On the convergence of a class of algorithms using linearly independent search directions

Powell has shown that the cyclic coordinate method with exact searches may not converge to a stationary point. In this note we consider a more general class of algorithms for unconstrained minimization, and establish their convergence under the assumption that the objective function has a unique minimum along any line.     

Radiochemical separation of Ru/III/ with 2-mercaptobenzothiazole into chloroform employing solvent extraction technique

The reagent 2-mercaptobenzothiazole /2-HMBT/ has been used for the solvent extraction of Ru/III/. The extraction coefficient value of Ru/III/ has been evaluated, based on various parameters such as, effect of molarity of the acid, time of equilibration, time of heating, effect of various solvents and effect of various salts. The stoichiometry of the metal to reagent was determined by the method of substoichiometric extraction of slope-ratio method and was found to be 13. Separation factor and decontamination factor for various elements have also been studied.     

Some Isoperimetric Inequalities in Electrochemistry and Hele Shaw Flows

Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry.     

Chromatographic and spectroscopic studies of the solvent properties of a new series of room-temperature liquid tetraalkylammonium sulfonates

Fifteen tetraalkylammonium salts of the functionalized sulfonic acids N,N-bis(2-hydroxy- ethyl)-2-aminoethanesulfonic acid, 2-(cyclohexylamino)ethanesulfonic acid and 2-hydroxy-4- morpholinopropanesulfonic acid were synthesized and the eight organic salts that were liquid at room temperature were characterized by physical, spectroscopic and chromatographic methods. All liquid salts were viscous at room temperature but after dilution with a suitable cosolvent could be used as mobile phases in liquid chromatography. For this application, the rapid deterioration of silica-based column packings was more of a deterrent than the physical properties of the salts. The tetraalkylammonium sulfonates had wide liquid ranges and were stable as column packings up to 150–180°C, making them suitable for use in gas chromatography. Their solvent properties were characterized by solvatochromic parameters [E_T(30), π*, α and β] and by thermodynamic parameters determined by gas chromatography. Good agreement was found between the predictions of the two methods. The liquid salts showed strong orientation and solvent hydrogen bond acceptor capacity with weak hydrogen bond donor capacity in spite of the functionalization of the anions. The most probable reason for the weak hydrogen bond donor capacity of the anions is the unavailability of these functional groups for solute interactions owing to their preferential involvement in the formation of anion association complexes. The chemically defined structure, unique solvent properties and wide usable temperature ranges make the tetraalkylammonium sulfonates useful stationary phases for gas chromatography.     

Raman spectroscopy--a new method for the intra-operative assessment of axillary lymph nodes

Sentinel Lymph Node Biopsy has become the standard surgical procedure for the sampling of axillary lymph nodes in breast cancer. Intra operative node assessment is currently not offered to the majority of patients but would allow definitive axillary surgery to take place immediately. This would confer benefits both to the patient and to the healthcare system. Our experimental study aims to demonstrate that a Raman spectroscopy probe device could overcome many of the disadvantages of current intra-operative analysis techniques. 38 axillary lymph nodes, 25 negative and 13 positive from 20 patients undergoing breast surgery for invasive breast cancer were assessed using a commercially available Raman spectroscopy probe. Spectra were assessed using principal component fed linear discriminant analysis trained by the histopathology results. Leave one node out cross validation achieved a sensitivity of up to 92% and a specificity of up to 100% in differentiating between normal and metastatic lymph nodes.     

Differentiation between intra-axial metastatic tumor progression and radiation injury following fractionated radiation therapy or stereotactic radiosurgery using MR spectroscopy, perfusion MR imaging or volume progression modeling

Objective

To determine the accuracy of magnetic resonance spectroscopy (MRS), perfusion MR imaging (MRP), or volume modeling in distinguishing tumor progression from radiation injury following radiotherapy for brain metastasis.

Methods

Twenty-six patients with 33 intra-axial metastatic lesions who underwent MRS (n=41) with or without MRP (n=32) after cranial irradiation were retrospectively studied. The final diagnosis was based on histopathology (n=4) or magnetic resonance imaging (MRI) follow-up with clinical correlation (n=29). Cho/Cr (choline/creatinine), Cho/NAA (choline/N-acetylaspartate), Cho/nCho (choline/contralateral normal brain choline) ratios were retrospectively calculated for the multi-voxel MRS. Relative cerebral blood volume (rCBV), relative peak height (rPH) and percentage of signal-intensity recovery (PSR) were also retrospectively derived for the MRPs. Tumor volumes were determined using manual segmentation method and analyzed using different volume progression modeling. Different ratios or models were tested and plotted on the receiver operating characteristic curve (ROC), with their performances quantified as area under the ROC curve (AUC). MRI follow-up time was calculated from the date of initial radiotherapy until the last MRI or the last MRI before surgical diagnosis.

Results

Median MRI follow-up was 16 months (range: 2-33). Thirty percent of lesions (n=10) were determined to be radiation injury; 70% (n=23) were determined to be tumor progression. For the MRS, Cho/nCho had the best performance (AUC of 0.612), and Cho/nCho >1.2 had 33% sensitivity and 100% specificity in predicting tumor progression. For the MRP, rCBV had the best performance (AUC of 0.802), and rCBV >2 had 56% sensitivity and 100% specificity. The best volume model was percent increase (AUC of 0.891); 65% tumor volume increase had 100% sensitivity and 80% specificity.

Conclusion

Cho/nCho of MRS, rCBV of MRP, and percent increase of MRI volume modeling provide the best discrimination of intra-axial metastatic tumor progression from radiation injury for their respective modalities. Cho/nCho and rCBV appear to have high specificities but low sensitivities. In contrast, percent volume increase of 65% can be a highly sensitive and moderately specific predictor for tumor progression after radiotherapy. Future incorporation of 65% volume increase as a pretest selection criterion may compensate for the low sensitivities of MRS and MRP.     

Particle multiplicities in the fission-like reactions of 340 MeV Si on Th

Pre-scission and post-scission multiplicities of neutrons and alpha particles have been simultaneously measured for the fission-like reactions of 340 MeV ²⁸Si on ²³²Th. Dynamical model calculations using HICOL code predict that about 90% of the observed events are of quasi-fission type while the remaining 10% are from compound nucleus fission decay. Moving source fits were carried out to the observed neutron and alpha particle spectra, measured at different angles with respect to the fragment directions. The pre-scission and post-scission neutron multiplicities are deduced to be 8.7±2.0 and 9.4±2.0, respectively. The corresponding multiplicity values for alpha particles are found to be 0.22±0.08 and 0.1±0.03. From the measured post-scission neutron multiplicity, it is inferred that about 65±20 MeV of the initial excitation energy remains at scission. This may be compared to the value of 85±30 MeV estimated from PACE2 statistical model calculations, adjusted to reproduce the measured pre-scission neutron multiplicity. From a comparison of the Statistical Model predictions with the measured pre-scission neutron multiplicity, the fission delay is estimated to be of 5⁺⁷₋₃×10⁻²⁰ s which overlaps with the average duration of fission-like process from the contact to the scission point (2×10⁻²⁰ s) as determined from HICOL-based dynamical calculations. For the delay time deduced as above, the pre-scission alpha particle multiplicity calculated by the PACE2 code is about a factor two larger than the experimental one, demonstrating the difficulties in modelling the alpha particle emission from highly elongated shapes that characterize the fissioning system from the contact point to scission.     

A Multifunctional Subphthalocyanine Nanosphere for Targeting,Labeling, and Killing of Antibiotic‐Resistant Bacteria

Developing a material that can combat antibiotic‐resistant bacteria, a major global health threat, is an urgent requirement. To tackle this challenge, we synthesized a multifunctional subphthalocyanine (SubPc) polymer nanosphere that has the ability to target, label, and photoinactivate antibiotic‐resistant bacteria in a single treatment with more than 99 % efficiency, even with a dose as low as 4.2 J cm⁻² and a loading concentration of 10 nM . The positively charged nanosphere shell composed of covalently linked SubPc units can increase the local concentration of photosensitizers at therapeutic sites. The nanosphere shows superior performance compared to corresponding monomers presumably because of their enhanced water dispersibility, higher efficiency of singlet‐oxygen generation, and phototoxicity. In addition, this material is useful in fluorescence labeling of living cells and shows promise in photoacoustic imaging of bacteria in vivo.     

Stable aluminium fluoride chelates with triazacyclononane derivatives proved by X-ray crystallography and 18F-labeling study

A single crystal structure of an aluminium-fluoride complex of a model compound (NODA-benzyl) was studied to understand the co-ordination chemistry. Series of ligands with an extra carboxylic acid linker for biomolecule conjugation were studied for improved (18)F-labeling applications.     

Stress Degradation Behavior of Entacapone and Development of LC Stability-Indicating Related Substances and Assay Method

A new, sensitive, stability indicating gradient RP-LC related substances and assay method has been developed for the quantitative determination of entacapone in bulk drugs. Efficient chromatographic separation was achieved on a C18 stationary phase with simple mobile phase combination of buffer and acetonitrile. Buffer consisted of 0.1% orthophosphoric acid, delivered in a gradient mode and quantitation was carried out using ultraviolet detection at 220 nm with a flow rate of 1.5 mL min^?1. In the developed LC method the resolution (R _s ) between entacapone and its three potential process impurities were found to be >2.0. Regression analysis showed an r ² value (correlation coefficient) >0.99 for entacapone and its three potential impurities. This method was capable to detect all three process impurities of entacapone at a level of 0.003% with respect to test concentration of 0.5 mg mL^?1 for a 20 μL injection volume. The inter- and intra-day precision values for all three impurities and for entacapone was found to be within 2.0% RSD. The method has shown good and consistent recoveries for entacapone in bulk drugs (99.2–101.5%) and its three impurities (99.5–102.2%). The test solution was found to be stable in diluent for 48 h. The drug substances were subjected to stress conditions of hydrolysis, oxidation, photolysis and thermal degradation. Considerable degradation was found to occur in acid stress, base stress and oxidative conditions. The stressed test solutions were assayed against the qualified working standard of entacapone and the mass balance in each case was close to 99.7% indicating that the developed method was stability-indicating. The developed RP-LC method was validated with respect to linearity, accuracy, precision and robustness.