bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficacy and cost‐effectiveness of physiotherapy following glenohumeral joint distension for adhesive capsulitis: A randomized trial
Authors: Buchbinder Rachelle , Youd Joanne M. , Green Sally , Stein Alicia , Forbes Andrew , Harris Anthony , Bennell Kim , Bell Simon , Wright Warwick J. L.
Published: July 2007

Objective

To determine whether an active physiotherapy program following arthrographic joint distension for adhesive capsulitis provides additional benefits.

Methods

We performed a randomized, placebo‐controlled, participant and single assessor blinded trial. A total of 156 participants with pain and stiffness in predominantly 1 shoulder for ≥3 months and restriction of passive motion >30° in ≥2 planes of movement entered the study, and 144 completed the study. Following joint distension, participants were randomly assigned to either manual therapy and directed exercise or placebo (sham ultrasound), both administered twice weekly for 2 weeks then once weekly for 4 weeks. Pain, function, active shoulder movements, participant‐perceived success, and quality of life were assessed at baseline, 6, 12, and 26 weeks. Costs were also collected.

Results

Both groups improved over time with no significant differences in improvement between groups for pain, function, or quality of life at any time point. Significant differences favored the physiotherapy group for all active shoulder movements (e.g., pooled difference in mean change between groups across all time points for total shoulder abduction was 10.6°, 95% confidence interval [95% CI] 3.1, 18.1) and participant‐perceived success (pooled relative risk 1.4, 95% CI 1.1, 1.65; number needed to treat = 5). Net cost of physiotherapy was $136.8 Australian (95% CI −177.5, 223.1) over the 6 months.

Conclusion

Physiotherapy following joint distension provided no additional benefits in terms of pain, function, or quality of life but resulted in sustained greater active range of shoulder movement and participant‐perceived improvement up to 6 months.
Sociodemographic associations with early disease damage in patients with systemic lupus erythematosus
Authors: Cooper Glinda S. , Treadwell Edward L. , William St.Clair E. , Gilkeson Gary S. , Dooley Mary Anne
Published: July 2007

Objective

To examine the extent of organ damage among recently diagnosed patients with systemic lupus erythematosus (SLE), and to assess the association between sociodemographic variables and total damage and organ‐specific damage scores.

Methods

We evaluated damage in 132 patients with SLE (70 African Americans and 62 whites), 2–6 years (median 4 years) after diagnosis, using the Systemic Lupus International Collaborating Clinics/American College of Rheumatology Damage Index. The associations between demographic characteristics and total damage and organ‐specific damage measures were evaluated using logistic regression, adjusting for age, income, and ethnicity.

Results

A total of 61% of patients scored ≥1 point on the damage index. Damage was most prevalent in the musculoskeletal (28%), skin (20%), neuropsychiatric (16%), and renal (12%) subscales. African American ethnicity and lower household income were independently associated with total damage scores (score ≥2: adjusted odds ratio [95% confidence interval] 6.0 [2.3–16.2] in African Americans and 2.7 [1.1–6.7] in patients with an annual household income ≤$30,000). The odds of having skin damage, alopecia, or diabetes were at least 5 times higher in African Americans compared with whites, but ethnicity was not associated with renal damage (adjusted odds ratio 1.6, 95% confidence interval 0.40–6.1).

Conclusion

Considerable damage is seen in SLE patients early in the disease course, and the pattern varies between ethnic groups. This analysis also highlights the importance of sociodemographic characteristics (particularly income) in predicting damage.
Self‐management education for persons with arthritis: Managing comorbidity and eliminating health disparities
Authors: Goeppinger Jean , Armstrong Brian , Schwartz Todd , Ensley Donald , Brady Teresa J.
Published: July 2007

Objective

To compare short‐term and long‐term effectiveness of the Arthritis Self‐Help Course (ASHC) and the Chronic Disease Self‐Management Program (CDSMP) for persons with arthritis concerning health care use, health‐related quality of life, health behaviors, and arthritis self‐efficacy.

Methods

Forty‐eight workshops were randomized to the ASHC (n = 26) or CDSMP (n = 22). A total of 416 individuals, including 365 African Americans, participated. The mean age for each group was 64 years, mean years of education was 11.7, mean number of chronic conditions was 4, and 75–80% of participants in each group were female. Multivariate statistical tests were used to assess effectiveness within and between programs for all workshop participants and African Americans.

Results

At 4 months all ASHC participants including African Americans, had significant improvements (P ≤ 0.05) in self‐efficacy, stretching and strengthening exercises, aerobic exercises, and general health. All CDSMP participants had statistically significant improvements in self‐efficacy, disability, pain, and general health. African American CDSMP participants showed statistically significant improvements in general health. Trends toward improvement (P = 0.051–0.100) were shown in 5 variables among African American CDSMP participants and in 4 variables among all CDSMP participants. Statistically significant differences between the 2 programs at 4 months were seen in pain and disability in both groups. The CDSMP produced stronger results. Significant results at 1 year within and between programs were minimal for both groups.

Conclusion

When populations with arthritis and multiple comorbid conditions are targeted, the CDSMP may be most cost effective.
Aerobic and anaerobic exercise capacity in adolescents with juvenile idiopathic arthritis
Authors: Lelieveld Otto T. H. M. , van Brussel Marco , Takken Tim , van Weert Ellen , van Leeuwen Miek A. , Armbrust Wineke
Published: July 2007

Objective

To examine the aerobic and anaerobic exercise capacity in adolescents with juvenile idiopathic arthritis (JIA) compared with age‐ and sex‐matched healthy individuals, and to assess associations between disease‐related variables and aerobic and anaerobic exercise capacity.

Methods

Of 25 patients enrolled in a JIA transition outpatient clinic, 22 patients with JIA were included in this study (mean ± SD age 17.1 ± 0.7 years, range 16–18 years). Aerobic capacity was examined using a Symptom Limited Bicycle Ergometry test. Anaerobic capacity was assessed with the Wingate Anaerobic Test. Functional ability was assessed with the Childhood Health Assessment Questionnaire. Pain and overall well‐being were measured using a visual analog scale. Disease duration and disease activity were also assessed.

Results

Absolute and relative maximal oxygen consumption in the JIA group were significantly impaired (85% and 83% for boys, respectively; 81% and 78% for girls, respectively) compared with healthy controls. Mean power was also significantly impaired (88% for boys and 74% for girls), whereas peak power was significantly impaired for girls and just failed significance for boys (67% for girls and 92% for boys). A post hoc analysis correcting for underweight and overweight demonstrated that body composition did not influence the results substantially.

Conclusion

This study demonstrated that adolescents with JIA have an impaired aerobic and anaerobic exercise capacity compared with healthy age‐ and sex‐matched peers. The likely cause for this significant impairment is multifactorial and needs to be revealed to improve treatment strategies.
Effectively measuring adherence to medications for systemic lupus erythematosus in a clinical setting
Authors: Koneru Sri , Shishov Michael , Ware Avis , Farhey Yolanda , Mongey Anne‐Barbara , Graham T. Brent , Passo Murray H. , Houk J. Lawrence , Higgins Gloria C. , Brunner Hermine I.
Published: July 2007

Objective

To assess the reliability and concurrent validity of the Medication Adherence Self‐report Inventory (MASRI) when used in systemic lupus erythematosus (SLE), to investigate the predictive validity of the MASRI using pharmacy refill information as the criterion standard, and to propose a sensible approach to the screening for nonadherence in a clinical setting.

Methods

Adherence to 2 medications (hydroxychloroquine and prednisone) was measured in 55 patients using the MASRI, pill counts, and physician ratings (MD scale). Adherence based on pharmacy refill information served as a criterion standard with nonadherence defined as adherence rates <80%. To determine test–rest reliability of the MASRI, 20 patients completed the measure twice within a 2‐week period.

Results

Using pharmacy information, 39% of the patients were nonadherent to prednisone and 51% to hydroxychloroquine. The MASRI had acceptable internal consistency (Cronbach's α 0.7) and good reliability. Irrespective of the drug assessed, MASRI ratings were moderately correlated with patient adherence (pharmacy), supporting the concurrent validity of the MASRI. The combination of adherence estimation by MD scale rating at <85% and by MASRI at <90% was 87% sensitive and 86% specific for identifying patients who were nonadherent to prednisone. These cutoff values also appeared suitable for identifying nonadherence to hydroxychloroquine.

Conclusion

The MASRI is a reliable measure of adherence to medications in SLE. The measure has concurrent and predictive validity. When combined with the MD scale, the MASRI appears to be a useful screening tool for nonadherence in patients with SLE that could be suitable for clinical practice.
Test–retest reliability of the peak knee adduction moment during walking in patients with medial compartment knee osteoarthritis
Authors: Birmingham Trevor B. , Hunt Michael A. , Jones Ian C. , Jenkyn Thomas R. , Giffin J. Robert
Published: July 2007

Objective

To estimate the test–retest reliability of the peak external knee adduction moment during walking in patients with medial compartment knee osteoarthritis (OA), and to describe the interpretation of the reported values.

Methods

A total of 31 patients diagnosed with knee OA confined primarily to the medial compartment underwent quantitative gait analyses during 2 separate test sessions at least 24 hours apart and within 1 week. The peak knee adduction moment was calculated for each patient at each session based on the mean of 5 walking trials. Reliability was estimated using the intraclass correlation coefficient (ICC2,1) and the standard error of measurement (SEM).

Results

The mean difference in peak adduction moments between test sessions was 0.1% body weight × height (BW × ht; 95% confidence interval [95% CI] −0.1, 0.3). The point estimate for the ICC was 0.86 (95% CI 0.73, 0.96). The point estimate for the SEM was 0.36% BW × ht (95% CI 0.29, 0.48).

Conclusion

The ICC suggests that the peak knee adduction moment is appropriate for use when distinguishing among patients, for example, in studies of various interventions intended to decrease dynamic load on the knee medial compartment. The SEM illustrates the importance of considering measurement error and incorporating confidence levels when interpreting an individual patient's peak knee adduction moment value.
Depression in patients with systemic sclerosis: A systematic review of the evidence
Authors: Thombs Brett D. , Taillefer Suzanne S. , Hudson Marie , Baron Murray
Published: July 2007

Objective

To assess the prevalence, course, and predictors of depression in patients with systemic sclerosis (SSc).

Methods

We conducted a comprehensive search in November 2006 of MEDLINE, PsycINFO, and CINAHL databases to identify original research studies published in any language that used a structured interview or validated questionnaire to assess major depressive disorder or clinically significant symptoms of depression in patients with SSc. The search was augmented by hand searching 26 selected journals through December 2006 and references from identified articles and reviews. Studies were excluded if only an abstract was provided or if depression was not measured by a validated method.

Results

No studies used a structured clinical interview to assess the prevalence of major depressive disorder. The prevalence of clinically significant depressive symptoms was 51–65% based on 2 studies that used a Beck Depression Inventory (BDI) score ≥10 and 46–56% based on 2 studies that used a BDI score ≥11. These rates and those reported in 4 other studies that used different assessment tools (36–43%) were consistently high compared with other medical patient groups assessed with the same instruments and cutoffs. Methodologic issues limited the ability to draw strong conclusions from studies of predictors.

Conclusion

Symptoms of depression are common among patients with SSc. The high rates reported across studies suggest that routine screening is recommended. There is a need for studies that examine depression at different time points from the diagnosis of SSc and that systematically investigate factors associated with high levels of depressive symptoms.
Cross‐cultural adaptation of the Systemic Lupus Erythematosus Quality of Life Questionnaire into Chinese
Authors: Kong Kok ooi , Ho Hsu Juang , Howe Hwee Siew , Thong Bernard Yu Hor , Lian Tsui Yee , Chng Hiok Hee , Leong Khai Pang ,   Tan Tock Seng Hospital Systemic Lupus Erythematosus Study Group
Published: July 2007

Objective

We have previously validated the English version of the Systemic Lupus Erythematosus Quality of Life Questionnaire (SLEQOL) in our patients with lupus. Many of our Chinese patients are not fluent in English and therefore a Chinese version (SLEQOL‐C) has been adapted for their use.

Methods

Two independent translators translated the SLEQOL into Chinese. A consensus version was derived from both sets of translations. Back translation of this version was performed by another 2 independent translators who had neither been involved in the forward translation nor encountered the SLEQOL. The final version, SLEQOL‐C, was finalized after rectifying the discrepancies revealed by the back translation. Linguistic validity was tested in open interviews with bilingual patients with lupus. The SLEQOL‐C and SLEQOL were administered to patients to determine whether they displayed differential item functioning (DIF).

Results

In general, most of the items in English could be expressed in Chinese precisely, although a few instructions had to be altered slightly to make them more idiomatic. The forward and back translations of the SLEQOL were accomplished without major difficulties. A total of 638 patients were interviewed (62.8% with the SLEQOL and 37.2% with the SLEQOL‐C). Using DIF analysis, there was no detectable test bias due to language use after controlling for repeated observations, age, sex, and ethnicity.

Conclusion

The SLEQOL‐C has semantic, idiomatic, and conceptual equivalence to the SLEQOL. The rigorous process of cross‐cultural translation provides some measure of quality in the content validity.
Pharmacokinetics of 6‐hydroxybuspirone and its enantiomers administered individually or following buspirone administration in humans
Authors: Dockens Randy C. , Tran Anh Q. , Zeng Jianing , Croop Robert
Published: July 2007

The objective of this study was to assess the pharmacokinetics of 6‐hydroxybuspirone (6OHB) when given orally via three forms: racemate (BMS‐528215), S‐enantiomer (BMS‐442606) and R‐enantiomer (BMS‐442608), versus following the administration of buspirone. A double‐blind, randomized, four‐period, four‐treatment, crossover study balanced for residual effects in healthy subjects was conducted (n=20). Subjects received single 10 mg doses of each compound in a randomized fashion with pharmacokinetics determined over a 24 h period. There was a 4‐day washout between each dosing period. All three forms of 6OHB (racemate, S‐enantiomer and R‐enantiomer) were well tolerated. There was nterconversion between enantiomers. The dominant enantiomer was the S‐enantiomer no matter which form of 6OHB was administered. All three forms of 6OHB produced approximately 2‐ to 3‐fold greater exposure to total 6OHB than did buspirone. All three forms produced equal exposure to 1‐(2‐pyrimidinyl)‐piperazine (1‐PP) which was approximately 30% less than the 1‐PP exposure derived from buspirone administration. All three forms of 6OHB produced approximately 3‐fold higher 6OHB:1‐PP ratios and approximately 2.5‐fold higher total 6OHB exposures than did buspirone administration. All compounds were well tolerated. There seemed to be no advantage of one of the enantiomers of 6OHB over the racemate. Therefore, the racemate was chosen for further clinical development. Copyright © 2007 John Wiley & Sons, Ltd.
Synästhesie – die Vermischung der Sinne. Eine Spielart der Evolution im neurophilosophischen Licht
Authors: Emrich Hinderk , Dillo Wolfgang , Zedler Markus
Published: July 2007

Farben hören – Geschmack sehen: Synästhetiker erleben eine Vermischung ihrer Sinne. Die Erforschung dieses Phänomens liefert spannende Einblicke in die Art und Weise, wie Sinneseindrücke im menschlichen Gehirn verarbeitet werden. Synästhesie als Lebensform erweist sich als Paradigma eines Selbstverständnisses des Menschen, jenseits einer Physik der Reversibilität, als Paradigma eines Selbstverhältnisses im Sinne einer Physik der Singularität: Die nicht‐lineare Dynamik ist somit in gewissem Sinne eine Physik der Einmaligkeit, des Singulären, des Nicht‐Wiederholbaren.
Herbizide – neue Wirkstoffe gegen die Malaria? Ein Zellorganell pflanzlichen Ursprungs macht Plasmodium verwundbar
Authors: Krause Kirsten
Published: July 2007

Der Malaria‐Erreger zeichnet sich wie fast alle Parasiten aus der Gruppe der Apicomplexa durch den Apicoplasten aus – einem Zellorganell, das von einer endosymbiontisch lebenden Rotalge stammt. Eine Reihe von einzigartigen Stoffwechselwegen in diesem ursprünglich pflanzlichen Organell, die beim Menschen nicht vorkommen, liefert die Grundlage für die Entwicklung von dringend benötigten neuartigen Wirkstoffen gegen die Malaria.
Michaelis‐Menten‐Kinetik von Urease. Enzymkinetik in der Schule
Authors: Müller Sara , Kromke Marianne , Vogt Helmut , Moll Daniela
Published: July 2007

In diesem Artikel wird ein Schulexperiment zur Michaelis‐Menten‐Kinetik vorgestellt. Die enzymatische Umsetzung von Harnstoff durch das Enzym Urease lässt sich mittels eines einfachen Versuchsaufbaus leicht verfolgen und in verschiedenen Komplexitätsebenen auswerten, wobei die ermittelte Michaelis‐Menten‐Konstante (KM) dem Literaturwert entspricht. Um mögliche thematische Anknüpfungspunkte für den Unterricht zu geben, werden zusätzlich Funktion und Vorkommen der Urease in der Natur beschrieben.
Klimawandel – ein Feigenblatt? Der Treibhauseffekt und die Folgen für die Tierwelt
Authors: Kinzelbach Ragnar K.
Published: July 2007

Die Folgen des weltweiten, durch die Emission von Treibhausgasen verursachten Temperaturanstiegs für die Tierwelt sind umfassend, müssen aber im Vergleich zu historischen Abläufen relativiert und von Fall zu Fall untersucht werden. Prognosen sind unsicher, denn Tiere besitzen eine hohe strukturelle, systematische und ökologische Vielfalt. Hier wird eine Synopse und Einordnung oft vernachlässigter Fakten versucht. Es erfolgt eine Warnung, alle derzeitigen Probleme der Tierwelt ungeprüft der “Klimakatastrophe” in die Schuhe zu schieben. Im Stimmengewirr um die Klimafolgen geht anderer, weit näherliegender Handlungsbedarf unter.
Milben machen Frösche giftig
Authors: Wendler Silke
Published: July 2007

Erdbeerfrösche (Oophaga pumilio) sekretieren aus ihren Hautdrüsen einen Giftcocktail mit tödlicher Wirkung. Da in Gefangenschaft gehaltene Tiere ihre Giftigkeit mit der Zeit verlieren, wurde angenommen, dass sie das Gift nicht selbst produzieren können, sondern aus ihrer Nahrung aufnehmen. Neuere Untersuchungen lassen auf Hornmilben als Ausgangsquelle schließen.
Histon‐Acetylierung – ein Schlüssel zum Gedächtnis?
Authors: Hille‐Rehfeld Annette
Published: July 2007

Die Verfügbarkeit von Gedächtnisinhalten kann vorübergehend blockiert sein, ohne dass die Information gelöscht wird. Ihre Reaktivierung durch Gedächtnistraining geht einher mit chemischen Veränderungen im Chromatin des Zellkerns von Nervenzellen. Wird die Histon‐Acetylierung im Tiermodell medikamentös stabilisiert, so verbessern sich Gedächtnisleistungen in ähnlicher Weise wie durch das Training.
Erstes Beuteltier‐Genom entschlüsselt
Authors: Kronberg Inge
Published: July 2007

Mensch, Schimpanse, Maus, Hund, Biene – die Liste der entzifferten Genome wächst ständig. Angesichts der aufwändigen Technik und Millionen rezenter Arten müssen die Sequenzierungsobjekte klug gewählt werden. Die meisten Erkenntnisse versprechen Arten, die entweder als Nutz‐ oder Labororganismen bereits gut untersucht sind, oder die durch ihre phylogenetische Nähe zu Homo sapiens die Organisation und Evolution des menschlichen Genoms besser verstehen lassen. Auf das erste sequenzierte Beuteltier trifft beides zu: Das südamerikanische Kurzschwanz‐Opossum (Monodelphis domestica) dient als Modelltier in der Immunologie, Neurologie, Embryologie und Tumorforschung, außerdem markieren Beuteltiere einen wichtigen Verzweigungspunkt in der Evolution der Säugetiere.
Fette Brummer verhungern trotz Reserven
Authors: Feil Sylvia
Published: July 2007

Wie viele Fettstoffwechselweg‐Systeme der Fruchtfliege Drosophila melanogaster steuern die Freisetzung von Speicherfett bei Energieknappheit? Diese Frage ist auch für das Verständnis des menschlichen Stoffwechsels interessant, denn die an der Speicherung und Freisetzung von Fettreserven beteiligten Proteine sind hoch konserviert.
Die genetischen Grundlagen der Aufmerksamkeitsdefizit‐Hyperaktivitätsstörung (ADHS)
Authors: Friedel Susann , Schimmelmann Benno G. , Hinney Anke , Hebebrand Johannes
Published: July 2007

Die Aufmerksamkeitsdefizit‐Hyperaktivitätsstörung (ADHS) ist die häufigste psychiatrische Störung bei Kindern und Jugendlichen. Wissenschaftler des Nationalen Genomforschungsnetzes (NGFN) haben drei genetische Varianten identifiziert, die an der Entwicklung der ADHS beteiligt sind. Diese Veränderungen befinden sich in dem Gen, das für den Transporter des Botenstoffs Dopamin codiert.
Gelelektrophorese zur Auftrennung von Proteinen
Authors: Schrödel Andrea
Published: July 2007

Die SDS‐PAGE (SDS‐Polyacrylamid Gelelektrophorese) wird oft eingesetzt, um Ergebnisse biochemischer Protein‐Experimente auszuwerten oder auch um die Reinheit isolierter Proteine zu überprüfen. Jeder, der schon einmal mit Proteinen im molekularbiologischen Labor geforscht hat, hat diese Methode mit großer Wahrscheinlichkeit schon durchgeführt. Doch warum wandern denn die kleinen Proteine schneller als die großen? Und warum muss man die Proben vor dem Gelauftrag in Ladepuffer kochen?
Reinhold Tüxen
Authors: Irsch Wilhelm
Published: July 2007

Sensible Artenkenner sind die tragende Säule der Biodiversitätsforschung. Nicht nur vor dem Hintergrund der aktuellen Klimadiskussion stehen Disziplinen wie Geobotanik und Vegetationskunde national und international vor neuen Herausforderungen. Zukünftige Entwicklungen lassen sich nur bewerten und abschätzen, wenn sich der Blick auch in die Vergangenheit richtet. Dabei stößt man unausweichlich auf Pioniere wie Reinhold Tüxen, die Wissenschaftsgeschichte geschrieben haben und deren geistiges Werk bis in die heutige Zeit nachwirkt.
Quality of life during potentially curative treatment for locally advanced oesophageal cancer
Authors: Avery K N L , Metcalfe C , Barham C P , Alderson D , Falk S J , Blazeby J M
Published: July 2007

Background

Combination chemoradiotherapy with or without surgery are internationally applied alternative strategies for potential cure of oesophageal cancer. This study compared health-related quality of life (HRQL) between patients selected for chemoradiation and those who had combination treatment including oesophagectomy.

Methods

Patients with stage II or III oesophageal cancer completed HRQL assessments at baseline, at the worst expected HRQL time point and at expected recovery. HRQL was compared between groups using linear regression, adjusting for age, sex, performance status, tumour stage and type, and baseline HRQL.

Results

Some 132 patients began treatment, of whom 51 had chemoradiotherapy and 81 combination treatment including surgery. Patients selected for chemoradiotherapy were older, more likely to have squamous cell cancer and reported poorer HRQL than those selected for surgery. At the worst expected time point after treatment, both groups reported multiple symptoms and poor function, but surgery was associated with a greater reduction in HRQL from baseline than chemoradiotherapy. Recovery of HRQL was achieved within 6 months after chemoradiotherapy, but complete recovery had not occurred 6 months after surgery and there was persistent significant deterioration in some aspects.

Conclusion

The negative treatment-related impact of chemoradiation on short-term HRQL is less than that experienced with combination treatment including surgery. Patients preferring early recovery should consider definitive chemoradiation.
Combined Enzyme and Substrate Design: Grafting of a Cooperative Two‐Histidine Catalytic Motif into a Protein Targeted at the Scissile Bond in a Designed Ester Substrate
Authors: Höst Gunnar E. , Razkin Jesus , Baltzer Lars , Jonsson Bengt‐Harald
Published: July 2007

A histidine‐based, two‐residue reactive site for the catalysis of hydrolysis of designed sulfonamide‐containing para‐nitrophenyl esters has been engineered into a scaffold protein. A matching substrate was designed to exploit the natural active site of human carbonic anhydrase II (HCAII) for well‐defined binding. In this we took advantage of the high affinity between the active site zinc atom and sulfonamides. The ester substrate was designed to position the scissile bond in close proximity to the His64 residue in the scaffold protein. Three potential sites for grafting the catalytic His–His pair were identified, and the corresponding N62H/H64, F131H/V135H and L198H/P202H mutants were constructed. The most efficient variant, F131H/V135H, has a maximum kcat/KM value of approximately 14 000 M−1 s−1, with a kcat value that is increased by a factor of 3 relative to that of the wild‐type HCAII, and by a factor of over 13 relative to the H64A mutant. The results show that an esterase can be designed in a stepwise way by a combination of substrate design and grafting of a designed catalytic motif into a well‐defined substrate binding site.
A two‐parametric class of predictors in multivariate regression
Authors: Björkström Anders , Sundberg Rolf
Published: July 2007

We demonstrate that a number of well‐established multivariate regression methods for prediction are related in that they are special cases of basically one general procedure. We try a more general method based on this procedure with two metaparameters. In a simulation study, based on a latent structure model, we compare this method to ridge regression (RR), multivariate partial least squares regression (PLSR) and repeated univariate PLSR. For most types of data sets studied, all methods do approximately equally well. There are some cases where RR and least squares ridge regression (LSRR) yield larger errors than the other methods, and we conclude that one‐factor methods are not adequate for situations where more than one latent variable are needed to describe the data. Among those based on latent variables, none of the methods tried is superior to the others in any obvious way. Copyright © 2007 John Wiley & Sons, Ltd.
The Change of the State of an Endohedral Fullerene by Encapsulation into SWCNT: A Raman Spectroelectrochemical Study of Dy3N@C80 Peapods
Authors: Kalbáč Martin , Kavan Ladislav , Zukalová Markéta , Yang Shangfeng , Čech Jiří , Roth Siegmar , Dunsch Lothar
Published: July 2007

Raman and in situ Raman spectroelectrochemical studies of Dy3N@C80@SWCNT peapods have been carried out for the first time. The formation of peapods by the encapsulation of gaseous Dy3N@C80 has been confirmed by HR‐TEM microscopy and by the successful transformation of Dy3N@C80@SWCNT into double‐walled carbon nanotubes. The Raman spectra of the endohedral fullerene cluster changed dramatically in the interior of the single‐walled carbon nanotube (SWCNT). The electrochemical charging of the peapod indicates a slight reversible attenuation of the Raman intensities of fullerene features during anodic doping. The results support the assignment of Raman bands to the Dy3N@C80 moiety inside a SWCNT.
Monomers That Form Conducting Polymers as Structure‐Directing Agents: Synthesis of Microporous Molecular Sieves Encapsulating Poly‐para‐phenylenevinylene
Authors: Atienzar Pedro , Díaz‐Cabañas María J. , Moliner Manuel , Peris Encarna , Corma Avelino , García Hermenegildo
Published: July 2007

We have developed a novel concept that uses monomers required for making conducting polymers as organic structure‐directing agents, for the synthesis of microporous molecular sieves. We show that these monomers facilitate the formation of crystalline and amorphous molecular sieves depending on the synthesis procedure. The monomers filling the pores of the silicates can be polymerized under certain conditions, resulting in a polymer immobilized and protected inside the matrix. The concept was exemplified with para‐phenylenemethylene‐bis(1‐tetrahydrothiophenium) and para‐phenylenemethylene‐bis(trimethylammonium) that were used to template microporous molecular sieves and subsequently to obtain poly‐para‐phenylenevinylene (PPV) inside the matrix. The organic self‐assembled organic–inorganic material was extensively characterized and the implication on electrical conductivity is presented.
Rational Tuning of Melting Entropies for Designing Luminescent Lanthanide‐Containing Thermotropic Liquid Crystals at Room Temperature
Authors: Escande Aude , Guénée Laure , Nozary Homayoun , Bernardinelli Gérald , Gumy Frédéric , Aebischer Annina , Bünzli Jean‐Claude G. , Donnio Bertrand , Guillon Daniel , Piguet Claude
Published: July 2007

The connection of twelve peripheral and divergent dodecyloxy chains to a central tridentate aromatic binding unit provides the dodecacatenar ligand L11, for which room‐temperature mesomorphism is detected. An enthalpically unbalanced large melting entropy (Δ${S{{{\rm L11}\hfill \atop {\rm m}\hfill}}}$=226 J mol−1 K−1) results from the programmed microsegregation induced in the crystalline phase, a phenomenon which is maintained in the associated lanthanide complexes [Ln(L11)(NO3)3] and [Ln(L11)(CF3CO2)3]2. Low‐temperature melting processes (−43≤Tm≤−25 °C) producing room‐temperature hexagonal columnar liquid‐crystalline phases thus result for these novel lanthanidomesogens. A combined photophysical (high‐resolution emission spectroscopy), thermodynamic (differential scanning calorimetry, DSC) and structural (small‐angle X‐ray diffraction, SA‐XRD) investigation of the melting process shows minor structural changes occurring between the crystal (Cr) and the hexagonal columnar mesophase (Colh) in the complexes, which allows the assignment of the existence of these unusual first‐order phase transitions to the negligible mixing entropy produced by the two viscous phases at low temperature. Extension of the concept of chemical tuning of melting entropies for the global design of room‐temperature metallomesogens and liquid crystals is discussed.
Comparison of Physicochemical Properties of New Ionic Liquids Based on Imidazolium, Quaternary Ammonium, and Guanidinium Cations
Authors: Kulkarni Prashant S. , Branco Luís C. , Crespo João G. , Nunes M. Cristiana , Raymundo Anabela , Afonso Carlos A. M.
Published: July 2007

More than 50 ionic liquids were prepared by using imidazolium, quaternary ammonium, and guanidinium cations and various anions. In these series, different cationic structures such as 1‐benzyl‐3‐methylimidazolium [Bzmim]+, 1,3‐dibenzylimidazolium [BzmiBz]+, 1‐octyl‐3‐methylimidazolium [C8mim]+, 1‐decyl‐3‐methylimidazolium [C10mim]+, tricapryl‐methylammonium [Aliquat]+, benzyltriethylammonium [BzTEA]+, phenyltrimethylammonium [PhTMA]+, and dimethyldihexylguanidinium [DMG]+ were combined with anions, p‐toluenesulfonate [TSA]−, dicyanoamide [DCA]−, saccharine (2‐sulfobenzoic acid imide sodium salt) [SAC]−, trifluoroacetate [TFA]−, bis(trifluoromethanesulfonyl)imide [Tf2N]−, trifluoromethanesulfonate [TfO]−, and thiocyanate [SCN]−. Important physical data for these ionic liquids are collated, namely solubility in common solvents, viscosity, density, melting point and water content. Apart from the viscosity, the Newtonian and non‐Newtonian behavior of these ionic liquids is also disclosed. Stability of these ionic liquids under thermal, basic, acidic, nucleophilic, and oxidative conditions was also studied. The features of the solid–liquid phase transition were analyzed, namely the glass transition temperature and the heat capacity jump associated with the transition from the non‐equilibrium glass to the metastable supercooled liquid. A degradation temperature of each ionic liquid was also determined. Comparisons of the properties of various ionic liquids were made.
Atropisomeric 3‐aryl‐2‐oxo‐4‐oxazolidinones and some thione analogues—Enantiodifferentiation and ligand competition in applying the dirhodium method
Authors: Gómez Edison Díaz , Doğan İlknur , Yilmaz Müjde , Demir‐Ordu Öznur , Albert Dieter , Duddeck Helmut
Published: July 2007

The atropisomeric 2‐oxo‐4‐oxazolidinones 1Z bind weakly to the rhodium atoms in the complex Rh[(R)‐(+)‐MTPA]4 (Rh*, MTPA‐H = methoxytrifluoromethylphenylacetic acid ≡ Mosher's acid), presumably via the C‐2 carbonyl oxygen atom. There are some 1H and 13C NMR signals in these compounds which show small dispersion effects suitable for enantiodifferentiation. In contrast, the thiocarbonyl sulfur atoms in 2Z and 3Z bind strongly so that significant complexation shifts (Δδ) and diastereomeric dispersion effects (Δν) can be observed, and chiral discrimination and the determination of enantiomeric ratios of these thiocarbonyl compounds is easy. So, it is shown that—as expected—CS is a much better binding site when competing with CO. In compounds of Series 2 a “syn‐methyl effect” was discovered which describes the dependence of dispersion effects of syn‐oriented methyl groups 6 on the nature of the substituents Z. A mechanism of combined steric and electronic interaction influencing the conformational equilibria inside the adducts is proposed. Determination of absolute configurations by correlation fails, at least on the basis of the data available. Chirality, 2008. © 2007 Wiley‐Liss, Inc.
The origin of an unusually large 19F chemical shift difference between the diastereomeric α‐cyano‐α‐fluoro‐p‐tolylacetic acid (CFTA) esters of 3′,4′,5,7‐tetra‐O‐methylepicatechin
Authors: Brand Dirk J. , Steenkamp Jacobus A. , Omata Kenji , Kabuto Kuninobu , Fujiwara Tomoya , Takeuchi Yoshio
Published: July 2007

During a study on the relationship between the 19F chemical shift difference for the diastereomeric α‐cyano‐α‐fluoro‐p‐tolylacetic acid (CFTA) esters of chiral secondary alcohols and the absolute configurations of the alcohols, an unusually large 19F chemical shift difference has been observed for the CFTA esters of 3',4',5,7‐tetra‐O‐methylepicatechin. This large chemical shift difference has been reproduced by ab initio calculations of molecular geometry and GIAO calculations of 19F chemical shifts on the stable conformations of the diastereomeric α‐cyano‐α‐fluorophenylacetic acid (CFPA) esters of cis‐flavan‐3‐ol as model systems. The origin of the large chemical shift difference has been further investigated using NBO analysis. This revealed that the interaction between π(CC) of the aryl group in the chiral auxiliary and σ*(CF) is a very important determinant of the 19F chemical shifts and this interaction depends on the torsion angle between the plane of aryl group and the CF bond. Chirality, 2008. © 2007 Wiley‐Liss, Inc.
The effects of conformation and solvation on optical rotation: Substituted epoxides
Authors: Wilson Shaun M. , Wiberg Kenneth B. , Murphy Michael J. , Vaccaro Patrick H.
Published: July 2007

The vapor‐phase optical rotation (or circular birefringence) of (S)‐1,2‐epoxybutane, (S)‐epichlorohydrin, and (S)‐epifluorohydrin has been measured at the nonresonant excitation wavelengths of 355 nm and 633 nm by means of Cavity Ring‐Down Polarimetry (CRDP). Complementary solution‐phase studies were performed in a wide variety of dilute solvent media to highlight the pronounced influence of solute–solvent interactions. Density functional theory calculations of optical activity have been enlisted to unravel the structural and electronic provenance of experimental observations. Three stable, low‐lying conformers have been identified and characterized for each of the targeted chiral species, with thermal (relative population weighted) averaging of their antagonistic chiroptical properties allowing specific rotation values to be predicted under both isolated and solvated conditions. For (S)‐epichlorohydrin and (S)‐epifluorohydrin, a self‐consistent isodensity polarizable continuum model (SCI‐PCM) has been exploited to gain further insight into the underlying nature of solvation effects. Chirality, 2008. © 2007 Wiley‐Liss, Inc.
Chiral NMR discrimination of amines: Analysis of secondary, tertiary, and prochiral amines using (18‐crown‐6)‐2,3,11,12‐tetracarboxylic acid
Authors: Lovely Ann E. , Wenzel Thomas J.
Published: July 2007

Enantiomeric discrimination is observed in the 1H and 13C NMR spectra of secondary and tertiary amines in the presence of (−)‐(18‐crown‐6)‐2,3,11,12‐tetracarboxylic acid (1). Nonequivalence of the resonances of prochiral nuclei in primary and secondary amines is also observed when they associate with 1. The amines are added in their neutral form and are protonated by the carboxylic acid groups of 1 to produce the corresponding ammonium and carboxylate ions. Secondary amines associate with 1 through two hydrogen bonds and an ion pair interaction. Tertiary amines can only form one hydrogen bond to accompany the ion pairing. Chiral discrimination in the 1H and 13C NMR spectra of a series of aryl‐containing secondary amines is of sufficient magnitude to determine enantiomeric purities. The discrimination in the spectra of tertiary amines with 1 is smaller, but 13C NMR spectra provided enough distinction for the determination of enantiomeric purity. Chirality, 2008. © 2007 Wiley‐Liss, Inc.
Analysis of pD‐Dependent complexation of N‐benzyloxycarbonylaminophosphonic acids by α‐cyclodextrin. Enantiodifferentiation of phosphonic acid pKa values
Authors: Rudzińska Ewa , Berlicki Łukasz , Mucha Artur , Kafarski Paweł
Published: July 2007

The influence of aqueous solution pD on stereoselective complexation of N‐benzyloxycarbonylaminophosphonic acids with α‐cyclodextrin was investigated by means of nuclear magnetic resonance spectroscopy. The highest enantiodiscrimination was achieved at pD close to the pKa of less acidic hydroxyl group of the phosphonic moiety of analytes (6.5–7.5). This effect results from the stereoselective differentiation of pKa (up to 0.28 pD unit) upon complexation with applied chemical shift reagent. Moreover, analysis of 2D‐ROESY spectra proved that the host–guest inclusion mode is strongly influenced by pD. Chirality, 2007. © 2007 Wiley‐Liss, Inc.
Spinnenseidenproteine: Grundlage für neue Materialien
Authors: Römer Lin , Scheibel Thomas
Published: July 2007

Spinnenseiden sind sehr stabil und gleichzeitig extrem dehnbar – eine Kombination die es in industriell eingesetzten Fasern in dieser Form nicht gibt. Es wird daher seit langem versucht, das große Potential der Spinnenseide in technische Produkte umzusetzen. Dieser Übersichtsartikel fasst den aktuellen Entwicklungsstand zur Seidenstruktur, biotechnologischen Seidenproduktion, und über den Seidenfaser‐Spinnprozess zusammen. Die neuesten Entwicklungen stellen eine Grundlage für neue technische Produkte auf Basis von Spinnenseide dar, was eine neue Generation umweltverträglicher Polymermaterialien ermöglicht.
Carl Hagemann ...ein Mensch von großer Güte, ein richtiger Chemiker...
Authors: Eiden Fritz
Published: July 2007

Der Chemiker Carl Hagemann (1867–1940), der bei den Farbenfabriken Bayer, Cassella und der I.G. Farben A.G. Karriere machte, ist durch eine Sammlung von Bildern Deutscher Expressionisten bekannt geworden. Es handelt sich um denselben Hagemann, der 1893 über eine einfache Methode zur Herstellung von Methyl‐cyclohexenon‐carbonsäureestern berichtete und dessen Name dann mit einem dieser Ester verknüpft wurde. Nach der Strukturaufklärung fand man, dass Hagemanns Ester und viele seiner Derivate sich als Bausteine zur Synthese von Natur‐ und Wirkstoffen eignen. Erstaunlich ist nicht nur, dass die heute hochgeschätzte Hagemannsche Bildersammlung die bösartigen Aktionen der Hitlerdiktatur und die vernichtenden Bombenangriffe der Alliierten überstand, sondern auch, dass das Interesse von Chemikern an Hagemanns Ester bis in unsere Zeit andauert.
Zelloberflächenrezeptor für die Aufnahme von Vitamin A
Authors: Hille‐Rehfeld Annette
Published: July 2007

Fettlösliche Vitamine können durch Zellmembranen frei diffundieren, dennoch erfolgt ihre Aufnahme am Wirkort und in Speicherorgane hochselektiv. Über im Serum zirkulierende Transportproteine binden sie an spezifische Zelloberflächenrezeptoren.
Platensimycin hemmt Bakterienmembran‐Synthese
Authors: Jaenicke Lothar
Published: July 2007

Die bisherigen Antibiotika greifen in die Bildung der Bakterienhülle oder in die DNA‐Verdoppelung ein. Bisher hat sich noch immer rasch eine Resistenz gegen neu eingeführte Bakterienhemmstoffe ausgebildet. Man diskutiert daher, gleichzeitig zwei unterschiedlich wirkende Antibiotika einzusetzen, da simultane Doppelresistenz sehr unwahrscheinlich ist. Man sucht aber eifrig nach neuen und neuartig wirkenden Natur‐ und Synthesestoffen, allerdings meist mit den alten Rezepten (wie in der Politik und allgemein im Leben).
Schloss Oranienburg in Brandenburg
Authors: Schwedt Georg
Published: July 2007

In der ersten Hälfte des 19. Jahrhunderts arbeitete der Chemiker Friedlieb Ferdinand Runge in einem Seitenflügel des Schlosses Oranienburg etwa 30 km nördlich des Standzentrums von Berlin und entdeckte dort u.a. Anilin, Chinolin, Pyrrol und Phenol im Steinkohlenteer. Von ihm stammen auch die berühmten “Professoren‐Kleckse”, Farbstoff‐Trennungen auf Papier nach einer Vorläufer‐Methode der Papier‐Chromatographie.
Improving colorectal cancer screening by using community volunteers
Authors: Katz Mira L. , Tatum Cathy , Dickinson Stephanie L. , Murray David M. , Long‐Foley Kristie , Cooper M. Robert , Daven Morgan , Paskett Electra D.
Published: July 2007

BACKGROUND.

The goal of the Carolinas Cancer Education and Screening (CARES) Project was to improve colorectal cancer (CRC) screening among low‐income women in subsidized housing communities in 11 cities in North and South Carolina who were traditionally underserved by cancer control efforts.

METHODS.

Cross‐sectional samples were randomly selected from housing authority lists at 5 timepoints in this nonrandomized community‐based intervention study. Face‐to‐face interviews focused on CRC knowledge, beliefs, barriers to screening, and screening behaviors. The intervention components were based on a previous evidence‐based program.

RESULTS.

A total of 2098 surveys were completed. Seventy‐eight percent of the respondents were African American, 62% were 65+ years, and 4% were married. At baseline, the rate of CRC screening within guidelines was 49.3% and physician recommendation was the strongest predictor (odds ratio [OR] = 21.9) of being within guidelines. There was an increase in positive beliefs about CRC screening (P = .010) and in the intention to complete CRC screening in the next 12 months (P = .053) after the intervention. The odds of being within CRC screening guidelines for women living in a city that had received the intervention were not significantly different from women living in a city that had not received the intervention (P = .496).

CONCLUSIONS.

Although CRC screening rates were not significantly better after the intervention, there was a positive change in beliefs about screening and intention to be screened. The results suggest that the dissemination of an evidence‐based behavioral intervention may require a longer duration to engage hard‐to‐reach populations and change behaviors. Cancer 2007. © 2007 American Cancer Society.
Inverse correlation between body mass index and clinical outcomes in men with advanced castration–recurrent prostate cancer
Authors: Halabi Susan , Ou San‐San , Vogelzang Nicholas J. , Small Eric J.
Published: July 2007

BACKGROUND.

Obesity has a variety of adverse health outcomes, but to the authors' knowledge, the effect of obesity on outcome in patients with advanced prostate cancer is not known. For this reason, the correlation between an elevated body mass index (BMI) and clinical outcomes in patients with metastatic, castration–recurrent prostate cancer (CRPC) was evaluated.

METHODS.

A total of 1226 men with CRPC who were enrolled in 9 prospective clinical trials conducted by the Cancer and Leukemia Group B (CALGB) for the treatment of metastatic disease were considered. Eligible patients had progressive prostate cancer during androgen deprivation therapy (with documented castrate levels of testosterone); an Eastern Cooperative Oncology Group performance status of 0 to 2; and adequate hematologic, renal, and hepatic function. Patients were classified based on BMI as normal (18.5–24.9 kg/m2), overweight (25–29.9 kg/m2), and mildly to severely obese (≥30 kg/m2).

RESULTS.

Approximately 24% of the patients had a normal BMI, 43% were overweight, and 33% were mildly to severely obese. On multivariable analysis, BMI was found to be a statistically significant predictor of overall survival and prostate cancer–specific mortality. Compared with men with normal BMIs, the hazard ratios for death for overweight men and mildly to severely obese men were 0.80 (95% confidence interval [95% CI], 0.68–0.93; P = .001) and 0.80 (95% CI, 0.68–0.94; P = .010), respectively.

CONCLUSIONS.

In patients with metastatic CRPC, obesity (as defined by an elevated BMI) appears to have a protective effect against overall mortality and prostate cancer–specific mortality. Alternatively, a higher BMI may reflect different cancer biology (ie, the lack of cachexia–producing substances). Further studies to gain a more comprehensive understanding of the mechanisms behind these clinical observations are needed. Cancer 2007. © 2007 American Cancer Society.