Combined wavelet transform-artificial neural network use in tablet active content determination by near-infrared spectroscopy

The pharmaceutical industry faces increasing regulatory pressure to optimize quality control. Content uniformity is a basic release test for solid dosage forms. To accelerate test throughput and comply with the Food and Drug Administration's process analytical technology initiative, attention is increasingly turning to nondestructive spectroscopic techniques, notably near-infrared (NIR) spectroscopy (NIRS). However, validation of NIRS using requisite linearity and standard error of prediction (SEP) criteria remains a challenge. This study applied wavelet transformation of the NIR spectra of a commercial tablet to build a model using conventional partial least squares (PLS) regression and an artificial neural network (ANN). Wavelet coefficients in the PLS and ANN models reduced SEP by up to 60% compared to PLS models using mathematical spectra pretreatment. ANN modeling yielded high-linearity calibration and a correlation coefficient exceeding 0.996.     

Determination of Pesticide Ethion by Linear Sweep Stripping Voltammetry

IntroductionOrganophosphorus pesticides( OPPs) are widelyused in agriculture as insecticides, but they are foundto contaminate agricultural products such as fruits andvegetables to variable extents. Because of their toxicproperties[1,2]and the potential r…     

Metal-organic frameworks from copper dimers with cis- and trans-1,4-cyclohexanedicarboxylate and cis,cis-1,3,5-cyclohexanetricarboxylate

Single crystals of three coordination networks containing the Cu(2)(COO)(4) core bridged by cyclohexane have been hydrothermally prepared by the reaction of 1,4-cyclohexanedicarboxylic (1,4-H(2)chdc) or 1,3,5-cyclohexanetricarboxylic (1,3,5-H(3)chtc) acid and Cu(NO(3))(2) x 6H(2)O. We report their characterizations by single-crystal X-ray structure determinations, IR spectroscopy, thermal analyses, and their magnetic properties. [Cu(2)(trans-1,4-chdc)(2)] (1) consists of 4 x 4 grids with the dimeric nodes connected by the trans-1,4-chdc, and these grids are then connected to each other by Cu-O bonds, resulting in a porous network (void volume of 130 Angstrom(3) per cell or 25%) with no solvent in its cavities. [Cu(2)(cis-1,4-chdc)(2)(H(2)O)(2)] (2) consists of two-legged ladders where the dimer nodes are bridged by pairs of cis-1,4-chdc and the water molecules cap the ends of the Cu dimers. [Cu(2)(1,3,5-Hchtc)(2)] (3) displays 4 x 4 grids, but each dimeric node is connected to its neighbors within the same grid by Cu-O bonds to form a layered network which further makes hydrogen-bond interactions with its neighbors. 2 and 3 have compact structures without any space for solvents. IR and DT-TGA confirm the absence of water in the empty channels of 1, while IR shows the presence of both protonated and deprotonated carboxyl groups for 3. The magnetic properties of all three compounds are dominated by the strong Cu-Cu antiferromagnetic interaction resulting in singlet-triplet gaps of 450-500 K.     

Laparoscopic photodynamic diagnosis of ovarian cancer peritoneal micro metastasis: an experimental study

The goal of this study was to assess the interest of photodynamic diagnosis (PDD) for laparoscopic detection of peritoneal micro metastasis in ovarian carcinoma. Using an experimental animal model, intraperitoneal injection of aminolevulinic acid (ALA) and hexylester of aminolevulinic acid (He-ALA) were compared in order to improve laparoscopic detection of ovarian peritoneal carcinomatosis. Twenty-one 344 Fischer female rats received an intra peritoneal injection of 106 NuTu-19 cells. At day 22, carcinomatosis with micro peritoneal metastasis was obtained. Rats were randomized in three groups concerning intra peritoneal injection before laparoscopic staging: 5-ALA hydrochloride, HE-ALA and sterile water. Using D Light system, laparoscopic peritoneal exploration was performed with white light (WL) first and then with blue light (BL). The main objective was to assess feasibility and sensibility of laparoscopic PDD for nonvisible peritoneal micro metastasis of ovarian cancer. The main parameter was the confirmation of neoplasic status of fluorescent foci by histology. Concerning PDD after intraperitoneal injection of 5-ALA, mean values of lesions seen is higher than without fluorescence (32 vs 20.7; P = 0.01). Using He-ALA, mean values of detected lesions is higher than without fluorescence (42.9 vs 33.6; P < 0.001). Neoplasic status of fluorescent foci was confirmed in 92.8% of cases (39/42). Using 5-ALA, fluorescence of cancerous tissue is significantly higher than that of normal tissue in all the rats (ratio 1.17) (P = 0.01). With He-ALA, intensity of fluorescence is significantly higher in cancerous tissue compared to normal tissue, irrespective of the rat studied (ratio 1.22; P < 0.001).     

Influence of electronic and steric effects on stability constants and electrochemical reversibility of divalent ion complexes with glycine and sarcosine. A glass electrode potentiometric, sampled direct current polarographic, virtual potentiometric, and molecular modelling study

Cd^II complexes with glycine (gly) and sarcosine (sar) were studied by glass electrode potentiometry, direct current polarography, virtual potentiometry, and molecular modelling. The electrochemically reversible Cd^II–glycine–OH labile system was best described by a model consisting of M(HL), ML, ML₂, ML₃, ML(OH) and ML₂(OH) (M = Cd^II, L = gly) with the overall stability constants, as log β, determined to be 10.30 ± 0.05, 4.21 ± 0.03, 7.30 ± 0.05, 9.84 ± 0.04, 8.9 ± 0.1, and 10.75 ± 0.10, respectively. In case of the electrochemically quasi-reversible Cd^II–sarcosine–OH labile system, only ML, ML₂ and ML₃ (M = Cd^II, L = sar) were found and their stability constants, as log β, were determined to be 3.80 ± 0.03, 6.91 ± 0.07, and 8.9 ± 0.4, respectively. Stability constants for the ML complexes, the prime focus of this work, were thus established with an uncertainty smaller than 0.05 log units. The observed departure from electrochemical reversibility for the Cd–sarcosine–OH system was attributed mainly to the decrease in the transfer coefficient . The MM2 force field, supplemented by additional parameters, reproduced the reported crystal structures of diaqua-bis(glycinato-O,N)nickel(II) and fac-tri(glycinato)-nickelate(II) very well. These parameters were used to predict structures of all possible isomers of (i) [Ni(H₂O)₄(gly)]⁺ and [Ni(H₂O)₄(sar)]⁺; and (ii) [Ni(H₂O)₃(IDA)] and [Ni(H₂O)₃(MIDA)] (IDA = iminodiacetic acid, MIDA = N-methyl iminodiacetic acid) by molecular mechanics/simulated annealing methods. The change in strain energy, ΔU_str, that accompanies the substitution of one ligand by another (ML + L′ → ML′ + L), was computed and a strain energy ΔU_str = +0.28 kcal mol⁻¹ for the reaction [Ni(H₂O)₄(gly)]⁺ + sar → [Ni(H₂O)₄(sar)]⁺ + gly was found. This predicts the monoglycine complex to be marginally more stable. By contrast, for the reaction [Ni(H₂O)₃IDA] + MIDA → [Ni(H₂O)₃MIDA] + IDA, ΔU_str = −0.64 kcal mol⁻¹, and the monoMIDA complex is predicted to be more stable. This correlates well with (i) stability constants for Cd–gly and Cd–sar reported here; and (ii) known stability constants of ML complex for glycine, sarcosine, IDA, and MIDA.     

Novel RPLC stationary phases for lipophilicity measurement: solvatochromic analysis of retention mechanisms for neutral and basic compounds

An RPLC was developed to rapidly determine lipophilicity of neutral and basic compounds using three base deactivated RPLC stationary phases particularly designed for the analysis of basic compounds, namely, Supelcosil ABZ(+)Plus, Discovery RP Amide C16, and Zorbax Extend C18. The work consisted of three sets of experiments. In the first log kw values of neutral compounds were extrapolated using hydroorganic mobile phases at different compositions. Good correlation between log kw and log Poct indicated that the method was appropriate for these supports, without adding a silanol masking agent. In the second set of experiments, isocratic log k values of neutral and basic compounds were measured with three different mobile phases. The best estimation of lipophilicity was obtained for neutral and basic compounds when the secondary interactions were strongly reduced (i. e., when basic compounds were under their neutral form). In the third set of experiments, isocratic retention factors of basic compounds (in their neutral form) were measured with a high-pH mobile phase, on a chemically stable support (Zorbax Extend C18). Under these chromatographic conditions, correlation between the isocratic retention factors and log Poct (log D10.5) for basic compounds was similar to that for neutral compounds.     

Efficient calculation of two-dimensional adiabatic and free energy maps: Application to the isomerization of the C13C14 and C15N16 bonds in the retinal of bacteriorhodopsin

Accurate calculation of potential energy and free-energy profiles along reaction coordinates of biological processes such as enzymatic reactions or conformational changes is fundamental to the obtention of theoretical insight into protein function. We describe here the practical implementation of the Automatic Map Refinement Procedure (AMRP) and two-dimensional Weighted Histogram Analysis Method (WHAM) for efficient computation of adiabatic potential energy and free-energy maps, respectively. Methods for efficiently sampling configuration space with high-energy barriers and for removing hysteresis in the case of periodic reaction coordinates are presented. The application of these techniques to the isomerization of the C13C14 and C15N16 bonds in the retinal of bacteriorhodopsin is described. In dark-adapted bacteriorhodopsin (bR), the retinal moiety exists in two conformers, all-trans and (13,15)cis, with the latter making ≃67% of the population. This experimental free energy difference is reproduced here to within k_BT. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1644–1658, 1999     

Spectroscopic and DFT investigation of [M{HB(3,5-iPr2pz)3}(SC6F5)] (M = Mn, Fe, Co, Ni, Cu, and Zn) model complexes: periodic trends in metal-thiolate bonding

A series of metal-varied [ML(SC6F5)] model complexes (where L = hydrotris(3,5-diisopropyl-1-pyrazolyl)borate and M = Mn, Fe, Co, Ni, Cu, and Zn) related to blue copper proteins has been studied by a combination of absorption, MCD, resonance Raman, and S K-edge X-ray absorption spectroscopies. Density functional calculations have been used to characterize these complexes and calculate their spectra. The observed variations in geometry, spectra, and bond energies are interpreted in terms of changes in the nature of metal-ligand bonding interactions. The metal 3d-ligand orbital interaction, which contributes to covalent bonding in these complexes, becomes stronger going from Mn(II) to Co(II) (the sigma contribution) and to Cu(II) (the pi contribution). This change in the covalency results from the increased effective nuclear charge of the metal atom in going from Mn(II) to Zn(II) and the change in the 3d orbital populations (d5-->d10). Ionic bonding also plays an important role in determining the overall strength of the ML(+)-SC6F5(-) interaction. However, there is a compensating effect: as the covalent contribution to the metal-ligand bonding increases, the ionic contribution decreases. These results provide insight into the Irving-Williams series, where it is found that the bonding of the ligand being replaced by the thiolate makes a major contribution to the observed order of the stability constants over the series of metal ions.     

The Au(n) cluster probe in secondary ion mass spectrometry: influence of the projectile size and energy on the desorption/ionization rate from biomolecular solids

A Au-Si liquid metal ion source which produces Au(n) clusters over a large range of sizes was used to study the dependence of both the molecular ion desorption yield and the damage cross-section on the size (n = 1 to 400) and on the kinetic energy (E = 10 to 500 keV) of the clusters used to bombard bioorganic surfaces. Three pure peptides with molecular masses between 750 and 1200 Da were used without matrix. [M+H](+) and [M+cation](+) ion emission yields were enhanced by as much as three orders of magnitude when bombarding with Au(400) (4+) instead of monatomic Au(+), yet very little damage was induced in the samples. A 100-fold increase in the molecular ion yield was observed when the incident energy of Au(9) (+) was varied from 10 to 180 keV. Values of emission yields and damage cross-sections are presented as a function of cluster size and energy. The possibility to adjust both cluster size and energy, depending on the application, makes the analysis of biomolecules by secondary ion mass spectrometry an extremely powerful and flexible technique, particularly when combined with orthogonal time-of-flight mass spectrometry that then allows fast measurements using small primary ion beam currents.