Intensification of ultrasound-assisted process for the preparation of spindle-shape sodium zinc molybdate nanoparticles.

In the present work, sodium zinc molybdate (SZM) nanoparticles were prepared using conventional and an innovative ultrasound assisted co-precipitation of sodium molybdate, zinc oxide and HNO3 at different temperatures. Prepared product was characterized by XRD, TEM, FT-IR, particle size distribution (PSD), TGA and DTA techniques. TEM analysis shows the spindle-shaped morphology of the formed SZM nanoparticles. The average particle size of SZM nanoparticles is found to be lower in case of sonochemical method (78.3 nm) compared to conventional method (340.2 nm) which is attributed to faster solute transfer rate due to ultrasonic irradiation leading to rapid nucleation and restricted growth of SZM nanoparticles. Further, the kinetics of synthesis of SZM nanoparticles are studied using the sonochemical method at different operating temperature and conventional method at 80°C. It is shown that the rate of reaction is significantly faster at 40°C compared to other temperatures and also conventional method. This can be attributed to intense cavity collapse at lower temperature (low vapour pressure) compared to higher temperature (high vapour pressure) of the reaction mixture.

Evolution of strategies to achieve baseline separation of ten anionic, water-soluble sulfated estrogens via achiral packed column supercritical fluid chromatography.

Near baseline separation of ten sulfated sodium salts of various structurally related estrogens employing a variety of bonded stationary phase packed columns was obtained using a conventional supercritical fluid chromatograph coupled with UV detection. Critical pairs 2/3 (8,9-dehydroestrone/17ß-dihydroequilin) and 6/7 (17α-estradiol or 17α-dihydroequilin/estrone), however, failed to baseline separate. In all preliminary separations, 10mM ammonium acetate and variable percentages of H2O were initially used as co-additives in conjunction with methanol as a modifier. Different modifier programs and temperatures were employed to optimize the separation in a timely manner. A 2-ethylpyridine column provided the best separation compared to bare silica, diol, and cyano-based bonded phase columns. The employment of both salt and water as additives to the methanol-modified CO2 mobile phase suggested a mixed mode separation mechanism involving both ion pairing of each anionic sulfated estrogen with ammonium ion and hydrophilic interaction facilitated by partitioning of analyte between the aqueous solvated stationary phase and the aqueous component of the mobile phase. Upon more extensive study with either iso-propylamine or formic acid-ammonium formate buffer, the critical anionic pairs were 95% baseline resolved.

Production of cerium zinc molybdate nano pigment by innovative ultrasound assisted approach.

Ultrasound assisted synthesis of yellow rare earth cerium zinc molybdate anticorrosion nanopigment is presented. This new class of pigment is eco-friendly alternatives to lead, cadmium and chromium pigment as these pigments contains carcinogenic species like Cr(6+) which is responsible for human disease. The synthesis of nanosized cerium zinc molybdate was carried out using cerium nitrate, sodium zinc molybdate as a precursor materials by conventional and ultrasound assisted chemical precipitation method without addition of emulsification agent. XRD, FTIR and elemental analysis confirm the formation of cerium zinc molybdate nanoparticles. The conductivity results indicate that conventional synthesis takes longer time, while in sonochemical technique (US), reaction completes within short period of time. Improved solute transfer rate, rapid nucleation, and formation of large number of nuclei are attributed to presence of cavitation. Saturation of the Ce(3+) ions reaches earlier in case of sonochemical technique which restricts the growth of particles hence smaller size is obtained. The crystallite size of cerium zinc molybdate was found to be 27nm from XRD analysis.

Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs.

Packed column supercritical fluid chromatography of isomeric polypeptide pairs.

The characterization and determination of peptides is of great importance in the pharmaceutical industry as is the ability to rapidly perform targeted determinations of bioactive peptides in complex matrices. The purpose of the presented work is to assess the feasibility of packed column supercritical fluid chromatography (SFC) for the separation of two-pairs of water soluble peptides of identical mass, composition and charge that differ only in amino acid sequence. Upon evaluating a variety of conditions, trifluoroacetic acid (HTFA) in conjunction with methanol as the modifier proved to be, in general, the most successful mobile phase additive for elution of the two isomeric peptide pairs from all nitrogenous stationary phases. In contrast, water and ammonium acetate gave distorted peak shapes and therefore proved to be less satisfactory as neutral additives. The basic additive, iso-propylamine (IPAm), coupled with HA-Pyridine yielded the highest resolution factor for the complete study. Aminopropyl and HA-Pyridine columns with 5 µm particle size and 60 Å pore size were found to be best for resolution of each peptide pair. Bare silica and phenyl-hexyl stationary phases did not afford any separation. The primary roles of the carbon dioxide and methanol modifier are believed to provide (a) stationary phase solvation and (b) peptide solubility and transport; while, HTFA is postulated to fully protonate each peptide and form ion pairs between its conjugate base and cationic peptide analyte. The separation process, therefore, is best viewed as ion pair supercritical fluid chromatography (IP-SFC). For the case where IPAm gave good resolution on the HA-Pyridine column, the peptides are probably in the neutral state.

A successful case of repeat thrombolysis in acute prosthetic valve thrombosis.

Acute heart failure is an important presentation in the Acute Medical Unit. We describe a case of successful repeat thrombolysis in an elderly woman presenting as an emergency with severe pulmonary oedema, due to acute prosthetic mitral valve thrombosis. The diagnostic imaging and therapeutic modalities available are also described.This case highlights the need for acute physicians to consider prosthetic valve thrombosis in the differential for patients with metallic heart valves who present with acute heart failure or cardiogenic shock.

Unusual case of laryngeal foreign body.

The Foreign bodies in respiratory tract have been major cause of morbidity and present as challenge to otolaryngologists. Despite improvement in medical care and public awareness, they are major concern for otolaryngologists. The spectrum of presentation varies widely from sudden death due to respiratory obstruction to accidental finding during routine investigations. A case of unusual presentation of laryngeal foreign body with just loss of voice is described here.

Comparison of bioimpedance versus thermodilution cardiac output during cardiac surgery: evaluation of a second-generation bioimpedance device.

OBJECTIVE: To compare a second-generation thoracic electrical bioimpedance (TEB) hemodynamic monitoring system with the clinically used pulmonary artery catheter thermodilution (TD-PAC) system. DESIGN: Blinded, simultaneous measurements at specified key time points during surgery. SETTING: University teaching hospital cardiac surgical operating rooms. PARTICIPANTS: Forty-seven patients undergoing primary elective coronary artery bypass surgery. INTERVENTIONS: Timed cardiac output measurements by thermodilution and continuous monitoring of bioimpedance were performed. MEASUREMENTS AND MAIN RESULTS: Cardiac index (TEB and TD-PAC) and other hemodynamic parameters were measured at 4 time points: (1) after anesthesia induction, (2) with the mediastinum open, (3) immediately after cardiopulmonary bypass, and (4) at the end of the case. Pearson's correlation and Bland-Altman analysis were carried out. Cardiac index by TEB and TD-PAC had an overall correlation of r = 0.71 (p < 0.0001). The Bland-Altman statistics showed a mean difference of -0.28 L/min/m2 and precision of 0.67 L/min/m2. The best correlation was at time 1, and the lowest correlation was at time 4. Mediastinal opening and cardiopulmonary bypass had little or no effect on the correlation between technologies. CONCLUSION: TEB reporting of cardiac index during coronary artery surgery generally agreed with TD-PAC cardiac index except at the end of the case (time 4).

Mycotic arch aneurysm and aortoesophageal fistula in a patient with melioidosis.

Aortoesophageal fistula due to an aortic arch aneurysm is a rare entity with an extremely high mortality. There are few reports of successfully managed cases and even fewer of long term survival. We report a case of an aortoesophageal fistula resulting from a mycotic pseudoaneurysm of the distal aortic arch in a patient with melioidosis, its surgical management, and outcome.

Factor XIIIA and clot strength after cardiopulmonary bypass.

Reduced factor XIIIA levels and decreased clot strength have been associated with increased bleeding after cardiopulmonary bypass (CPB). The purpose of this study was to evaluate the relationship between hemostatic factors, including factor XIIIA, and clot strength before, during and after CPB. Factor XIIIA antigen, platelet counts, fibrinogen, factor V activity, tissue plasminogen activator and clot strength (by thromboelastograph) were measured at baseline, after 45 min of CPB, at the end of CPB and 4 h post-operatively in 34 patients. Baseline factor XIIIA antigen was 5.2 +/- 1.4 mg/l. On average, factor XIIIA levels dropped to 64% and clot strength to 77% of baseline values after 45 min on CPB and remained below baseline during the immediate post-operative period. Clot strength was significantly correlated (r = 0.81) with platelet count and fibrinogen but not plasma factor XIIIA levels. Addition of 10 mg/l recombinant factor XIII[a2] significantly increased clot strength. Postoperative bleeding at 2 h was inversely correlated with platelet count, factor XIIIA antigen and clot strength measured at the end of CPB. Maintenance of adequate platelet counts and factor XIIIA levels at the end of CPB may play a role in maintaining clot strength and reducing blood loss.

Role of myocardial temperature measurement in monitoring the adequacy of myocardial protection during cardiac surgery.

Inadequate myocardial protection continues to be encountered despite improved methods of cardioplegia delivery. Although myocardial temperature is commonly monitored to assess the adequacy of cardioplegia delivery, its relationship to the metabolic status of the myocardium has not been investigated. We prospectively reviewed patients who underwent valvular heart surgery with blood (n = 47) or crystalloid (n = 48) cardioplegia and continuous measurement of intraoperative myocardial tissue pH and temperature. We previously demonstrated a high correlation (r = 0.99) between extracellular myocardial pH, levels of intracellular hydrogen ion concentration, and a lowering of tissue ATP during coronary occlusion. Clinically, optimal metabolic protection was defined as the absence of myocardial tissue acidosis during the period of aortic occlusion as quantified by a temperature-corrected integrated mean pH of 6.8 or greater, which has been shown to be predictive of a favorable postoperative outcome. Age, bypass time, myocardial temperature, myocardial tissue pH at the onset of aortic occlusion, cross-clamp time, and volume of cardioplegia were not significantly different between blood and crystalloid groups. Linear regression analysis demonstrated no significant correlation between mean myocardial tissue pH and the corresponding mean myocardial temperature in either group during aortic occlusion. There was also no correlation between the mean myocardial tissue pH and volume of cardioplegia delivered in both groups. These data demonstrate wide intercardiac and intracardiac variability in the degree of regional tissue acidosis encountered during of hypothermic cardioplegia. Cardioplegia delivery guided by measurement of myocardial temperature or by standardized protocol did not prevent the occurrence of tissue acidosis and thus, did not ensure optimal metabolic protection of the heart. In 95 patients undergoing valvular heart surgery with cold blood or crystalloid cardioplegia, there was no correlation between myocardial tissue pH and mycardial temperature or between myocardial tissue pH and volume of cardioplegia administered. Temperature is a poor indicator of the metabolic state of the myocardium.

Effects of hemofiltration on serum aprotinin levels in patients undergoing cardiopulmonary bypass.

OBJECTIVE: To determine the effects of hemofiltration on serum aprotinin levels during cardiopulmonary bypass (CPB) surgery. DESIGN: Prospective, randomized study. SETTING: University of Washington Medical Center, single institution. PARTICIPANTS: Patients undergoing cardiac surgery without contraindications to aprotinin administration. INTERVENTIONS: Patients were randomized to full-Hammersmith and half-Hammersmith dosing regimens of aprotinin and were further randomized to hemofiltration or no hemofiltration. MEASUREMENTS AND MAIN RESULTS: Serum aprotinin levels were studied before CPB, 60 and 120 minutes into CPB, and at the end of CPB before protamine administration. Each group experienced a decrease in serum aprotinin levels with the institution of CPB, attributable to hemodilution and redistribution of aprotinin outside of the vascular compartment. During CPB, aprotinin levels declined further, but no significant difference was observed between patients who received hemofiltration and those who did not. Hematocrit values were significantly higher at the end of CPB in the hemofiltration groups. Patients receiving half-Hammersmith dosing regimens maintained aprotinin levels throughout CPB, which have been shown to inhibit plasmin but were lower than levels previously shown to inhibit kallikrein. CONCLUSIONS: Hemofiltration during CPB did not significantly alter serum aprotinin levels in patients receiving half-Hammersmith and full-Hammersmith dosing regimens of aprotinin.

Essential cysteines in 3-deoxy-D-manno-octulosonic acid 8-phosphate synthase from Escherichia coli: analysis by chemical modification and site-directed mutagenesis.

The enzyme 3-deoxy-D-manno-octulosonic acid 8-phosphate synthase (EC 4.1. 2.16) (KDO 8-P synthase) that catalyzes the condensation of D-arabinose 5-phosphate (A 5-P) with phosphoenolpyruvate (PEP) to give 3-deoxy-D-manno-octulosonic acid 8-phosphate (KDO 8-P) and inorganic phosphate (Pi) was inactivated by the thiol-modifying reagents 5,5-dithiobis (2-nitrobenzoate) (DTNB) and methyl methanethiosulfonate (MMTS). Reaction of cloned native KDO 8-P synthase with DTNB correlated with modification of two of the four cysteine sulfhydryls per monomer of enzyme and total loss of enzymatic activity which could be partially restored by treatment with dithiothreitol (DTT). Cyanolysis of the DTNB-inactivated enzyme with KCN led to the elimination of 2 equiv of 5-thio-2-nitrobenzoate and partial recovery of activity. The presence of either substrate(s) or product(s) provided no protection against inactivation nor affected the number of cysteines modified, indicating that the cysteines modified are most likely not at the active site of KDO 8-P synthase. Titration of denatured enzyme with DTNB resulted in the modification of all four cysteines. After treatment of native enzyme with MMTS, no cysteines could be titrated with DTNB and no enzymatic activity could be detected. Treatment of the MMTS-inactivated KDO 8-P synthase with DTT resulted in restoration of enzymatic activity and the presence of two DTNB-titratable cysteine residues. Based on these observations and a report that KDO 8-P synthase is inactivated in a time-dependent manner with 3-bromopyruvate and that the substrate PEP protects against this inactivation, all four cysteines (38, 166, 206, and 249) were individually mutated to alanines via a modified PCR methodology. The C206A and C249A mutants were both enzymatically active with K(m) and Vmax values approximately identical to those of wild-type KDO 8-P synthase, and both native mutants reacted with DTNB to modify only one of the three remaining cysteine sulfhydryls per monomer of enzyme. Titration of denatured C206A and C249A mutants resulted in the modification of three cysteines. The C38A and C166A mutants were both for the most part enzymatically inactive. Titration of native C38A and C166A with DTNB resulted in modification of two cysteines while titration of the denatured mutant protein resulted in modification of the three remaining cysteines. Circular dichroism measurements of wild-type KDO 8-P synthase and the four C --> A mutants indicate modest but significant changes in the structure of the mutants. These results indicate that C206 and C249 in native KDO 8-P synthase are readily accessible to the modification reagent DTNB and therefore inactivation may result from structural changes in the DTNB-modified KDO 8-P synthase or blockage of access of substrates to the active site. The C38 and C166 in native KDO 8-P synthase are inaccessible to the modification reagent DTNB, indicating that they are located in the interior of KDO 8-P synthase, and loss of activity in the C38A and C166A mutants suggests their essentiality in the KDO 8-P synthase reaction.