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Enhancement of dissolution of cyclosporine A using solid dispersions with polyoxyethylene (40) stearate.

A solid dispersion containing cyclosporine A (CyA) and polyoxyethylene (40) stearate (PS) was prepared by the solvent-melt method and characterized by powder X-ray diffraction (PXRD), hot-stage microscopy (HSM), scanning electron microscopy (SEM) and dissolution studies. The crystalline peaks of CyA disappeared in the PXRD spectra of solid dispersions but were seen in those of physical mixtures, demonstrating the amorphous state of the drug in solid dispersions. The solubility of CyA in aqueous solutions of PS was increased linearly with increasing amount of PS in water. Dissolution of the drug from solid dispersions and physical mixtures was dramatically enhanced compared to the drug powder alone in water at 37 degrees C.

Algorithms↗

Structure and microstructure of hexagonal Ba3Ti2RuO9 by electron diffraction and microscopy.

We have used electron microscopy and diffraction to refine the structure and investigate the microstructure of Ba(3)Ti(2)RuO(9). The parent compound is hexagonal BaTiO(3) with the space group P6(3)/mmc. Using convergent-beam electron diffraction (CBED) combined with electron-sensitive image plates we have found that the space group of Ba(3)Ti(2)RuO(9) is the non-centrosymmetric group P6(3)mc at room temperature and at approximately 110 K. This is consistent with the Ru and Ti atoms occupying alternate face-sharing octahedral sites in the 0001 direction. This maintains the c-glide, but breaks the mirror normal to the c axis and consequently removes the centre of symmetry. Using powder X-ray diffraction, we have measured the lattice parameters from polycrystalline samples to be a = 5.7056 +/- 0.0005, c = 14.0093 +/- 0.0015 A at room temperature. Using high-resolution electron microscopy (HREM) we observed highly coherent, low-strain {10\bar 10} grain boundaries intersecting at 60 and 120 degrees . From CBED we deduce that adjacent grains are identical but for the relative phase of the Ti and Ru atom ordering along the c axis. HREM also revealed occasional stacking faults, normal to the c-axis.

Journal Article↗

Nanoparticles of poorly water-soluble drugs prepared by supercritical fluid extraction of emulsions.

PURPOSE: The aim of the study was to develop and evaluate a new method for the production of micro- and nanoparticles of poorly soluble drugs for drug delivery applications. METHODS: Fine particles of model compounds cholesterol acetate (CA), griseofulvin (GF), and megestrol acetate (MA) were produced by extraction of the internal phase of oil-in-water emulsions using supercritical carbon dioxide. The particles were obtained both in a batch or a continuous manner in the form of aqueous nanosuspensions. Precipitation of CA nanoparticles was used for conducting a mechanistic study on particle size control and scale-up. GF and MA nanoparticles were produced in several batches to compare their dissolution behavior with that of micronized materials. The physical analysis of the particles produced was performed using dynamic light scattering (particle size), scanning electron microscopy (morphology), powder X-ray diffraction (crystallinity), gas chromatography (residual solvent), and a dissolution apparatus. RESULTS: Particles with mean volume diameter ranging between 100 and 1000 nm were consistently produced. The emulsion droplet size, drug solution concentration, and organic solvent content in the emulsion were the major parameters responsible for particle size control. Efficient and fast extraction, down to low parts-per-million levels, was achieved with supercritical CO2. The GF and MA nanoparticles produced were crystalline in nature and exhibited a 5- to 10-fold increase in the dissolution rate compared with that of micronized powders. Theoretical calculations indicated that this dissolution was governed mainly by the surface kinetic coefficient and the specific surface area of the particles produced. It was observed that the necessary condition for a reliable and scalable process was the sufficient emulsion stability during the extraction time. CONCLUSION: The method developed offers a viable alternative to both the milling and constructive nanoparticle formation processes. Although preparation of a stable emulsion can be a challenge for some drug molecules, the new technique significantly shortens the processing time and overcomes the current limitations of the conventional precipitation techniques in terms of large waste streams, product purity, and process scale-up.

Algorithms↗

Establishment of new preparation method for solid dispersion formulation of tacrolimus.

The aim of this study was to establish a new preparation method for solid dispersion formulation (SDF) of tacrolimus, a poorly water-soluble drug, without dichloromethane, because no use of dichloromethane is recommended by ICH harmonized tripartite guideline. To select the appropriate carrier, three different SDFs with polyethylene glycol 6000 (PEG 6000), polyvinylpyrrolidone (PVP) and hydroxypropylmethylcellulose (HPMC) were prepared by the conventional solvent method, in which tacrolimus and the carrier were completely dissolved in the mixture of dichloromethane and ethanol. Powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC) patterns indicated that tacrolimus exists in an amorphous state in all three SDFs. The supersaturated dissolution profiles of tacrolimus were observed in all SDFs, and the highest level of supersaturation for tacrolimus was obtained and maintained for 24h from SDF with HPMC. On the other hand, the supersaturated level from SDF with PEG 6000 or PVP decreased rapidly. The in vivo oral absorption study in dogs showed that bioavailability of tacrolimus from SDF with HPMC was remarkably improved compared with the crystalline powder. It was clarified that HPMC is the most appropriate carrier for SDF of tacrolimus. Then, SDF of tacrolimus was prepared by the new method, which allows us to make SDF of tacrolimus by swelling HPMC with ethanol, in which tacrolimus was completely dissolved. This new method does not need dichloromethane. The physicochemical properties of SDF with HPMC prepared by the new method were the same as those of SDF prepared by the conventional solvent method. Furthermore, SDF with HPMC prepared by the new method was still stable after stored at 40 degrees C for 3 months. The pharmacokinetic parameters after oral administration in monkeys showed no significant difference (P>0.01) between SDFs with HPMC prepared by the two methods. In conclusion, we have established the new preparation method for SDF of tacrolimus with HPMC and the new method makes it possible to prepare SDF of tacroliumus without dichloromethane.

Administration, Oral↗

Properties of tablets containing granulations of ibuprofen and an acrylic copolymer prepared by thermal processes.

The objective of this study was to investigate the properties of tablets containing granulations of ibuprofen (Ibu) and Ammonio Methacrylate Copolymer, Type B (Eudragit RS PO) prepared by hot-melt processing. Tablets were compressed from granules prepared by hot-melt granulation (HMG) or direct compression (DC). For the hot-melt extrusion (HME) process, tablets were prepared by cutting the extrudate, manually. The physicochemical properties of tablets were investigated using thermal analysis, powder X-ray diffraction analysis, tablet hardness, and drug dissolution. The effect of thermal treatment of tablets on the dissolution characteristics of Ibu was also investigated. The results demonstrated that the Ibu lowered the glass transition temperature (Tg) of the Eudragit RS PO and the softened polymer functioned as a thermal binder in the granulation. Ibu was demonstrated to be an effective plasticizer for Eudragit RS PO in the thermal processes. The efficiency of the granulation process increased with increasing levels of Eudragit RS PO in the powder blend. Higher levels of Eudragit RS PO in the tablets prepared by HMG or HME resulted in a decrease in the dissolution rate of the Ibu. An increase in the amount of Ibu in the tablets prepared by HMG or DC led to a decrease in the initial dissolution rate of the Ibu. Following the thermal treatment of the Ibu tablets prepared by HMG, the dissolution rate was significantly decreased due to structural changes in the tablets that resulted from the fusion and coalescence of plasticized polymer particles, causing a reduction in tablet porosity. The Ibu tablets prepared by HME demonstrated minimal changes in their release properties following thermal treatment even at temperatures higher than the Tg of the polymer. HME was shown to be a novel method to prepare matrix tablets and stable dissolution properties were obtained when tablets were stored at 40 degrees C for 30 days.

Acrylic Resins↗

Synthesis, structural characterization, and thermal stability of a new layered germanate structure, Na4Ge16O28(OH)12.

The new layered germanate structure Na4Ge16O28(OH)12 has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, FTIR, and SEM. The crystal lattice parameters are a = 7.3216(6) A, b = 14.3986(9) A, c = 7.7437(6) A, alpha = 90.0 degrees, beta = 100.179(7) degrees, gamma = 90.0 degrees, and V = 803.5(1) A3. The space group is C2/m with Z = 1. The germanium oxide sheets are connected non-covalently via electrostatic interactions with the sodium cations and H-bridging. At temperatures above 400 degrees C, the structure starts decomposing into sodium enneagermanate (Na4Ge9O20), germanium dioxide, and water as determined by powder X-ray diffraction, TGA, DTA, DSC, and GCMS.

Journal Article↗

1D and 2D homochiral metal-organic frameworks built from a new chiral elongated binaphthalene-derived bipyridine.

Six homochiral coordination polymers 1-6 based on a new enantiopure elongated (S)-2,2'-diethoxy-1,1'-binaphthyl-6,6'-bis(4-vinylpyridine) ligand (L) and divalent metal (Zn, Cd, and Ni) connecting points were synthesized and characterized by single-crystal X-ray diffraction studies. These new homochiral coordination polymers adopt two distinct framework structures: a one-dimensional infinite chain structure with bridging L ligands occupying the axial positions of the metal centers and a two-dimensional rhombic grid structure formed by linking octahedrally coordinated metal centers with four pyridyl groups of bridging L ligands in the equatorial positions. The structures of these coordination polymers are sensitive to the nature of the anions as well as the solvents from which the coordination polymer crystals were grown. Powder X-ray diffraction studies showed that the two-dimensional chiral rhombic grids exhibited porosity, which could potentially find applications in enantioselective separations and catalysis.

2,2'-Dipyridyl↗

Molecular precursors for ferroelectric materials: synthesis and characterization of Bi2M2(mu-O)(sal)4(Hsal)4(OEt)2 and BiM4(mu-O)4(sal)4(Hsal)3(O(i)Pr)4 (sal = O2CC6H4O, Hsal = O2CC6H4OH) (M = Nb, Ta).

Reactions between triphenyl bismuth, salicylic acid, and niobium or tantalum ethoxide have been explored. Four new coordination complexes incorporating bismuth and the group 5 metals niobium or tantalum have been synthesized and characterized spectroscopically, by elemental analysis, and by single crystal X-ray diffraction. The new complexes are Bi(2)M(2)(mu-O)(sal)(4)(Hsal)(4)(OEt)(2) (1a, M = Nb; 1b, M = Ta) and BiM(4)(mu-O)(4)(sal)(4)(Hsal)(3)(O(i)Pr)(4) (sal = O(2)CC(6)H(4)-2-O, Hsal = O(2)CC(6)H(4)-2-OH) (2a, M = Nb; 2b, M = Ta). Complexes 1a and 1b are isomorphous, as are 2a and 2b. The thermal and hydrolytic decomposition of 1a has been explored by DT/TGA and powder X-ray diffraction, while scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) were used to characterize the morphology and composition of the oxides. The heterobimetallic molecules are completely converted to the amorphous bimetallic oxide by heating to 500 degrees C in air. Decomposition of 1a or 1b at 650 degrees C produces the metastable high temperature form of BiNbO(4) as the major crystalline oxide phase. Heating samples of 1a to 850 degrees C favors conversion of the materials to the low temperature phase as well as disproportionation into Bi(5)Nb(3)O(15) and Nb(2)O(5). Thermal decomposition of 1a and 1b produces porous oxides, while hydrolytic decomposition of the complexes has been shown to produce nanometer scale bimetallic oxide particles. The potential of the complexes to act as single-source precursors for ferroelectric materials is considered.

Journal Article↗

AVSeO(5) (A = Rb, Cs) and AV(3)Se(2)O(12) (A = K, Rb, Cs, NH(4)): Hydrothermal Synthesis in the V(2)O(5)-SeO(2)-AOH System and Crystal Structure of CsVSeO(5).

Hydrothermal reactions in the V(2)O(5)-SeO(2)-AOH systems (A = Na, K, Rb, Cs, NH(4)) were studied with various reagent mole ratios. Typical millimole ratios were V(2)O(5)/SeO(2)/AOH = 5 or 3/15/x in 10-mL aqueous solutions, where x was 5, 10, 15, and 20. The reactions with x = 5 for A = K, Rb, Cs, and NH(4) at 230 degrees C produced single-phase products of the general formula AV(3)Se(2)O(12) with the (NH(4))(VO)(3)(SeO(3))(2) structure type. The x = 15 reactions for A = Rb and Cs yielded AVSeO(5) phases with a new structure type. The crystal structure for CsVSeO(5) was determined with X-ray single-crystal diffraction techniques to be monoclinic (P2(1) (No. 4), a = 7.887(3) Å, b = 7.843(2) Å, c = 9.497(3) Å, beta = 92.13(3) degrees, Z = 4). The structure of this compound consists of interwoven helixes extended in all three directions. The spires are composed of alternating SeO(3) and VO(5) units sharing common-edge oxygens in all three directions. For A = K and NH(4), the reactions of this mole ratio did not produce any identifiable phases. Each of the compounds is characterized by powder X-ray diffraction, infrared spectroscopic, and thermogravimetric techniques. The dependency of the synthesis results on the reaction conditions is discussed and rationalized.

Journal Article↗

Homologous phases built by boron clusters and their vibrational properties.

We have found a series of new rare earth boron-rich solids in REBC(N) (RE: Y, Ho, Er, Tm, and Lu), systems and their structures are solved from single crystal and/or powder X-ray diffraction data. Structure analysis results show that they are homologous with B(4)C and also show trigonal symmetry. As the two basic structural units, boron icosahedra and octahedra in the new phases form in layers and stack in different sequences which form different phases. With increasing number of icosahedral layers stacking between two neighboring octahedral layers, the c-axis of the unit cell is increased and the other two edges of the unit cell are only changed slightly. Three monophases of the series have been synthesized both in powders and as single crystals. The vibrational modes of the homologous phases are analyzed from the Raman spectra and compared with that of B(4)C.

Journal Article↗

Syntheses and structural properties of rare earth carbodiimides.

Crystalline samples of rare earth carbodiimides were synthesized by solid-state metathesis reactions of rare earth trichlorides with lithium cyanamide in sealed silica ampules. Two distinct structures were determined by single-crystal X-ray diffraction. The structure determined for Sm2(CN2)3 [C2/m, Z = 2, a = 14.534(2) A, b = 3.8880(8) A, c = 5.2691(9) A, beta = 95.96(2) degrees , R1 = 0.0267, and wR2 = 0.0667] was assigned for RE2(CN2)3 compounds with RE = Y, Pr, Nd, Sm, Gd, Tb, Dy, Ho, and Er, and the structure determined for Lu2(CN2)3 [R32, Z = 3, a = 6.2732(8) A, c = 14.681(2) A, R1 = 0.0208, and wR2 = 0.0526] was assigned for the smallest rare earth ions with RE = Tm, Yb, and Lu by powder X-ray diffraction. Both types of crystal structures are characterized by layers of [NCN](2-) ions whose arrangements can be derived from the motif of a closest packed layer of sticks. These layers alternate with layers of rare earth ions in a one-by-one sequence. Different tilting arrangements of the N-C-N-axes relative to the stacking directions (c) and different arrangements of RE3+ ions within metal atom layers account for the two distinct structures in which Sm3+ and Lu3+ ions adopt the coordination numbers 7 and 6, respectively.

Journal Article↗

The hydroxyapatite solubility product of human dental enamel as a function of pH in the range 4.6-7.6 at 20 degrees C.

Samples of 200 mg powdered enamel apatite were suspended in 10 ml of aqueous solutions made from phosphoric acid and calcium hydroxide for 60 days at 20 degrees C. Calcium and phosphate concentrations were determined by spectroscopy; pH and the concentrations of fluoride and carbonate by electrometry. The solubility product of hydroxyapatite varied linearly from 10-56.9 at pH 4.6 to 10-52.8 at pH 7.6. The carbonate concentration in the aqueous phase was too low to account for calcium carbonate complex formation of significance to the solubility product. After the equilibration, X-ray diffraction analysis of the powder showed that the salt was unchanged pure apatite with no trace of a transformation to brushite or any other calcium phosphate. A re-equilibration of some of the powder samples for another 60 days produced similar solubility products. Thus the change of the solubility product was most likely attributable to a pH-induced change of the ionic composition of the enamel crystal surface.

Calcium Carbonate↗

Preparation and characterization of spray-dried oxidized cellulose microparticles.

The goal of this study was to investigate the feasibility of spray drying to produce microparticles of oxidized cellulose (OC), a biocompatible and bioresorbable polymer. OCs containing 7, 13, and 20 wt% carboxylic groups were converted into stable aqueous dispersions and then spray dried using a Yamoto G-32 spray dryer equipped with a standard fluid nozzle with an orifice of 406 microm. The following operating conditions were investigated: inlet temperature 140, 170, and 190 degrees C; feed rate 3, 6, and 9 mL/min; and atomization airpressure 0.5, 1, and 1.5 kg f/cm2. The amounts of OC used in feed were 1, 2.5, and 5%. OC microparticles produced under these conditions were shrunken spheres, ranging in size between 0.98+/-0.47 and 2.05+/-0.98 microm. The different operating conditions used had no significant effect on the size and shape of particles. The use of a water-soluble plasticizer (glycerin, polyethylene glycol 400, or polyethylene glycol 6000) in the dispersion yielded microparticles with a good sphericity and a smooth surface morphology, whereas no change in the shape or size of microparticles was noted with water-insoluble plasticizers, Triacetin and dibutyl phthalate. Powder X-ray diffraction and Fourier transform infrared spectral analyses of spray-dried microparticles showed no change in the solid-state structure of OC. In conclusion, results show that OC can be converted into stable aqueous dispersions and used to produce microparticles by spray drying.

Capsules↗

Ab initio structure determination of a small-pore framework sodium stannosilicate.

The structure of a small-pore framework sodium stannosilicate Na(2)SnSi(3)O(9).2H(2)O (AV-10) has been determined ab initio from powder X-ray diffraction data (XRD). The unit cell is orthorhombic (space group C222(1), Z = 4) with cell dimensions a = 7.9453(5), b = 10.3439(7), c = 11.6252(7) A, V = 955 A(3). The structure of AV-10 is composed of corner sharing SnO(6) octahedra and SiO(4) tetrahedra, forming a three-dimensional framework structure. The SiO(4) tetrahedra form helix chains along [001] interconnected by SnO(6) octahedra. The SnO(6) octahedra are isolated by SiO(4) tetrahedra and, thus, there are no Sn-O-Sn linkages. AV-10 has been characterized by chemical analysis, powder XRD, scanning electron microscopy, (29)Si, (119)Sn, single- and (FAM) triple-quantum (23)Na MAS NMR spectroscopy, thermogravimetry (TGA), and nitrogen adsorption isotherms. The zeolitic water of AV-10 is reversibly lost. The dehydrated material has been studied in situ by powder XRD, TGA, and, in particular, triple-quantum (23)Na MAS NMR.

Journal Article↗

Low-Temperature Syntheses and Characterization of Novel Layered Tellurites, A(2)Mo(3)TeO(12) (A = NH(4), Cs), and "Zero-Dimensional" Tellurites, A(4)Mo(6)Te(2)O(24).6H(2)O (A = Rb, K).

Hydrothermal synthetic investigations to prepare new A(2)Mo(3)TeO(12) (A = NH(4), Cs, Rb, K) compounds are described. Novel noncentrosymmetric layered tellurites, (NH(4))(2)Mo(3)TeO(12) (1) and Cs(2)Mo(3)TeO(12) (2), have been synthesized by hydrothermal methods. Their structures contain two-dimensional hexagonal tungsten oxide related (Mo(3)TeO(12))(2)(-) anionic layers interleaved with NH(4)(+)/Cs(+) ions. New "zero-dimensional" tellurites, Rb(4)Mo(6)Te(2)O(24).6H(2)O (3) and K(4)Mo(6)Te(2)O(24).6H(2)O (4), containing discrete centrosymmetric (Mo(6)Te(2)O(24))(4)(-) anionic aggregates and alkali metal ions have been synthesized by simple refluxing of stoichiometric reactants in water. In this hexamolybdoditellurite anion, the Mo(6)O(24) flat hexagonal ring, formed from edge sharing of six MoO(6) octahedra, is capped by tellurium on both sides. The two types of anions have the same empirical formula. Cs(2)Mo(3)TeO(12) (2) could be prepared by a solid state reaction as well. All four new tellurites have been structurally characterized by single-crystal X-ray diffraction studies. Pertinent crystal, data are as follows: for 1, hexagonal space group P6(3), a = 7.332(2) Å, c = 12.028(4) Å, Z = 2; for 2, hexagonal space group P6(3), a = 7.3956(10) Å, c = 12.186(2) Å, Z = 2; for 3, monoclinic space group P2(1)/c, a = 10.0564(14) Å, b = 9.877(8) Å, c = 15.724(3) Å, beta = 109.988(11) degrees, Z = 2; for 4, monoclinic space group P2(1)/c, a = 9.878(3) Å, b = 9.724(4) Å, c = 15.301(3) Å, beta = 108.57(2) degrees, Z = 2. Low-temperature syntheses, structure, and powder X-ray diffraction, spectroscopic, and thermal studies of compounds 1-4 are described.

Journal Article↗

Synthesis, Characterization, and Reactivity of Group 12 Metal Thiocarboxylates, M(SOCR)(2)Lut(2) [M = Cd, Zn; R = CH(3), C(CH(3))(3); Lut = 3,5-Dimethylpyridine (Lutidine)].

A series of group 12 metal thiocarboxylate species, M(SOCR)(2)Lut(2) [M = Cd, Zn; R = CH(3), C(CH(3))(3); Lut = 3,5-dimethylpyridine (lutidine)], were synthesized to investigate their potential to act as precursors for the formation of metal sulfide materials. These species were expected to undergo thiocarboxylic anhydride elimination to give stoichiometric metal sulfides and remove the organic supporting ligands cleanly. These species were characterized by (1)H, (13)C, and (where appropriate) (113)Cd NMR spectroscopies, TGA, elemental analysis, and single-crystal X-ray diffraction. The spectroscopic and analytical data were consistent with the formulas identified above, and in the solid state the compounds are monomeric with approximate tetrahedral metal coordination environments and monodentate S-bond thiocarboxylate ligands. Crystal data for Cd(SOCCH(3))(2)Lut(2): crystallized in the triclinic space group P&onemacr;, with a = 8.267(1) Å, b = 9.467(1) Å, c = 14.087(1) Å, alpha = 94.04(1) degrees, beta = 91.49(1) degrees, gamma = 104.03(1) degrees, and Z = 2. Thermal decomposition of these compounds in the solid state or in solution resulted in formation of the corresponding metal sulfide at low temperatures, as seen by powder X-ray diffraction. Evidence for thiocarboxylic anhydride elimination was documented by NMR in solution phase reactions. The effects on thiocarboxylic anhydride elimination, resulting from varying M, R, or solvent media, were examined by heating NMR tube solutions of M(SOCR)(2)Lut(2) in pyridine or toluene. Heating toluene or pyridine solutions of Cd(SOCCH(3))(2)Lut(2) resulted in formation of nanocrystalline, sphalerite CdS, as determined by X-ray diffraction and TEM. These preliminary reactivity studies have revealed the great potential of this highly tailorable chemical system as precursors to group 12 metal sulfido species.

Journal Article↗

BCNU-loaded poly(D, L-lactide-co-glycolide) wafer and antitumor activity against XF-498 human CNS tumor cells in vitro.

Implantable polymeric device that can release chemotherapeutic agent directly into central nervous system (CNS) has had an impact on malignant glioma therapy. The purpose of our study was to develop an implantable polymeric device, which can release intact 1,3-bis(2-chloroethyl)-1-nitrosourea (BCNU) for long-term period over 1 month, and to evaluate its cytotoxicity against XF 498 human CNS tumor cells in vitro. BCNU was incorporated into biodegradable poly(D,L-lactide-co-glycolide) (PLGA), by using spray-drying method. BCNU-loaded PLGA microparticles were characterized by scanning electron microscopy (SEM), powder X-ray diffraction, and differential scanning calorimetry. SEM observation of the microparticles showed that the microparticles were spherical, i.e. microspheres. Homogeneous distribution of BCNU in PLGA microsphere was confirmed by significant reduction of crystallinity of BCNU. Microspheres were fabricated into wafers with flat and smooth surface by direct compression method. In vitro release of BCNU in pH 7.4 phosphate buffered saline was prolonged up to 8 weeks after short initial burst period. Antitumor activity of BCNU-loaded PLGA wafer against XF 498 human CNS tumor cells continued over 1 month and, PLGA only did not affect the growth of the cells. Meanwhile, the cytotoxic activity of BCNU powder disappeared within 12 h. These results strongly suggest that the BCNU/PLGA formulations increase release period of carmustine in vivo and also be useful in the development of implantable polymeric device for malignant glioma.

Antineoplastic Agents, Alkylating↗

Arsenate adsorption mechanisms at the allophane-water interface.

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As-(V)]0 from 50 to 1000 microM (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0-10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline Al-As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane-water interface are attributable to ligand exchange reactions between As-(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H2PO42- and H2AsO4(2-)) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The inner-sphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments.

Adsorption↗