4-methyl-4-azaheptane-1,7-diamine), [Pd(dmf)(Bn2Medptn)](BF4)2 (2) (dmf = N,N-dimethylformamide), and [Pd(dmso)(Bn2Medptn)](BF4)2 (3) (dmso = dimethyl sulfoxide), their cyclopalladated complex, [Pd(H−1Bn2Medptn-C,N,N′,N″)]CF3SO3 (4), the solvated monobenzyl complex, [Pd(CH3CN)(BnMedptn)](BF4)2 (5) (BnMedptn = N-(3-aminopropyl)-N′-benzyl-N-methyl-1,3-propanediamine), and its deuterated complex, [Pd(CH3CN)(BnMedptn-d7)](BF4)2 (6) (BnMedptn-d7 = N-(3-aminopropyl)-N′-heptadeuteriobenzyl-N-methyl-1,3-propanediamine). The crystal structures of 1·CH3CN·CH2Cl2, 2, and 4 have been determined by X-ray structure analysis to characterize the reactant and the product for the cyclopalladation of the solvated complexes, where one of the ortho carbons of 1 is directed toward the palladium(II) center (Pd···C(1) = 3.513(9) Å). The rate constants for the cyclopalladation of 1 at 25 °C in various solvents increase in the order DMF < DMSO << pyridine, but the reaction does not proceed in acetonitrile or nitromethane. The activation parameters for the cyclopalladation in neat solvent have been obtained as follows: k298 = 5.74 × 10−6 s−1, ΔH‡ = 104.0 ± 1.2 kJ mol−1 and ΔS‡ = 3.5 ± 3.9 J K−1 mol−1 for 1 in DMF, k298 = 3.13 × 10−4 s−1, ΔH‡ = 83.8 ± 2.6 kJ mol−1 and ΔS‡ = −31.0 ± 8.8 J K−1 mol−1 for 1 in DMSO, k298 = 1.30 × 10−4 s−1, ΔH‡ = 81.2 ± 0.5 kJ mol−1 and ΔS‡ = −47.0 ± 1.8 J K−1 mol−1 for 5 in DMF, k298 = 1.76 × 10−3 s−1 for 5 in DMSO, k298 = 1.26 × 10−5s−1, ΔH‡ = 92.8 ± 1.4 kJ mol−1 and ΔS‡ = −27.5 ± 4.4 J K−1 mol−1 for 6 in DMF and k298 = 2.69 × 10−4 s−1 for 6 in DMSO. The activation enthalpy is reduced as the solvent basicity increases. The kinetic isotope effects (kH/kD) for the cyclopalladation of the monobenzyl complex at 25 °C are calculated to be 10.3 in DMF and 6.5 in DMSO using the rate constants for 5 and 6. It is confirmed from the kinetic results obtained that the nucleophilic attack of the basic solvent on the ortho proton is essential for the C–H bond cleavage observed in the activation process. In addition, the fact that the rate constant for the cyclopalladation is proportionally dependent on the concentration of DMSO in nitromethane strongly suggests that the solvent-dissociation pre-equilibrium is negligible in neat basic solvent.
Solvatochromic Linear Solvation Energy Relationships for Solubility of O2 in Various Solvents
Authors: Che Yong , Tokuda Koichi , Ohsaka Takeo
Published: August 2005

Linear solvation energy relationships for solution of O2 in 27 solvents have been examined. Multiple linear regression equations for mole fraction solubility of O2 are developed based on Hildebrand’s solubility parameter as well as the π*, α, and β solvatochromic parameters describing the solvent polarizability/dipolarity, hydrogen bond acidity and hydrogen bond basicity, respectively. Use of the combination of these parameters enables the medium effect on solution of O2 to be correlated and interpreted in a conceptually simple manner.
Preparation, Stereochemistry, and Reactivity of Linear-Type S-Bridged MCrIIIM (M = RhIII, IrIII) Trinuclear Complexes with 2-Aminoethanethiolate (aet). Crystal Structures of ΔΛ-[Cr{M(aet)3}2]3+
Authors: Miyashita Yoshitaro , Sakagami Narumi , Yamada Yasunori , Konno Takumi , Hidaka Jinsai , Okamoto Ken-ichi
Published: August 2005

S-Bridged trinuclear complexes, [CrIII{M(aet)3}2]3+, (M = RhIII (1), IrIII (2); aet = NH2CH2CH2S−) were newly prepared by the reaction of fac(S)-[M(aet)3] with chromium(III) nitrate. They were separated and optically resolved into the ΔΔ, ΛΛ, and ΔΛ isomers. Of these isomers for 1 and 2, the crystal structures of the ΔΛ isomers (1a and 2a) were determined by an X-ray diffraction method. Each of 1a and 2a consists of two fac(S)-[M(aet)3] subunits, a central Cr atom, three nitrates, and three water molecules, [Cr{M(aet)3}2](NO3)3·3H2O, in which three metals are aligned so as to be exactly linear. The central Cr atom is situated in an octahedral environment with the CrIIIS6 chromophore, which is formed by the coordination of two terminal fac(S)-[M(aet)3] units. The other isomers for 1 and 2 were characterized by the absorption and CD spectra, the molar conductivity, and the magnetic susceptibility. Each cyclic voltammogram of ΔΛ-[Cr{M(aet)3}2]3+ in water showed a reversible redox couple (M(IV)/M(III)) and an irreversible reduction wave (Cr(III)/Cr(II)). The stabilities of the S-bridged MCrIIIM complexes are also discussed in relation to the Cr–S bond strengths.
Photodimerizations of 1,5- and 1,7-Azulenequinones: Solvent, Substituent, and Concentration Effects on the Product Distribution
Authors: Kawakami Hiroko , Yan Yong Zhe , Kato Nobuo , Mori Akira , Takeshita Hitoshi , Nozoe the late Tetsuo
Published: August 2005

Azulenequinones gave dimers when they were irradiated with a high-pressure mercury lamp. In polar solvents, head-to-head dimers were predominant, whereas head-to-tail dimers increased in less polar solvents. From 3-methoxy-1,5-azulenequinone, four products were obtained, while bromoazulenequinones and 1,5-azulenequinone gave a single dimer. The product distribution was dependent on the polarity of solvents, substituents, and concentrations.
The Reaction of Phthalic Anhydride with Diethylenetriamine and Triethylenetetramine. A Literature Correction
Authors: Onopchenko Anatoli , Harrison James J , Chan Carrie Y
Published: August 2005

A report that phthalic anhydride reacts with diethylenetriamine in acetic acid to form hydrogen phthalate salt of bis(2-phthalimidoethyl)amine predominantly was reinvestigated. The major product that we obtained was bis(2-phthalimidoethyl)amine, some amide, and very little of the salt. With linear triethylenetetramine, we did not obtain N,N′-bis(2-phthalimidoethyl)ethylenediamine, nor the rearranged tris(2-phthalimidoethyl)amine or 1,4-bis(2-phthalimidoethyl)piperazine reported. A novel amide — 2-{N-2-phthalimidoethyl-N-[2-(2-phthalimidoethyl)aminoethyl]carbamoyl}benzoic acid — was formed as the major product instead. The products reported in the literature are attributed to branched and cyclic amines in their triethylenetetramine, and not to rearrangement reactions. Such possibility is supported by analysis of triethylenetetramine from the same supplier (ca. 65% linear), and our failure to duplicate the results with an authentic triethylenetetramine. Several reported compounds were prepared from pure amines, with no evidence of isomerization.
Direct Carbonylation of Benzyl Alcohol and Its Analogs Catalyzed by Palladium and HI in Aqueous Systems and Mechanistic Studies
Authors: Lin Yong-Shou , Yamamoto Akio
Published: August 2005

Carbonylation of benzyl alcohol, benzyl formate, dibenzyl ether, and benzyl phenylacetate catalyzed by palladium complexes and promoted by hydrogen iodide gives phenylacetic acid in moderate to excellent yields in aqueous systems. Application of the carbonylation process to other arylmethanol analogs provides convenient means to prepare 2-naphthaleneacetic acid, 3-isochromanone, 1,4-benzenediacetic acid, and o-hydroxybenzeneacetic acid. A mechanism for the catalytic reaction is proposed, which involves (1) formation of benzyl iodide by the reaction of benzyl alcohol with HI in situ, (2) oxidative addition of benzyl iodide to palladium(0) to form a benzylpalladium iodide species, (3) CO insertion into the Pd-benzyl bond to form a (phenylacetyl)palladium iodide species, (4) reductive elimination of phenylacetyl iodide, and (5) its hydrolysis into phenylacetic acid. Evidence supporting the mechanism was obtained by examining the properties of benzyl- and (phenylacetyl)palladium iodide and chloride complexes. Formation of benzyl(carbonyl)palladium species and migratory insertion of the benzyl group to CO was confirmed by means of NMR at low temperature under high pressure.
Optical Resolution by Preferential Crystallization of (RS)-Bromosuccinic Acid
Authors: Shiraiwa Tadashi , Ohkubo Masanori , Miyazaki Hideya , Kubo Motoki , Nishigawa Hiroki , Tsujimoto Toshihiro , Kurokawa Hidemoto
Published: August 2005

The racemic structure of (RS)-bromosuccinic acid [(RS)-BSA] was examined based on the melting-point, solubility, infrared spectrum, and binary and ternary phase diagrams. The results indicated that (RS)-BSA exists as a conglomerate at room temperature, although it forms a racemic compound at the melting point. The optical resolution by preferential crystallization of (RS)-BSA yielded (R)- and (S)-BSA with optical purities of 81—93%. In addition, (RS)-BSA was optically resolved using (1S,2S)-2-amino-1-phenyl-1,3-propanediol as a resolving agent, to yield (R)- and (S)-BSA with optical purities of 99 and 83%, respectively. The obtained (R)- and (S)-BSA were recrystallized from water to obtain optically pure BSA enantiomers.
Theoretical Studies of Multiple Metal–Metal Bonds between Divalent Molybdenum Ions in Dimers, Tetramers, and Clusters
Authors: Nishino Masamichi , Yoshioka Yasunori , Yamaguchi Kizashi , Mashima Kazushi , Tani Kazuhide , Nakamura Akira
Published: August 2005

The multiple metal–metal bonds between divalent molybdenum (Mo(II)) ions in dimers and tetramers were investigated theoretically. The orbital energy gaps, occupation numbers of natural orbitals (NO) and effective bond orders for the naked Mo(II)2 dimer (1) were calculated by ab initio UHF MO and density functional (DFT) methods. The effective exchange integrals (Jab) of 1 were calculated by approximately spin-projected UHF and DFT methods, and the complete active space (CAS) CI by the use of UHF NO. The calculated Jab values were discussed in relation to the temperature-dependent paramagnetism observed for the edge-sharing and face-sharing bioctahedral molybdenum complexes. The CAS CI calculations showed that the Heisenberg model is not appropriate for 1 under the condition that the Mo–Mo distance is shorter than 2.5 Å. The UHF and DFT MO calculations were also performed for the linear naked Mo(II)4 tetramer (2) to elucidate possible electronic structures of the d–d conjugated systems. The continuous changes from closed-shell (diamagnetic) electronic structures to antiferromagnetic states were investigated by elongating the Mo–Mo distances. Similarities and differences between Mo(II)2 (1) and naked Cr(II)2 (3) or between Mo(II)4 (2) and Cr(II)4 (4) were examined and compared, since the nature of direct exchange couplings between divalent chromium ions in 3 and 4 was already studied extensively in relation to the electron correlation effect. The metal-insulator transitions induced by elongation of the Mo(II)–Mo(II) distance in Mo(II) clusters were discussed from the viewpoint of electron correlation and size effects in mesoscopic systems.
Direct Electrochemistry of Horseradish Peroxidase Immobilized on the Surface of Au Ring/AET/Au Electrode
Authors: Jiang Li-Ping , Cai Sheng , Liu Bo , Xu Jin-Zhong , Zhang Jian-Rong , Zhu Jun-Jie
Published: August 2005

In this letter, single crystal gold nanorings were assembled on the surface of Au electrode with a self-assembly monolayer (SAM) of 2-aminoethanethiol hydrochloride (AET). The direct electrochemistry of horseradish peroxidase immobilized on the surface was explored using electrochemical methods.
Methods for Preparing Standard Nitrate Radical (NO3) Gas to Calibrate the LIF-based Instrument for Measurements in the Atmosphere
Authors: Matsumoto Jun , Imai Hidekazu , Kosugi Naohiro , Kajii Yoshizumi
Published: August 2005

Preparation of standard NO3 gas is explored at the level of ppbv for atmospheric measurements utilizing an LIF instrument. The sequence of thermal decomposition of N2O5 and gas phase titration of NO3 by adding NO is useful. To reduce NO2 contamination in N2O5, N2O5 trapping after mixing NOx and O3 was adopted. As a convenient method in the field studies, dynamic mixing of NOx and O3 was explored.
Facile Sythesis of Dioscin and Its Analogues
Authors: Hou Shujie , Zou Chuanchun , Zhou Liang , Lei Pingsheng , Yu Dequan
Published: August 2005

Three representative spirostanol saponins that have typical structure of the sugar moiety, diosgenyl 2,3-di-O-α-l-rhamnopyranosyl-β-d-glucopyranoside, diosgenyl 2,4-di-O-α-l-rhamnopyranosyl-β-d-glucopyranoside (dioscin), and diosgenyl 2,6-di-O-α-l-rhamnopyranosyl-β-d-glucopyranoside, were synthesized in a facile way. An approach to selectively mask the C3-hydroxyl of diosgenyl 4,6-O-benzylidene β-d-glucopyranoside was described. A procedure using cerium(IV) ammonium nitrate for selective removal of tert-butyldimethylsilyl group while retaining levulinyl group is afforded.
Soft Template Synthesis of Highly Crystalline Microscale Nanotubules of PbO
Authors: Zhou Qin , Liu Xiaoying , Liu Ling , Li Yanguang , Jiang Zhiyu , Zhao Dongyuan
Published: August 2005

Highly crystalline microscale nanotubules of PbO with diameters in the range of 90–600 nm and lengths up to 15 μm have been synthesized by using triblock copolymer P123 as the template via a practical electrodeposition process.
Social and Psychiatric Influences on Urban–Rural Differentials in Australian Suicide
Authors: Taylor Richard , Page Andrew , Morrell Stephen , Harrison James , Carter Greg
Published: August 2005

The purpose of this study was to investigate urban–rural differentials in Australian suicide rates, and to examine influences that previously have remained largely speculative. Suicide rates for males (all ages and young adults) were significantly higher in rural areas compared to urban areas. Urban–rural suicide rate differences in males were rendered nonsignificant after adjustment for migrant and area socioeconomic status. Adjusting for mental disorder prevalence, in addition to migrant status, reduced the excess suicide risk in rural areas; the excess was reduced further with addition of mental health service utilization. The implications of this study are that socioeconomic circumstances in rural populations contribute to higher male suicide rates compared to urban areas, but these conditions may be partly mediated by mental disorder prevalence and mental health service utilization.