Capillary electrophoretic determination of acetic acid and trifluoroacetic acid in synthetic peptide samples

Synthetic peptide samples may contain counter-ions such as acetate or trifluoroacetate as a result of their method of preparation. Furthermore, because acetic acid (HOAc) and trifluoroacetic acid (TFA) are frequently used reagents in peptide synthesis, these acids may be found in synthetic peptide samples as impurities. This paper describes a method validation to determine HOAc and TFA in synthetic peptide samples by capillary electrophoresis (CE) using an internal standard (I.S.) with indirect UV detection. Typical analytical parameters such as precision, linearity, accuracy, specificity, limit of detection and ruggedness were evaluated during the validation. In addition, the contents of HOAc and TFA in two synthetic opioid peptide samples, TIPP[psi] and Orphanin FQ, were determined using the validated method. A unique feature of the method is that it offers determination of both acids in a single assay using a common I.S. The method is very efficient because of relatively short electrophoretic migration times (typically 2 to 8 min) for the acids investigated. This paper also discusses the factors that affect precision in a CE assay.     

Determination of Pb complexation in oxic and sulfidic waters using pseudovoltammetry

Pseudovoltammetry was used to evaluate the actual Pb complexation occurring in natural water samples of varying oxygen and sulfide concentration. In pseudovoltammetry, the potential at which metal-ligand complexes are broken up to form the metal amalgam is used to determine the complexes' thermodynamic stability constants (KTHERM; corrected for metal and ligand side reaction coefficients) via the Nernst expression. This methodology removes the need for any metal additions and for subsequent modeling using fitting criteria, which provide only conditional stability constant data (KCOND). Using known organic ligands, a chelate scale ranging from log KTHERM = 4 to log KTHERM = 20 was developed as a template for comparison with samples collected from two stations of different salinities and at several depths in the Chesapeake Bay. These samples were observed to contain up to five different ligand compounds of unknown structural composition (log KTHERM > 8) with the strongest ligand fraction exceeding log KTHERM > 39 (the maximum observable thermodynamic stability constant due to the reduction of Na+). One possible explanation for the observed complexation is the existence of lead sulfide clusters. This was supported by laboratory experiments using electrochemistry and ICR-FTMS, which confirmed the formation of electrochemically inert multinuclear clusters with high stability constants (e.g., M3S3, log KTHERM = 62.9). However, in all field samples, (sub)nanomolar levels of acid-leachable sulfide were recovered at pH 5.0-6.2, which could be attributed to dissociation of lead sulfide complexes with moderate acidity. Recovery of sulfide increased from < 10% of the total dissolved Pb concentration (Pbdiss) in surface waters to 100% of the Pbdiss in the sulfide-rich bottom waters at the higher salinity location.     

Microstructural effects on microbial survival: phase-separating dextran solutions

Evolving microstructure in a model dextran solution is shown to exert a major influence on the survival of Escherichia coli K-12 frag 1 and Salmonella typhimurium LT2. The microstructure results from microscopic phase separation, which develops over several hours resulting in hardening of the solution into a glassy state. The microstructure is characterized by an array of physical methods including image analysis, electron spin resonance and bulk rheology, and it is shown that bacterial survival depends on the formation of microscopic. water-rich domains and not primarily on bulk water activity or hardness.     

AN INTERPRETATIVE BIOGRAPHY OF WINSOME HALL ANDREW (1905-1997)

This biographical account of Winsome Hall Andrew is a largely chronological account of an early twentieth century NSW architect whose work deserves further serious evaluation. It is also a demonstration of biographical narrative as an strategy for bringing women into a particular kind of historical presence, stressing the complexity of social expectations of women as fundamental to an understanding of their public productivity. It is also a somewhat poignant story which depends upon the honesty and courage of Hall Andrew's friends and relatives in acknowledging the difficulties in her life as well as the niceties. Finally, it is presented as an example of the complex interpretative strategy of my PhD thesis, an attempt to be accessible, relevant, critical, honest and fair.     

Couple relationship education at home: Does skill training enhance relationship assessment and feedback?

To evaluate the effective components of couple relationship education, 59 newlywed couples were randomly assigned to one of two couple relationship programs (CRE): (1) RELATE, which involved receiving feedback on their relationship based on the on-line RELATE assessment; or (2) RELATE + Couple CARE, which was RELATE plus completing the 6 unit Couple CARE relationship skill training program. Relative to RELATE, RELATE + Couple CARE produced more improvement in couple communication, and high relationship satisfaction across the next 12 months in women. Men sustained high and similar relationship satisfaction in either condition. Skill training CRE has additional benefits for couples beyond assessment and feedback. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Silver sulfide as a staining agent for scanning electron microscopy of nylon 6/MXD6 blends

BACKGROUND: In transmission and scanning electron microscopy imaging, the ability to obtain sufficient contrast between the components of a blend when they are both of a similar chemical structure still remains problematic. This paper investigates the domain morphology of a polymer blend containing two polyamides, nylon 6 and the semi‐aromatic polyamide poly(m‐xylene adipamide) (MXD6), using scanning electron microscopy in backscattered electron imaging mode. The efficiency of three staining agents, ruthenium tetroxide, phosphotungstic acid and silver sulfide, in obtaining optimum phase contrast between the two polymers is discussed. RESULTS: The use of silver sulfide as a staining agent was found to be a fast and reliable approach which required basic sample preparation and provided excellent compositional contrast between the phases present in the nylon 6/MXD6 blends compared to the other staining agents. CONCLUSIONS: The technique described in this paper is believed to be a novel and versatile method that has the potential to further improve the ability to study complex polymer blends where one polymer contains an aromatic ring. Copyright © 2009 Society of Chemical Industry     

Pretreatment hemoglobin level influences local control and survival of T1-T2 squamous cell carcinomas of the glottic larynx

PURPOSE: A number of reports have documented the relationship between pretreatment hemoglobin level and local control and/or survival in the treatment of cervix, bladder, and advanced head and neck tumors. Consideration of correcting anemia before initiation of radiation therapy may prove increasingly important as clinical trials use intensive induction chemotherapy in the treatment of head and neck carcinomas. Neoadjuvant chemotherapy may produce anemia, which in turn may reduce the effectiveness of subsequent irradiation. MATERIALS AND METHODS: One hundred nine patients with T1-2N0 squamous cell carcinoma of the glottic larynx were treated with definitive radiotherapy at the Fox Chase Cancer Center between June 1980 and November 1990. Follow-up times ranged from 26 to 165 months (median, 82). RESULTS: The 2-year local control rate for patients who presented with a hemoglobin level < or = 13 g/dL was 66%, compared with 95% for patients with a hemoglobin level more than 13 g/dL (P = .0018). The 2-year survival rate for patients with a hemoglobin level < or = 13 g/dL was 46%, compared with 88% for patients with a hemoglobin level more than 13 g/dL (P < .001). Cox proportional hazards regression analysis showed that hemoglobin level (P = .0016) was the only variable that significantly influenced local control (P = .0016) and survival (P < .0001). CONCLUSION: Patients who presented with hemoglobin levels more than 13 g/dL had significantly higher local control and survival rates. The strong apparent correlation between hemoglobin level, local control, and survival supports consideration of correcting anemia before initiation of radiation therapy.     

The tyranny of distance prevails: HTTP protocol latency and returns to fast fibre internet access network deployment in remote economies

Public policies to deploy enhanced local broadband access infrastructure in locations physically very far removed from the firms and customers with whom they transact are frequently justified by claims of increased competitiveness arising from the elimination of the ‘tyrannies of distance’. Yet relative distance-based disadvantages remain in respect of time-dependent applications and those hosted on distant infrastructures or requiring data sourced from distant locations. Trading off the effects of faster local access and latency on the time taken to load a Web page based on the HTTP Web protocol, we demonstrate that the increasing returns to distance rapidly overcome the effect of faster local access bandwidth as the distance the data must travel increases. We conclude that claims that investment in ultra-fast local broadband access will unconditionally facilitate a step-change in national economic performance are without foundation. In the absence of some compelling underlying competitive advantages, the ‘transformational’ economic benefits will be local rather than international in nature. At best, government investment in nationwide fast fibre networks is a defensive strategy that enables ongoing participation in the international economy, but at relatively higher costs than those faced by larger economies in closer proximity to end markets.     

Augmentation of lung liquid clearance via adenovirus-mediated transfer of a Na,K-ATPase beta1 subunit gene

The gastrointestinal hormone, glucagon-like peptide-1(7-36)amide (GLP-1) is released after a meal. The potency of synthetic GLP-1 in stimulating insulin secretion and in inhibiting glucagon secretion indicates the putative physiological function of GLP-1. In vitro, the nonmammalian peptide, exendin(9-39)amide [ex(9-39)NH2], is a specific and competitive antagonist of GLP-1. This in vivo study examined the efficacy of ex(9-39)NH2 as an antagonist of exogenous GLP-1 and the physiological role of endogenous GLP-1. Six healthy volunteers underwent 10 experiments in random order. In each experiment, a 30-min period of euglycemia was followed by an intravenous infusion of glucose for 150 min that established a stable hyperglycemia of 8 mmol/liter. There was a concomitant intravenous infusion of one of the following: (1) saline, (2) GLP-1 (for 60 min at 0.3 pmol . kg-1 . min-1 that established physiological postprandial plasma levels, and for another 60 min at 0.9 pmol . kg-1 . min-1 to induce supraphysiological plasma levels), (3-5) ex(9-39)NH2 at 30, 60, or 300 pmol . kg-1 . min-1 + GLP-1, (6-8) ex(9-39)NH2 at 30, 60, or 300 pmol . kg-1 . min-1 + saline, (9 and 10) GIP (glucose-dependent insulinotropic peptide; for 60 min at 0.8 pmol . kg-1 . min-1, with saline or ex(9-39)NH2 at 300 pmol . kg-1 . min-1). Each volunteer received each of these concomitant infusions on separate days. ex(9-39)NH2 dose-dependently reduced the insulinotropic action of GLP-1 with the inhibitory effect declining with increasing doses of GLP-1. ex(9-39)NH2 at 300 pmol . kg-1 . min-1 blocked the insulinotropic effect of physiological doses of GLP-1 and completely antagonized the glucagonostatic effect at both doses of GLP-1. Given alone, this load of ex(9-39)NH2 increased plasma glucagon levels during euglycemia and hyperglycemia. It had no effect on plasma levels of insulin during euglycemia but decreased plasma insulin during hyperglycemia. ex(9-39)NH2 did not alter GIP-stimulated insulin secretion. These data indicate that in humans, ex(9-39)NH2 is a potent GLP-1 antagonist without any agonistic properties. The pancreatic A cell is under a tonic inhibitory control of GLP-1. At hyperglycemia, the B cell is under a tonic stimulatory control of GLP-1.