bluuebunny/crossref_metadata_2025 huggingface dataset:
Intramolecular Charge Transfer in Pyrromethene Laser Dyes: Photophysical Behaviour of PM650
Authors: López Arbeloa F. , Bañuelos Prieto J. , Martínez Martínez V. , Arbeloa López T. , López Arbeloa I.
Published: November 2004

Absorption and fluorescence (steady‐state and time‐correlated) techniques are used to study the photophysical characteristics of the pyrromethene 650 (PM650) dye. The presence of the cyano group at the 8 position considerably shifts the absorption and fluorescence bands to lower energies with respect to other related pyrromethene dyes; this is attributed to the strong electron‐acceptor character of the cyano group, as is theoretically confirmed by quantum mechanical methods. The fluorescence properties of PM650 are intensively solvent‐dependent. The fluorescence band is shifted to lower energies in polar/protic solutions, and the evolution of the corresponding wavelength with the solvent is analysed by a multicomponent linear regression. The fluorescence quantum yield and the lifetime strongly decrease in polar/protic solvents, which can be ascribed to an extra nonradiative deactivation, via an intramolecular charge‐transfer state (ICT state), favoured in polar media.
Torsional Barriers in Aromatic Molecular Clusters as Probe of the Electronic Properties of the Chromophore
Authors: Jacoby Christoph , Schmitt Michael
Published: November 2004

We present a computer program that is capable of fitting n‐fold torsional barriers Vn (n=2–6) and torsional constants F simultaneously to high‐ and low‐resolution spectroscopic data of different isotopomeric internal rotors. The program has been utilized to fit independently barriers and torsional constants for both electronic states of several aromatic clusters. The constant F of the ammonia moiety in the phenol–ammonia cluster is shown to decrease upon electronic excitation, thus imaging the formation of a hydrogen‐bonded complex between the phenoxy radical and the NH4 radical in the excited state. In contrast, for the naphthol–ammonia 1:1 clusters no change of F of ammonia could be found. For phenol–methanol cluster we found a decrease of F upon excitation which points to a stronger hydrogen bond between phenol and methanol in the excited state. A strong reduction of the torsional barrier upon excitation points to the formation of a methoxonium radical in a similar photoreaction as in phenol–ammonia cluster. For the phenol–water system we postulate the same mechanism, a photoreaction, which leads to a translocated hydrogen atom in the S1 state what can be deduced from the change of the torsional constant upon electronic excitation.
Infrared Absorption Features of Gaseous Isopropyl Carbocations
Authors: Chiavarino Barbara , Crestoni Maria E. , Fornarini Simonetta , Lemaire Joel , Mac Aleese Luke , Maître Philippe
Published: November 2004

C3H7+ ions were formed in the cell of a Fourier transform ion cyclotron resonance mass spectrometer and assayed by their multiphoton dissociation (MPD) behavior, triggered by the absorption of tunable IR radiation from a free‐electron laser source providing a high fluence. The derived experimental IRMPD spectrum, which reflects the active vibrational modes of the ion, was compared with the IR spectra calculated for the optimized structures of the most‐stable species on the C3H7+ potential energy surface, namely, a chiral iC3H7+ ion of C2 symmetry and an asymmetric corner‐protonated cyclopropane, cC3H7+. The significant features in the IRMPD spectra of both the unlabeled and the perdeuterated ions obtained by ionization and fragmentation of isobutane or 2‐chloro[D7]propane confirm the presence of the isopropyl cation, the ground‐state isomer, whose IR spectroscopic features can thus be comparatively checked in the gas phase and in condensed superacid media. Details of the IRMPD features are suggested to result from the nearly barrierless interconversion of the two C2 enantiomers.
Socratic dialogue in the Swedish political context
Authors: Karlsson Ove
Published: November 2004

Evaluation practice conceived in terms of a Socratic dialogue offers a particular kind of benefit for evaluation in a Swedish political context.
Evaluation research and sociology in Denmark: A tale of two cultures
Authors: Hansson Finn
Published: November 2004

The development of and prospects for Danish evaluation practice are best understood in light of an examination of two cultures of Danish social science.
Evaluation of industrial development in Norway
Authors: Torvatn Hans
Published: November 2004

The author provides a brief history of the role that evaluation has played in Norwegian industrial development efforts and offers a critical commentary on the current state of the art.
Identifying interacting SNPs using Monte Carlo logic regression
Authors: Kooperberg Charles , Ruczinski Ingo
Published: November 2004

Interactions are frequently at the center of interest in single‐nucleotide polymorphism (SNP) association studies. When interacting SNPs are in the same gene or in genes that are close in sequence, such interactions may suggest which haplotypes are associated with a disease. Interactions between unrelated SNPs may suggest genetic pathways. Unfortunately, data sets are often still too small to definitively determine whether interactions between SNPs occur. Also, competing sets of interactions could often be of equal interest. Here we propose Monte Carlo logic regression, an exploratory tool that combines Markov chain Monte Carlo and logic regression, an adaptive regression methodology that attempts to construct predictors as Boolean combinations of binary covariates such as SNPs. The goal of Monte Carlo logic regression is to generate a collection of (interactions of) SNPs that may be associated with a disease outcome, and that warrant further investigation. As such, the models that are fitted in the Markov chain are not combined into a single model, as is often done in Bayesian model averaging procedures. Instead, the most frequently occurring patterns in these models are tabulated. The method is applied to a study of heart disease with 779 participants and 89 SNPs. A simulation study is carried out to investigate the performance of the Monte Carlo logic regression approach. Genet. Epidemiol. 28:157–170, 2005. © 2004 Wiley‐Liss, Inc.
Efficacy and tolerability of venlafaxine in geriatric outpatients with major depression: a double‐blind, randomised 6‐month comparative trial with citalopram
Authors: Allard Per , Gram Lars , Timdahl Kristina , Behnke Kirsten , Hanson Martin , Søgaard Jesper
Published: November 2004

Background

The objectives of the study were to compare efficacy and tolerability of venlafaxine ER 75–150 mg/day with that of citalopram 10–20 mg/day in elderly patients with major depression according to DSM‐IV criteria.

Methods

A randomised, double‐blind, parallel group 6‐month study. Efficacy was assessed by MADRS, CGI Global Improvement, CGI Severity of Illness and GDS‐20 scores and safety by physical examinations, vital signs, adverse events and UKU side effect rating. Plasma levels of venlafaxine, its major metabolite O‐desmethylvenlafaxine and citalopram were followed.

Results

One hundred and fifty‐one male and female patients (64–89 years) were enrolled and 118 patients completed the study. Comparable improvements in MADRS, CGI Severity of Illness, CGI Global Improvement and GDS‐20 were observed during venlafaxine and citalopram treatment. The MADRS remission rate was 19% for venlafaxine and 23% for citalopram. Side effects were common during both treatments but differed in tremor being more common during citalopram and nausea/vomiting during venlafaxine treatment. There were no clinically significant changes in blood pressure or body weight.

Conclusion

The observed benefits of venlafaxine treatment in elderly patients with major depression were similar to those observed in younger adults as were reported adverse events and side effects. Treatment with venlafaxine ER was well tolerated and induced beneficial effects of similar magnitude as those of citalopram. Copyright © 2004 John Wiley & Sons, Ltd.
Neuropsychological performance in early and late onset Alzheimer's disease: comparisons in a memory clinic population
Authors: Suribhatla Srinivas , Baillon Sarah , Dennis Michael , Marudkar Mangesh , Muhammad Saquib , Munro Dena , Spreadbury Christine , Lindesay James
Published: November 2004

Objectives

To compare the neuropsychological performance associated with early and late onset Alzheimer's disease (AD), in order to identify differences and compare these with previous reports.

Methods

Patients attending a memory clinic were given a detailed multi‐disciplinary diagnostic assessment, including a battery of neuropsychological tests. From those meeting ICD‐10 criteria for Alzheimer's disease (AD), an early‐onset (EO) group (n = 40) and a late‐onset (LO) group (n = 90) were identified, and their performances compared. Patients with mixed dementia and co‐morbid depression were excluded.

Results

After adjustment, the EO and LO groups performed at a comparable level on the majority of the neuropsychological tests. The LO group performed better on the WAIS digit span test, AMIPB Complex Design and the written picture description, and the EO group performed better on the WAIS similarities test and the Boston naming test.

Conclusions

These findings suggest that, after adjusting for overall dementia severity and pre‐morbid IQ, there is greater fronto‐parietal/right hemisphere involvement in early‐onset AD, and greater temporal/left hemisphere involvement in late‐onset AD. This may be due to different genetic risk profiles for AD at different ages. Copyright © 2004 John Wiley & Sons, Ltd.
Symptoms of depression and anxiety (MHI) following acute medical/surgical hospitalization and post‐discharge psychiatric diagnoses (DSM) in 839 geriatric US veterans
Authors: Gerson Sylvia , Mistry Ritesh , Bastani Roshan , Blow Fred , Gould Robert , Llorente Maria , Maxwell Annette , Moye Jennifer , Olsen Edwin , Rohrbaugh Robert , Rosansky Joel , Van Stone William , Jarvik Lissy
Published: November 2004

Objective

We addressed the relatively unexplored use of screening scores measuring symptoms of depression and/or anxiety to aid in identifying patients at increased risk for post‐discharge DSM‐IV Axis I diagnoses. We were unable to find such studies in the literature.

Method

Elderly veterans without recent psychiatric diagnoses were screened for depression and anxiety symptoms upon admission to acute medical/surgical units using the Mental Health Inventory (MHI). Following discharge, those who had exceeded cut‐off scores and had been randomized to UPBEAT Care (Unified Psychogeriatric Biopsychosocial Evaluation and Treatment, a clinical demonstration project) were evaluated for DSM diagnoses. We report on 839 patients, mostly male (96.3%; mean age 69.6 ± 6.7 years), comparing three groups, i.e. those meeting screening criteria for symptoms of (i) depression only; (ii) anxiety only; and (iii) both depression and anxiety.

Results

Despite absence of recent psychiatric history, 58.6% of the 839 patients received a DSM diagnosis post‐discharge (21.8% adjustment; 15.4% anxiety; 7.5% mood; and 14.0% other disorders). Patients meeting screening criteria for both depression and anxiety symptoms received a DSM diagnosis more frequently than those meeting criteria for anxiety symptoms only (61.9% vs 49.0%, p = 0.017), but did not differ significantly from those meeting criteria for depressive symptoms only (61.9% vs 56.8%, p = 0.174). Although exceeding the MHI screening cut‐off scores for depression, anxiety, or both helped to identify patients with a post‐discharge DSM diagnosis, the actual MHI screening scores failed to do so.

Conclusion

Screening hospitalized medical/surgical patients for symptoms of depression, anxiety, and particularly for the combination thereof, may help identify those with increased risk of subsequent DSM diagnoses, including adjustment disorder. Copyright © 2004 John Wiley & Sons, Ltd.
Prevalence of major and minor depression in elderly persons with mild cognitive impairment—MADRS factor analysis
Authors: Gabryelewicz T. , Styczynska M. , Pfeffer A. , Wasiak B. , Barczak A. , Luczywek E. , Androsiuk W. , Barcikowska M.
Published: November 2004

Objective

The aim of the study was to detect the prevalence of depressive syndromes and symptoms in the sample of elderly persons with Mild Cognitive Impairment (MCI), and to analyse Montgomery‐Asberg Depression Rating (MADRS) item scores.

Method

The subjects of the study were 102 consecutive out‐patients with MCI. All subjects were assessed by an experienced psychiatrist and MADRS was applied. Major and minor depressive episodes were defined according to DSM‐IV criteria. Factor analysis was used to analyse baseline MADRS item scores.

Results

Three patient groups emerged according to the depressive symptoms distribution and severity scores basis: those with major depression constituted 19.6% (n = 20), with minor depression 26.5% (n = 27), and with very few depressive symptoms 53.9% (n = 55). Three interpretable MADRS factors were identified, using the factor analysis with Varimax rotation: the first consisting of apparent and reported sadness, inability to feel, pessimistic thoughts, the second consisting of inner tension, reduced sleep, reduced appetite, suicidal thoughts, and the third with concentration difficulties and lassitude.

Conclusions

It was concluded that both major and minor depression is common in MCI. Three MADRS factors were identified and labelled as anhedonia‐pessimism, anxiety‐vegetative, and cognitive‐inhibition. Copyright © 2004 John Wiley & Sons, Ltd.
Adaptation of the ACE for a Malayalam speaking population in southern India
Authors: Mathuranath P. S. , Hodges John R. , Mathew Robert , Cherian P. Joseph , George Annamma , Bak Thomas H.
Published: November 2004

Objective

To adapt the Addenbrooke's Cognitive Examination (ACE) as a dementia‐screening tool in a community in south India. To establish that items in the adapted version are equivalent to that in the original.

Methods

The ACE was adapted into the local language, Malayalam (m‐ACE), following cultural/linguistic modifications. To establish equivalence, qualitative comparisons were made (on the distribution of scores, percentage scoring at ceiling, and relative difficulty across items) between a UK sample receiving the ACE (n = 50; mean age = 67.9 ± 7.4; education ≥ 9, mean = 10.9 ± 2.5) and a community‐based educationally‐stratified Indian sample receiving the m‐ACE: ‘India ≥ 9’ (n = 50; mean age = 67.8 ± 5.2; education ≥ 9, mean = 13.9 ± 2.7) and ‘India ≤ 8’ (n = 50; mean age = 67.1 ± 5.3; education ≤ 8, mean = 3.1 ± 2.0).

Results

Most ACE items were retained. The score distribution (mean ± 1SD), percentage at ceiling, and relative difficulties across items is comparable between the UK and the educationally equivalent India ≥ 9 groups. Language, Naming, Attention and Orientation are relatively easy (≥ 80% at ceiling) and Recall and Verbal fluency are relatively difficult (≤ 22% at ceiling). Although the percentage at ceiling were lower for the India ≤ 8 group, the order of relative difficulty was similar and the percentage scoring at floor was ≤ 10% on all except visuospatial item.

Conclusions

The m‐ACE provides a culture‐fair Malayalam adaptation of the ACE with component items of equivalent difficulty. Copyright © 2004 John Wiley & Sons, Ltd.
Flow and heat transfer of natural convection around an upward‐facing horizontal plate with a vertical plate at the edge
Authors: Kimura Fumiyoshi , Ishihara Suguru , Kitamura Kenzo
Published: November 2004

Natural convective flows around an upward‐facing horizontal heated plate with a vertical plate at the edge were investigated experimentally. Of particular concern were the influences of the vertical plate on the fluid flow and the heat transfer of the horizontal plate. The flow and temperature fields adjacent to the horizontal plate were visualized with dye and a liquid‐crystal thermometry. The results show that the vertical plate obstructs the flow from the top of the vertical plate, while the flow from the open edge of the horizontal plate covers the whole horizontal surface when the height of the vertical plate exceed H/W = 0.14 for adiabatic vertical plate and H/W = 0.1 for the heated vertical plate. The local heat‐transfer‐coefficients of the horizontal plate were also measured. It was found that the vertical adiabatic plates deteriorate the heat transfer, while the heated vertical plates enhance the heat transfer from the horizontal plates. © 2004 Wiley Periodicals, Inc. Heat Trans Asian Res, 33(8): 527–539, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/htj.20033
Preterm behavior, maternal adjustment, and competencies in the newborn period: What influence do they have at 12 months postnatal age?
Authors: Veddovi M. , Gibson F. , Kenny D.T. , Bowen J. , Starte D.
Published: November 2004

This article examines whether preterm newborns' behavior and their mother's adjustment to the premature birth and infant hospitalization have an influence on subsequent infant development and behavior, maternal adjustment, and mother–infant relationship. The behavioral competencies of 42 well, singleton preterm infants (mean gestational age=31 weeks) were assessed, as were their mothers' adjustment (depression and coping) and competencies (knowledge of child development). At 12 months of postnatal age, child competencies (development and behavior) were assessed, together with maternal adjustment (parenting stress and depression). Mother–infant interaction also was observed. Regression analyses indicated that in the newborn period, maternal positive reappraisal and a planful coping style, more knowledge of child development, and previous experience with baby‐sitting were associated with better infant development (p=.002), maternal adjustment (p=.012), and mother–child relationship (p=.002) at 12 months. Newborn infant muscle‐tone maturity was predictive of better motor quality at 12 months (p=.011), and being a firstborn infant who was more sleepy and drowsy was associated with subsequent higher maternal parenting stress (p=.007). Social and educational support groups combined with an approach that assists mothers to develop problem‐solving coping styles may have a beneficial influence on infant development.
Impact of fathers' alcoholism and associated risk factors on parent–infant attachment stability from 12 to 18 months
Authors: Edwards Ellen P. , Eiden Rina D. , Leonard Kenneth E.
Published: November 2004

This study examined short‐term attachment stability and sought to identify predictors of stability and change within a sample characterized by fathers' alcoholism. Results suggest moderate stability of attachment classifications (60% for mothers, 53% for fathers) from 12 to 18 months. Higher paternal and maternal alcohol symptoms, maternal depression, and maternal antisocial behavior were found in families with stable insecure mother–infant attachment compared to those who were stable secure. Mother–infant stable insecurity was associated with higher levels of maternal negative affect expression during play. Father–infant stable insecurity was associated with lower levels of paternal positive affect expression and decreased sensitivity during play. Stable insecure children also had higher levels of negative affect during parent–infant interactions and higher negative emotionality during other episodes compared to stable secure children. Results indicate that infants who were insecure at both time points had the highest constellation of family risk characteristics.
Identification, quantification and comparison of major non‐polar lipids in normal and dry eye tear lipidomes by electrospray tandem mass spectrometry
Authors: Ham Bryan M. , Jacob Jean T. , Keese Monica M. , Cole Richard B.
Published: November 2004

Millions of individuals suffer from a health condition known as keratoconjunctivitis sicca (KCS, also known as ‘dry eye’). Studies have indicated that the lipids in the tear film layer, which covers the outer portion of the eye, may be directly correlated with the existence of dry eye syndrome. By identifying and comparing the major, non‐polar lipids in normal eye tears with a dry eye model, it may be possible to identify a symptom of, or a contributing factor to, dry eye. Electrospray tandem mass spectrometry (ES‐MS/MS) was used to identify and compare the non‐polar lipids, detected as lithium adducts, from normal and dry eye tear samples obtained from rabbits. A limited number of normal human tear samples were also examined for lipid content, and a close resemblance to rabbit was observed. Three distinct regions were delineated in the ES mass spectra of the non polar lipids, m/z 20–500, 500–800 and 800–1100. A common feature noted among identified lipid components was a glycerol backbone with fatty acyl substituents attached. Product ion spectra were obtained for lithiated monoacyl‐, 1,2‐ and 1,3‐diacyl‐ and triacylglyceride standards. Newly proposed structures and fragmentation pathways for the major product ions are presented for the 1,2‐ and 1,3‐diglycerides, and also for the monoglyceride. New approaches to distinguishing asymmetric 1,2‐diglycerides and 1,2‐ from 1,3‐diglycerides are proposed. For the rabbit tear samples, the m/z 20–500 range contains monoester diols with empirical formulas CnH2nO4, the m/z 500–800 range includes diesters with empirical formulas CnH2n−2O5 and the m/z 800–1100 range contains triesters with empirical formulas CnH2n−4O6. Also found in the extracts were three isoprene acetals (terpenoids). Copyright © 2004 John Wiley & Sons, Ltd.
Structural elucidation and identification of alkaloids in Rhizoma Coptidis by electrospray ionization tandem mass spectrometry
Authors: Wang Daowu , Liu Zhiqiang , Guo Mingquan , Liu Shuying
Published: November 2004

Simple, convenient, sensitive and accurate analytical methods are needed for the structural characterization and identification of alkaloid components in Rhizoma Coptidis in traditional Chinese herbal medicine, which has important bioactivity. In this work, the identification of alkaloid compounds in Rhizoma Coptidis was investigated by obtaining molecular mass information using electrospray ionization mass spectrometry (ESI‐MS). Multi‐stage tandem mass spectrometric (ESI‐MSn) data for the alkaloid compounds were used for detailed structural characterization, then structure information was obtained by comparison of the fragmentation mechanisms of both alkaloids in Rhizoma Coptidis and standard samples of berberine, palmatine, coptisine and jatrorrhizine by MS. Based on the results obtained, the structure of a novel compound was elucidated. The results of the experiments demonstrate that ESI‐MSn is a sensitive, selective and effective tool for the rapid determination of alkaloids in Rhizoma Coptidis. Copyright © 2004 John Wiley & Sons, Ltd.
Firm or subgroup culture: where does fitting in matter most?
Authors: Adkins Bryan , Caldwell David
Published: November 2004

Using the Organizational Culture Profile (OCP), this research investigated the extent to which fit between individuals (n = 136) and their competency groups (P–G fit) and the organization (P–O fit) were related to job satisfaction. Even in a consulting firm with a strong organization culture, we found small, but interpretable, differences between the value‐based cultures of the competency groups in the firm. Although the two forms of fit were highly correlated, both individual consultants' fit with the culture of their competency group and the organization as a whole were significant predictors of job satisfaction. Copyright © 2004 John Wiley & Sons, Ltd.
Stability, sensory quality, texture properties and nutritional value of fish oil‐enriched spreadable fat. Wojciech Kolanowski, Franciszek Swiderski, Danuta Jaworska, Stanislaw Berger Journal of the Science of Food and Agriculture 84(15):2135–2141 (2004) DOI: 10.1002/jsfa.1770 (published online 3 August 2004)
Authors: Kolanowski Wojciech , Swiderski Franciszek , Jaworska Danuta , Berger Stanislaw
Published: November 2004

The original article to which this Correction refers was published in Journal of the Science of Food and Agriculture 84(15):2135–2141 (2004) DOI: 10.1002/jsfa.1770 (published online 3 August 2004)
Level sets of the first eigenfunction from the rearrangement point of view
Authors: Chu Chie‐Ping
Published: November 2004

The level curves of the first Dirichlet eigenfunction for the Laplace operator of a convex plane domain is convex. We make this observation by a new rearrangement technique. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Lagrangian solutions to systems of real principal type
Authors: Hansen Sönke , Röhrig Daniel
Published: November 2004

We derive a transport equation for the principal symbol of a Fourier integral operator which solves a real principal type system. We apply this to Lamé's system of elastodynamics and obtain transport equations which remain valid at caustics. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
The interior transmission problem for anisotropic Maxwell's equations and its applications to the inverse problem
Authors: Haddar Houssem
Published: November 2004

The interior transmission problem appears naturally in the study of the inverse scattering problem of determining the shape of a penetrable medium from a knowledge of the time harmonic incident waves and the far field patterns of the scattered waves. We propose a variational study of this problem in the case of Maxwell's equations in an inhomogeneous anisotropic medium. Then we apply the obtained results to build an ‘extented far field’ operator and give a characterization of the medium from the knowledge of the range of this operator. We then show how the linear sampling method can be viewed as an approximation of this characterization. Copyright © 2004 John Wiley & Sons, Ltd.
Degenerate scale problem when solving Laplace's equation by BEM and its treatment
Authors: Chen J. T. , Lin S. R. , Chen K. H.
Published: November 2004

In this paper, Laplace problems are solved by using the dual boundary element method (BEM). It is found that a degenerate scale problem occurs if the conventional BEM is used. In this case, the influence matrix is rank deficient and numerical results become unstable. Both the circular and elliptical bars are studied analytically in the continuous system. In the discrete system, the Fredholm alternative theorem in conjunction with the SVD (Singular Value Decomposition) updating documents is employed to sort out the spurious mode which causes the numerical instability. Three regularization techniques, method of adding a rigid body mode, hypersingular formulation and CHEEF (Combined Helmholtz Exterior integral Equation Formulation) concept, are employed to deal with the rank‐deficiency problem. The addition of a rigid body term, c, in the fundamental solution is proved to shift the original degenerate scale to a new degenerate scale by a factor e−c. The torsion rigidities are obtained and compared with analytical solutions. Numerical examples including elliptical, square and triangular bars were demonstrated to show the failure of conventional BEM in case of the degenerate scale. After employing the three regularization techniques, the accuracy of the proposed approaches is achieved. Copyright © 2004 John Wiley & Sons, Ltd.
Effect of DMSO used as solvent in copper mediated living radical polymerization
Authors: Monge Sophie , Darcos Vincent , Haddleton David M.
Published: November 2004

The use of DMSO as solvent for transition metal mediated living radical polymerization was investigated using copper (I) bromide/N‐(n‐propyl)‐2‐pyridyl‐methanimine catalyst system and ethyl‐2‐bromoisobutyrate as initiator. The best conditions for polymerization in DMSO of different methacrylates (MMA, BMA, DMAEMA, HEMA) were determined. In all cases, the measured number‐average molar mass of the product increased linearly with monomer conversion in agreement with the theoretical Mn with low polydispersity products (1.16 < PDI < 1.4) achieved. Solvent was found to play a crucial role in the process. The effect of the polar solvent has been investigated and it was shown that DMSO could coordinate copper (II), increasing the activation process, or copper (I), changing the nature of the copper catalyst by competitive complexation of ligand and DMSO. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6299–6308, 2004
Influence of the alkene structure on the mechanism and kinetics of thiol–alkene photopolymerizations with real‐time infrared spectroscopy
Authors: Roper Todd M. , Guymon C. A. , Jönsson E. S. , Hoyle C. E.
Published: November 2004

The effect of the chemical structure on the reactivity of alkenes used in thiol–ene photopolymerizations has been investigated with real‐time infrared spectroscopy. Model studies of thiol–ene photoreactions with various monofunctional hydrocarbon alkenes and the monofunctional thiol ethyl‐3‐mercaptopropionate have been performed to identify and understand structure–reactivity relationships. The results demonstrate that terminal enes react very rapidly with thiol, achieve complete conversion, and are independent of the aliphatic hydrocarbon substituent length. Disubstitution on a single carbon of a terminal ene significantly reduces the reactivity, whereas substitution on the carbon α to the terminal ene has a minimal influence on the reactivity. Internal trans enes display reduced reactivity and a lower overall conversion and deviate from the standard thiol–ene reaction mechanism because of steric strain induced by 1,3‐interactions. The reactivity and conversion of internal trans enes decrease as the substituents on the ene become larger, reaching a minimum when the substituent size is greater than or equal to that of propyl groups. Internal cis enes react rapidly with thiol; however, they undergo a fast isomerization–elimination reaction sequence generating the trans ene, which proceeds to react at a reduced rate with thiol. The reactivity of cyclic enes is dictated by ring strain, stereoelectronic effects, and hydrogen abstractability. The reactivity trends in the model studies have been used to explain the photopolymerization mechanism and kinetics of a series of multifunctional thiol–ene systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6283–6298, 2004
Effect of the composition ratio of copolymerized poly(carbonate) glycol on the microphase‐separated structures and mechanical properties of polyurethane elastomers
Authors: Kojio Ken , Nonaka Yoshiteru , Masubuchi Tetsuo , Furukawa Mutsuhisa
Published: November 2004

Randomly copolymerized poly(carbonate) glycols were employed as starting materials for the synthesis of polyurethane elastomers (PUEs). The poly(carbonate) glycols had hexamethylene (C6) and tetramethylene (C4) units between carbonate groups in various composition ratios (C4/C6 = 0/100, 50/50, 70/30, and 90/10), and the number‐average molecular weights of these poly(carbonate) glycols were 1000 and 2000. The PUEs were synthesized with these poly(carbonate) glycols, 4,4′‐diphenylmethane diisocyanate, and 1,4‐butanediol by a prepolymer method. Differential scanning calorimetry measurements revealed that the difference between the glass‐transition temperature of the soft segment in the PUEs and the glass‐transition temperature of the original glycol polymer decreased and the melting point of the hard‐segment domain increased with an increasing C4 composition ratio. The microphase separation of the poly(carbonate) glycol‐based PUEs likely became stronger with an increasing C4 composition ratio. Young's modulus of these PUEs increased with an increasing C4 composition ratio. This was due to increases in the degree of microphase separation and stiffness of the soft segment with an increase in the C4 composition ratio. The molecular weight of poly(carbonate) glycol also influenced the microphase‐separated structure and mechanical properties of the PUEs. The addition of different methylene chain units to poly(carbonate) glycol was quite effective in controlling the microphase‐separated structure and mechanical properties of the PUEs. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4448–4458, 2004
Density functional theory with finite electric field
Authors: Umari P. , Pasquarello Alfredo
Published: November 2004

The method for treating finite electric fields within periodic boundary conditions is used to formally define a density functional depending on the electric field. An exchange and correlation energy functional depending on the electric field is introduced and related to the functional at zero field by a formal expansion with respect to the field. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005
Optical properties of molecules in solution via hybrid TDDFT/MM simulations
Authors: Sulpizi M. , Röhrig U. F. , Hutter J. , Rothlisberger U.
Published: November 2004

The optical properties of molecules in complex environments were investigated within hybrid time‐dependent density functional theory / molecular mechanics (TDDFT/MM) simulation studies. The potential energy surface in the excited state is described within time‐dependent density functional theory (TDDFT). The solvent is described through a molecular mechanics approach and the effects due to the inhomogeneities of the electric field of the solvent molecules are fully included. The results for different systems including both n → π* and π → π* transitions are discussed. We apply this TDDFT/MM technique to the study of the properties of the ground state and of the first excited singlet state of two different systems: acetone in water and aminocoumarins in water and acetonitrile. Our approach yields quantitative information on the solvent‐induced shifts, both batho‐ and hypsochromic, of the electronic absorption spectra, and on the effect of a protic and an aprotic solvent on the spectral shift. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005
Crystalline diamond polymorphs analyzed with first‐principles 13C NMR chemical shift calculations
Authors: Sebastiani Daniel
Published: November 2004

We present the fully periodic calculation of nuclear magnetic resonance (NMR) chemical shifts in crystalline diamond polymorphs within density functional theory. The carbon atoms in these systems have identical fourfold coordination, their topology up to their first neighbors is completely the same. The differences occur only with respect to their second neighbors, which are oriented differently in the considered crystals. We focus on the 2H, 4H, 6H, and 15R polymorphs and compare their computed 13C NMR chemical shift spectra to that of cubic diamond. The results show that it should be possible to discriminate between the only slightly different topologies of the diamond polymorphs by means of magic‐angle‐spinning solid‐state NMR experiments. The predicted variations in the solid‐state NMR spectrum are strong enough to allow for a quantitative experimental analysis of such systems. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005
Unilateral Surgery for Hyperparathyroidism: Indications, Limits, and Late Results—New Philosophy or Expensive Selection without Improvement of Surgical Results?
Authors: Mortier Pierre‐E. , Mozzon Marta M. , Fouquet Olivier P. , Soudan Benoit C. , Huglo Damien G. , Cussac Jean‐F. , Proye Charles A.G.
Published: November 2004

We assessed the “late” results after unilateral parathyroidectomy (PTX) performed for selected indications. From October 1998 throughout March 2001 we operated on 454 patients for hyperparathyroidism (HPT). A positive unifocal 99mtc‐MIBI scan was required for the unilateral approach to be used. Intact parathormone (PTH) measurements were done intraoperatively. Postoperative calcium and PTH serum levels of unilaterally operated patients were checked. Follow‐up has been 16.2 months (range 6–40 months). Of the 454 patients, 336 (74.0%) were not eligible for the unilateral approach; and 125 (27.5%) of the 454 patients had renal HPT. Among the 329 patients with primary HPT, 125 (38.0%) were excluded for well established reasons, and in 77 other cases (23.5%) preoperative imaging results did not allow the unilateral approach. Altogether, 126 patients (38.3%) with primary HPT were selected for the unilateral approach. Of the 126 unilateral operations, 8 (6.3%) had to be converted to a bilateral procedure. Among the 118 patients with a unilateral approach, 3 patients have been reoperated for overlooked contralateral disease, and 13 dropped out of the study. A total of 102 postoperative calcium and PTH serum late levels are known: 90 (88.2%) patients had normal levels; 10 (9.8%) had a high PTH level, and 2 (1.9%) had high ionized calcium levels. The failure rate in selected cases was 4.2% (5/118) (three were reoperated, and two had a supranormal postoperative ionized Ca level). Even with stringent indications, the late results of unilateral surgery (95.8% cure rate) barely matched those of conventional bilateral surgery (97.6% cure rate). The economic impact of such a surgical strategy should be clarified.
Open Minimally Invasive Parathyroid Surgery
Authors: Udelsman Robert , Donovan Patricia I.
Published: November 2004

Outpatient minimally invasive parathyroidectomy (MIP) employs (1) preoperative parathyroid localization with high quality sestamibi scans, (2) cervical block anesthesia, (3) limited exploration, and (4) the rapid intraoperative parathyroid hormone assay to confirm an adequate resection. The technical aspects of this procedure are described, and the results obtained in 255 patients who underwent MIP are compared with those of 401 patients who underwent conventional bilateral cervical exploration under general anesthesia. MIP and standard exploration were indistinguishable with regard to high cure and low complication rates. MIP, however, was superior with regard to operating time, length of hospital stay, patient comfort, and costs.
Endoscopic Parathyroid Surgery: Results of 365 Consecutive Procedures
Authors: Henry Jean‐François , Sebag Frédéric , Tamagnini Paola , Forman Céline , Silaghi Horatiu
Published: November 2004

In recent years, several series have documented the feasibility of endoscopic approaches for parathyroid diseases. We performed a retrospective study to evaluate the results of endoscopic parathyroidectomy (EP) in the management of our patients with primary hyperparathyroidism (PHPT). During a 5.5 year period (1998–2003), we operated on 644 patients with PHPT. EP was proposed for patients with sporadic PHPT, without associated goiter, and without previous neck surgery in whom a single adenoma was localized by means of sonography and sestamibi scanning. EP was performed by the lateral approach with insufflation for patients with an adenoma located deep in the neck and by a gasless midline approach for patients whose adenoma was located anteriorly. A quick parathyroid (QPTH) assay was used during the surgical procedures. Among 644 patients with PHPT, 279 (43.3%) were not eligible for EP for the following reasons: associated nodular goiter (116 cases), previous neck surgery (52 cases), suspicion of multiglandular disease (31 cases), lack of preoperative localization (61 cases), and miscellaneous causes (19 cases). EP was performed in 365 patients with sporadic PHPT: 339 lateral access, 25 midline access, and one thoracoscopy. The median operating time was 49 minutes (16–130 minutes). Conversion to conventional parathyroidectomy was required in 49 patients (13.4%) for these reasons: missed adenomas (14 cases), difficulty with the dissection (8 cases), multiglandular disease correctly predicted by QPTH (11 cases), false‐negative QPTH assay results (4 cases), false‐positive sestamibi scan results (11 cases), and 1 false‐positive sonography result. One patient presented with definitive recurrent nerve palsy. Three patients remained hypercalcemic, and one other patient had recurrent hypercalcemia. In conclusion, EP can be proposed for more than half of the patients with PHPT. Immediate results of EP are similar to those obtained with conventional parathyroidectomy, but no conclusions can be drawn in terms of the influence of EP on the outcome of the patients operated on for PHPT.
Single Center Experience in Primary Surgery for Medullary Thyroid Carcinoma
Authors: Ukkat Jörg , Gimm Oliver , Brauckhoff Michael , Bilkenroth Udo , Dralle Henning
Published: November 2004

Medullary thyroid carcinoma (MTC) is a rare disease, and most studies are either based on small numbers or multicenter studies with their inherent difficulties. Since 1995, a total of 440 patients with MTC underwent surgery in our clinic. A primary operation was performed in 188 patients (43% of 440). In 60 patients, the primary operation was performed because of a germline RET mutation (“prophylactic surgery”). Most (84%, 158/188) of the patients had pathologic calcitonin levels. Notably, MTC was found in almost 10% (3/30) of patients with normal calcitonin levels. However, all patients with lymph node metastases (LNMs) had elevated calcitonin levels. Total thyroidectomy (TTx) was performed in all patients. Lymph node dissection (LND) was performed at various extensions: one‐compartment LND in 35% (66/188), three‐compartment LND in 31% (58/188), and four‐compartment LND in 29% (22/188). In general, lymph node dissection increased the likelihood of complications. LNM and distant metastases (DM) correlated with the extent of the primary tumor (pT category). The presence of LNM ranged from 17% (pT1 tumor) to 100% (pT4 tumor), whereas the presence of DM ranged from 0% (pT1 tumor) to 81% (pT4 tumor). Biochemical cure (normal calcitonin levels) was obtained in 72% (137/188) of patients. All 60 patients undergoing prophylactic surgery (tumor stage pT0/pT1) were biochemically cured. In contrast, only 60% (77/128) of the remaining patients were cured. The data suggest that primary surgery should be scheduled as soon as possible to treat patients at a node‐negative stage. In the case of normal basal and elevated stimulated calcitonin levels, TTx and cervicocentral LND is recommended. If the basal calcitonin level is elevated, LND should include the cervicolateral compartment.
Biochemical Effects from Treatment with Bisphosphonate and Surgery in Patients with Primary Hyperparathyroidism
Authors: Jansson Svante , Morgan Eric
Published: November 2004

Patients with primary hyperparathyroidism (pHPT) are sometimes treated with bisphosphonates (BPs) as an alternative to surgery despite sparse documentation of the efficacy in this disorder. It is therefore of interest to study the biochemical effects from BPs in patients with pHPT. A series of 21 pHPT patients with serum calcium levels > 2.8 mmol/L were included. One month before surgery the patients underwent intravenous infusions of 30 to 40 mg pamidronate. Study parameters were total and ionized serum calcium, intact parathormone (PTH), alkaline phosphatase (ALP) and isoenzymes, creatinine, osteocalcin, 25‐OH vitamin D3, 1,25‐OH2 vitamin D3, urine calcium/creatinine, and osmolality. Registration of hypercalcemia‐related symptoms were done by questionnaire. After pamidronate there was a temporary reduction in serum calcium with a nadir at 6 to 10 days. Normalization of serum calcium was achieved only by surgery. Intact PTH rose after pamidronate, with a maximum on day 6. Urinary calcium excretion was reduced after both pamidronate and surgery. ALP was reduced 30 days after pamidronate and also after surgery. Serum osteocalcin was not influenced by pamidronate. No statistically significant differences in symptoms were reported after treatment. In conclusion, there was a short, limited calcium‐lowering effect from pamidronate in pHPT patients and a transient increase in PTH corresponding to the reduced calcium concentration. An obvious change in bone markers was found only after surgery. Treatment with BPs should not be considered an alternative to surgery, which is still the only method to cure patients with pHPT.
Multiple Endocrine Neoplasia 2B Syndrome due to Codon 918 Mutation: Clinical Manifestation and Course in Early and Late Onset Disease
Authors: Brauckhoff Michael , Gimm Oliver , Weiss Carl‐Ludwig , Ukkat Jörg , Sekulla Carsten , Brauckhoff Katrin , Thanh Phuong Nguyen , Dralle Henning
Published: November 2004

More than 50% of patients with typical MEN‐2B have a de novo M918T germline mutation of the RET protooncogene. However, even in typical MEN‐2B, extrathyroidal manifestations of MEN‐2B can be found to be differently expressed. We analyzed the clinical manifestation and course in 21 patients harboring a de novo RET M918T mutation. Mean age at MEN‐2B diagnosis was 14.2 years (range: 1–31 years). All patients had medullary thyroid carcinoma (MTC). At the time of syndrome diagnosis, oral manifestations (bumpy lips, ganglioneuroma), ocular manifestations (corneal fibers, conjunctivitis sicca), intestinal dysfunctions, musculoskeletal manifestations, and pheochromocytoma were found in 86%, 90%, 74%, 79%, and 19% of the patients, respectively. At the time of follow‐up examination, the symptoms were found at higher frequency. Severe intestinal manifestation was predominantly found in patients with prepubertal onset (≤ 12 years) of MTC (n = 4/10) compared with patients with late onset (> 12 years) of MTC (n = 0/11) (40% versus 0%; p = 0.019). Although biochemical cure was found only in four patients with early onset of MTC, the long‐term prognosis for patients with early onset of MTC was poorer than for patients presenting with late onset of MTC (p = 0.005). During mean follow‐up of 55.8 months (range: 3–161 months), seven patients (33%) died from MTC. In conclusion, whereas most typical MEN‐2B symptoms were found to be age‐related, severe intestinal manifestation was found to be predominantly expressed in patients with early onset of MTC. Furthermore, in patients with early onset of MTC who could not be biochemically cured, the long‐term prognosis was found to be worse than that of non‐cured patients with late onset of MTC, suggesting an additional pathological process in the younger subgroup reinforcing the very high transforming in vitro activity of the M918T RET mutation.
Results of Video‐assisted Parathyroidectomy: Single Institution’s Six‐year Experience
Authors: Miccoli Paolo , Berti Piero , Materazzi Gabriele , Massi Marco , Picone Antonella , Minuto Michele N.
Published: November 2004

Endoscopic surgery for primary hyperparathyroidism (PHPT) started in 1996 with a parathyroidectomy performed by Michel Gagner. The technique we propose and have been using for 6 years is based on a unique central access and external retraction. From February 1997 to October 2003, 370 of 520 patients affected with PHPT (71%) underwent minimally invasive video‐assisted parathyroidectomy (MIVAP). There were 72 men and 298 women, with a mean age of 55.8 years. Twenty‐four patients (6.5%) of the 370 in this series underwent MIVAP under loco‐regional anesthesia, and the others had general anesthesia. Eleven patients were lost to follow‐up. Surgical cure of PHPT was achieved in 353 patients (98,3%), as confirmed by a median follow‐up of 35.1 months (range: 2–82 months). Video‐assisted exploration was successfully performed in 350 patients (94%). The mean operative time was 36.2 minutes. In 21 cases (5.6%) a concomitant procedure was performed: a thyroid lobectomy in 14 cases and a total thyroidectomy in 7 cases. Patients were generally discharged the day after surgery. Most of the patients (91%) were satisfied with the cosmetic result 6 or more months after the procedure. Complications developed in 14 cases: 10 cases (2.7%) of transient hypoparathyroidism 3 cases (0.8%) of definitive palsies of the recurrent nerve, and 1 case of postoperative bleeding (0.27%). After 6 years of experience, MIVAP appears to be as safe and curative as traditional surgery, with better cosmetic results and better postoperative outcome.