Crystalloid strong ion difference determines metabolic acid-base change during acute normovolaemic haemodilution

Objective. To study the acid-base effects of crystalloid strong ion difference (SID) during haemodilution. Design. Prospective in vivo study. Setting. University laboratory. Subjects. Anaesthetised, mechanically ventilated Sprague-Dawley rats. Interventions. Rats were studied in seven groups of three. Each group underwent normovolaemic haemodilution with one of seven crystalloids, with SID values from 0 to 40 mEq/l. Six exchanges of 9 ml crystalloid for 3 ml blood were performed. Measurements and main results. [Hb] fell from 142+/-17 to 44+/-10 g/l (p

Tuning the photophysical behavior of luminescent cyclam derivatives by cation binding and excited state redox potential

The emission from two photoactive 14-membered macrocyclic ligands, 6-((naphthalen-1-ylmethyl)-amino)trans-6,13-dimethyl- 13-amino- 1,4,8,11 -tetraaza-cyclotetradecane (L-1) and 6-((anthracen-9-ylmethyl)-amino)trans-6,13 -dimethyl - 13 -amino- 1,4,8, 1 1-tetraaza-cyclotetradecane (L-2) is strongly quenched by a photoinduced electron transfer (PET) mechanism involving amine lone pairs as electron donors. Time-correlated single photon counting (TCSPC), multiplex transient grating (TG), and fluorescence upconversion (FU) measurements were performed to characterize this quenching mechanism. Upon complexation with the redox inactive metal ion, Zn(II), the emission of the ligands is dramatically altered, with a significant increase in the fluorescence quantum yields due to coordination-induced deactivation of the macrocyclic amine lone pair electron donors. For [ZnL2](2+), the substituted exocyclic amine nitrogen, which is not coordinated to the metal ion, does not quench the fluorescence due to an inductive effect of the proximal divalent metal ion that raises the ionization potential. However, for [ZnL1](2+), the naphthalene chromophore is a sufficiently strong excited-state oxidant for PET quenching to occur.

A cyclopropabenzenylidenethenone (Propadienone) via a new route to alkylidenecycloproparenes

Reaction of 1,1-dichloro-2,5-diphenylcyclopropabenzene 6 with Meldrum's acid 8 in the presence of pyridine leads to coupling of the cycloproparenyl cation 7 with the stabilized diketo anion 9. Subsequent, spontaneous, base-induced dehydrochlorination gives the alkylidenecyclopropabenzene 11 in a one-pot reaction. Flash vacuum thermolysis of 11 at 650 degreesC ejects acetone and carbon dioxide, giving cyclopropabenzenylldenethenone 12 that is isolated in an Ar matrix at 20 K and characterized by a strong ketene band at 2107 cm(-1) in the IR spectrum.

The crystal structure of a bacterial Class II ketol-acid reductolsomerase: Domain conservation and evolution

Ketol-acid reductoisomerase (KARI; EC 1.1.1.86) catalyzes two steps in the biosynthesis of branched-chain amino acids. Amino acid sequence comparisons across species reveal that there are two types of this enzyme: a short form (Class 1) found in fungi and most bacteria, and a long form (Class 11) typical of plants. Crystal structures of each have been reported previously. However, some bacteria such as Escherichia coli possess a long form, where the amino acid sequence differs appreciably from that found in plants. Here, we report the crystal structure of the E. coli enzyme at 2.6 A resolution, the first three-dimensional structure of any bacterial Class 11 KARI. The enzyme consists of two domains, one with mixed alpha/beta structure, which is similar to that found in other pyridine nucleotide-dependent dehydrogenases. The second domain is mainly alpha-helical and shows strong evidence of internal duplication. Comparison of the active sites between KARI of E. coli, Pseudomonas aeruginosa, and spinach shows that most residues occupy conserved positions in the active site. E. coli KARI was crystallized as a tetramer, the likely biologically active unit. This contrasts with P. aeruginosa KARI, which forms a dodecamer, and spinach KARI, a dimer. In the E. coli KARI tetramer, a novel subunit-to-subunit interacting surface is formed by a symmetrical pair of bulbous protrusions.

Erosion-corrosion of mild steel in hot caustic. Part II: The effect of acid cleaning

Corrosion rates of 1020 steel in 2.75 M NaOH solution at a temperature of 160 degrees C and velocities of 0.32 and 2.5 m/s were studied. The focus was on the effect of the acid cleaning which was performed by using strong, inhibited sulphuric acid in between the exposures to caustic. In situ electrochemical methods were used to measure the corrosion rate such as the potentiodynamic sweep and the polarization resistance method. Also used were the weight-loss method and scanning electron microscopy (SEM). Eight electrodes/coupons were used to monitor the metal loss rate, four were placed at the low velocity section, while the other four were placed in the high velocity section of a high temperature flow. The first three coupons in each section were placed within the disturbed flow region, while the fourth was placed in a fully developed flow region. During the exposure of mild steel to the inhibited acid, following the first caustic period, the corrosion rate increased significantly to between 3 and 10mm/y with a few electrodes experiencing as high as 50 mm/y. The second caustic period following the acidic period typically started with very high corrosion rates (20-80 mm/y). The length of this corrosion period was typically 2-3 h with a few exceptions when the high corrosion period lasted 7-10 h. Following the very high corrosion rates experienced at the beginning of the second caustic period, the corrosion rates were reduced sharply (as the corrosion potential increased) to nearly the same levels as those observed during the passive part of the first caustic period. (c) 2005 Elsevier Ltd. All rights reserved.

A blank slate? Layer-by-layer deposition of hyaluronic acid and chitosan onto various surfaces

Although poly(alpha-hydroxy esters), especially the PLGA family of lactic acid/glycolic acid copolymers, have many properties which make them promising materials for tissue engineering, the inherent chemistry of surfaces made from these particular polymers is problematic. In vivo, they promote a strong foreign-body response as a result of nonspecific adsorption and denaturation of serum proteins, which generally results in the formation of a nonfunctional fibrous capsule. Surface modification post-production of the scaffolds is an often-utilized approach to solving this problem, conceptually allowing the formation of a scaffold with mechanical properties defined by the bulk material and molecular-level interactions defined by the modified surface properties. A promising concept is the so-called blank slate: essentially a surface that is rendered resistant to nonspecific protein adsorption but can be readily activated to covalently bind bio-functional molecules such as extracellular matrix proteins, growth factors or polysaccharides. This study focuses on the use of the quartz crystal microbalance (QCM) to follow the layer-by-layer (LbL) electrostatic deposition of high molecular weight hyaluronic acid and chitosan onto PLGA surfaces rendered positively charged by aminolysis, to form a robust, protein-resistant coating. We further show that this surface may be further functionalized via the covalent attachment of collagen IV, which may then be used as a template for the self-assembly of basement membrane components from dilute Matrigel. The response of NIH-3T3 fibroblasts to these surfaces was also followed and shown to closely parallel the results observed in the QCM.