bluuebunny/crossref_metadata_2025 huggingface dataset:
Expectations of recovery from revision knee replacement
Authors: Venkataramanan Viji , Gignac Monique A. , Mahomed Nizar N. , Davis Aileen M.
Published: March 2006

Objective

To evaluate outcome expectations of patients undergoing revision total knee replacement (TKR) and to examine personal factors, patient functioning, previous experiences with knee replacement surgery, concerns about surgery, and general health as predictors of expectations.

Methods

Revision TKR patients (n = 184, 54% women; mean age 69 years) completed a questionnaire up to 2 weeks before surgery. This included demographics, experience with previous knee surgery, concerns about surgery, the Life Orientation Test (LOT), the Arthritis Helplessness Scale, the Western Ontario and McMaster Universities Osteoarthritis Index, and a rating of overall health. Outcome expectations were evaluated as 5 questions assessing global benefit; relief of pain; ease of disability; expectations of having complications; and whether the person expected to be fully recovered from surgery in <6 months, 6–12 months, >12 months, or did not expect to recover. Predictors of each of the 5 outcome expectations were evaluated using univariable and multivariable regression analyses.

Results

Expectations are a multidimensional construct (Cronbach's α = 0.63). Expectation of global benefit of surgery was high, but was lower for benefits related to ease of pain and improved function. Concerns about surgery were a consistent predictor of all expectation outcomes in multivariable modeling. When concerns about surgery and general health were entered into the model as an interaction with expectation of recovery time as the outcome, past experience (P = 0.05), pain (P = 0.03), LOT (P = 0.03), and interaction between concerns about surgery and general health were significant predictors.

Conclusion

Clinicians need to understand and help patients shape appropriate expectations for recovery from revision TKR.
Transitions to mobility difficulty associated with lower extremity osteoarthritis in high functioning older women: Longitudinal data from the Women's Health and Aging Study II
Authors: Ling Shari M. , Xue Qian Li , Simonsick Eleanor M. , Tian Jing , Bandeen‐roche Karen , Fried Linda P. , Bathon Joan M.
Published: March 2006

Objective

To assess the impact of lower extremity osteoarthritis (OA) on transitions to mobility difficulty, and to assess the influence of pain, excess weight, and quadriceps strength on these transitions.

Methods

We analyzed longitudinal data acquired from 199 participants in the Women's Health and Aging Study II (ages 70–79 years) who initially reported no lower extremity limitation (e.g., difficulty walking one‐quarter mile) or difficulty in activities of daily living (ADL; e.g., transferring). Prevalent lower extremity OA was determined from validated algorithms encompassing multiple data sources. Markov transition models were created to analyze the first transition from no difficulty at baseline to lower extremity limitations, ADL difficulty, or both 18, 36, and 72 months later.

Results

Compared with women without OA (n = 140), a higher proportion of women with lower extremity OA (n = 59) initially reported pain on most days and more severe pain while walking (P< 0.05). Women with OA were also heavier, with a higher proportion being obese or overweight (P< 0.001). Lower extremity OA, higher body mass index, and lower knee extensor strength independently increased the risk of transition to combined lower extremity and ADL difficulty first over 72 months.

Conclusion

Lower extremity OA increased the likelihood of developing difficulty in both lower extremity tasks and ADL over 72 months in a cohort of initially high functioning older women. Two modifiable factors, higher relative weight and lower knee extensor strength, substantially impacted these transitions, and therefore warrant increased attention in the management of lower extremity OA.
Maternal panic disorder and congenital abnormalities: A population‐based case‐control study
Authors: ács Nándor , Bánhidy Ferenc , Horváth‐Puhó Erzsébet , Czeizel Andrew E.
Published: March 2006

BACKGROUND

Maternal panic disorder in pregnancy is the most common manifestation of anxiety disorders in Hungary. The association between panic disorder during pregnancy and structural birth defects, i.e., congenital abnormalities, was studied.

METHODS

The prevalence of maternal panic disorder in cases with different congenital abnormalities was compared to that of matched controls in the population‐based Hungarian Case‐Control Surveillance System of Congenital Abnormalities.

RESULTS

Of 22,843 cases with congenital abnormalities, 210 (0.9%) had mothers with panic disorder during pregnancy compared to 187 (0.5%) of 38,151 controls (adjusted prevalence odds ratio [POR] 1.6; 95% CI, 1.3–2.0). Specific groups of congenital abnormalities were also assessed versus controls. Cases with isolated cleft lip with or without cleft palate (CL/P) (adjusted POR, 3.4; 95% CI, 1.3–9.0) and multiple congenital abnormalities (adjusted POR, 3.0; 95% CI, 1.2–7.2) were more likely to have had mothers with panic disorder during the study pregnancy. Notably, among mothers with panic disorders, the associations were found only in offspring of untreated mothers.

CONCLUSIONS

A higher rate of isolated CL/P and multiple congenital abnormalities may be caused by the direct biological effect of panic disorder or by the interaction of maternal panic disorder and lifestyle factors. Antipanic drug treatment seems to have a protective effect for isolated CL/P and multiple congenital abnormalities. Birth Defects Research (Part A), 2006. © 2006 Wiley‐Liss, Inc.
Alternative Anschlußbewehrung für im Fundament eingespannte Stützen und Wände
Authors: Zahn Franz A. , Köpfer Axel , Püschel Wolfram , Zehnle David
Published: March 2006

Es wird eine alternative Ausführungsform der Fundamentanschlußbewehrung für am Fuß eingespannte Stützen und Wände diskutiert. Anstatt der üblichen, sich gegenseitig durchdringenden L‐förmigen Abbiegungen wird die Anschlußbewehrung schlaufenförmig ausgebildet, was zu erheblichen Erleichterungen bei der Ausführung führt. Das Verhalten der vorgeschlagenen Form der Anschlußbewehrung wurde in zwei Versuchsreihen sowie durch rechnerische Vergleiche mit Hilfe eines nichtlinearen Finite Element Programms untersucht, deren Ergebnisse hier diskutiert werden.
Flachdecken in Elementbauweise. Hinweise zum Durchstanznachweis nach DIN 1045‐1
Authors: Furche Johannes , Bauermeister Ulrich
Published: March 2006

Flachdecken werden zunehmend aus vorgefertigten Stahlbetonplatten und einer aufbetonierten Ortbetonschicht hergestellt. Das Tragverhalten dieser Elementdecken mit Gitterträgern ist ähnlich dem reiner Ortbetondecken und das gilt prinzipiell auch für durchstanzgefährdete Bereiche. Dieses konnte in Bauteilversuchen gezeigt werden, welche als Grundlage für die Herleitung von Bemessungs‐ und Konstruktionsregelungen dienten. Jedoch sind bei der Bemessung und Konstruktion von Elementdecken gegenüber der von reinen Ortbetondecken einige Besonderheiten zu beachten. Die Umstellung von Zulassungen für Durchstanzsysteme auf das Konzept der neuen DIN 1045‐1 erfolgte zum Teil zeitgleich mit der Einführung einer neuen Durchstanzbewehrung für Elementdecken. Die erforderlichen Nachweise im Durchstanzbereich von Elementdecken werden für unterschiedliche Systeme zusammengestellt und erläutert.
Flachdecken mit Vorspannung ohne Verbund. Ein Beispiel aus der Praxis
Authors: Tremmel Ferdinand , Metzler Helmut
Published: March 2006

Verbundlos vorgespannte Flachdecken ermöglichen gegenüber der konventionellen Bauweise einen größeren Gestaltungsfreiraum für Architekten und Nutzer. Anhand einer ausgeführten Produktionshalle werden Tragwerkskonzepte und Bemessungsansätze erläutert sowie Konstruktionsdetails dargestellt.
Genormte Nachhaltigkeit im Baubereich? Zum Zwischenstand der Normungsarbeiten bei ISO und CEN
Authors: Lützkendorf Thomas
Published: March 2006

Die Umsetzung von Prinzipien einer nachhaltigen Entwicklung im Baubereich führt unter anderem zu einem wachsenden Bedarf an umwelt‐ und gesundheitsrelevanten Informationen zu Bauprodukten sowie an Ergebnissen einer Beurteilung der Umweltqualität von Gebäuden. Derartige Fragestellungen sind derzeit Gegenstand internationaler und europäischer Normungsaktivitäten bei ISO und CEN. Es wird der aktuelle Stand der Normung beschrieben, hinsichtlich möglicher Konsequenzen diskutiert und in einen Gesamtzusammenhang der Unterstützung einer nachhaltigen Entwicklung im Baubereich eingeordnet. Die intensive Beobachtung dieser Entwicklung sowie die normenkonforme und bedarfsgerechte Bereitstellung und Weitergabe von Informationen werden zum Wettbewerbsfaktor.
Erläuterungen zu einigen Auslegungen der DIN 1045‐1
Authors: Fingerloos Frank
Published: March 2006

Seit der bauaufsichtlichen Einführung der Norm DIN 1045‐1 im Jahre 2002 in der Bundesrepublik Deutschland sind im Rahmen ihrer praktischen Umsetzung Fragen der planenden und ausführenden Ingenieure entstanden, die der Interpretation und Auslegung bedürfen. Der Normenausschuß Bauwesen (NABau) im DIN bearbeitet diese Fragen und veröffentlicht die Ergebnisse als offizielle Antworten zu Auslegungsfragen regelmäßig im Internet, um den Praktikern Hilfen zu geben und Unsicherheiten bei der Anwendung der Norm zu reduzieren. Zur weiteren Erhöhung der Normenakzeptanz sollen in diesem Beitrag Erläuterungen zu den Hintergründen einiger Auslegungen gegeben werden, die aufgrund des gebotenen reduzierten Antwortumfangs im Internet fehlen. Die angesprochenen Auslegungsthemen sind: Fundamentbemessung, Expositionsklassen, innerer Hebelarm bei der Querkraftbemessung, Verbundfuge und Stützenkonstruktionsregeln.
Massive Brücken in Mitteldeutschland
Authors: Weller Bernhard , Tasche Martin
Published: March 2006

Anhand ausgewählter Brücken aus Sachsen, Thüringen und Sachsen‐Anhalt soll die Entwicklung des Massivbrückenbaus in Ausschnitten nachgezeichnet werden. Beginnend mit der frühen Steinbrücke über die Werra in Creuzburg, der bekannten Göltzschtalbrücke bei Netzschkau und der Syratalbrücke in Plauen werden mit einer Möllerbrücke und einem Visintini‐Träger zwei weniger bekannte Bauweisen aus den Anfängen des Stahlbetonbaus vorgestellt. Hervorzuheben ist die erste Spannbetonbrücke Deutschlands in Aue/Sachsen ebenso wie die Entwicklung der weltweit ersten textilbewehrten Brücke durch die Technische Universität Dresden.
Femoral nerve entrapment: A new insight
Authors: Vázquez M.T. , Murillo J. , Maranillo E. , Parkin I.G. , Sanudo J.
Published: March 2006

Compression of the femoral nerve in the iliac fossa has been reported as a consequence of several pathologies, but never as a result of muscular compression. Aberrant slips of iliacus, however, have occasionally been reported to cover or split the femoral nerve. This study aimed to assess such variations as potential factors in femoral nerve compression. A large and homogeneous sample of 121 embalmed cadavers (242 specimens) was studied. Statistical comparisons were made using the chi‐squared test. Muscular slips from iliacus and psoas, piercing or covering the femoral nerve, were found in 19 specimens (7.9%). No significant differences by sex or side were found. The more frequent variation was piercing of the femoral nerve by a muscular slip (17 specimens, 7.0%). The nerve then entered the thigh as one or more branches. The less frequent variation found was a muscular slip or sheet covering the femoral nerve as it lay on iliacus (2 specimens, 0.8%). Each disposition may be a potential risk for nerve entrapment. Clin. Anat. 20:175–179, 2007. © 2006 Wiley‐Liss, Inc.
Medial and lateral pectoral nerves: Course and branches
Authors: Macchi Veronica , Tiengo Cesare , Porzionato Andrea , Parenti Anna , Stecco Carla , Mazzoleni Francesco , De Caro Raffaele
Published: March 2006

During modified radical mastectomy or cosmetic surgery, denervation of the lower part of the pectoralis major frequently occurs and may reduce muscle spasm, with consequent better reconstruction of the breast. The aim of this study was to determine the relationship between the pectoral nerves and the pectoral muscles. Eight unembalmed female cadavers were dissected and vascular and radiologic studies performed. The lateral pectoral nerves showed a constant course, parallel to the thoraco‐acromial vessels. They coursed for 55 ± 7 mm inferomedially on the deep surface of pectoralis major, under its fascia. The medial pectoral nerves showed two main patterns of branching, which correlated with the extent of the costal attachments of the pectoralis minor muscles. In pattern A (56%), associated with costal attachments narrower than 6.0 cm, the nerve pierced the deep aspect of the pectoralis minor as a single trunk, ramified in the muscle, and gave some branches that appeared on the superficial aspect to enter the pectoralis major. In pattern B (44%), associated with costal attachments wider than 6.6 cm, the nerve divided before entering pectoralis minor and its branches passed through the muscle or round its lower border to reach pectoralis major. The most medial branch of the medial pectoral nerve directed to the pectoralis major muscle emerged from pectoralis minor at the third intercostal space in the midclavicular line, a mean of 10.3 cm lateral to the margin of the sternum. Knowledge of the relationship between the extent of the costal attachment of pectoralis minor and the two patterns of branching of the medial pectoral nerve may be useful when performing elective denervation of the major pectoralis muscle. Clin. Anat. 20:157–162, 2007. © 2006 Wiley‐Liss, Inc.
Probing the Ligand‐Binding Specificity and Analyzing the Folding State of SPOT‐Synthesized FBP28 WW Domain Variants
Authors: Przezdziak Jana , Tremmel Sandra , Kretzschmar Ines , Beyermann Michael , Bienert Michael , Volkmer‐Engert Rudolf
Published: March 2006

The WW domains are known as the smallest naturally occurring, monomeric, triple‐stranded, antiparallel β‐sheet domains. Hence, we chose the FBP28 WW domain as a model to investigate the stability of the β‐sheet structure at the amino acid level in the context of its function (ligand binding). The structure–function relationship was investigated through a complete substitution analysis of the FBP28 WW domain, with variants synthesized as a cellulose‐bound peptide array. The functionality of the FBP28 WW domain variants was examined by probing the peptide array for ligand binding. In addition, selected FBP28 WW domain variants were investigated by CD measurements to determine the stability of the antiparallel β‐sheet structure. We discuss the correlation between structure stability and functionality for the FBP28 WW domain, as well as the effect of ligand‐induced structure stabilization.
RebG‐ and RebM‐Catalyzed Indolocarbazole Diversification
Authors: Zhang Changsheng , Albermann Christoph , Fu Xun , Peters Noel R. , Chisholm John D. , Zhang Guisheng , Gilbert Eric J. , Wang Peng George , Van Vranken David L. , Thorson Jon S.
Published: March 2006

Rebeccamycin and staurosporine represent two broad classes of indolocarbazole glycoside natural products with antitumor properties. Based upon previous sequence annotation and in vivo studies, rebG encodes for the rebeccamycin N‐glucosyltransferase, and rebM for the requisite 4′‐O‐methyltransferase. In the current study, an efficient in vivo biotransformation system for RebG was established in both Streptomyces lividans and Escherichia coli. Bioconversion experiments revealed RebG to glucosylate a set of indolocarbazole surrogates, the products of which could be further modified by in vitro RebM‐catalyzed 4′‐O‐methylation. Both RebG and RebM displayed substrate promiscuity, and evidence for a remarkable lack of RebG regioselectivity in the presence of asymmetric substrates is also provided. In the context of the created indolocarbazole analogues, cytotoxicity assays also highlight the importance of 4′‐O‐methylation for their biological activity.
Transhepatic closure of atrial septal defect and assisted closure of modified Blalock/Taussig shunt
Authors: Ebeid Makram R. , Joransen James A. , Gaymes Charles H.
Published: March 2006

The details of transhepatic closure of moderate – large size atrial septal defect as well as assisted closure of a modified Blalock Taussing shunt in a 2 1/2 year old patient with occluded femoral vessels are discussed. The technical variations as well as the potential advantages of this route are outlined. © 2006 Wiley‐Liss, Inc.
The paclitaxel‐eluting Coroflex™ please stent pilot study (PECOPS I): Acute and 6‐month clinical and angiographic follow‐up
Authors: Unverdorben Martin , Degenhardt Ralf , Vallbracht Christian , Wiemer Marcus , Horstkotte Dieter , Schneider Henrik , Nienaber Christoph , Bocksch Wolfgang , Gross Michael , Boxberger Michael
Published: March 2006

Background and Objectives: Various active stent coatings significantly reduce restenosis rates and target lesion revascularization compared to bare metal stents. Therefore, the procedural and 6‐month performance of the new paclitaxel‐eluting Coroflex™. Please stent was investigated. Methods: Ninety‐seven patients (66 ± 7.6 years, 34/97(35.1%) diabetics, 11/97(11.3%) unstable angina) were enrolled per protocol for elective single stent deployment into native coronary de‐novo or post‐PTCA restenotic lesions (stenosis: ≥ 70%, < 100%; reference diameter ≥ 2.25 mm and <3.3 mm; lesion length ≤ 16 mm) with 13/97(13.4%) lesion type A, 64/97(66%) type B1, 20/97(20.6%) type B2). The mean reference diameter was 2.88 ± 0.42 mm, the lesion length 10.03 ± 2.93 mm, and the minimal lumen diameter 0.64 ± 0.22 mm. Results: The success rates of procedure and study stent deployment were 100% and 94.8%, respectively. In 5/97(5.2%) two stents were implanted. Follow‐up was performed clinically in 86/87(98.9%) and angiographically in 77/87(88.5%) patients after 6.1 ± 0.7 months. Major adverse cardiac events occurred in 7/87(8%) 1/87(1.2%) subacute thrombosis 10.3hrs post procedure, 1/87(1.2%) myocardial infarction, 5/87(5.7%) target lesion revascularizations. The in‐segment stenosis declined from 78 ± 7.2% to 9.4 ± 6.2% after stenting increasing to 31.9 ± 18.6% at follow‐up. The in‐segment late loss and the late loss index were 0.47 ± 0.6 mm and 0.23 ± 0.29 resulting in 6/77(7.8%) in‐segment restenoses three each of which were located either within or beyond the stent structure. The outcome was neither influenced by the prevalence of diabetes ( p = 0.4), hypercholesterolemia ( p = 1), hypertension ( p = 1), overweight ( p = 1), nor by the family history of coronary artery disease ( p = 0.7). Conclusion: The data of the paclitaxel‐eluting Coroflex™. Please stent tested in PECOPS I are within the range other available paclitaxel‐eluting stent. © 2006 Wiley‐Liss, Inc.
Bioabsorbable metal stents for percutaneous treatment of critical recoarctation of the aorta in a newborn
Authors: Schranz Dietmar , Zartner Peter , Michel‐Behnke Ina , Akintürk Hakan
Published: March 2006

In neonates and infants with critical aortic coarctation, balloon angioplasty is considered for rescue therapy of heart failure. The use of conventional stents is limited because of further vessel growth, the need of redilation, and later surgical removal. However, a novel bioabsorbable magnesium stent (AMS) might overcome such restrictions of vessel stenting in newborns. Presented is the first use of an AMS for acute treatment of a newborn with severely impaired heart function due to a long segment recoarctation after a complex surgical repair. We hypothesize that bioabsorbable stents will dramatically change the treatment of coarctation and recoarctation in newborns. © 2006 Wiley‐Liss, Inc.
Interaction Energies for the Purine Inhibitor Roscovitine with Cyclin‐Dependent Kinase 2: Correlated Ab Initio Quantum‐Chemical, DFT and Empirical Calculations
Authors: Dobeš Petr , Otyepka Michal , Strnad Miroslav , Hobza Pavel
Published: March 2006

The interaction between roscovitine and cyclin‐dependent kinase 2 (cdk2) was investigated by performing correlated ab initio quantum‐chemical calculations. The whole protein was fragmented into smaller systems consisting of one or a few amino acids, and the interaction energies of these fragments with roscovitine were determined by using the MP2 method with the extended aug‐cc‐pVDZ basis set. For selected complexes, the complete basis set limit MP2 interaction energies, as well as the coupled‐cluster corrections with inclusion of single, double and noninteractive triples contributions [CCSD(T)], were also evaluated. The energies of interaction between roscovitine and small fragments and between roscovitine and substantial sections of protein (722 atoms) were also computed by using density‐functional tight‐binding methods covering dispersion energy (DFTB‐D) and the Cornell empirical potential. Total stabilisation energy originates predominantly from dispersion energy and methods that do not account for the dispersion energy cannot, therefore, be recommended for the study of protein–inhibitor interactions. The Cornell empirical potential describes reasonably well the interaction between roscovitine and protein; therefore, this method can be applied in future thermodynamic calculations. A limited number of amino acid residues contribute significantly to the binding of roscovitine and cdk2, whereas a rather large number of amino acids make a negligible contribution.
Site‐Selective Formation of Optically Active Inclusion Complexes of Alkoxo‐Subphthalocyanines with β‐Cyclodextrin at the Toluene/Water Interface
Authors: Adachi Kenta , Watarai Hitoshi
Published: March 2006

Several subphthalocyanine derivatives that contain an alkoxo substituent as an axial ligand (RO‐Subpc, R = 9‐anthracenemethyl, benzyl, phenyl, 3,5‐dimethylbenzyl, 3,5‐dimethylphenyl, 4‐methylbenzyl, and 4‐methylphenyl) were synthesized. The formation of inclusion complexes of RO‐Subpc with β‐CD in DMSO and at the toluene/water interface was investigated by UV/Vis absorption spectroscopy, induced circular dichroism (ICD), and nuclear magnetic resonance (NMR) measurements. Interfacial tension measurements suggested that β‐CD adsorbed as a monolayer at the toluene/water interface and probably orientated towards the toluene phase with its primary face. The 1:1 composition of β‐CD⋅RO‐Subpc inclusion complexes was confirmed in DMSO and at the toluene/water interface for BzO‐Subpc, PhO‐Subpc, MeBzO‐Subpc, and MePhO‐Subpc. A 2:1 inclusion complex of AnO‐Subpc formed in DMSO. The observed ICD spectra of β‐CD⋅RO‐Subpc inclusion complexes are discussed with respect to molecular modeling and the simulation based on Tinoco–Kirkwood theory. Interestingly, the ICD spectra of β‐CD⋅BzO‐Subpc and β‐CD⋅MeBzO‐Subpc inclusion complexes exhibited a negative sign in DMSO and a positive sign at the toluene/water interface. This reversal of the ICD sign strongly suggests a difference in the structure of the inclusion complexes: β‐CD at the interface formed the inclusion complex with its primary face, whereas the secondary face of β‐CD bound favorably to RO‐Subpc in DMSO.
trans‐1‐Sulfonylamino‐2‐isoborneolsulfonylaminocyclohexane Derivatives: Excellent Chiral Ligands for the Catalytic Enantioselective Addition of Organozinc Reagents to Ketones
Authors: Forrat Vicente J. , Prieto Oscar , Ramón Diego J. , Yus Miguel
Published: March 2006

The catalytic enantioselective addition of different organozinc reagents (such as alkyl and aryl derivatives or in situ generated aryl, allyl alkenyl, and alkynyl derivatives obtained through different transmetallation processes) to simple ketones has been accomplished by using titanium tetraisopropoxide and chiral ligands derived from substituted trans‐1‐sulfonylamino‐2‐isoborneolsulfonylaminocyclohexane, producing the corresponding tertiary alcohols with enantiomeric excesses (ee) up to >99 %. A simple and efficient procedure for the synthesis of the chiral ligands used in these reactions is described.
Fullerene Polypyridine Ligands: Synthesis, Ruthenium Complexes, and Electrochemical and Photophysical Properties
Authors: Zhou Zhiguo , Sarova Ginka H. , Zhang Sheng , Ou Zhongping , Tat Fatma T. , Kadish Karl M. , Echegoyen Luis , Guldi Dirk M. , Schuster David I. , Wilson Stephen R.
Published: March 2006

Fullerene coordination ligands bearing one bipyridine or terpyridine unit were synthesized, and their coordination to ruthenium(II) formed linear rod‐like donor–acceptor systems. Steady‐state fluorescence of [Ru(bpy)2(bpy‐C60)]2+ showed a rapid solvent‐dependent, intramolecular quenching of the ruthenium(II) MLCT excited state. Time‐resolved flash photolysis in CH3CN revealed characteristic transient absorption changes that have been ascribed to the formation of the C60 triplet state, suggesting that photoexcitation of [Ru(bpy)2(bpy‐C60)]2+ results in a rapid intramolecular transduction of triplet excited state energy. The electrochemical studies on both [Ru(bpy)2(bpy‐C60)]2+ and [Ru(tpy)(tpy‐C60)]2+ indicated electronic coupling between the metal center and the fullerene core.
Enantio‐ and Diastereoselective Michael Addition Reactions of Unmodified Aldehydes and Ketones with Nitroolefins Catalyzed by a Pyrrolidine Sulfonamide
Authors: Wang Jian , Li Hao , Lou Bihshow , Zu Liansuo , Guo Hua , Wang Wei
Published: March 2006

Chiral (S)‐pyrrolidine trifluoromethanesulfonamide has been shown to serve as an effective catalyst for direct Michael addition reactions of aldehydes and ketones with nitroolefins. A wide range of aldehydes and ketones as Michael donors and nitroolefins as acceptors participate in the process, which proceeds with high levels of enantioselectivity (up to 99 %ee) and diastereoselectivity (up to 50:1 d.r.). The methodology has been employed successfully in an efficient synthesis of the potent H3agonist Sch 50917. In addition, a practical three‐step procedure for the preparation of (S)‐pyrrolidine trifluoromethanesulfonamide has been developed. The high levels of stereochemical control attending Michael addition reactions catalyzed by this pyrrolidine sulfonamide, have been investigated by using ab initio and density functional methods. Transition state structures for the rate‐limiting CC bond‐forming step, corresponding tore‐andsi‐face addition to the reactive conformation of the key enamine intermediates have been calculated. Analysis of these structures indicates that hydrogen bonding plays an important role in catalysis and that the energy barrier forsi‐face attack in reactions of aldehydes to form2R,3Sproducts is lower than that for there‐face attack leading to2S,3Rproducts. In contrast, the energy barrier forre‐face addition is lower than that forsi‐face addition in reactions of ketones. The computational results, which are in good agreement with the experimental observations, are discussed in the context of the stereochemical course of these Michael addition reactions.
Phase II trial of intracerebrospinal fluid etoposide in the treatment of neoplastic meningitis
Authors: Chamberlain Marc C. , Tsao‐Wei Denice D. , Groshen Susan
Published: March 2006

BACKGROUND

The purpose of the current study was to determine the toxicity and response of a fixed dose intracerebrospinal fluid (CSF) etoposide in the treatment of patients with newly diagnosed neoplastic meningitis (NM). NM reportedly occurs in 1% to 5% of patients with known cancer. Currently available treatment options are limited and provide only modest benefit.

METHODS

Twenty‐seven patients (median age, 55 yrs) with clinically and cytologically documented NM received intra‐CSF etoposide. Tumor histologies included lung (8 patients), breast (5 patients), primary brain tumor (4 patients), non‐Hodgkin lymphoma (4 patients), melanoma (4 patients), colon (1 patient), and prostate (1 patient). Concurrent involved‐field radiotherapy (19 of 27 patients) or systemic chemotherapy (17 of 27 patients) was administered based on clinical indications. Etoposide was administered at a fixed dose (0.5 mg every day given 5 days per week every other week for 8 weeks [induction]). Patients were evaluated by CSF cytology and neurologic examination at the conclusion of induction therapy. Responding patients continued to receive etoposide (5 consecutive days every 4 weeks) with monthly evaluations.

RESULTS

Seven of 27 patients (26%) treated with etoposide had a cytologic response and either stable or improved neurologic status at the conclusion of induction. Eight patients (30%) developed disease progression during induction therapy and did not complete the 8‐week induction course of therapy. At the conclusion of induction therapy, 12 patients (44%) had persistently positive CSF cytology, although they were clinically stable. In responding patients, time to neurologic disease progression ranged from 8 weeks to 40 weeks (median, 20 wks). Toxicity manifested as transient chemical arachnoiditis (5 of 27 patients; 13% of all treatment cycles). The 6‐month neurologic disease progression‐free survival was 11%.

CONCLUSIONS

Etoposide appears to have modest activity against NM and easily managed toxicity. Cancer 2006. © 2006 American Cancer Society.
The influence of comorbidities, age, and performance status on the prognosis and treatment of patients with metastatic carcinomas of unknown primary site
Authors: Seve Pascal , Sawyer Michael , Hanson John , Broussolle Christiane , Dumontet Charles , Mackey John R.
Published: March 2006

BACKGROUND

The authors investigated how comorbidities, age, and performance status were related to the choice of chemotherapy and to the prognosis of patients with carcinomas of unknown primary site (CUP).

METHODS

Patients in Northern Alberta who were diagnosed with CUP during 2000 to 2003 were included (n = 389 patients). Survival was compared by age at diagnosis (ages <65 years, 65‐74 years, and >75 years), comorbidity score (Adult Comorbidity Evaluation‐27 [ACE‐27] scores of 0‐1 and >2), performance status (PS), and other explanatory variables, such as gender, histology, and site and number of metastases.

RESULTS

The median age was 68 years, and the median overall survival was 12 weeks. An ACE‐27 overall comorbidity score >2 was found in 34% of patients, and a PS >2 was observed in 50% of patients. Multivariate analysis showed that patients who had a PS ≥2 and a high overall ACE‐27 score had a worse prognosis. The impact of comorbidities on survival was limited to patients with low PS. Patients who were not evaluated at a cancer center were older, had a worse functional status, and had more moderate or severe comorbidities. Among the 257 patients who were evaluated at a cancer center, 108 patients received chemotherapy, and 121 patients had a good PS (0‐1). Age was the only independent variable that was related to the likelihood of not receiving chemotherapy among patients who had a good PS. The median overall survival of the 121 patients who had a good PS was 317 days, and overall survival was not associated significantly with chemotherapy. A logistic regression analysis that included all patients who were evaluated at a cancer center identified young age, good PS, lymph node/pleural involvement, and few comorbidities as variables that were associated independently with receiving chemotherapy.

CONCLUSIONS

Patients with CUP who were not evaluated at a cancer center were older, had a worse functional status, and had more moderate or severe comorbidities; this referral bias largely explained the differences between data from registries and from tertiary centers. Moderate and severe comorbidities impacted survival in patients with who had a PS ≥2. An age‐related decline was observed in the percentage of adults with good PS who received chemotherapy. The current results suggested that older patients with CUP were under treated and that factors other than PS were involved in the decision to use chemotherapy for the treatment of patients with CUP. Cancer 2006. © 2006 American Cancer Society.
A Down syndrome patient treated with peritoneal dialysis
Authors: Horcicka Vladko , Zadrazil Josef , Zahálková Jana , Krejcí Karel , Strebl Pavel , Al Jabry Sadek
Published: March 2006

Background

Down syndrome patients are not always suited for peritoneal dialysis, mainly due to their lack of compliance with the procedure. We report a case of a 42‐year‐old male Down syndrome patient successfully treated with peritoneal dialysis.

Methods

The patient suffered from end‐stage renal disease caused by chronic pyelonephritis due to a dysplastic urinary tract. Comorbid conditions included hypothyroidism, hypertension, hyperlipidemia, malnutrition with obesity, left ventricle dysfunction, multiple corneal erosions, and glaucoma. Because, in this case, the patient's mother would be required to sit full time at his bedside during a hemodialysis procedure, a peritoneal dialysis program was preferred. The treatment was complicated by peritoneal catheter dysfunction leading to the prolongation of the draining out time and the need to change the position of the body during drainage in the 29th month of treatment.

Results

Three months later, when the patient became overhydrated and a dry ultrafiltration procedure in the hemodialysis unit became necessary, the peritoneal catheter was replaced, which solved this problem.

Conclusion

Although the peritoneal dialysis procedure in mentally retarded patients is prone to failure mainly because of an increased risk of peritonitis and a burn‐out syndrome among their parents, this patient's mother has been successfully treating him by for more than 4 years without a single episode of peritonitis.
Reactivity of Polyiodides Towards 1,3‐Bis(4‐pyridyl)propane (bpp): A New CuI Cluster Polycatenane Framework and a Novel 2D AgI Cluster Motif
Authors: Niu Yunyin , Song Yinglin , Zhang Ning , Hou Hongwei , Che Deji , Fan Yaoting , Zhu Yu , Duan Chunying
Published: March 2006

The solution‐phase reactions of metal iodides or iodine with 1,3‐bis(4‐pyridyl)propane (bpp) yields four new organic–inorganic hybrid frameworks, namely [(CuI)4(bpp)4]n(1), [(AgI)6(bpp)]n (2), [PbI2(bpp)]n (3), and [I3(bppH)] (4), each of which adopts a different structural motif. For example, complex 1 is a 2D “open” coordination polymeric cluster consisting of a CuI2Cu rhomboid cluster core coordinated by anti‐anti and anti‐gauche bpp interactions to produce an interpenetrating 2D (4,4) polycatenane net; 2 is a novel bpp inclusion compound with a unique 2D polymeric hexagonal prism‐shaped [Ag6I6]n cluster motif; compound 3 is also a 2D “open” supramolecular cluster made from [PbI2]n “ribbons” and bpp bridges; compound 4 is a triiodide made up of organic [bppH]+ cations and a I3– anion chain. The clusters 1–3 obtained from the reaction between polyiodide complexes and an organic ligand suggest that this simple synthetic approach is likely to be applicable to the construction of polymeric clusters. The third‐order NLO effects of 1 were studied by Z‐scan techniques. The polymeric cluster exhibits good nonlinearities and the effective third‐order NLO refractive index (n2) value is 2.56 × 10–12 esu which is comparable to those of most cluster monomers and polymers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Hydrogen Bonding and Proton Transfer to the Trihydride Complex [Cp*MoH3(dppe)]: IR, NMR, and Theoretical Investigations
Authors: Belkova Natalia V. , Revin Pavel O. , Besora Maria , Baya Miguel , Epstein Lina M. , Lledós Agustí , Poli Rinaldo , Shubina Elena S. , Vorontsov Evgenii V.
Published: March 2006

The interaction between [Cp*MoH3(dppe)] (dppe = Ph2PCH2CH2PPh2) and a variety of proton donors hasbeen investigated by a combination of experiments andDFT calculations. Weak proton donors [2‐monofluoroethanol (MFE) and trifluoroethanol (TFE)] allow the determination of basicity factor (Ej = 1.42 ± 0.02) and thermodynamicparameters for the hydrogen bond formation (ΔHHB =–4.9 ± 0.2 and –6.1 ± 0.3 kcal mol–1; ΔSHB = –15.7 ± 0.7 and–20.4 ± 1 cal mol–1 K–1 for MFE and TFE, respectively). For TFE, a stable low‐temperature proton‐transfer equilibrium (220–240 K) with the cationic classical tetrahydrido derivative [Cp*MoH4(dppe)]+ could be investigated independently by UV/Vis (ΔH°PT = –2.8 ± 0.4 kcal mol–1 and ΔS°PT =–15 ± 2 cal mol–1 K–1) and 1H NMR (ΔH°PT = –2.7 ± 0.5kcal mol–1 and ΔS°PT = –11 ± 2 cal mol–1 K–1) spectroscopy. Upon warming, however, the tetrahydride evolves by dihydrogen loss and formation of a hydride‐free diamagnetic product. Stronger proton donors [hexafluoroisopropanol (HFIP), p‐nitrophenol (PNP), perfluoro‐tert‐butyl alcohol (PFTB), and HBF4·OEt2] lead to more extensive proton transfer at lower donor/Mo ratios. A 1:1 proton‐transfer stoichiometry is indicated independently by a titration experiment with UV/Vis monitoring for the [Cp*MoH3(dppe)]–PNP reaction, and by a stopped‐flow kinetics investigation for the [Cp*MoH3(dppe)]–HFIP reaction. For all proton‐transfer processes investigated, the classical tetrahydrido cation forms directly, without the observation of a nonclassical intermediate. DFT calculations have been carried out on the interaction between TFE and HFIP and the model compound [CpMoH3(dpe)] (dpe = H2PCH2CH2PH2) both in the gas phase and in CH2Cl2 solvent with the polarizable continuum model and, to a more limited extent, on the full [Cp*MoH3(dppe)] system. A detailed comparison of the observed and calculated frequency shifts for the M–H vibrations is presented. The calculations have explored therelative energy and geometry of various configurations involving either a hydride ligand or the metal as the principal proton‐accepting site. They have also probed two principal proton‐transfer pathways, leading to the unobserved nonclassical intermediate and to the observed classical product. From these studies, it appears that a nonclassical intermediate may be obtained by a kinetically controlled proton transfer to a hydride site, followed by an intramolecular rearrangement through a very low energy barrier. However, a competitive low‐energy pathway for direct proton transfer at the metal site is also revealed by the calculations. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Basicity of Amines in the Gas Phase – Analysis of the Base‐Strengthening Effect of an N‐Trityl Group by Use of a Triadic Formula
Authors: Vianello Robert , Maskill Howard , Maksić Zvonimir B.
Published: March 2006

An ab initio theoretical method based on a triadic formula has been employed to calculate changes in proton affinities (PAs) after sequential substitution of C–H by C–phenyl in methylamine and in the N‐methyl component of N‐methylacetamide. The overall objective was to investigate the cause of the recently reported unexpected basicity‐enhancing effect of the N‐trityl group in several amines and in acetamide. The triadic method indicates that the increase in PA from NH3 to CH3NH2 is principally due to destabilisation of the lone pair, compensated to some degree by a smaller bond energy term. The increasing PAs along the series CH3NH2, PhCH2NH2, Ph2CHNH2 and Ph3CNH2 are mainly due to an increasing relaxation energy effect following increasing phenyl substitution, supported by increasing bond energy terms. Introduction of para‐methoxy substituents in tritylamine would be calculated to result in small incremental increases in PA, in agreement with experimental findings. The PA of tricyclohexylmethylamine (233.6 kcal·mol–1) is calculated to be similar to that of trimethoxytritylamine (233.5 kcal·mol–1), a consequence of the destabilisation of the lone pair on nitrogen by the three bulky cyclohexyl groups. Results for acetamide indicate that protonation on oxygen is more favourable than on nitrogen, which supports the intuitive argument that conventional π‐electron resonance stabilisation of the O‐protonated cation should be appreciably greater than hyperconjugative stabilisation of the N‐protonated isomer. The increase in PA along the series MeCONHCH3, MeCONHCH2Ph, MeCONHCHPh2 and MeCONHCPh3 parallels the increase from CH3NH2 to Ph3CNH2 and is again principally a consequence of the increasing relaxation energies, which dominate the negative bond energy term contributions. Prior to protonation, the nitrogen atom of MeNHAc is perfectly planar, consistently with resonance delocalisation of the nitrogen lone pair into the carbonyl group. In contrast, there is a 6.5 % degree of pyramidalisation at the nitrogen in TrNHAc [calculated at the B3LYP/6‐31G(d) level], indicating a reduced resonance interaction due to steric crowding, in support of a previous suggestion. Finally, the computed PAs and predicted first adiabatic ionisation energies are in satisfactory agreement with experimental results where these are available.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Synthesis of Pyrazoles by Treatment of 3‐Benzylchromones, 3‐Benzylflavones and Their 4‐Thio Analogues with Hydrazine
Authors: Lévai Albert , Silva Artur M. S. , Cavaleiro José A. S. , Alkorta Ibon , Elguero José , Jekő József
Published: March 2006

The synthesis of pyrazoles 13–24 has been accomplished by treatment of 3‐benzylchromones 1–5, 3‐benzylflavones 6–12 and their 4‐thio analogues 25–29 with hydrazine hydrate in hot pyridine. A plausible reaction mechanism for the formation of pyrazoles 13–24 is discussed. A 1H NMR study in [D6]DMSO allowed the presence of both pyrazole annular tautomers to be observed, due to the presence of intramolecular hydrogen bonds in each tautomer (OH‐‐N and NH‐‐O). GIAO/B3LYP/6‐311++G** calculations were carried out on some model pyrazoles to provide a theoretical basis for the NMR experimental observations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Access to Variously Substituted 5,6,7,8‐Tetrahydro‐3H‐quinazolin‐4‐ones via Diels–Alder Adducts of Phenyl Vinyl Sulfone to Cyclobutene‐Annelated Pyrimidinones
Authors: Dalai Suryakanta , Belov Vladimir N. , Nizamov Shamil , Rauch Karsten , Finsinger Dirk , de Meijere Armin
Published: March 2006

Under basic conditions (Et3N, dioxane), the aromatic amidines 4 and also S‐methylisothiourea 4g cleanly undergo Michael addition to methyl 2‐chloro‐2‐cyclopropylideneacetate (5), followed by intramolecular nucleophilic substitution, cyclopropyl to cyclobutyl ring enlargement, deprotonation and cyclization with elimination of methanol to afford the cyclobutene‐annelated pyrimidinones 6 in 43–83 % yield (7 examples). Thermal cyclobutene‐ring opening of the latter at 175 °C followed by regioselective Diels–Alder cycloaddition with phenyl vinyl sulfone gives the 2‐aryl‐6‐(phenylsulfonyl)‐5,6,7,8‐tetrahydroquinazolinone derivatives 12 in 39–83 % yield (7 examples). Base‐induced elimination of benzenesulfinic acid and subsequent catalytic hydrogenation leads to the 2‐aryltetrahydroquinazolinone derivatives 14 in excellent yields (6 examples). Deprotonation at the sulfonyl‐substituted center, alkylation and subsequent elimination of benzenesulfinic acid followed by catalytic hydrogenation gives the 2,6‐disubstituted tetrahydroquinazolinones 17a‐R. Nucleophilic substitution of the methylthio group in 12g by secondary amines yields the 2‐(dialkylamino)tetrahydroquinazolinones 14i–k.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Star‐Shaped Push‐Pull Compounds Having 1,3,5‐Triazine Cores
Authors: Meier Herbert , Karpuk Elena , Christof Holst Hans
Published: March 2006

The 1,3,5‐triazines 9–11 having OPV chains in the 2‐, 4‐ and 6‐position represent star‐shaped compounds which exhibit strong push‐pull effects. Their long‐wavelength absorption S0 → S1 is characterized by an intramolecular charge transfer (ICT) from the dialkylamino group as electron donor D via the conjugated chain to the 1,3,5‐triazine core as electron acceptor A. Protonation of the dialkylamino group removes the donor capability, whereas protonation of the 1,3,5‐triazine ring enhances the acceptor strength. Thus, the prevailing protonation site has a crucial influence on the push‐pull effect and the ICT. The transition energies ΔE (S0 → S1) pass through a minimum for the second generation 10 in the electroneutral series 9–11; on the contrary they pass through a maximum for 10b in the protonated series 9a, 10b, 11b. These unexpected results are explained by the superposition of different effects, namely the extension of the conjugation from 9 to 11, the decreasing ICT for growing distances of D and A, the aggregation, and the positions of the protonation in the presence of increasing amounts of CF3COOH. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Enantiodifferentiation of Aliphatic Ethers by the Dirhodium Method
Authors: Díaz Gómez Edison , Albert Dieter , Duddeck Helmut , Kozhushkov Sergei I. , de Meijere Armin
Published: March 2006

The enantiomers of chiral aliphatic ethers can easily bedifferentiated by the dirhodium method, i.e. by 1H and13C NMR spectroscopy in the presence of the chiral auxiliary Rh2[(+)‐MTPA]4. This is the first direct chiral recognitionby spectroscopic methods in this class of ligand compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Intermolecular [4+2] Cycloadditions of a Reactive Cyclopentadienone
Authors: Harmata Michael , Gomes Maria G.
Published: March 2006

A reactive cyclopentadienone gives Diels–Alder cycloadducts with a variety of dienes in high yield and often with extremely high levels of regio‐ and stereoselectivity. The high degree of generality of this reaction suggests it will be of use in organic synthesis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Transformation of tertiary butyl mercaptan in aerobic environments
Authors: Kalainesan S. , Erickson L.E. , Hutchinson S.L.L. , Urban J.E. , Karthikeyan R.
Published: March 2006

Tertiary butyl mercaptan (TBM) is a malodorant that is added to natural gas in small quantities to aid in its detection. The objective of this study was to investigate the degradation of TBM under aerobic conditions.

A bacterial culture was found that grew well on TBM in liquid minimal media under aerobic conditions. The doubling time was about 98 h at 30° C. In cultures where iron fillings were added, the growth rate increased and the doubling time was 44 h. In studies with manganese dioxide and potassium permanganate, TBM was oxidized chemically at rates that were rapid compared to those in the microbiological studies.

Soil microcosms containing soil, water, and TBM were set up using two different soils and their headspace was sampled during a 62‐day period of study. In the first set, there was significantly greater reduction in TBM and production of carbon dioxide in the treatments compared to that of the sterilized controls. An intermediate product di‐tertiary‐butyl disulfide (DTBD) was identified. The experimental results show that TBM appears to be biodegradable in soil–water systems under aerobic conditions. © 2006 American Institute of Chemical Engineers Environ Prog, 2006