An analysis of the numerical path dependence of the J-integral

Path dependent behaviour of the J-integral computed from the results of a finite element analysis may have two sources. The first is the history dependence of the strain energy, which causes J to lose its crack tip strain field characterizing property. The second is rooted in the principle of the finite element displacement method which ensures equilibrium only for each element as a whole, not for points within an element. It is of the utmost importance for a J-based safety assessment that these two sources be clearly distinguished as the latter may be reduced by mesh refinement whereas the former may serve as a criterion for assessing whether J can still be interpreted in its crack tip characterizing sense.The present paper proposes a numerical procedure for this distinction. Two examples confirm the procedure's validity and illustrate the practical necessity of careful evaluation of computed J-values.     

Mechanistic insights into the development of optical chloride sensors based on the [9]mercuracarborand-3 ionophore

Fluorescent sensing microspheres based on perhaps the most selective and practically useful chloride ionophore known, the recently reported [9]mercuracarborand-3 (MC-3), have been prepared and optimized for physiological measurements. In initial work, this ionophore was shown to yield functional optical sensing films in combination with an electrically neutral chromoionophore, ETH 5418. Unfortunately, however, these optodes suffered from unacceptably high levels of sodium interference under physiological conditions. To better understand the sensing mechanism, optical and potentiometric binding experiments were used to characterize the stoichiometry and the complex formation constants for this ionophore. It was found that the preferred stoichiometry is 1:2, rather than 1:1 as assumed earlier. The 1:2 complex is extremely stable (logbeta2 = 13.4), but a relatively strong 1:1 complex also exists (log K1 = 9.9). These characteristics were used to fabricate chloride optodes that make use of the stepwise ion-ionophore decomplexation equilibrium, by adding a calculated amount of lipophilic anion exchanger to the polymer film. Such optodes showed dramatically reduced sodium interference while maintaining the excellent selectivity of the traditional formulation. The optimized composition also shifted the measuring range to physiological conditions, making them useful for the assessment of chloride in undiluted and 10-fold-diluted blood at pH 7.4. After necessary alterations of the particle preparation procedure and sensor formulation, the new insights were used to fabricate mass-produced optical sensing microspheres with characteristics essentially identical to those of the optode sensing films.     

Ion-pairing ability,chemical stability,and selectivity behavior of halogenated dodecacarborane cation exchangers in neutral carrier-based ion-selective electrodes

Recently, it has been discovered that carba-closo-dodecaborates can be used as cation exchangers in neutral carrier-based ion-selective chemical sensors. Because of their inherent chemical stability and versatile functionalization chemistries, they offer many advantages that may potentially be exploited for ion analyses that require nontraditional sample conditions, including strongly acidic media. In this work, trimethylammonium salts of undecachlorinated (UCC), undecabrominated (UBC), hexabrominated (HBC), and undecaiodinated (UIC) carborane anions were prepared and evaluated for their potential use in solvent polymeric membrane-based sensors. Computational methods including Natural population analysis and electrostatic mapping were used to predict the ion-exchanging ability of each lipophilic anion. In addition, the sandwich membrane technique was used to evaluate the ion-pairing ability of each carborane anion in situ (i.e., within bis(2-ethylhexyl) sebacate (DOS)- and 2-nitrophenyl octyl ether (o-NPOE)-plasticized ISE membranes). The results of the computational and potentiometric studies found that binding affinity of the anions followed the generalized trend HBC > UCC > UBC > UIC. PVC-DOS bulk optode thin films containing the chromoionophore ETH 5315 and a respective anion were used to determine the chemical stability/lipophilicity of the carboranes and tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (TFPB) in acidic media (0.2 M HOAc) under flowing conditions. The studies found that in terms of stability/lipophilicity UIC > UBC > TFPB approximately UCC > HBC. Electrodes containing a Pb(2+)-selective ionophore, tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide)(lead IV), were used to evaluate the functionality of each cation exchanger. An evaluation of response characteristics such as slope and selectivity found that UIC and UBC were quite comparable to the behavior of TFPB. Interestingly, both UIC and UBC showed a marked selectivity improvement over cadmium, with log K(pot)(pb),(Cd) values of -7.19 and -7.29, respectively, with TFPB giving a value of -5.89. Demonstrating excellent stability and suitable electrostatic properties, the carboranes, UIC in particular, are a very promising alternative to the tetraphenylborates and should find widespread application in the field of chemical sensors.     

Low-temperature phase diagram of the heavy-fermion superconductor UPt3

The transition to the superconducting state of UPt₃ has been studied in specific-heat experiments on polycrystalline and single-crystalline samples in dependence of heat treatment, purity of starting materials and deviations from stoichiometry, as well as on substituted compounds. The concepts behind the splitting of the transition in two anomalies that are 60 mK apart are critically reviewed. The superconducting phase diagram in the B-T plane has been studied with the use of a sensitive dilatometric technique. The three superconducting phases meet at a tetracritical point and all four phase lines are of second order. From the length anomalies at the phase boundaries the pressure derivatives of the phase lines have been determined and the most stable phase under uniaxial pressure along the c-axis has been identified.     

蜕变测试和断言检查的比较与实验研究

在软件测试中,测试预言是一种用于检查程序在测试中是否正常运行的机制.然而在某些实际情况下,还无法制定测试预言或者难以有效地应用测试预言.针对此类测试预言问题,蜕变测试于近年应运而生,但蜕变测试的效率问题还没有被充分地加以研究.作者用控制实验的方法研究了使用蜕变测试的成本及效率,进而将蜕变测试和常用的断言检查两种方法的错误检测率和时间成本进行了比较和分析.实验结果表明,相比于断言检查方法,蜕变测试具有检测到更多错误的潜力.通过分析蜕变测试的效率和性能,与断言测试相比,蜕变测试的错误检测率更高效而效率有待提高,可适用于较为粗粒度的测试需求.     

Predictors of long-term smoking cessation in head and neck cancer patients

Cigarette smoking is a major risk factor for head and neck cancer, and individuals who continue to smoke past diagnosis and treatment are at elevated risk for further disease. In a randomized controlled trial, a state of the art provider-delivered smoking cessation intervention was compared to a usual care advice control condition. The intervention consisted of surgeon- or dentist-delivered advice to stop smoking, a contracted quit date, tailored written materials, and booster advice sessions. Subjects were 186 patients with newly diagnosed first primary squamous cell carcinomas of the upper aerodigestive tract who had smoked cigarettes within the past year. At randomization, 88.2% of subjects were current smokers. At 12-month follow-up, 70.2% of subjects completing the trial (n = 114) were continuous abstainers; among baseline smokers alone the continuous abstinence (CA) rate was 64.6%. The cotinine validation rate at 12 months was 89.6%. Modeling techniques were utilized in order to derive expected CA rates, which included noncompleter subjects (n = 72). The CA rate expected at 1 year for the entire patient population was 64.2%, and for smokers alone the expected CA rate was 59.4%. Logistic regression analysis carried out on baseline smokers identified predictors of 12-month CA status. These included medical treatment, stage of change, age, nicotine dependence, and race. The intervention effect was not significant, although the sign of the effect was positive. Based on these findings, we recommend systematic brief advice to stop smoking for head and neck cancer patients, with a stepped care approach for patients less able to quit.     

Finances and Well-Being: A Dynamic Equilibrium Model of Resources.

This study of 513 Dutch farmers tested a dynamic equilibrium model of resources (an extension of the conservation of resources theory; S. E. Hobfoll, 1989, 1998, 2001). With structural equation modeling, the advantages of a 3-wave longitudinal design were comprehensively used, such as addressing bidirectional causal effects and within-individual vs. between-individual change. This allowed for a careful analysis of the management function of resources in the stress process. Results showed that well-being had stronger within-person stability than finances. Increased levels of financial problems temporarily increased psychological distress but not self-reported illness. Conversely, farmers with higher stable baselines of psychological distress also had higher baselines of self-reported illness and experienced more negative changes in their financial situation. (PsycINFO Database Record (c) 2010 APA, all rights reserved)