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1.
J Synchrotron Radiat ; 31(Pt 4): 955-967, 2024 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-38900456

RESUMEN

The demand for powder X-ray diffraction analysis continues to increase in a variety of scientific fields, as the excellent beam quality of high-brightness synchrotron light sources enables the acquisition of high-quality measurement data with high intensity and angular resolution. Synchrotron powder diffraction has enabled the rapid measurement of many samples and various in situ/operando experiments in nonambient sample environments. To meet the demands for even higher throughput measurements using high-energy X-rays at SPring-8, a high-throughput and high-resolution powder diffraction system has been developed. This system is combined with six sets of two-dimensional (2D) CdTe detectors for high-energy X-rays, and various automation systems, including a system for automatic switching among large sample environmental equipment, have been developed in the third experimental hutch of the insertion device beamline BL13XU at SPring-8. In this diffractometer system, high-brilliance and high-energy X-rays ranging from 16 to 72 keV are available. The powder diffraction data measured under ambient and various nonambient conditions can be analysed using Rietveld refinement and the pair distribution function. Using the 2D CdTe detectors with variable sample-to-detector distance, three types of scan modes have been established: standard, single-step and high-resolution. A major feature is the ability to measure a whole powder pattern with millisecond resolution. Equally important, this system can measure powder diffraction data with high Q exceeding 30 Å-1 within several tens of seconds. This capability is expected to contribute significantly to new research avenues using machine learning and artificial intelligence by utilizing the large amount of data obtained from high-throughput measurements.

2.
Microb Pathog ; 190: 106639, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38616002

RESUMEN

BACKGROUND INFORMATION: The advancement of biological-mediated nanoscience towards higher levels and novel benchmarks is readily apparent, owing to the use of non-toxic synthesis processes and the incorporation of various additional benefits. This study aimed to synthesize stable tin oxide nanoparticles (SnO2-NPs) using S. rhizophila as a mediator. METHODS: The nanoparticles that were created by biosynthesis was examined using several analytical techniques, including Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), X-ray diffraction (XRD), UV-visible (UV-vis) spectroscopy, and energy dispersive X-ray spectroscopy (EDS). RESULTS: The results obtained from the characterization techniques suggest that S. rhizophila effectively catalyzed the reduction of SnCl2 to SnO2-NPs duration of 90 min at ambient temperature with the ƛmax of 328 nm. The size of the nano crystallite formations was measured to be 23 nm. The present study investigates nanoscale applications' antibacterial efficacy against four bacterial strains, including Klebsiella Sp, Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli. The observed zone of inhibition for the nanoparticles (NPs) varied from 10 to 25 mm. The research findings demonstrate that the nanoparticles (NPs) are effective as antibacterial, phytotoxic, and cytotoxic agents.


Asunto(s)
Antibacterianos , Biopelículas , Pruebas de Sensibilidad Microbiana , Compuestos de Estaño , Difracción de Rayos X , Compuestos de Estaño/química , Compuestos de Estaño/farmacología , Biopelículas/efectos de los fármacos , Antibacterianos/farmacología , Antibacterianos/química , Animales , Staphylococcus aureus/efectos de los fármacos , Nanopartículas/química , Bacterias/efectos de los fármacos , Nanopartículas del Metal/química , Nanopartículas del Metal/toxicidad , Escherichia coli/efectos de los fármacos , Pseudomonas aeruginosa/efectos de los fármacos , Microscopía Electrónica de Transmisión , Microscopía Electrónica de Rastreo , Tamaño de la Partícula
3.
Chemistry ; 30(11): e202302138, 2024 Feb 21.
Artículo en Inglés | MEDLINE | ID: mdl-37957130

RESUMEN

Three different devices: ball mill, hot stage melting, and magic angle spinning (MAS) NMR rotor were used for the preparation of ethenzamide (ET) cocrystals with glutaric acid (GLU), ethylmalonic acid (EMA) and maleic acid (MAL) as coformers. In each case, well-defined binary systems (ET:EMA, ET:GLU, ET:MAL) were obtained. The common features of the two solvent free methods of cocrystal formation (grinding, melting) are presented on the basis of arguments obtained by solid state NMR spectroscopy. Thermal analysis (Differential Scanning Calorimetry) proved that the eutectic phase arises over a wide range of molar ratios of components for each of the binary systems. NMR techniques, supported by theoretical calculations, allowed to provide details about the pathway of the reaction mechanism with atomic accuracy. It was found that the formation of ET cocrystals is a complex process that requires five steps. Each step has been recognized and described. Variable temperature 1D and 2D MAS NMR experiments allowed to track physicochemical processes taking place in a molten state. Moreover, it was found that in a multicomponent mixture consisting of all four components, ET, EMA, GLU, and MAL, ET in the molten phase behaves as a specific selector choosing only one partner to form binary cocrystals according to energy preferences. The process of exchange of coformers in binary systems during grinding, melting, and NMR measurements is described. The stabilization energies (Estab ) and molecular electrostatic potential (MEP) maps computed for the cocrystals under discussion and their individual components rationalize the selection rules and explain the relationships between individual species.

4.
Small ; 19(19): e2206772, 2023 05.
Artículo en Inglés | MEDLINE | ID: mdl-36755199

RESUMEN

Nanozymes are nanomaterials with biocatalytic properties under physiological conditions and are one class of artificial enzymes to overcome the high cost and low stability of natural enzymes. However, surface ligands on nanomaterials will decrease the catalytic activity of the nanozymes by blocking the active sites. To address this limitation, ligand-free PtAg nanoclusters (NCs) are synthesized and applied as nanozymes for various enzyme-mimicking reactions. By taking advantage of the mutual interaction of zeolitic imidazolate frameworks (ZIF-8) and Pt precursors, a good dispersion of PtAg bimetal NCs with a diameter of 1.78 ± 0.1 nm is achieved with ZIF-8 as a template. The incorporation of PtAgNCs in the voids of ZIF-8 is confirmed with structural analysis using the atomic pair-distribution function and powder X-ray diffraction. Importantly, the PtAgNCs present good catalytic activity for various enzyme-mimicking reactions, including peroxidase-/catalase- and oxidase-like reactions. Further, this work compares the catalytic activity between PtAg NCs and PtAg nanoparticles with different compositions and finds that these two nanozymes present a converse dependency of Ag-loading on their activity. This study contributes to the field of nanozymes and presents a potential option to prepare ligand-free bimetal biocatalysts with sizes in the nanocluster regime.


Asunto(s)
Nanopartículas del Metal , Imitación Molecular , Peroxidasa/química , Peroxidasa/metabolismo , Nanopartículas del Metal/química , Platino (Metal)/química , Plata/química , Aleaciones/química
5.
J Synchrotron Radiat ; 30(Pt 5): 1003-1012, 2023 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-37462688

RESUMEN

Following Phase 2 of the upgrade of the ESRF in which the storage ring was replaced by a new low-emittance ring along with many other facility upgrades, the status of ID22, the high-resolution powder-diffraction beamline, is described. The beamline has an in-vacuum undulator as source providing X-rays in the range 6-75 keV. ID22's principle characteristics include very high angular resolution as a result of the highly collimated and monochromatic beam, coupled with a 13-channel Si 111 multi-analyser stage between the sample and a Dectris Eiger2 X 2M-W CdTe pixel detector. The detector's axial resolution allows recorded 2θ values to be automatically corrected for the effects of axial divergence, resulting in narrower and more-symmetric peaks compared with the previous fixed-axial-slit arrangement. The axial acceptance can also be increased with increasing diffraction angle, thus simultaneously improving the statistical quality of high-angle data. A complementary Perkin Elmer XRD1611 medical-imaging detector is available for faster, lower-resolution data, often used at photon energies of 60-70 keV for pair-distribution function analysis, although this is also possible in high-resolution mode by scanning up to 120°â€…2θ at 35 keV. There are various sample environments, allowing sample temperatures from 4 K to 1600°C, a capillary cell for non-corrosive gas atmospheres in the range 0-100 bar, and a sample-changing robot that can accommodate 75 capillary samples compatible with the temperature range 80 K to 950°C.

6.
J Synchrotron Radiat ; 30(Pt 2): 327-339, 2023 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-36891846

RESUMEN

This study describes the capabilities and limitations of carrying out total scattering experiments on the Powder Diffraction (PD) beamline at the Australian Synchrotron, ANSTO. A maximum instrument momentum transfer of 19 Å-1 can be achieved if the data are collected at 21 keV. The results detail how the pair distribution function (PDF) is affected by Qmax, absorption and counting time duration at the PD beamline, and refined structural parameters exemplify how the PDF is affected by these parameters. There are considerations when performing total scattering experiments at the PD beamline, including (1) samples need to be stable during data collection, (2) highly absorbing samples with a µR > 1 always require dilution and (3) only correlation length differences >0.35 Šmay be resolved. A case study comparing the PDF atom-atom correlation lengths with EXAFS-derived radial distances of Ni and Pt nanocrystals is also presented, which shows good agreement between the two techniques. The results here can be used as a guide for researchers considering total scattering experiments at the PD beamline or similarly setup beamlines.

7.
Chemistry ; 29(67): e202302290, 2023 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-37669904

RESUMEN

The design and synthesis of covalent organic frameworks (COFs) with high chemical stability pose significant challenges for practical applications. Although a growing number of robust COFs have been developed and employed for a broad scope of applications, the assessment of COF stability has primarily relied on qualitative descriptions, lacking a rational and quantitative assessment. Herein, a novel assessment method is presented that enables visual and quantitative depiction of COF stability. By analyzing the PXRD patterns of chemically stable ß-ketoenamine-based COFs (KEA-COFs), two crystallinity-dependent parameters are identified, the relative intensity (I2θrel ) and the relative area (A2θrel ) of the main peak (2θ), which are expected to establish a standardized criterion for assessing COF crystallinity. Based on these parameters, the crystalline changes after stability tests can be visually presented, which provides a rational and quantitative assessment of their stability. This study not only demonstrates the remarkable chemical stability of KEA-COFs, but also provides valuable insights into the quantitative evaluation of COFs' crystallinity and stability.

8.
Chemistry ; 29(57): e202302057, 2023 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-37449834

RESUMEN

The structure and vibrational spectroscopy of centrohexaindane, 1, was investigated. This unusual molecule has a quaternary carbon atom that is coordinated to four further such quaternary carbon atoms as its core, each pair of which is bonded to an ortho-phenylene unit. Previous NMR studies have shown that the molecule has tetrahedral (Td ) symmetry in solution. The infrared and Raman spectra of chloroform and deuterochloroform solutions of 1 are completely in agreement with this conclusion, as the only modes that are visible are those allowed for Td symmetry. This is not the case in the solid state: X-ray powder diffraction indicates that the unit cell is triclinic or monoclinic with a volume in excess of 4000 Å3 . The vibrational spectroscopy is consistent with C1 site symmetry and the presence of at least two molecules in the primitive cell. It is likely that the space group is centrosymmetric.

9.
Chemphyschem ; 24(7): e202200884, 2023 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-36507917

RESUMEN

In this work, we present results for loading of well-defined binary systems (cocrystal, solid solution) and untreated materials (physical mixtures) into the voids of MCM-41 mesoporous silica particles employing three different filling methods. The applied techniques belong to the group of "wet methods" (diffusion supported loading - DiSupLo) and "solvent-free methods" (mechanical ball-mill loading - MeLo, thermal solvent free - TSF). As probes for testing the guest1-guest2 interactions inside the MCM-41 pores we employed the benzoic acid (BA), perfluorobenzoic acid (PFBA), and 4-fluorobenzoic acid (4-FBA). The guests intermolecular contacts and phase changes were monitored employing magic angle spinning (MAS) NMR Spectroscopy techniques and powder X-ray diffraction (PXRD). Since mesoporous silica materials are commonly used in drug delivery system research, special attention has been paid to factors affecting guest release kinetics. It has been proven that not only the content and composition of binary systems, but also the loading technique have a strong impact on the rate of guests release. Innovative methods of visualizing differences in release kinetics are presented.

10.
Philos Trans A Math Phys Eng Sci ; 381(2258): 20220330, 2023 Oct 16.
Artículo en Inglés | MEDLINE | ID: mdl-37634541

RESUMEN

We report on the synthesis of tin(IV) nitride with spinel structure, γ-Sn3N4, from the elements at high pressures and temperatures using a laser-heated diamond anvil cell, and on the Rietveld refinement of the product structure. The procedure described here is, in our opinion, the most reliable method of obtaining high-purity nitrides which are thermodynamically stable only at high pressures. Raman spectroscopy and powder X-ray diffraction were used to characterize the synthesis products. Pressure dependences of the Raman-band frequencies of γ-Sn3N4 were measured and used to determine its average mode Grüneisen parameter, 〈γ〉 = 0.95. Using this value, we estimated the thermal-shock resistance of γ-Sn3N4 to be about half that of γ-Si3N4, which, in turn, is moderately surpassed by ß-Si3N4, known to be highly thermal-shock resistant. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

11.
Chem Pharm Bull (Tokyo) ; 71(8): 633-640, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37532533

RESUMEN

Nobiletin (NOB) is a flavonoid with attractive pharmaceutical characteristics, including anti-Alzheimer's, anti-inflammation, and anti-cancer properties, but it has low solubility in water, resulting in reduced bioavailability. Its solubility must be improved to develop NOB as a drug. Cocrystal engineering can change the physicochemical properties of an active pharmaceutical ingredient and generate remarkable drug candidates that are superior in drug formulation. In this report, extensive co-crystal screening of NOBs with 31 cocrystal formers (coformers) with various functional groups was carried out by the liquid-assisted grinding method. As a result, four cocrystals (NOB with urea (URE), oxalic acid, gallic acid and salicylic acid) and one solvate crystal (NOB with formic acid (FOR)) were found. Powder X-ray diffraction and thermal analysis revealed the unique crystal morphology of all the obtained samples. In addition, the crystal structures of two of them (NOB-URE and NOB-FOR) were determined by single crystal X-ray diffraction. The results revealed that NOB-URE and NOB-FOR are new cocrystals or solvate crystals consisting of molar ratios of 1 : 2 and 1 : 0.73, respectively. In NOB-URE, we could observe a transient increase in solubility due to supersaturation, suggesting that URE is one of the better coformers of NOB.


Asunto(s)
Citrus , Flavonoides , Cristalización , Difracción de Rayos X , Solubilidad , Preparaciones Farmacéuticas
12.
Int J Mol Sci ; 24(8)2023 Apr 21.
Artículo en Inglés | MEDLINE | ID: mdl-37108827

RESUMEN

Sustained interest in the use of renewable resources for the production of medical materials has stimulated research on bacterial cellulose (BC) and nanocomposites based on it. New Ag-containing nanocomposites were obtained by modifying various forms of BC with Ag nanoparticles prepared by metal-vapor synthesis (MVS). Bacterial cellulose was obtained in the form of films (BCF) and spherical BC beads (SBCB) by the Gluconacetobacter hansenii GH-1/2008 strain under static and dynamic conditions. The Ag nanoparticles synthesized in 2-propanol were incorporated into the polymer matrix using metal-containing organosol. MVS is based on the interaction of extremely reactive atomic metals formed by evaporation in vacuum at a pressure of 10-2 Pa with organic substances during their co-condensation on the cooled walls of a reaction vessel. The composition, structure, and electronic state of the metal in the materials were characterized by transmission and scanning electron microscopy (TEM, SEM), powder X-ray diffraction (XRD), small-angle X-ray scattering (SAXS) and X-ray photoelectron spectroscopy (XPS). Since antimicrobial activity is largely determined by the surface composition, much attention was paid to studying its properties by XPS, a surface-sensitive method, at a sampling depth about 10 nm. C 1s and O 1s spectra were analyzed self-consistently. XPS C 1s spectra of the original and Ag-containing celluloses showed an increase in the intensity of the C-C/C-H groups in the latter, which are associated with carbon shell surrounding metal in Ag nanoparticles (Ag NPs). The size effect observed in Ag 3d spectra evidenced on a large proportion of silver nanoparticles with a size of less than 3 nm in the near-surface region. Ag NPs in the BC films and spherical beads were mainly in the zerovalent state. BC-based nanocomposites with Ag nanoparticles exhibited antimicrobial activity against Bacillus subtilis, Staphylococcus aureus, Escherichia coli bacteria and Candida albicans and Aspergillus niger fungi. It was found that AgNPs/SBCB nanocomposites are more active than Ag NPs/BCF samples, especially against Candida albicans and Aspergillus niger fungi. These results increase the possibility of their medical application.


Asunto(s)
Antiinfecciosos , Nanopartículas del Metal , Plata/farmacología , Plata/química , Nanopartículas del Metal/química , Celulosa/química , Dispersión del Ángulo Pequeño , Difracción de Rayos X , Antiinfecciosos/química , Bacterias , Antibacterianos/farmacología , Antibacterianos/química , Pruebas de Sensibilidad Microbiana , Espectroscopía Infrarroja por Transformada de Fourier
13.
Int J Mol Sci ; 23(19)2022 Oct 10.
Artículo en Inglés | MEDLINE | ID: mdl-36233346

RESUMEN

Since the formation of organic salts can improve the solubility, bioavailability, and stability of active pharmaceutical ingredients, the aim of this work was to prepare an organic salt of chlordiazepoxide with saccharin. To achieve this goal, the saccharin salt of chlordiazepoxide was obtained from a physical mixture of both components by grinding them with a small volume of solvent and by crystallizing them with complete evaporation of the solvent. The resulting salt was examined by methods such as Powder X-ray Diffraction (PXRD), Single Crystal X-ray Diffraction (SCXRD), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), Fourier Transform Infrared (FT-IR), and Raman spectroscopy. The results of the studies proved that saccharin salt of chlordiazepoxide crystallizes in the orthorhombic Pbca space group with one chlordiazepoxide cation and one saccharin anion in the asymmetric unit. In the crystal of the title compound, the chlordiazepoxide cation and the saccharin anion interact through strong N-H···O hydrogen bonds and weak C-H···O hydrogen bonds. The disappearance of the N-H band in the FT-IR spectrum of saccharin may indicate a shift of this proton towards chlordiazepoxide, while the disappearance of the aromatic bond band in the chlordiazepoxide ring in the Raman spectrum may suggest the formation of intermolecular hydrogen bonds between chlordiazepoxide molecules. The melting point of the salts differs from that of the starting compounds. Thermal decomposition of the salt begins above 200 °C and shows at least two overlapping stages of mass loss. In summary, the results of the research showed that the crystalline salt of the saccharin and chlordiazepoxide can be obtained by various methods: grinding with the addition of acetonitrile and crystallization from acetonitrile or a mixture of methanol with methylene chloride.


Asunto(s)
Clordiazepóxido , Sacarina , Acetonitrilos , Rastreo Diferencial de Calorimetría , Metanol , Cloruro de Metileno , Polvos , Protones , Sales (Química)/química , Solubilidad , Solventes , Espectroscopía Infrarroja por Transformada de Fourier , Difracción de Rayos X
14.
Molecules ; 27(14)2022 Jul 07.
Artículo en Inglés | MEDLINE | ID: mdl-35889235

RESUMEN

Three-dimensional liquid crystal (LC) phases, cubic LC phases, have been extensively studied as fascinating molecular assembled systems formed by amphiphilic compounds. However, similar structures have only been seen in rare instances in lipid crystal states in glycolipid crystal studies. In this study, we prepared short-chain n-alkyl ß-D-glucosides (CnG) with an alkyl chain length n ranging from 4 to 6 and investigated their crystal structures. First, differential thermal analysis (DTA) and thermogravimetric analysis (TG) measurements showed the formation of hydrated crystals for C4G and C5G, respectively. Second, the crystal structures of CnG (n = 4, 5, 6) in both anhydrous and hydrated states were examined using a temperature-controlled powder X-ray diffraction (PXRD) measurement. Both hydrate and anhydrous crystals of C4G and C5G with critical packing parameters (CPPs) less than 0.33 formed cubic crystal phases. Bilayer lengths, calculated from the main diffraction peaks in each PXRD profile, depended on crystalline moisture for C5G, but no significant change was confirmed for C4G, indicating that the properties of each hydrophilic layer differ. However, C6G with a CPP of 0.42 formed a crystal structure with a modulated lamellar structure similar to C7G and C8G with similar CPP values. Thus, a glycolipid motif concept with a cubic crystal structure was demonstrated.


Asunto(s)
Glucósidos , Cristales Líquidos , Rastreo Diferencial de Calorimetría , Glucósidos/química , Glucolípidos , Difracción de Rayos X
15.
Molecules ; 27(23)2022 Nov 30.
Artículo en Inglés | MEDLINE | ID: mdl-36500469

RESUMEN

The new homochiral 1D metal-organic coordination polymer [Cu2(EDPB)•H2O]n was synthesized starting from the original 3,3'-ethyne-1,2-diylbis[6-(L-prolylamino)benzoic acid] (H4EDPB). The unique crystal structure of the new compound was established by powder X-ray diffraction. The [Cu2(EDPB)•H2O]n system shows catalytic activity and enantioselectivity in a Henry reaction of p-nitrobenzaldehyde with nitromethane.


Asunto(s)
Cobre , Polímeros , Polímeros/química , Estructura Molecular , Cobre/química , Metales , Difracción de Rayos X
16.
Coord Chem Rev ; 426: 213544, 2021 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-32981945

RESUMEN

Progress in metal-organic frameworks (MOFs) has advanced from fundamental chemistry to engineering processes and applications, resulting in new industrial opportunities. The unique features of MOFs, such as their permanent porosity, high surface area, and structural flexibility, continue to draw industrial interest outside the traditional MOF field, both to solve existing challenges and to create new businesses. In this context, diverse research has been directed toward commercializing MOFs, but such studies have been performed according to a variety of individual goals. Therefore, there have been limited opportunities to share the challenges, goals, and findings with most of the MOF field. In this review, we examine the issues and demands for MOF commercialization and investigate recent advances in MOF process engineering and applications. Specifically, we discuss the criteria for MOF commercialization from the views of stability, producibility, regulations, and production cost. This review covers progress in the mass production and formation of MOFs along with future applications that are not currently well known but have high potential for new areas of MOF commercialization.

17.
J Synchrotron Radiat ; 28(Pt 1): 146-157, 2021 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-33399563

RESUMEN

For high-resolution powder diffraction in material science, high photon energies are necessary, especially for in situ and in operando experiments. For this purpose, a multi-analyser detector (MAD) was developed for the high-energy beamline P02.1 at PETRA III of the Deutsches Elektronen-Synchrotron (DESY). In order to be able to adjust the detector for the high photon energies of 60 keV, an individually adjustable analyser-crystal setup was designed. The adjustment is performed via piezo stepper motors for each of the ten channels. The detector shows a low and flat background as well as a high signal-to-noise ratio. A range of standard materials were measured for characterizing the performance. Two exemplary experiments were performed to demonstrate the potential for sophisticated structural analysis with the MAD: (i) the structure of a complex material based on strontium niobate titanate and strontium niobate zirconate was determined and (ii) an in situ stroboscopy experiment with an applied electric field on a highly absorbing piezoceramic was performed. These experiments demonstrate the capabilities of the new MAD, which advances the frontiers of the structural characterization of materials.

18.
Chemistry ; 27(37): 9708-9715, 2021 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-33871114

RESUMEN

The switching mechanism of the flexible framework Zn4 O(benztb)1.5 (benztb=N,N,N',N'-benzidine tetrabenzoate), also known as DUT-13, was studied by advanced powder X-ray diffraction (PXRD) and gas physisorption techniques. In situ synchrotron PXRD experiments upon physisorption of nitrogen (77 K) and n-butane (273 K) shed light on the hitherto unnoticed guest-induced breathing in the MOF. The mechanism of contraction is based on the conformationally labile benztb ligand and accompanied by a reduction in specific pore volume from 2.03 cm3 g-1 in the open-pore phase to 0.91 cm3 g-1 in the contracted-pore phase. The high temperature limit for adsorption-induced contraction of 170 K, determined by systematic temperature variation of methane adsorption isotherms, indicates that the DUT-13 framework is softer than other mesoporous MOFs like DUT-49 and does not support the formation of overloaded metastable states required for negative gas-adsorption transitions.

19.
Mikrochim Acta ; 188(4): 108, 2021 03 04.
Artículo en Inglés | MEDLINE | ID: mdl-33660036

RESUMEN

A molybdenum-based coordination polymer {[Mo(PDA)(NO)(µ-O)MoO3]·1.42H2O·0.58C2H5OH}n (1) (PDA is 1,10-phenanthroline-2,9-dicarboxylate) was synthesized using solvothermal reaction conditions and characterized using a suite of analytical techniques. Single-crystal X-ray diffraction studies reveal a 1D chain structure, with close contacts expanding the structure into 3D including π-interactions and hydrogen bonding. The utility of 1 as a sorbent for dispersive micro solid-phase extraction (D-µSPE) of basic organic compounds such as antidepressants is supported by the presence of many functional groups on the surface of 1 (such as pendant carboxylates, Mo=O, Mo-NO, and CH groups) as well as extensive electrostatic interactions. Therefore, 1 can be a suitable choice as sorbent in the D-µSPE of antidepressant drugs from human plasma samples via appreciable adsorbate-adsorbent interactions. Determination of the extracted antidepressant drugs was conducted using high-performance liquid chromatography-ultraviolet (HPLC-UV), with calibration plots being linear in the concentration range 0.1-500 ng mL-1 for amitriptyline and nortriptyline, 0.2-500 ng mL-1 for imipramine, and 0.5-300 ng mL-1 for sertraline. The relative standard deviation (RSD) values were calculated for both intra-day and inter-day precision, and the RSD% values were in the range 3.9 to 5.2% and 4.6-5.4%, respectively. The limits of detection (LODs) was determined as 0.03-0.2 ng mL-1. Due to the good stability and reusability of the sorbent, the adsorption capacity had no obvious decrease after being used 20 times. Finally, the D-µSPE-HPLC-UV method was applied for the determination of antidepressant drugs in human plasma samples with recoveries of the analytes in the range 94.9 to 102%. The article describes the synthesis of a robust molybdenum-based coordination polymer, and its application as sorbent for dispersive micro solid-phase extraction of antidepressant drugs from human plasma samples.


Asunto(s)
Antidepresivos/sangre , Complejos de Coordinación/química , Polímeros/química , Microextracción en Fase Sólida/métodos , Adsorción , Antidepresivos/química , Cromatografía Líquida de Alta Presión , Femenino , Humanos , Límite de Detección , Molibdeno/química , Espectrofotometría Ultravioleta
20.
Pharm Dev Technol ; 26(2): 193-208, 2021 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-33211618

RESUMEN

In this work, the tabletability and dissolution of spray-dried forms of naproxen and its sodium salt were compared with those of unprocessed drugs. Solutions of naproxen or naproxen sodium alone or with HPMC (5% w/w of drug content) were spray dried. Scanning electron micrographs showed that naproxen sodium spray-dried particles were spherical, whereas those of naproxen were non-spherical but isodiametric. Powder x-ray diffraction and thermal analysis indicated that co-spray drying with HPMC resulted in reduced crystallinity of naproxen and higher naproxen sodium dihydrate content. FTIR and Raman analysis showed shifting, merging or elimination of bands in the spectra of the co-spray dried products signifying solid-state alterations. When mixed with suitable processing aids (7% w/w), all co-spray dried powders produced satisfactory tablets in the pressure range 73-295 MPa. Conversely, physical mixtures of naproxen compressed with the same aids failed tableting, whereas naproxen sodium produced weak tablets. Dissolution tests showed significant improvement for co-spray dried drugs tablets. Therefore, since the large therapeutic doses of naproxen and sodium naproxen limit the use of tableting aids, the improved compaction and dissolution performance of the spray-dried forms may be a formulation alternative.


Asunto(s)
Antiinflamatorios no Esteroideos/administración & dosificación , Química Farmacéutica , Derivados de la Hipromelosa/química , Naproxeno/administración & dosificación , Antiinflamatorios no Esteroideos/química , Cristalización , Composición de Medicamentos/métodos , Liberación de Fármacos , Excipientes/química , Naproxeno/química , Solubilidad , Secado por Pulverización , Comprimidos
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