bluuebunny/crossref_metadata_2025 huggingface dataset:
New Cascade Syntheses of Nitronyl Nitroxides and a New Synthetic Approach to Imino Nitroxides
Authors: Tretyakov Eugene , Tolstikov Svyatoslav , Mareev Aleksander , Medvedeva Alevtina , Romanenko Galina , Stass Dmitry , Bogomyakov Artem , Ovcharenko Victor
Published: April 2009

Suspensions of MxOy (MnO2, Co2O3, Ni2O3) in protic solvents (MeOH, EtOH) have been found to be suitable systems for use in a cascade transformation of 4,4,5,5‐tetramethyl‐2‐[2‐(trimethylsilyl)ethynyl]imidazolidine‐1,3‐diol (1a) into 2‐ethynyl‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazole‐1‐oxyl 3‐oxide (3). In MnO2/MeOH, the products of further transformation of 3, (Z)‐ and (E)‐2‐(2‐methoxyvinyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazole‐1‐oxyl 3‐oxides, were obtained by the regiospecific addition of MeOH to the triple bond of 3. In the reaction in MnO2/MeOH+H2O (1:1), the Z isomer was the sole product. A multistep one‐pot transformation of 1 into 4,4,5,5‐tetramethyl‐2‐[2‐oxo‐1‐(4,4,5,5‐tetramethylimidazolidin‐2‐ylidene)ethyl]‐4,5‐dihydro‐1H‐imidazole‐1‐oxyl 3‐oxide occurred in MnO2/EtOH. For (E)‐2‐[2‐(diethylamino)vinyl]‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazole‐1‐oxyl 3‐oxide, it was shown that use of the MnO2/secondary amine system provided a one‐pot transformation of 1a and gave (E)‐aminovinyl‐substituted nitronyl nitroxide as the sole product. In combined MnO2/ROH/K2CO3 systems (R = Me, Et), the imidazolidine‐1,3‐diol 1a was transformed into (E)‐2‐(2‐ethoxyvinyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazole‐1‐oxyl 3‐oxide and the acetals 2‐(2,2‐dimethoxyethyl)‐ and 2‐(2,2‐diethoxyethyl)‐4,4,5,5‐tetramethyl‐4,5‐dihydro‐1H‐imidazole‐1‐oxyl 3‐oxide. In MnO2/MeNO2 we obtained the products of the transformations of different 2‐substituted 4,4,5,5‐tetramethylimidazolidine‐1,3‐diols (R = C≡C–SiMe3, aryl, hetaryl, alkyl) or nitronyl nitroxides into the corresponding imino nitroxides (13 products); this reaction is a new method for the preparation of imino nitroxides and allowed us to synthesize the first α‐acetylenyl‐substituted imino nitroxides. The majority of paramagnetic compounds, including the derivatives of 1a, were obtained as perfect crystals, and their structures were determined by X‐ray structure analysis (14 solved structures). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Cationic Rhodium(I)/H8‐binap Complex Catalyzed [2+2+2] Cycloadditions of 1,6‐ and 1,7‐Diynes with Carbonyl Compounds
Authors: Otake Yousuke , Tanaka Rie , Tanaka Ken
Published: April 2009

We have established that a cationic rhodium(I)/H8‐binap complex catalyzes [2+2+2] cycloadditions of a variety of 1,6‐ and 1,7‐diynes with both electron‐deficient and electron‐rich carbonyl compounds, leading to dienones in high yield under mild reaction conditions. In the reactions with acyl phosphonates, the reactivity of 1,6‐ and 1,7‐diynes was highly dependent on their own structures. The addition of chelating diethyl oxalate effectively promoted the [2+2+2] cycloadditions involving acyl phosphonates, presumably due to the equilibrium formation of the desired 1:1 rhodium complex of the diyne and the acyl phosphonate by facile ligand exchange between the diyne and weakly coordinated diethyl oxalate. In the reactions involving bifunctional carbonyl compounds or unsymmetrical 1,6‐diynes, high chemo‐ or regioselectivities were observed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Modeling monthly temperature data in Lisbon and Prague
Authors: Alpuim Teresa , El‐Shaarawi Abdel
Published: April 2009

This paper examines monthly average temperature series in two widely separated European cities, Lisbon (1856–1999) and Prague (1841–2000). The statistical methodology used begins by fitting a straight line to the temperature measurements in each month of the year. Hence, the 12 intercepts describe the seasonal variation of temperature and the 12 slopes correspond to the rise in temperature in each month of the year. Both cities show large variations in the monthly slopes. In view of this, an overall model is constructed to integrate the data of each city. Sine/cosine waves were included as independent variables to describe the seasonal pattern of temperature, and sine/cosine waves multiplied by time were used to describe the increase in temperature corresponding to the different months. The model also takes into account the autoregressive, AR(1), structure that was found in the residuals. A test of the significance of the variables that describe the variation of the increase in temperature shows that both Lisbon and Prague had an increase in temperature that is different according to the month. The winter months show a higher increase than the summer months. Copyright © 2009 John Wiley & Sons, Ltd.
Coupled Navier–Stokes—Molecular dynamics simulations using a multi‐physics flow simulation framework
Authors: Steijl R. , Barakos George N.
Published: April 2009

Simulation of nano‐scale channel flows using a coupled Navier–Stokes/Molecular Dynamics (MD) method is presented. The flow cases serve as examples of the application of a multi‐physics computational framework put forward in this work. The framework employs a set of (partially) overlapping sub‐domains in which different levels of physical modelling are used to describe the flow. This way, numerical simulations based on the Navier–Stokes equations can be extended to flows in which the continuum and/or Newtonian flow assumptions break down in regions of the domain, by locally increasing the level of detail in the model. Then, the use of multiple levels of physical modelling can reduce the overall computational cost for a given level of fidelity. The present work describes the structure of a parallel computational framework for such simulations, including details of a Navier–Stokes/MD coupling, the convergence behaviour of coupled simulations as well as the parallel implementation. For the cases considered here, micro‐scale MD problems are constructed to provide viscous stresses for the Navier–Stokes equations. The first problem is the planar Poiseuille flow, for which the viscous fluxes on each cell face in the finite‐volume discretization are evaluated using MD. The second example deals with fully developed three‐dimensional channel flow, with molecular level modelling of the shear stresses in a group of cells in the domain corners. An important aspect in using shear stresses evaluated with MD in Navier–Stokes simulations is the scatter in the data due to the sampling of a finite ensemble over a limited interval. In the coupled simulations, this prevents the convergence of the system in terms of the reduction of the norm of the residual vector of the finite‐volume discretization of the macro‐domain. Solutions to this problem are discussed in the present work, along with an analysis of the effect of number of realizations and sample duration. The averaging of the apparent viscosity for each cell face, i.e. the ratio of the shear stress predicted from MD and the imposed velocity gradient, over a number of macro‐scale time steps is shown to be a simple but effective method to reach a good level of convergence of the coupled system. Finally, the parallel efficiency of the developed method is demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.
Physico–chemical and in vitro biological study of zinc‐doped calcium sulfate bone substitute
Authors: Hesaraki Saeed , Nemati Roghayeh , Nazarian Hamid
Published: April 2009

In the present study, series of Zn incorporated calcium sulfate bone cements, with different amounts of doped Zn(0, 0.74, 1.97, 3.05, 4.21 wt %) were prepared by mixing a calcium sulfate hemihydrate powder and solutions of zinc sulfate, and the effect of zinc‐doping on some physical, physico–chemical, and biological properties of the cements were investigated. Pure calcium sulfate cement was also made as control, with the mentioned powder and distilled water as liquid phase. The initial setting time and compressive strength of the cement significantly changed from 17 min and 3.2 MPa for the pure calcium sulfate to 6 min and 6 MPa for the Zn‐added calcium sulfate, respectively. Compared to pure calcium sulfate, more gypsum precipitates were formed in the zinc sulfate added samples with a morphology of thin, elongated, and rod‐shaped crystals. The biological properties of the samples were analyzed in the terms of cell viability and cell activity on human osteosarcoma (G‐292) using MTT assay and alkaline phosphatase (ALP) activity in the cell culture medium. The best increased cell density and ALP activity were achieved for the calcium sulfate cement with a content of 0.74 wt % Zn, whereas a toxic behavior was observed for the samples with Zn concentrations more than 1.97%. © 2009 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2009
Stability of climate signal in carbon and oxygen isotope records and ring width from Scots pine (Pinus sylvestris L.) in Finland
Authors: Hilasvuori Emmi , Berninger Frank , Sonninen Eloni , Tuomenvirta Heikki , Jungner Högne
Published: April 2009

Four hundred year long records of carbon and oxygen stable isotope ratios and ring width were measured from Scots pine (Pinus sylvestris L.) from sites in Northern and Eastern Finland. Responses of isotope ratios to temperature and precipitation were analysed for the 20th century. Carbon isotope ratios responded strongly to summer temperature at both sites, whereas an influence of precipitation on the record was observed only at the site in Eastern Finland. Oxygen isotope ratios were less responsive to climatic variation than carbon at the high‐frequency level. To shed light on the role of the possible divergence problem during last decades the climate responses were studied separately in the first and in the second half of the 20th century. The responses to temperature were stable in the north but in Eastern Finland the significant period of summer occurred earlier during the later half of the century. Relationships between records were studied during the 400 a period. All proxies correlated positively with each other, although temporal changes occurred. Common forcing, discovered in Northern Finland between carbon isotope and ring width records, was weaker in the earlier period studied. Three climate reconstructions were created: temperature reconstruction for Northern Finland and temperature and precipitation reconstructions for Eastern Finland. Copyright © 2009 John Wiley & Sons, Ltd.
The last deglaciation in the Picos de Europa National Park (Cantabrian Mountains, northern Spain)
Authors: Moreno Ana , Valero‐Garcés Blas L. , Jiménez‐Sánchez Montserrat , Domínguez‐Cuesta María José , Mata M. Pilar , Navas Ana , González‐Sampériz Penélope , Stoll Heather , Farias Pedro , Morellón Mario , Corella J. Pablo , Rico Mayte
Published: April 2009

A sedimentological and geochemical study of the Lago Enol sequence (Cantabrian Mountains, northern Spain), together with detailed geomorphological mapping, provides a first record of glacier evolution and climate change over the last 40 ka in the Picos de Europa National Park. The Enol glacier retreated from its maximum extent prior to 40 ka BP as demonstrated by the onset of proglacial lacustrine sedimentation in two glaciated depressions: the Comella hollow to the north (before 40 ka BP) and the Lago Enol (before 38 ka BP). These results support previous evidence that the maximum extent of southern European glaciers occurred earlier than in northern Europe. Alternation of homogeneous and laminated proglacial sediments during the glacier retreat illustrate a dynamic glacial evolution during the Marine Isotope Stage (MIS) 3 (40–26 ka BP). A slight warming is detected at 26 ka ago with the change from proglacial sediments (in a lake located in contact to the glacier) to glaciolacustrine sedimentation (in a non‐contact or distal lake). Finally, the onset of organic‐rich sediments took place at 18 ka ago. This last transition occurred in two phases, similarly to the North Atlantic Last Termination, suggesting a link between North Atlantic Deep Water formation oscillations and palaeohydrological variability in the Cantabrian Mountains. Copyright © 2009 John Wiley & Sons, Ltd.
FT‐IR, FT‐Raman and DFT calculations of the salicylanilide derivate 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate
Authors: Varghese Hema Tresa , Panicker C. Yohannan , Madhavan V.S. , Mathew Samuel , Vinsova Jarmila , Van Alsenoy Christian
Published: April 2009

FT‐IR and FT‐Raman spectra of 4‐chloro‐2‐(4‐bromophenylcarbamoyl)phenyl acetate were recorded and analyzed. The vibrational wavenumbers and corresponding vibrational assignments were examined theoretically using the Gaussian03 set of quantum chemistry codes. The red shift of the NH stretching wavenumber in the infrared (IR) spectrum from the computed wavenumber indicates the weakening of the NH bond resulting in proton transfer to the neighbouring oxygen atom. The simultaneous IR and Raman activations of the CO stretching mode give the charge transfer interaction through a π‐conjugated path. Optimized geometrical parameters of the title compound are in agreement with similar reported structures. From the optimized structure, it is clear that the hydrogen bonding decreases the double bond character of CO bond and increases the double bond character of the CN bonds. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with the reported values of similar derivatives and is an attractive object for future studies of non‐linear optics. The assignments of the normal modes are done by potential energy distribution (PED) calculations. Copyright © 2009 John Wiley & Sons, Ltd.
Ten‐year results of cartilage palisades versus fascia in eardrum reconstruction after surgery for sinus or tensa retraction cholesteatoma in children
Authors: Cayé‐Thomasen Per , Andersen Janne , Uzun Cem , Hansen Søren , Tos Mirko
Published: April 2009

Objectives/Hypothesis:

To compare cartilage palisades with fascia grafting in reconstruction of the eardrum after surgery for sinus or tensa retraction cholesteatoma in children, with respect to long‐term postoperative eardrum retraction and perforation, cholesteatoma recurrence, and hearing acuity.

Methods:

A total of 64 children underwent surgery for either sinus or tensa retraction cholesteatoma during the period 1995 to 2000 (mean age 9 years, range 5–15). The eardrum was reconstructed using cartilage palisades in 32 children (32 ears) and fascia or perichondrium in 32 children (33 ears). The patients were followed for at least one year postoperatively and re‐evaluated 4 years after surgery, and again recently at a mean of 10 years. The main outcome measures were postoperative drum retraction and perforation, cholesteatoma recurrence, and hearing acuity (pure tone average, speech reception threshold, and pure tone air‐bone gap).

Results:

All but two patients in both groups attended the 10‐year follow‐up examination (94% attendance). The mean overall follow‐up period was 119 months (115 months in the palisade and 125 months in the fascia group). Total number of retractions during follow‐up and at the 10‐year examination was six (19%) for the palisade group and 14 (42%) for the fascia group (P = .03; chi‐square test). The accumulated numbers for a perforation were four (13%) for the palisade group and seven (21%) for the fascia group (difference not significant). Two residual cholesteatomas, which are not related to the graft material, occurred in the palisade group (6%), whereas both recurrencies, which may be related to the graft material, occurred in the fascia group (6%). The hearing acuity for children operated on for a sinus cholesteatoma and for children with type III tympanoplasties was significantly better when cartilage palisade grafting had been employed.

Conclusions:

The cartilage palisade grafting technique appears superior with respect to prevention of long‐term eardrum retraction. The occurrence of cholesteatoma recurrency and eardrum perforation seem to be independent of grafting material, although these results may be due to type 2 error (low number of ears). In sinus cholesteatoma surgery and in type III tympanoplasty, the long‐term hearing results appear better when grafting cartilage palisades. Laryngoscope, 2009
Carcinoma of the nasal cavity and paranasal sinuses
Authors: Mendenhall William M. , Amdur Robert J. , Morris Christopher G. , Kirwan Jessica , Malyapa Robert S. , Vaysberg Mikhail , Werning John W. , Mendenhall Nancy P.
Published: April 2009

Objectives/Hypothesis:

To determine the outcomes after radiotherapy (RT) alone or combined with surgery at the University of Florida for patients with carcinomas of the nasal cavity and paranasal sinuses.

Methods:

Between November 1964 and June 2005, 109 patients were treated with curative intent. Patients with maxillary sinus carcinomas were excluded. Fifty‐six patients were treated with definitive RT, and 53 patients received surgery and preoperative (eight patients) or postoperative (45 patients) RT. Median follow‐up was 4.3 years (range, 0.2–35.9 years). Median follow‐up on living patients was 9.4 years (range, 2.0–35.9 years).

Results:

The 5‐year local control rates were: T1‐T3, 82%; T4, 50%; and overall, 63%. Local control at 5 years was 43% after definitive RT versus 84% after surgery and adjuvant RT (P< .0001). Multivariate analysis of local control revealed that both overall stage and treatment group (definitive RT versus surgery and adjuvant RT) significantly impacted this endpoint. Cause‐specific survival rates were: stages I to III, 81%; stage IV, 54%; and overall, 62%. Multivariate analysis revealed that T‐stage, N‐stage, and treatment group significantly influenced this endpoint. Thirty‐one (20%) of 109 patients sustained severe complications; 17 of 56 patients (16%) after definitive RT and 14 of 53 patients (25%) after surgery and adjuvant RT.

Conclusions:

The probability of local control and cause‐specific survival is better after surgery and RT compared with definitive RT. There is a modest increase in the risk of complications after surgery and RT. Thus, the preferred treatment is surgery combined with preoperative or postoperative RT. Laryngoscope, 2009
Effect of comorbidity on post‐treatment quality of life scores in patients with head and neck squamous cell carcinoma
Authors: Gourin Christine G. , Boyce Brian J. , Vaught Creighton C. , Burkhead Lori M. , Podolsky Robert H.
Published: April 2009

Objectives/Hypothesis:

To determine the effect of comorbidity on 1‐year post‐treatment quality of life (QOL) in patients with head and neck squamous cell cancer (HNSCC).

Methods:

One hundred twenty‐five previously untreated HNSCC patients participated in longitudinal QOL analysis over a 28‐month period. The University of Washington QOL questionnaire, Performance Status Scale, and Karnofsky score were used to measure QOL. Generalized estimating equations were used to analyze the effects of patient variables and their interaction with time.

Results:

The majority of patients (74%) had advanced stage (III/IV) disease; advanced comorbidity was present in 30%. Early tumor, node, metastases (TNM) stage was associated with significantly greater decreases in 1‐year chewing and swallowing scores (P < .0001) than advanced stage disease. Nonoperative treatment was associated with significantly poorer 1‐year shoulder and taste scores for early TNM stage, in contrast to advanced stage disease (P = .01). Comorbidity alone did not affect any of the QOL indices, but showed an interaction with treatment and primary site for appearance and chewing scores, respectively. Patients with high‐grade comorbidity had poorer 1‐year survival (80% for early stage disease, 55% for advanced stage disease) than patients with low‐grade comorbidity (100% for early stage disease, 69% for advanced stage disease).

Conclusions:

These data suggest that patient perception of disability, rather than the extent and severity of disease, influences the majority of head and neck disease‐specific QOL indices. Analysis of the effects of comorbidity on post‐treatment QOL is limited by increased mortality in patients with advanced comorbidity. Laryngoscope, 2009
Functional outcomes following secondary free flap reconstruction of the head and neck
Authors: Iseli Tim A. , Yelverton Joshua C. , Iseli Claire E. , Carroll William R. , Magnuson J. Scott , Rosenthal Eben L.
Published: April 2009

Objectives/Hypothesis:

To evaluate head and neck patients undergoing secondary (delayed) free flap reconstructions.

Study Design:

Retrospective chart review.

Methods:

Of the 523 free flaps between October 2004 and May 2008, 70 patients underwent 71 secondary free flaps. Outcomes include: hospital stay, complications, flap operative time, enterogastric tube, and tracheostomy requirement. Variables assessed include donor site, indication, prior radiation, and extra‐cervical vascular anastomosis.

Results:

Radial forearm (40.8%) and fibula free flaps (29.6%) were most commonly used. Mean hospital stay was 7.9 days, follow‐up 23.5 months, and operative time 323 minutes. Complications occurred in 39.4% in hospital (early) and 31.4% after discharge (late). Many required further surgery (33.8%), tracheostomy at discharge (26.8%), and prolonged enterogastric tube feeding (31%). In‐hospital mortality was 1.4%, total flap failure 1.4%, and partial failure 5.6%. The radial forearm required the least operative time (P = .002), and had least tracheostomies at discharge (P = .040). Osteocutaneous fibula took longest (P = .0001), and had the highest tracheostomy rate (P = .047). Early complications were highest with anterolateral thigh flaps (P = .001). Osteoradionecrosis resulted in higher tracheostomy rates at discharge (P = .0001). Osteocutaneous flaps took 111 minutes longer (P = .001), and required more tracheostomies on discharge (P = .031), but with lower fistula rates (P = .046). Previous irradiation and extra‐cervical vessels did not significantly impact outcomes.

Conclusions:

Secondary free flaps are technically feasible for head and neck reconstruction with low mortality and flap failure rates. The extra‐cervical and external carotid vessels were equally effective. Patients considering semi‐elective free flap reconstruction for osteoradionecrosis should be cautioned about complication rates and tracheostomy retention. Laryngoscope, 2009
Positron emission tomography–computed tomography surveillance for the node‐positive neck after chemoradiotherapy
Authors: Rabalais Amy G. , Walvekar Rohan , Nuss Daniel , McWhorter Andrew , Wood Charles , Fields Robert , Mercante Donald E. , Pou Anna M.
Published: April 2009

Objectives/Hypothesis:

To review our results with positron emission tomography and computed tomography fusion imaging (PET‐CT) surveillance of the postchemoradiotherapy neck in patients with advanced head and neck squamous cell carcinoma.

Study Design:

Retrospective.

Methods:

Four hundred twenty‐eight patients with advanced head and neck squamous cell carcinoma were treated with nonsurgical therapy from September 2002 to March 2007 and followed with post‐treatment PET‐CT surveillance of the neck. Fifty‐two patients meeting inclusion criteria were analyzed. Sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV), and accuracy of PET‐CT were determined.

Results:

Ten patients had a positive post‐treatment PET‐CT for residual neck disease, and 42 patients had negative scans. The NPV and PPV were 100% and 40%, respectively. The sensitivity, specificity, and accuracy were 100%, 87.5%, and 88%, respectively.

Conclusions:

Planned neck dissection can be deferred with a negative post‐treatment PET‐CT. Assuming a complete response at the primary site and a negative PET‐CT scan, there may be a role for serial PET‐CT surveillance in patients with residual palpable cervical lymphadenopathy. Laryngoscope, 2009
Management of oral feeding in children undergoing airway reconstruction
Authors: Smith Lee P. , Otto Staci E. , Wagner Kathrine A. , Chewaproug Linda , Jacobs Ian N. , Zur Karen B.
Published: April 2009

Objectives:

To systematically evaluate perioperative management of oral feeding in children undergoing airway reconstruction.

Study Design:

A retrospective chart review of all patients who underwent open airway reconstruction from February 1, 2006 through July 31, 2008 at a tertiary care children's hospital.

Methods:

During the study period, a multidisciplinary protocol for perioperative management of alimentation was instituted. Swallowing function was evaluated pre‐ and postoperatively as part of a clinical management protocol.

Results:

Fifty‐one patients underwent 55 reconstructions. Forty‐eight of the patients (94%) have been decannulated. Eighteen single‐stage procedures were performed on patients who were considered oral feeders, and oral feeding was successfully completed for three patients while the endotracheal tube was in place. Twenty‐two double‐stage procedures were performed on patients who were considered oral feeders. Oral feeding was initiated while the stent was in place for 16 patients. Nine patients (56%) did not tolerate oral feeding with the stent in place, five of whom had evidence of gross aspiration. Thirty‐four of the 40 patients (85%) who were considered oral feeders at the time of their reconstruction returned to their preoperative diet with minimal therapy from the speech pathology service 1.9 days (range, 0–8 days) following extubation or stent removal. Six patients (15%) had clinically significant dysphagia.

Conclusions:

Safe oral alimentation early in the postoperative period is possible with a rigorous multidisciplinary approach. To minimize complications, postoperative oral feeding should be initiated in conjunction with a speech pathologist. Laryngoscope, 2009
Quantification of the mitochondrial DNA common deletion in presbycusis
Authors: Markaryan Adam , Nelson Erik G. , Hinojosa Raul
Published: April 2009

Objectives/Hypothesis:

This study was conducted to evaluate the association between the mitochondrial DNA (mtDNA) common deletion (CD) level in cochlear tissue and the severity of hearing loss in individuals with presbycusis.

Study Design:

Nineteen individuals with presbycusis, ranging from 60 to 87 years of age, who met strict audiometric criteria were compared with four age frequency‐matched normal hearing controls ranging from 51 to 76 years of age. Five additional normal hearing individuals, ranging from 9 to 50 years of age, were also studied.

Methods:

A duplex real time polymerase chain reaction assay was used to quantify the mtDNA in archival cochlear tissue samples. Linear regression models were used for comparison of the CD level between groups.

Results:

The presbycusis group had a mean CD level of 32% with a standard deviation of 14%, and the normal hearing age matched control group had a mean CD level of 12% with a standard deviation of 2%. This difference in CD levels reached statistical significance (P = .011) and remained significant after adjusting for any differences in age between the two groups (age‐adjusted P = .007). Furthermore, there was evidence for a significant association between the CD level and the severity of hearing loss based on audiometric thresholds at 8 kHz (r = 0.44, P = .034; age‐adjusted partial correlation = 0.55, P = .007).

Conclusions:

For the first time, to our knowledge, these results demonstrate a relationship between quantitatively measured levels of the CD in human cochlear tissue and the severity of hearing loss in individuals with presbycusis. Laryngoscope, 2009
Asymptomatic lower extremity deep venous thrombosis resulting in fibula free flap failure
Authors: Jacobson Adam S. , Khorsandi Azita S. , Buchbinder Daniel , Urken Mark L.
Published: April 2009

Objectives/Hypothesis:

The successful harvest and transplant of a fibular flap depends on many factors, including healthy inflow and outflow systems. A contraindication to harvesting a fibular flap is disease of the lower extremity arterial system; therefore, preoperative evaluation of the arterial system is routine. Preoperative evaluation of the venous system is not routine, unless there is clinical suspicion of venous disease.

Methods:

Retrospective chart review.

Results:

Two cases of occult deep venous thrombosis (DVT) were encountered intraoperatively resulting in nontransplantable flaps.

Conclusions:

This finding represents a serious concern, and we believe that venous imaging should be considered in patients with significant risk factors for harboring an occult DVT. Laryngoscope, 2009
Local stability of anSIRepidemic model and effect of time delay
Authors: Tchuenche Jean M. , Nwagwo Alexander
Published: April 2009

We describe an SIR epidemic model with a discrete time lag, analyse the local stability of its equilibria as well as the effects of delay on the reproduction number and on the dynamical behaviour of the system. The model has two equilibria—a necessary condition for local asymptotic stability is given. The proofs are based on linearization and the application of Lyapunov functional approach. An upper bound of the critical time delay for which the model remains valid is derived. Numerical simulations are carried out to illustrate the effect of time delay which tends to reduce the epidemic threshold. Copyright © 2009 John Wiley & Sons, Ltd.
Identification of degradation products in stressed tablets of Rabeprazole sodium by HPLC‐hyphenated techniques
Authors: Vasu Dev R. , Sai Uday Kiran G. , Venkata Subbaiah B. , Suresh Babu B. , Moses Babu J. , Dubey P. K. , Vyas K.
Published: April 2009

Three unknown impurities of Rabeprazole, a proton pump inhibitor, were formed in the formulated drug under the stress conditions, [40 °C/75% relative humidity (RH) for 6 months] with relative retention times (RRTs) 0.17, 0.22 and 0.28. The Impurity‐I (0.17 RRT) was isolated using preparative HPLC and characterized by NMR and MS. The other two impurities, Impurity‐II (RRT 0.22) and Impurity‐III (RRT 0.28) could not be isolated, hence they are characterized by HPLC‐hyphenated techniques, LC–NMR and high‐resolution LC–MS. On the basis of the spectral data, the Impurity‐I, Impurity‐II and Impurity‐III were characterized as 1‐(1H‐benzo[d]imidazol‐2‐yl)‐3‐methyl‐4‐oxo‐1,4‐dihydropyridine‐2‐carboxylic acid, 1H‐benzo [d] imidazole‐2‐sulfonic acid and 4‐(3‐methoxy propoxy)‐3‐methyl‐2‐pyridine carboxylic acid, respectively. Copyright © 2009 John Wiley & Sons, Ltd.
An alternative TLM method for steady‐state convection–diffusion
Authors: Kennedy Alan , O'Connor William J.
Published: April 2009

Recent papers have introduced a novel and efficient scheme, based on the transmission line modelling (TLM) method, for solving one‐dimensional steady‐state convection–diffusion problems. This paper introduces an alternative method. It presents results obtained using both techniques, which suggest that the new scheme outlined in this paper is the more accurate and efficient of the two. Copyright © 2009 John Wiley & Sons, Ltd.
Institutionalizing deliberative democracy
Authors: Hartz‐Karp Janette , Briand Michael K.
Published: April 2009

In the mass democratic polities of today, the role of citizens remains confined largely to that of voting for members of elected legislatures. Beyond that, there is scant opportunity for ‘the public’ to participate in any meaningful sense in most of the tasks that make up the policy‐making process. Indeed, influencing that process is typically viewed as the sole prerogative of technocratic experts, organized interests, and elected officials. This presumption is buttressed (and rationalized) by a too‐ready acceptance of the platitude that citizens are generally uninformed, unskilled, and uninterested in the work of democratic self‐government.

We begin with a definition of ‘deliberative democracy’.

We then briefly consider its connection to the concept of democracy more generally and argue that the moral authority of the former follows from that of the latter.

From both the developing and the developed worlds, we draw several examples of institutionalized deliberative participation. In some, institutionalization has been sustained; in others, it has not been sustained.

Reflecting on these examples, we consider the ‘lessons learned’ from these and other cases. We identify costs, difficulties and limitations associated with institutionalizing participatory public deliberation as well as the benefits and advantages thereof.

Finally, we briefly outline a proposal for an Australian experiment that might serve as a learning model for subsequent efforts there and elsewhere to ‘institutionalize’ participatory citizen deliberation.

Institutionalizing deliberative participation would not replace representative government, but rather would supplement it, enabling democratic governments to reflect and respond better to the values, priorities and aspirations of the people they ostensibly serve.

We offer this practice‐orientated paper as a discussion paper intended to introduce readers to the idea of institutionalizing participatory public deliberation and to generate constructive debate concerning it. We do not presume to provide a rigorous analysis of the concept or of any of the many issues surrounding it.

Copyright © 2009 John Wiley & Sons, Ltd.
DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution
Authors: Buemi Giuseppe
Published: April 2009

The molecular geometries of the possible conformations of formic, oxalic, glyoxylic and pyruvic acids have been fully optimized at DFT B3LYP/6‐311++G(d,p) levels of calculation in vacuum as well as in water and acetone solution. Solutions were treated according to the SCRF PCM approach but some formic acid–water and formic acid–acetone clusters as well as adducts of oxalic acid with two or four water molecules were also taken into account for testing the importance of specific solute–solvent effects. All the most stable isomers of the title compounds are characterized by weak intramolecular hydrogen bonds, whose strengths (EHB) cannot be correctly estimated as stability difference between the open and chelate forms since the energy of the former isomer is, in turn, stabilized by a weak hydrogen bridge due to the formic acid moiety. Following the Rotation Barrier Method (RBM), proposed some years ago, EHB in the examined molecules (gas phase) falls in the range of 18–22 kJ/mol for oxalic acid (9.6 kJ/mol for the c‐C‐t isomer), 16.8 kJ/mol for glyoxylic acid and 19.8 kJ/mol for pyruvic acid. Most of them disappear at all, or nearly at all, both in acetone and aqueous solution, in consequence of the solvent effect. The frequencies of the OH and CO stretching modes, calculated according to the anharmonic oscillator model, are in very good agreement with the experimental literature data, where available. Copyright © 2009 John Wiley & Sons, Ltd.
Functional regulation and proteomic characterization of human natural killer cells through recombinant human granulocyte‐colony stimulating factor treatment
Authors: Chen Yu‐Jen , Yu Chih‐Chia , Chen Shui‐Tein , Chen Tai‐Yuan , Liao Hui‐Fen
Published: April 2009

Recombinant human granulocyte‐colony stimulating factor (rhG‐CSF) is the most common hematopoietic growth factor used for chemotherapy‐induced neutropenia or mobilization of stem cells. Natural killer (NK) cells are critical for host defense against infected cells and tumors. However, the cellular and molecular events of NK cells responding to rhG‐CSF remain unclear. Toward this end, we treated human NK cells with rhG‐CSF and assessed their cytotoxic function as well as proteomic characteristics. Unlike the other tested hematopoietic cytokines, rhG‐CSF decreased NK cell‐mediated cytotoxicity without affecting the viability of NK cells. The rhG‐CSF also reduced the production of nitric oxide and expression of inducible nitric oxide synthase in recombinant human interleukin (rhIL)‐2‐activated NK cells. By using cytokine array, rhG‐CSF reduced secretion of growth‐related oncogene‐α from NK cells. Intriguingly, rhG‐CSF did not affect production of various inflammatory cytokines [MCP‐1, IL‐6, tumor necrosis factor‐α (TNF‐α), granulocyte‐macrophage colony‐stimulating factor (GM‐CSF) and IL‐8], which are markedly stimulated by rhGM‐CSF. Proteomic analysis of rhG‐CSF‐ and rhGM‐CSF‐treated NK cells uncovered unique proteins possibly involving rhG‐CSF effect. These proteins were classified into six groups as follows: glycolysis, apoptosis, cytotoxicity, inflammation, antigen processing and presentation, and the others. We conclude that rhG‐CSF may impair NK‐mediated cytotoxicity accompanied by alterations in protein expression profile distinct from that of rhGM‐CSF.
Combustion synthesis and characterization of nano‐crystalline LaFeO3 powder
Authors: Shen Hui , Cheng Guofeng , Wu Anhua , Xu Jiayue , Zhao Jingtai
Published: April 2009

Nano‐crystalline LaFeO3 was synthesized by a sol–gel auto‐combustion method from a mixed aqueous solution of lanthanum and iron nitride, using citric acid as the fuel. Powder X‐ray diffraction and TG/DTA analysis show that the LaFeO3 crystallites can be directly obtained by the sol–gel combustion process, without any other undesired phase. The results of SEM and TEM reveal that the as‐burnt samples and powder calcined at 700 °C are agglomerated with particle size in the range of 25–50 nm and 60–80 nm, respecitvely. The M (T) and M (H) curves measurements show the existence of a weak ferromagnetism and the mainly anti‐ferromagnetic ordering of the spins in the calcined sample. Compared with the powder calcined at 600 °C and 700 °C, the as‐burnt LaFeO3 exhibits much stronger ferromagnetic behavior, with larger magnetization and smaller coercive field. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Nanoelectromagnetics: Circuit and Electromagnetic Properties of Carbon Nanotubes
Authors: Rutherglen Chris , Burke Peter
Published: April 2009

This Review presents a discussion of the electromagnetic properties of nanoscale electrical conductors, which are quantum mechanical one‐dimensional systems. Of these, carbon nanotubes are the most technologically advanced example, and are discussed mainly in this paper. The properties of such systems as transmission electron microscopy waveguides for on‐chip signal propagation and also the radiation properties of such systems are discussed. This work is primarily aimed at microwave, nanometer‐wave, and THz electronics. However, the use of nanotubes as antennas in the IR and optical frequency range is not precluded on first principles and remains an open research area.

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Das Dachtragwerk der O2 World in Berlin
Authors: Andrä Hans‐Peter , Svensson Nils , Kraiß Sonja , Bloch Daniel
Published: April 2009

In Berlin wurde im September 2008 die O2 World der weltweit tätigen Anschutz Entertainment Group (AEG) eröffnet. Die Veranstaltungshalle ist die neue Heimat der Berliner Eisbären und bietet Platz für bis zu 17000 Zuschauer. Das Dachtragwerk ist ein maßgebender Faktor für die Flexibilität der Hallennutzung und entscheidet über die Art der Veranstaltungen, die in der O2 World stattfinden können. Der folgende Beitrag berichtet über Entwurf, Bemessung und Ausführung des Hallendachs.
Nondestructive elemental depth profiling of Japanese lacquerware ‘Tamamushi‐nuri’ by confocal 3D‐XRF analysis in comparison with micro GE‐XRF
Authors: Nakano Kazuhiko , Tsuji Kouichi
Published: April 2009

We have applied recently two XRF (micro x‐ray fluorescence) methods [micro‐Grazing Exit XRF (GE‐XRF) and confocal 3D‐XRF] to Japanese lacquerware ‘Tamamushi‐nuri.’ A laboratory grazing‐exit XRF (GE‐XRF) instrument was developed in combination with a micro‐XRF setup. A micro x‐ray beam was produced by a single capillary and a pinhole aperture. Elemental x‐ray images (2D images) obtained at different analyzing depths by micro GE‐XRF have been reported. However, it was difficult to directly obtain depth‐selective x‐ray spectra and 2D images. A 3D XRF instrument using two independent polycapillary x‐ray lenses and two x‐ray sources (Cr and Mo targets) was also applied to the same sample. 2D XRF images of a Japanese lacquerware showed specific distributions of elements at the different depths, indicating that ‘Tamamushi‐nuri’ lacquerware has a layered structure. The merits and disadvantages of both the micro GE‐XRF and confocal micro XRF methods are discussed. Copyright © 2009 John Wiley & Sons, Ltd.
Wavelength dispersive x‐ray fluorescence spectrometry for the analysis of laser active lanthanides (Ln) in NaT1−xLnx(WO4)2 crystals
Authors: Valle F. J. , Ortega P. , Pablos A. de , Zaldo C. , Esteban‐Betegón F. , Serrano M. D.
Published: April 2009

Four crystals with nominal compositions, NaLa0.95Tm0.05(WO4)2 (1.32 wt% of Tm), NaGd1−xTmx(WO4)2 x = 0.05, 0.07 (1.24 and 1.32 wt% of Tm, respectively) and NaY0.9Yb0.1(WO4)2 (2.81 wt% of Yb), were analyzed by wavelength dispersive x‐ray fluorescence spectrometry. A procedure for sample preparation was developed using lithium tetraborate as flux to obtain glass disks and to circumvent precipitation problems of lanthanides and tungsten experienced in their dissolution by wet routes. For this purpose three specific calibration standards with pure oxides were prepared for each analyzed element with near to constant W and Na concentrations, so that matrix effects could be properly addressed. The procedure allows measurement of the Tm and Yb concentrations above the determination limits of 0.017 wt% and 0.042 wt% for Tm in the first two crystals, respectively, and of 0.039 wt% of Yb in the last one. Further analyses show an excess with regard to the nominal formula of ≈5 mol% in the total concentration of trivalent ions incorporated to the crystal and some deficiency of Na (≈10 mol%) and W (≈2 mol%) ions. Copyright © 2009 John Wiley & Sons, Ltd.
Classroom processes and positive youth development: Conceptualizing, measuring, and improving the capacity of interactions between teachers and students
Authors: Pianta Robert C. , Hamre Bridget K.
Published: April 2009

The National Research Council's (NRC) statement and description of features of settings that have value for positive youth development have been of great importance in shifting discourse toward creating programs that capitalize on youth motivations toward competence and connections with others. This assets‐based approach to promote development is consistent with the Classroom Assessment Scoring System (CLASS) framework for measuring and improving the quality of teacher‐student interactions in classroom settings. This chapter highlights the similarities between the CLASS and NRC systems and describes the CLASS as a tool for standardized measurement and improvement of classrooms and their effects on children. It argues that the next important steps to be taken in extending the CLASS and NRC frameworks involve reengineering assessments of teacher and classroom quality and professional development around observations of teachers' performance. This might include using observations in policies regarding teacher quality or a “highly effective teacher” that may emanate from the reauthorization of No Child Left Behind and moving away from a course or workshop mode of professional development to one that ties supports directly to teachers' practices in classroom settings.
Quality and accountability in the out‐of‐school‐time sector
Authors: Smith Charles , Devaney Thomas J. , Akiva Tom , Sugar Samantha A.
Published: April 2009

In the fragmented out‐of‐school‐time sector, defining and measuring quality in terms of staff behaviors at the point of service provides a common framework that can reduce obstacles to cross‐sector and cross‐program performance improvement efforts and streamline adoption of data‐driven accountability policies. This chapter views the point of service, that is, the microsettings where adults and youth purposefully interact, as the critical unit of study because it is ubiquitous across out‐of‐school‐time programs and because it is the place where key developmental experiences are intentionally delivered. However, because point‐of‐service behaviors are embedded within multilevel systems where managers set priorities and institutional incentives constrain innovation, effective quality interventions must contend with and attend to this broader policy environment.

The Youth Program Quality Assessment (Youth PQA) is one of an emerging class of observational assessment tools that measure staff performances at the point of service and, depending on methodology of use, can help create the conditions that managers and youth workers need to accept, adopt, and sustain accountability initiatives. Observational assessment tools can be flexible enough to be used for program self‐assessment (appropriate for low‐stakes, non‐normative learning purposes), external assessment (appropriate for higher stakes, normative comparisons, and performance accountability), and various hybrids that combine elements from each. We provide advice for decision makers regarding how to most effectively use the Youth PQA and similar measurement tools depending on the articulation of clear purposes for which accountability and improvement policies are enacted and effective sequencing of implementation.
Chemical Hardness and the Adaptive Coordination Behavior of the d0 Transition Metal Oxide Fluoride Anions
Authors: Marvel Michael R. , Pinlac Rachelle Ann F. , Lesage Julien , Stern Charlotte L. , Poeppelmeier Kenneth R.
Published: April 2009

Five new isostructural d0 transition metal oxide fluoride compounds Rb3Na(NbOF5)2·H2O and A3Na(MO2F4)2·H2O (A = K, Rb and M = Mo, W) have been synthesized by hydrothermal methods and their original structures determined by single‐crystal X‐ray diffraction. In these compounds, the sodium ions preferentially engage in strong electrostatic interactions with the least polarizable fluoride ions and concurrently the Nb5+, M6+ (M = Mo, W) metal centers displace toward the oxide ion(s) located trans to the fluorides in order to maintain atomic valences. Consequently, the oxide and fluoride sites retain unequal charge and the most negatively charged ions form the most/strongest interactions with the cations. The electrostatic potentials and the chemical hardness differences of the oxide and fluoride ions thus determine the anion connectivities: the cis‐oxo MO2F42– anions (M = Mo, W) engage in the most/strongest electrostatic interactions with the alkali counter‐cations through the two fluorides trans to the cis oxides. The NbOF52– anion forms its most/strongest electrostatic interactions with the cations through the one fluoride position trans to the oxide.
Contributions on thermal behaviour and crystal chemistry of anhydrous phosphates. XXXXIII [1] – Rhenium(VI) Oxidephosphate: Chemical Vapour Transport, Crystal Structure, Spectroscopic Characterisation and Magnetic Behaviour [2]
Authors: Islam Saiful M. , Glaum Robert
Published: April 2009

Re2O3(PO4)2 was obtained as microcrystalline, dark‐red powder at 450 °C by reaction of ReO3 with P4O10. Crystallisation was achieved through chemical vapour transport in a temperature gradient 600 → 500 °C using iodine as transport agent. Re2O3(PO4)2 (Pmcn, Z = 4, a = 6.2986(6) Å, b = 7.79654(5) Å, c = 15.2714(12) Å], 86 parameters, 1185 independent reflections, R1 = 0.027, wR2 = 0.066) adopts its own structure type. The crystal structure consists of isolated double‐octahedra [ReVI2O11] and [PO4] tetrahedra. Re2O3(PO4)2 shows a weak temperature dependent magnetic moment (0.05 ≤ μexp/μB ≤ 0.27; 3 K ≤ T ≤ 300 K). Its single‐crystal electronic absorption spectrum exhibits a weak band around =ν = 12000 cm–1, above =ν = 16000 cm–1 the UV/Vis spectrum is completely dark.