| 1. |
- Abebe, Mihret, et al.
(author)
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Spherical and Porous Particles of Calcium Carbonate Synthesized with Food Friendly Polymer Additives
- 2015
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 15:8, s. 3609-3616
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Journal article (peer-reviewed)abstract
- Porous calcium carbonate particles were synthesized by adding solutions of Ca2+ to solutions of CO32- containing polymeric additives. Under optimized conditions well-defined aggregates of the anhydrous polymorph vaterite formed. A typical sample of these micrometer-sized aggregates had: a pore volume of 0.1 cm(3)/g, a pore width of similar to 10 nm, and a specific surface area of similar to 25-30 m(2)/ g. Only one mixing Order (calcium to carbonate) allowed the formation of vaterite, which was ascribed to the buffering capacity and relatively high pH of the CO32- solution. Rapid addition of the calcium chloride solution and rapid stirring promoted the formation of vaterite, due to the high supersaturation levels achieved. With xanthan gum, porous and micrometer-sized vaterite aggregates could be synthesized over a wide range of synthetic conditions. For the Other food grade polymers, hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), and sodium carboxyl methylcellulose, several intensive and extensive synthetic parameters had to be optimized to obtain pure vaterite and porous aggregates. HPMC and MC allowed well-defined spherical micrometer-sited particles to form. We expect that these spherical and porous particles of vaterite could be relevant to model studies as well as a controlled delivery of particularly large molecules.
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| 2. |
- Adawy, Alaa, et al.
(author)
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High Resolution Protein Crystals Using an Efficient Convection-Free Geometry
- 2013
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 13:2, s. 775-781
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Journal article (peer-reviewed)abstract
- Macromolecular crystallography is the most direct and accurate approach to determine the three-dimensional structure of biological macromolecules. The growth of high quality single crystals, yielding diffraction to the highest X-ray resolution, remains a bottleneck in this methodology. Here we show that through a modification of the batch crystallization method, an entirely convection-free crystallization environment is achieved, which enhances the purity and crystallinity of protein crystals. This is accomplished by using an upside-down geometry, where crystals grow at the “ceiling” of a growth-cell completely filled with the crystallization solution. The “ceiling crystals” experience the same diffusion-limited conditions as in space microgravity experiments. The new method was tested on bovine insulin and two hen egg-white lysozyme polymorphs. In all cases, ceiling crystals diffracted X-rays to resolution limits beyond that for other methods using similar crystallization conditions without further optimization. In addition, we demonstrate that the ceiling crystallization method leads to crystals with much lower impurity incorporation.
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| 3. |
- Agarwal, Parminder, et al.
(author)
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Effect of polymeric additives on calcium carbonate crystallization as monitored by nephelometry
- 2004
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 4:3, s. 479-483
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Journal article (peer-reviewed)abstract
- The effect of polymaleimide polymers on calcium carbonate crystallization was studied using nephelometry. Induction time and percent growth inhibition were determined for polymeric additives from the nephelometric data. The polymaleimide synthesized by KOH-initiated polymerization exhibited the greatest growth inhibition and longest nucleation time among the polymers investigated. Raman spectroscopy was used to determine the calcium carbonate polymorph formed in the presence of these polymeric additives.
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| 4. |
- Agarwal, Parminder, et al.
(author)
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In situ monitoring of calcium carbonate polymorphs during batch crystallization in the presence of polymeric additives using Raman spectroscopy
- 2003
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 3:6, s. 941-946
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Journal article (peer-reviewed)abstract
- Polycarboxylic acids are well-known to affect calcium carbonate crystallization. Agarwal et al. (Ind. Eng. Chem. Res. 2003, in press) reported previously the synthesis of polymaleimide by a variety of techniques and initiators. In the present work, the effect of these polymers on calcium carbonate crystallization was studied by a variety of techniques. Crystallization experiments were carried out in a 1-L LABMAX automated batch reactor, and the concentration of calcium in solution was determined in real time. Raman spectroscopy was used to determine the relative amount of various calcium carbonate polymorphs as the crystallization occurred. However, Raman spectroscopy is a scattering technique, which may make it surface selective, and therefore results from solids may not be representative of bulk of sample. X-ray diffraction (XRD) was used to compare the results obtained by Raman spectroscopy. Peak intensity ratios were used for both Raman spectroscopy and XRD for calibration and measurement purposes. The results obtained by these two techniques for final percent vaterite for calcium carbonate crystallization in the presence of polymeric additives were in agreement within 2%. Therefore, use of Raman spectroscopy for in situ measurement of polymorph composition during calcium carbonate crystallization appears accurate. Scanning electron microscopy (SEM) data were useful in understanding the crystal morphology and to determine crystal size.
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| 5. |
- Aisling, Lynch, et al.
(author)
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Crystal Growth of Single Salicylamide Crystals
- 2019
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 19:12, s. 7230-7239
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Journal article (peer-reviewed)abstract
- Growth of single salicylamide crystals was investigated in a nonstirred growth cuvette and on a rotating disk. In the growth cuvette the crystal growth rates were measured for both primary nucleated crystals and seed crystals manually inserted into the cuvette. In the rotating disk experiments multiple seed crystals were attached to a disk that was rotated in a supersaturated solution. The crystal growth rates in the length and width direction were precisely measured in situ for each individual crystal, and growth rates were also extracted for a specific crystal facet, that is, (200). In all cases, the growth rate was considerably faster in the rotating disk experiments, shown to be governed by surface integration. Solvent was found to impact the growth rates of the crystal facets in part by creating different surface features. The influence of the supersaturation on the crystal growth rate depended on the solvent; in general, an increasing trend was observed. At relatively low supersaturations, it was discovered that the growth process will focus on repairing morphological defects. Within the range of experimental conditions, the growth kinetics were strongly affected by the temperature as was further indicated by the relatively high activation energy values obtained. The crystal seed quality was found to have a substantial impact on the growth rate, with rougher crystals leading to quicker growth. A wide growth rate dispersion was obtained for both crystal growth methods, found to be reduced by using seed crystals with high quality, lower supersaturations, and also within certain solvents.
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| 6. |
- Akhtar, Sohel, et al.
(author)
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Designing Multifunctional MOFs Using the Inorganic Motif [Cu3(μ3-OH)(μ-Pyz)] as an SBU and Their Properties
- 2018
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 19:2, s. 992-1004
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Journal article (peer-reviewed)abstract
- In a continuation of our interest in pyrazole-based multifunctional metal–organic frameworks (MOFs), we report herein the construction of a series of Cu(II) MOFs using pyrazole and various 5-substituted isophthalic acids. The central theme is to generate MOFs using the crystal engineering strategy of spacer and node; however, for the node we have introduced a well-known inorganic motif, a [Cu3(μ3-OH)(μ-Pyz)3] unit. The appearance of the SBU in five MOFs confirms the robustness and reproducibility of the motif with some interesting structures of various dimensionality ranging from 1D helical and 2D herringbone grid to a complex 3D framework. The deployment of bent acids brings chirality via helicity in the system, as further confirmed by solid-state CD spectra. A detailed investigation of the porous MOFs reveals their importance as zeolite analogues for environment remediation. MOF-1–MOF-5 show some interesting photodegradation of harmful organic dyes. MOF-4 and MOF-5 show impressive selective CO2 gas sorption properties. Furthermore, magnetic properties associated with the trinuclear and hexanuclear SBUs of MOF-1 and MOF-3–MOF-5 have also been investigated.
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| 7. |
- Alhalaweh, Amjad, et al.
(author)
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1:1 and 2:1 urea-succinic acid cocrystals : structural diversity, solution chemistry, and thermodynamic stability
- 2010
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 10:11, s. 4847-4855
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Journal article (peer-reviewed)abstract
- The aim of this work was to study the crystal structures of 1:1 and 2:1 urea-succinic acid (U-SA) cocrystals and to investigate the role of solution chemistry in the formation and stability of different stoichiometric cocrystals. The structural diversity of other urea-dicarboxylic acid cocrystals is also discussed. The 1:1 U-SA cocrystal was stabilized by an acid-amide heterosynthon while acid-amide heterosynthons and amide-amide homosynthons stabilized the 2:1 cocrystals. The hydrogen bonding motifs in 1:1 and 2:1 U-SA cocrystals were consistent with other urea-dicarboxylic acid systems with similar stoichiometries. The 1:1 cocrystals were transformed to 2:1 cocrystals upon slurrying in various solvents at 25 °C. The phase solubility diagram was used to define the stability regions of different solid phases in 2-propanol at 25 °C. While no phase stability region for 1:1 cocrystal could be found, the stable regions for the 2:1 cocrystals and their pure components were defined by eutectic points. The solubility of the 2:1 cocrystals was dependent on the concentration of the ligand in the solution and explained by the solubility product and 1:1 solution complexation. The mathematical models predicting the solubility of the 2:1 cocrystals were evaluated and found to fit the experimental data
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| 8. |
- Alhalaweh, Amjad, et al.
(author)
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Effects of polymer and surfactant on the dissolution and transformation profiles of cocrystals in aqueous media
- 2014
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 14:2, s. 643-648
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Journal article (peer-reviewed)abstract
- Capturing solubility advantages of cocrystals is of great interest, and thus to understand the mechanism by which different excipients could maintain the supersaturation generated by cocrystals at the course of absorption in aqueous media is essential. To achieve this aim, the impact of different excipients on dissolution behavior of indomethacin-saccharin (IND-SAC) were monitored by measuring the concentrations of cocrystal components in the absence and presence of various concentration of excipients by HPLC, and solid phases were analyzed by differential scanning calorimetry after each experiment and the potential of Raman spectroscopy for monitoring phase transformations in situ was tested. No dissolution advantage was offered by cocrystals in the absence of any solution additive. The polymer and surfactant used in the study increased the solubility of IND but not SAC. This differential solubilization effect is believed to have stabilized the cocrystals for a relevant period for the absorption to take place. This could be attributed to either decreased gap between supersaturation and saturation of the drug or drug interaction with the additives. Understanding the effects of excipients type and concentration on the transformation profile is vital for designing enabling formulations for cocrystals. The eutectic constant may be useful in selecting excipients for stabilizing cocrystals.
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| 9. |
- Alhalaweh, Amjad, et al.
(author)
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Formation of cocrystals from stoichiometric solutions of incongruently saturating systems by spray drying
- 2010
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 10:8, s. 3302-3305
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Journal article (peer-reviewed)abstract
- Spray drying is a well established technique for material processing and scale-up. This study investigated the formation of pharmaceutical cocrystals by spray drying. The cocrystal formation mechanisms in spray-drying and solution methods, based on triangular phase diagrams, are discussed. The solvent evaporation of stoichiometric solutions of incongruently saturating cocrystals resulted in a mixture of phases, as dictated by the thermodynamic phase diagram. In contrast, spray drying of similar solutions of incongruently saturating systems generated pure cocrystals. It is thus suggested that the formation of cocrystals by spray drying could be kinetically controlled and/or mediated by the glassy state of the material.
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| 10. |
- Alhalaweh, Amjad, et al.
(author)
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Solubility behavior and solution chemistry of indomethacin cocrystals in organic solvents
- 2011
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In: Crystal Growth & Design. - : American Chemical Society (ACS). - 1528-7483 .- 1528-7505. ; 11:9, s. 3923-3929
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Journal article (peer-reviewed)abstract
- The main objective of this study was to investigate the solubility behavior and solution chemistry of indomethacin-saccharin (IND-SAC) cocrystals in organic media. We also evaluated previously proposed models of cocrystal solubility in organic solvents. In addition, the solubility behavior of IND-SAC cocrystals was compared with that of indomethacin-nicotinamide (IND-NIC) cocrystals using the eutectic constant approach. Phase solubility diagrams of IND-SAC cocrystals in various solvents were generated and the transition concentrations, at which drug and cocrystals are in equilibrium with the solvents, were determined. The solubility of IND-SAC cocrystals was explained by the solubility product and solution complexation. The tested models were found to fit the experimental data and to adequately explain the solubility behavior of the cocrystals. The solution complexation of IND and SAC is negligible in ethyl acetate and low in methanol and ethanol. The IND-NIC cocrystals were more soluble than the IND-SAC cocrystals in all the solvents studied. The eutectic constants predicted both the solubility and the stability of the cocrystals. Understanding the solubility behavior and solution chemistry of cocrystals has important implications for the screening, scale-up, and formulation development of this solid form. Further, the determination of eutectic constants is a simple and resource sparing means of obtaining key information on cocrystal stability and solution behavior
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