Sources and source regions effecting the aerosol composition of the Eastern Mediterranean

Positive matrix factorization (PMF) was used to deduce the aerosol sources at a rural site on the Mediterranean coast of Turkey, using sample collected between February 1992 and December 1993. Approximately 600 daily aerosol samples were collected and 40 elements and compounds were analyzed by atomic absorption spectrometry, instrumental neutron activation analysis, ion chromatography and colorimetry.Seven factors were identified with PMF, namely local dust, Saharan dust, sea salt, long range transport, smelter, arsenic and fertilizer factors. The non-parametric bootstrapped potential source contribution function (PSCF) was then used to help identify likely locations of the regional sources of pollution. Besides, explained variance, enrichment factors, seasonal variation of G-score values and back trajectories were used to define the source regions of the factors. Results demonstrated that there are major potential source areas, for the pollution-derived component in aerosol mass, on the Aegean coast, Northwest Turkey, Balkan countries, Ukraine and regions located northern part of Ukraine.     

Quaternary indides LaTIn3Mg (T = Rh and Ir) and CeIrIn3Mg with LaCoAl4 type structure

The quaternary indides LaTIn₃Mg (T = Rh and Ir) and CeIrIn₃Mg were prepared from the elements in sealed tantalum ampoules in an induction furnace. The samples were characterized by X-ray powder and single crystal data: LaCoAl₄ type, Pmma, Z = 2, a = 830.5(1), b = 436.1(1), c = 745.1(1) pm, wR2 = 0.038, 467 F ² values for LaRhIn_3.075Mg_0.925, a = 832.9(1), b = 436.5(1), c = 746.9(1) pm, wR2 = 0.077, 471 F ² values for LaIrIn_3.091Mg_0.909, and a = 832.2(1), b = 434.1(1), c = 743.9(1) pm, wR2 = 0.066, 465 F ² values for CeIrIn_3.07Mg_0.93 with 25 variables for each refinement. The transition metal, indium, and magnesium atoms build up three-dimensional [TIn₃Mg] networks which leave pentagonal prismatic voids for the lanthanum and cerium atoms. The transition metal atoms have tricapped trigonal prismatic coordination and the magnesium atoms fill distorted square prisms. All three crystals revealed a small degree of Mg/In mixing on the latter site.     

Cobalt Centered Trigonal RE6 Prisms and Mg4 Clusters as Basic Structural Units in RE4CoMg (RE = Y,La, Pr,Nd, Sm,Gd–Tm)

The new rare earth metal rich intermetallic compounds RE₄CoMg (RE = Y, La, Pr, Nd, Sm, Gd–Tm) were prepared via melting of the elements in sealed tantalum tubes in a water‐cooled sample chamber of a high‐frequency furnace. The compounds were investigated by X‐ray diffraction of powders and single crystals: Gd₄RhIn type, , a = 1428.38(9) pm, wR2 = 0.0638, 680 F² values, 20 variables for La₄CoMg, a = 1399.5(2) pm, wR2 = 0.0584, 589 F² values, 20 variables for Pr₄CoMg, a = 1390.2(3) pm, wR2 = 0.0513, 634 F² values, 20 variables for Nd_3.90CoMg_1.10, a = 1381.0(3) pm, wR2 = 0.0730, 618 F² values, 22 variables for Sm_3.92Co_0.93Mg_1.08, a = 1373.1(4) pm, wR2 = 0.0586, 611 F² values, 20 variables for Gd_3.92CoMg_1.08, a = 1362.1(3) pm, wR2 = 0.0576, 590 F² values, 20 variables for Tb_3.77CoMg_1.23, a = 1344.8(2) pm, wR2 = 0.0683, 511 F² values, 20 variables for Dy_3.27CoMg_1.73, and a = 1343.3(2) pm, wR2 = 0.0560, 542 F² values, 20 variables for Er_3.72CoMg_1.28. The cobalt atoms have trigonal prismatic rare earth coordination. Condensation of the CoRE₆ prisms leads to a three‐dimensional network which leaves larger voids that are filled by regular Mg₄ tetrahedra at a Mg–Mg distance of 316 pm in La₄CoMg. The magnesium atoms have twelve nearest neighbors (3 Mg + 9 RE) in icosahedral coordination. In the structures with Nd, Sm, Gd, Tb, Dy, and Er, the RE1 positions which are not involved in the trigonal prismatic network reveal some RE1/Mg mixing and the Sm_3.92Co_0.93Mg_1.08 structure shows small cobalt defects. Considering La₄CoMg as representative of all studied systems an analysis of the chemical bonding within density functional theory closely reproduces the crystal chemistry scheme and shows the role played by the valence states of the different constituents in the electronic band structure. Strong bonding interactions were observed between the lanthanum and cobalt atoms within the trigonal prismatic network.     

A sensitive and rapid determination of ranitidine in human plasma by HPLC with fluorescence detection and its application for a pharmacokinetic study

A novel precolumn derivatization reversed-phase high-performance liquid chromatography method with fluorescence detection is described for the determination of ranitidine in human plasma. The method was based on the reaction of ranitidine with 4-fluoro-7-nitrobenzo-2-oxa-1,3-diazole forming yellow colored fluorescent product. The separation was achieved on a C(18) column using methanol-water (60:40, v/v) mobile phase. Fluorescence detection was used at the excitation and emission of 458 and 521 nm, respectively. Lisinopril was utilized as an internal standard. The flow rate was 1.2 mL/min. Ranitidine and lisinopril appeared at 3.24 and 2.25 min, respectively. The method was validated for system suitability, precision, accuracy, linearity, limit of detection, limit of quantification, recovery and robustness. Intra- and inter-day precisions of the assays were in the range of 0.01-0.44%. The assay was linear over the concentration range of 50-2000 ng/mL. The mean recovery was determined to be 96.40 ± 0.02%. This method was successfully applied to a pharmacokinetic study after oral administration of a dose (150 mg) of ranitidine.     

Strong valid inequalities for fluence map optimization problem under dose-volume restrictions

Fluence map optimization problems are commonly solved in intensity modulated radiation therapy (IMRT) planning. We show that, when subject to dose-volume restrictions, these problems are NP-hard and that the linear programming relaxation of their natural mixed integer programming formulation can be arbitrarily weak. We then derive strong valid inequalities for fluence map optimization problems under dose-volume restrictions using disjunctive programming theory and show that strengthening mixed integer programming formulations with these valid inequalities has significant computational benefits.     

Validated spectrophotometric method for the determination,spectroscopic characterization and thermal structural analysis of duloxetine with 1,2-naphthoquinone-4-sulphonate

A novel, selective, sensitive and simple spectrophotometric method was developed and validated for the determination of the antidepressant duloxetine hydrochloride in pharmaceutical preparation. The method was based on the reaction of duloxetine hydrochloride with 1,2-naphthoquinone-4-sulphonate (NQS) in alkaline media to yield orange colored product. The formation of this complex was also confirmed by UV-visible, FTIR, ¹H NMR, Mass spectra techniques and thermal analysis. This method was validated for various parameters according to ICH guidelines. Beer’s law is obeyed in a range of 5.0–60 μg/mL at the maximum absorption wavelength of 480 nm. The detection limit is 0.99 μg/mL and the recovery rate is in a range of 98.10–99.57%. The proposed methods was validated and applied to the determination of duloxetine hydrochloride in pharmaceutical preparation. The results were statistically analyzed and compared to those of a reference UV spectrophotometric method.     

Rare‐Earth‐Rich Magnesium Compounds RE23Rh7Mg4 (RE = La,Ce, Pr,Nd, Sm,Gd) with Tetrahedral Mg4 Clusters

The rare earth‐rich compounds RE₂₃Rh₇Mg₄ (RE = La, Ce, Pr, Nd, Sm, Gd) were prepared by induction‐melting the elements in sealed tantalum tubes. The new compounds were characterized by X‐ray powder diffraction. They crystallize with the hexagonal Pr₂₃Ir₇Mg₄ type structure, space group P6₃mc. The structures of La₂₃Rh₇Mg₄ (a = 1019.1(1), c = 2303.7(4) pm, wR2 = 0.0827, 1979 F² values, 69 variables), Nd₂₃Rh₇Mg₄ (a = 995.4(2), c = 2242.3(5) pm, wR2 = 0.0592, 2555 F² values, 74 variables) and Gd₂₃Rh_6.86(5)Mg₄ (a = 980.5(2), c = 2205.9(5) pm, wR2 = 0.0390, 2083 F² values, 71 variables) were refined from single crystal X‐ray diffractometer data. The three crystallographically different rhodium atoms have trigonal prismatic rare earth coordination with short RE–Rh distances (283–300 pm in Nd₂₃Rh₇Mg₄). The prisms are condensed via common edges, leading to a rigid three‐dimensional network in which isolated Mg₄ tetrahedra (312–317 pm Mg–Mg in Nd₂₃Rh₇Mg₄) are embedded. Temperature dependent magnetic susceptibility data of Ce₂₃Rh₇Mg₄ indicate Curie‐Weiss behavior with an experimental magnetic moment of 2.52(1) μ_B/Ce atom, indicative for stable trivalent cerium. Antiferromagnetic ordering is evident at 2.9 K.     

Preparation of an Electrochromatographic Stationary Phase Using a New Polymethacrylate Monolith with Chloropropyl Functionality

A new reactive capillary monolith as an alternative to the commonly employed glycidyl methacrylate-based stationary phases in capillary electrochromatography (CEC) applications was synthesized and post-functionalized with charge-bearing groups. For this purpose, a hydrophilic capillary monolith with reactive 3-chloro-2-hydroxypropyl moiety was first obtained by the copolymerization of a new methacrylate-based monomer, 3-chloro-2-hydroxypropyl methacrylate (HPMA-Cl), with a methacrylic crosslinking agent, ethylene glycol dimethacrylate (EDMA). The presence of 3-chloro-2-hydroxypropyl functionality in poly(HPMA-Cl-co-EDMA) monolith allowed the synthesis of monoliths carrying strongly ionizable anionic, cationic or neutral groups such as sulfonic acid, quaternary ammonium or octadecyl, respectively, via simple and single-stage reactions. In the present study, a reactive poly(HPMA-Cl-co-EDMA) capillary monolith was functionalized with sodium bisulfite (NaHSO₃) to have a strongly ionizable sulfonic acid group on the monolith. The resulting monolith providing cathodic electroosmotic flow in CEC was successfully used for the separation of phenol derivatives. The theoretical plate numbers up to 63,000 plates/column were achieved. The results showed that a new promising, reactive support that could be functionalized with different chromatographic ligands for different chromatographic applications was obtained in the study.     

A new temperature-sensitive polymer: Poly(ethoxypropylacrylamide)

In this study, a new temperature sensitive polymer was obtained by the solution polymerization of ethoxypropylacrylamide. The monomer, N-(3-ethoxypropyl)-acrylamide was synthesized by the nucleophilic substitution reaction of 3-ethoxy-propylamine and acryloyl chloride. The solution polymerization was performed in ethanol at 70 °C, by using azobisizobutyronitrile as the initiator. Poly(N-(3-ethoxypropyl)acrylamide), PEPA, exhibited a reversible phase transition by the temperature. The effects of polymer and salt concentrations on the lower critical solution temperature, (LCST) behaviour were investigated. LCST was found to be strongly dependent on the polymer concentration. The dynamic light scattering (DLS) measurements confirmed the formation of aggregates by the association of nucleated polymer chains at the temperatures higher than LCST. However an unusual behaviour, a marked decrease in the hydrodynamic diameter by the increasing PEPA concentration was observed below the LCST. The effect of salt concentration on the critical flocculation temperature of PEPA was reasonably similar to poly(isopropylacrylamide), PNIPA. In the ethanol-water media, the reversible phase transition behaviour was observed up the ethanol concentration of 30% v/v. This study indicated that PEPA was a new alternative thermally reversible material for PNIPA. With respect to the well-defined temperature-sensitive polymers like PNIPA, polymer concentration dependent LCST of PEPA can provide significant advantages in the applications like drug targeting, affinity separation and immobilization of bioactive agents.