Elimination of dimer formation in InIIIporphyrin-based anion-selective membranes by covalent attachment of the ionophore

The spontaneous hydroxy-bridged dimer formation of metalloporphyrins in ion-selective membranes gives rise to a short sensor lifetime (typically days), triggered by solubility problems, the occurrence of a super-Nernstian response slope, and a pH cross response. This dimer formation is eliminated here by covalent attachment of the ionophore to the polymer matrix. Specifically, two different indium(III)porphyrins containing polymerizable groups, the chloride-selective chloro(3-[18-(3-acryloyloxypropyl)-7,12-bis(1-methoxyethyl)-3,8,13,17-tetramethylporphyrin-2-yl]propyl ester)indium(III) and the nitrite-selective Chloro(5-(4-acryloyloxyphenyl)-10,15,20-triphenylporphyrinato)indium(III), were synthesized and copolymerized with methyl methacrylate and decyl methacrylate. The covalent attachment of the ionophore to the polymer matrix indeed prevents the metalloporphyrin from forming dimeric species, as confirmed by UV/visible spectroscopy. The ion-selective membranes with grafted indium porphyrin showed Nernstian response slopes to chloride, nitrite, perchlorate, and thiocyanate anions, with a selectivity comparable to membranes with freely dissolved or underivatized metalloporphyrin. The membranes containing grafted ionophores showed a lifetime of at least two months, apparently since crystallization of the poorly soluble dimeric species may no longer occur. This is one of the first examples where the covalent attachment of an ionophore drastically improves on a number of important sensor characteristics.     

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.     

An investigation of early research experience and research self-efficacy.

Graduate students in psychology typically report that they either love research or hate research. Despite the fact that most doctoral students in psychology enter some type of clinical practice upon graduation, research is a requirement for all students enrolled in scientist-practitioner programs regardless of their career aspirations beyond graduation. Research advances knowledge in the field of psychology and often guides clinical practice, yet very few psychologists conduct research after graduate school (C. J. Gelso, 1993). Efforts have been undertaken to determine factors that contribute to graduate students' research productivity. One such factor may be research self-efficacy. This study examined the influence of early research experience as a factor to bolster research self-efficacy. Results indicated that supportive peers and mentors contributed to positive research experiences. Additionally, positive team research experiences significantly predicted research self-efficacy. Implications for training programs and students are provided. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Proteins Marking the Sequence of Genotoxic Signaling from Irradiated Mesenchymal Stromal Cells to CD34+ Cells

Non-targeted effects (NTE) of ionizing radiation may initiate myeloid neoplasms (MN). Here, protein mediators (I) in irradiated human mesenchymal stromal cells (MSC) as the NTE source, (II) in MSC conditioned supernatant and (III) in human bone marrow CD34+ cells undergoing genotoxic NTE were investigated. Healthy sublethal irradiated MSC showed significantly increased levels of reactive oxygen species. These cells responded by increasing intracellular abundance of proteins involved in proteasomal degradation, protein translation, cytoskeleton dynamics, nucleocytoplasmic shuttling, and those with antioxidant activity. Among the increased proteins were THY1 and GNA11/14, which are signaling proteins with hitherto unknown functions in the radiation response and NTE. In the corresponding MSC conditioned medium, the three chaperones GRP78, CALR, and PDIA3 were increased. Together with GPI, these were the only four altered proteins, which were associated with the observed genotoxic NTE. Healthy CD34+ cells cultured in MSC conditioned medium suffered from more than a six-fold increase in γH2AX focal staining, indicative for DNA double-strand breaks, as well as numerical and structural chromosomal aberrations within three days. At this stage, five proteins were altered, among them IQGAP1, HMGB1, and PA2G4, which are involved in malign development. In summary, our data provide novel insights into three sequential steps of genotoxic signaling from irradiated MSC to CD34+ cells, implicating that induced NTE might initiate the development of MN.     

Comment on interview with Dr. Peter Fonagy.

One of the fine things about the psychoanalytic community is that we have forums for discussing ideas. Accordingly, I want to add a couple of different reactions to Dr. Fonagy’s interview with Elliot Jurist. In the interview, Dr. Fonagy raises the ultimate question of what is psychoanalytic when he offers a couple of throw-away lines suggesting that emphasis upon the unconscious is old-fashioned and discardable. Nonetheless, it seems to me that more can be said about a number of Dr. Fonagy’s points in this interview. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Effect of acetaldehyde and several acids on the formation of vitisin A in model wine anthocyanin and colour evolution

Summary It was found that the reaction between malvidin 3-glucoside and added pyruvic acid (PA), leading to the formation of vitisin A in model wine solutions, was not prevented by the addition of either acetaldehyde (A) or several organic acids. The acylated forms of vitisin A (3-acetylvitisin A and 3- p -coumarylvitisin A) were formed through the interaction of malvidin 3-acetylglucoside and malvidin 3- p -coumarylglucoside. Disappearance of the three main anthocyanins (malvidin 3-glucoside, malvidin 3-acetylglucoside and malvidin 3- p- coumarylglucoside) from the model wine with time followed first order kinetics. Acetaldehyde had the effect of increasing the total amount of these losses but producing smaller amounts of vitisin A. During ageing model solutions developed some browness. The brownest solution was obtained without A and a reduced rate of browning was found in the presence of A. This latter result can be explained by the assumption of a superimposition of a blueing effect upon reactions of A with anthocyanins. In the presence of PA the formation of vitisin A compounds gave an intermediate colour, contributing a reddish hue to the solution. A good correlation (r²= 0.96) between the percentage of vitisin A, of the total anthocyanins and the hue angle was observed. The addition of large amounts of organic acids that are normally found in wine into the model solutions did not lead to the formation of new anthocyanins. The linear loss of PA in all model systems indicates that a first order reaction occurs and 35.35 times more PA than total anthocyanin was lost to form the new compounds.     

Review of Wounded by reality: Understanding and treating adult onset trauma.

Reviews the book, Wounded by reality: Understanding and treating adult onset trauma by Ghislaine Boulanger (see record 2007-04674-000). In this book, Boulanger closes the circle on psychoanalytic speculation about the significance of trauma to personality, and goes beyond this to add significantly to both theory and clinical practice. Rado's 1925 paper on dismissing abreaction for understanding and treating the effects of adult onset trauma, with Freud's agreement, pushed the psychoanalytic gaze inward to memories of past trauma (Etchegoyen, 1991, p. 446). It was assumed that childhood trauma determined the reactions to later ones in adulthood. The very concept of trauma was diluted to include sudden hardship or confusion, leaving adult onset horror in an undifferentiated place on the continuum of human misfortune. In this book, there is no doubt. Adults are traumatized when they face imminent and seemingly inescapable death. This book is the sixth in a series of books called "Psychoanalysis in a New Key" that Donnel Stern is editing for The Analytic Press. That new key is relational thinking. Boulanger uses it along with the latest information from neuroscience to forge a special new key for unlocking the frozen affect of adults who have survived only physically from the most extreme of trauma. (PsycINFO Database Record (c) 2010 APA, all rights reserved)