The effects of the different drying conditions and the amounts of maltodextrin addition during spray drying of sumac extract

Sumac (Rhus coriaria L.) is a spice which is obtained by grinding of whole sumac berries. The aim of this study is to survey the feasibility of a spray dried sumac extract process along with the effects of adding maltodextrin (MD) and the effects of the inlet and outlet temperatures of the drying air on the properties of the powdered product obtained from the spray drying of the sumac extract. A pilot scale spray dryer was used for the production of the sumac extract powder. The inlet/outlet air temperatures were adjusted to 160/80, 180/90, and 200/100 °C where outlet air temperature was controlled by regulating the feed flow rate. The total soluble solid content of the sumac extract was measured as 3.5% and adjusted to 10, 15, 20, and 25% (w/w) with the addition of maltodextrin with a Dextrose Equivalence (DE) of 10–12. The obtained powders were analyzed for moisture content, water activity, ash content, pH, colour, total phenolic content, antioxidant activity, bulk density, wettability, solubility, and microstructure.Depending on the analysis of the results, the temperature, maltodextrin, and the interaction between temperature and maltodextrin have an important effect on the performed analysis (P < 0.05) except for the pH value analysis (P > 0.05).     

Effect of spray drying conditions and feed composition on the physical properties of black mulberry juice powder

In this study, the effects of some processing parameters on moisture content, water activity, drying yield, bulk density, solubility, glass transition temperature (T_g), and microstructure of spray dried black mulberry (Morus nigra) juice powders were investigated. A pilot-scale spray dryer was employed for the spray drying process and maltodextrin with different dextrose equivalent (6, 9, and 20DE) and gum Arabic were used as carrier agent. Independent variables were inlet air temperature (110, 130, and 150 °C), compressed air flow rate (400, 600, and 800 L/h), concentration of drying aids (8, 12, and 16%) and percent replacement of maltodextrin (6 and 9DE) by gum Arabic and maltodextrin 20DE (25, 50, and 75%). Between the different drying aids, maltodextrin 6DE shows the best effect on the properties of black mulberry juice powders. The process drying yield ranges from 45 to 82%. The highest drying yield (82%) and solubility (87%) refer to the blend of maltodextrin 6DE and gum Arabic. The lowest moisture content powders (1.5%) produced at the compressed air flow rate of 800 L/h. Inlet air temperature negatively influenced the bulk density due to the increase of powder's porosity. The lower the bulk density, the higher the solubility of powder is. With regard to morphology, powders produced with maltodextrin and gum Arabic presented the smallest size.     

A predictive method for the solubility of drug in supercritical carbon dioxide

We present a predictive approach for the solubility of drug in supercritical CO₂. The fugacity of drug in the solid phase is estimated from its melting temperature and heat of fusion, and the fugacity of the drug in its hypothetical liquid state. The fugacity of the drug is calculated from the Peng–Robinson (PR) EOS. Temperature and composition dependence of the interaction parameters a(T,x) and b(x) of the PR EOS are obtained from the quantum mechanics-based, COSMO-SAC solvation model. As a consequence, the method does not require input of experimental data of the mixture. The average logarithmic deviation (ALD-x) in predicted solubility of 46 drugs in subcritical and supercritical carbon dioxide (T = 293.15–473 K, P = 8.5–50 MPa, and 1160 solubility data ranging from 10⁻⁷ to 10⁻²) was found to be 0.81 (a factor of 5.3). The same method was also examined for solid solubility in a variety of solvents (60 solids including 34 different solvents (with different polarities) and 190 drug-solvent pairs) at ambient pressure. The ALD-x was found to be slightly better (0.58 or a factor of 2.89). The proposed method, the PR + COSMOSAC EOS, is thus a useful tool for a priori prediction of solid solubility in scCO₂, as well as for other solvents.     

High pressure density and solubility for the CO2 + 1-ethyl-3-methylimidazolium ethylsulfate system

The solubility and density of the CO₂ + 1-ethyl-3-methylimidazolium ethylsulfate system were investigated. The carbon dioxide solubility in the IL was measured in the temperature range 273–413 K, for pressure up to 5 MPa and CO₂ mole fractions ranging from 0.02 to 0.5 using the isochoric method, while the system density was carried out at temperatures ranging from 278.15 K to 398.15 K, pressures from 10 MPa to 120 MPa and 0.2, 0.4, 0.7 and 0.8 CO₂ mole fractions. Similar to what was previously observed for phosphonate-based ILs, the ionic liquid high polarity leads to positive deviations from ideality resulting from unfavorable interactions with the CO₂.The results from the density and solubility derived properties show that the system presents important negative excess molar volumes, over the whole range of compositions and temperatures, and a negative entropy of solvation that suggests an increase in ordering of the solvent molecules surrounding the solute. The observed negative excess molar volumes result from the large difference between the molecular volumes of the species involved, with the small carbon dioxide molecules occupying the empty spaces between the larger IL ions, supporting the notion that the carbon dioxide, upon dissolution, occupies essentially the bulk free volume since the IL does not significantly expand upon gas absorption. These results portray ionic liquids as a porous media, like a soft sponge, with a huge free volume in which large amounts of carbon dioxide are able to accommodate during the dissolution process.     

Phase behavior of 1,3,5-tri-tert-butylbenzene–carbon dioxide binary system

1,3,5-tri-tert-butylbenzene (TTBB) is solid at ambient conditions, and has substantial solubility in liquid and supercritical carbon dioxide. We present the phase behavior of TTBB–CO₂ binary system at temperatures between 298 and 328 K and at pressures up to 20 MPa. Phase diagrams showing the liquid–vapor, solid–liquid and solid–vapor equilibrium envelopes are constructed by pressure–volume–temperature measurements in a variable-volume sapphire cell. TTBB is highly soluble in CO₂ over a wide range of compositions. Single-phase states are achieved at moderate pressures, even with very high TTBB concentrations. For example, at 328 K, a binary system containing TTBB at a concentration of 95% by weight forms a single-phase above 2.04 MPa. TTBB exhibits a significant melting-point depression in the presence of CO₂, 45 K at 3.11 MPa, where the normal melting point of 343 K is reduced to 298 K. With its high solubility in carbon dioxide, TTBB has potential uses as a binder or template in materials forming processes using dense carbon dioxide.     

Determination and calculation for solubility of m-nitroaniline and its mixture in supercritical carbon dioxide

Equilibrium solubility of m-nitroaniline and p-nitroaniline in supercritical carbon dioxide (SCCO₂) is essential to design the process of SCCO₂ extraction and to investigate the effect of each solute on the solubility in SCCO₂ ternary system. However, the solubility data is not reported so far. We performed the solubility measurements at the temperatures of 308–328 K and in the pressure range of 11.0–21.0 MPa. The experimental results showed the solubility of m-nitroaniline and p-nitroaniline was enhanced in m-nitroaniline + p-nitroaniline + SCCO₂ ternary system. The improvement factor (i), separation factor (μ) and separation efficiency (HE) in the ternary system were defined and calculated, and the best separation result could be obtained at 21.0 MPa and 328 K using SCCO₂ extraction, where the separation efficiency was up to 90.9%. Based on the chemical association theory, a new model was developed to calculate the solubility of mixed solutes in SCCO₂. The correlation result of the new model was tested by about 500 solubility data from 15 kinds of two solutes mixtures in SCCO₂. The correlated result showed that the new model could achieve much better AARD (%) than those of frequently used Sovova and Sovova-T models.     

Supercritical antisolvent micronization of PVP and ibuprofen sodium towards tailored solid dispersions

The supercritical antisolvent technology is used to precipitate polyvinylpyrrolidone (PVP) particles and crystallise ibuprofen sodium (IS) crystals separately and in the form of solid dispersion together. Supercritical carbon dioxide (scCO₂) is used as antisolvent. For PVP particle generation, ethanol, acetone and mixtures of ethanol and acetone are used as solvents. The initial concentration of PVP in the solution was varied between 0.5 wt% and 1.5 wt%, the operation pressure between 10 MPa and 30 MPa and the composition of ethanol/acetone solvent mixtures between 100 wt% and 0 wt% of ethanol at a constant temperature of 313 K. Furthermore, the mean molecular weight of the polymer was varied between 40 kg mol⁻¹, 360 kg mol⁻¹ and 1300 kg mol⁻¹. An increase of the content of the poor solvent acetone in the initial solvent mixture as well as the usage of PVP with a higher molecular weight, leads to a significant decrease in mean particle size. At all the investigated parameters always fully amorphous PVP powder precipitates. For IS, only ethanol was used as the solvent, the initial IS concentration in the solution was varied between 1 wt% and 3 wt% and the operation pressure between 10 MPa and 16 MPa. A variation of these parameters leads to a manipulation of the size and the morphology of the crystallised IS crystals. Irrespective of the parameters used, always the same polymorphic form of ibuprofen sodium is produced. The solid dispersions were generated at different compositions of PVP to IS and with two different molecular weights of PVP at otherwise constant conditions. Fully amorphous solid dispersions consisting of IS and PVP together were generated at different ratios of PVP to IS.The mechanisms that control the final particle properties are discussed taking into account two different models for “ideal” and “non-ideal” solutes. Furthermore, the study of the “unconventional” SAS parameters, molecular weight and solvation power of the solvent shows that these parameters qualify to tailor polymer particle properties via SAS processing. Next to the investigation into the behaviour of both solutes separately, fully amorphous solid dispersions consisting of IS and PVP together were generated. While X-ray diffraction was used to analyze the crystalline structure of the particles, respectively, solid dispersions, their morphology was analysed using scanning electron microscopy (SEM).     

Experimental measurement and correlation for solubility of piroxicam (a non-steroidal anti-inflammatory drugs (NSAIDs)) in supercritical carbon dioxide

Since the knowledge of pharmaceutical solubilities in the supercritical carbon dioxide is one of the first essential necessities for designing the supercritical carbon dioxide-based processes, solubility of piroxicam a non-steroidal anti-inflammatory drug was experimentally measured. In this regard, a static method coupled with gravimetric method was used to measure the solubility of piroxicam in the supercritical carbon dioxide in temperature and pressure range of 308.15–338.15 K and 16–40 MPa, respectively. The obtained solubility data were in the range of 1.17 × 10⁻⁵ and 5.12 × 10⁻⁴ based on the mole fraction (mole piroxicam/(mole piroxicam + mole CO₂)) then modeled using four different density based correlations namely Bartle et al., Mendez-Santiago-Teja, Chrastil and Kumar and Johnston models. The results of error analysis revealed that the used correlations were potential to correlate the solubility of piroxicam with minimum and maximum average absolute relative deviation percents (AARD%) of 14.4% and 15.2%, respectively.     

Solubility of Disperse Red 82 and modified Disperse Yellow 119 in supercritical carbon dioxide or nitrous oxide with ethanol as a cosolvent

Ethanol was used as a cosolvent to enhance the solubility of disperse dyestuffs in supercritical fluids. In the presence of ethanol, from (1 to 5) mol%, the gas–solid equilibrium data of the Disperse Red 82 and modified Disperse Yellow 119 in supercritical carbon dioxide or nitrous oxide have been measured at temperatures from (353.2 to 393.2) K and pressures from (15.0 to 30.0) MPa. The experimental results show that the solubility increases substantially, up to (9 to 25)-fold, by adding 5 mol% of ethanol to the supercritical fluids. In the presence of cosolvent ethanol, the solubility enhancements in nitrous oxide system are much greater than that in carbon dioxide system for modified Disperse Yellow 119 at the same temperature and pressure. The solubility data were correlated with the Chrastil and the Méndez-Santiago and Teja models. The Méndez-Santiago and Teja model yields slightly better results than Chrastil model.     

Spray drying conditions and encapsulating composition effects on formation and properties of sodium diclofenac microparticles

This paper reports the preparation and characterization of sustained release sodium diclofenac microparticles by spray drying. Aqueous dispersions of ethyl cellulose (Surelease®) and Eudragit RS 30 D® were evaluated as controlled release polymers. The product properties (product moisture, size distribution, particle morphology, flow properties, total drug load, in-vitro dissolution studies, and encapsulating efficiency) were determined as a function of inlet temperature of the spray drying, the feed flow rate and composition of the microencapsulating formulation. In general, lower values of the product moisture content were observed at higher drying temperatures. The spray-dried product was composed mainly by rounded-shape and multi-size particles. The mean particle diameters of the Eudragit based microparticles tended to be slight bigger than the Surelease based microparticles. The spray dried microparticles showed delayed drug dissolution rates, sustaining the drug release for several hours. These findings confirm the feasibility of the spray drying for preparation of microparticles with sustained release properties. The physical and chemical properties of the microparticles can be changed by varying the spray drying parameters as well as the microencapsulating formulation.     

Production of silica aerogel microparticles loaded with ammonia borane by batch and semicontinuous supercritical drying techniques

Silica aerogel microparticles were prepared by supercritical drying and used as support for hydrogen-storing ammonia borane (AB). The formation of aerogel microparticles was done using two different processes: batch supercritical fluid extraction and a semicontinuous drying process. Silica aerogel microparticles with a surface area ranging from 400 to 800 m²/g, a volume of pores of 1 cm³/g, and a mean particle diameter ranging from 12 to 27 μm were produced using the two drying techniques. The particle size distribution (PSD) of the microparticles was influenced by shear rate, amount of catalyst, hydrophilic–hydrophobic solvent ratio and hydrophobic surface modification. In particular, irregular aerogel particles were obtained from hydrophilic gels, while regular, spherical particles with smooth surfaces were obtained from hydrophobic gels. AB was loaded into silica aerogel microparticles in concentrations ranging from 1% till 5% wt. Hydrogen release kinetics from the hydride-loaded aerogel was analyzed with a volumetric cell at 80 °C. By stabilization of AB into the silica aerogel microparticles, an improvement of the release rate of hydrogen from AB was observed.     

Solubility of niflumic acid and celecoxib in supercritical carbon dioxide

The solubility data of two fluorinated and non-steroidal anti-inflammatory drugs, niflumic acid (CAS No. 4394-00-7) and celecoxib (CAS No. 169590-42-5), in supercritical carbon dioxide were measured with a semi-flow type phase equilibrium apparatus at temperatures ranging from 313.2 K to 353.2 K and pressures up to 31 MPa. At the highest extraction temperature and pressure, the solubilities are 2.09 × 10⁻⁵ and 1.52 × 10⁻⁵ in mole fraction for niflumic acid and celecoxib, respectively. The saturated solubility data were correlated with the Chrastil model, the Mendez-Santiago–Teja equation, and the Peng–Robinson equation of state. The Chrastil model fitted the experimental data to about within the experimental uncertainty. The correlated results of the Mendez-Santiago–Teja model confirmed the consistency of the solubility data over the entire experimental conditions. Incorporating with two-parameter van der Waals one-fluid mixing rules, the Peng–Robinson equation of state represents satisfactorily the gas–solid equilibrium behavior of niflumic acid and celecoxib in supercritical carbon dioxide.     

High-pressure phase equilibria of Polystyrene dissolutions in Limonene in presence of CO2

Dissolution with terpenic solvents is presented as an alternative and original route to recycle Polystyrene wastes at room temperature. Limonene was the chosen solvent to carry out the dissolution process because it presents high compatibility with Polystyrene besides being natural, non toxic and relatively low cost. The solvent removal is possible thanks to supercritical CO₂ since it provides high solubility of Limonene and complete PS insolubility at moderated pressures and temperature. In order to determine the proper working conditions to conduct the precipitation of the polymer, accurate knowledge of the phase equilibrium for mixtures of carbon dioxide, Limonene and Polystyrene should be known.In this work, the solubility of Limonene in the ternary system CO₂/Limonene/Polystyrene was determined. The phase equilibrium experiments were conducted in a variable-volume view cell employing the static method. These experiments were carried out in the temperature range of 298.15–313.15 K, at pressures up to 15 MPa and in the concentration range of 0.05–0.80 g PS/ml Limonene. Initially the binary systems were studied by means of equations of state: Peng–Robinson in the case of CO₂/Limonene and Sanchez–Lacombe in the case of Limonene/PS and CO₂/PS. Predicted data were collected together with the experimental to check the agreement and to determine the limits of the ternary system formed by CO₂–Limonene–PS. It is indispensable to determine the behaviour of the ternary system to know completely the fluid phase equilibrium. The results indicate that the solubility of Limonene in the vapour phase is favoured by high pressure and temperature as well as low concentration.     

Spray Congealing of Pharmaceuticals: Study on Production of Solid Dispersions Using Box-Behnken Design

This work aimed at evaluating the spray congealing method for the production of microparticles of carbamazepine combined with a polyoxylglyceride carrier. In addition, the influence of the spray congealing conditions on the improvement of drug solubility was investigated using a three-factor, three-level Box-Behnken design. The factors studied were the cooling air flow rate, atomizing pressure, and molten dispersion feed rate. Dependent variables were the yield, solubility, encapsulation efficiency, particle size, water activity, and flow properties. Statistical analysis showed that only the yield was affected by the factors studied. The characteristics of the microparticles were evaluated using X-ray powder diffraction, scanning electron microscopy, differential scanning calorimetry, and hot-stage microscopy. The results showed a spherical morphology and changes in the crystalline state of the drug. The microparticles were obtained with good yields and encapsulation efficiencies, which ranged from 50 to 80% and 99.5 to 112%, respectively. The average size of the microparticles ranged from 17.7 to 39.4 µm, the water activities were always below 0.5, and flowability was good to moderate. Both the solubility and dissolution rate of carbamazepine from the spray congealed microparticles were remarkably improved. The carbamazepine solubility showed a threefold increase and dissolution profile showed a twofold increase after 60 min compared to the raw drug. The Box-Behnken fractional factorial design proved to be a powerful tool to identify the best conditions for the manufacture of solid dispersion microparticles by spray congealing.     

High-pressure phase equilibria for the binary system carbon dioxide + dibenzofuran

The experimental solubility of dibenzofuran in near-critical and supercritical carbon dioxide and the solid–liquid–vapor (SLV) equilibrium line for the CO₂ + dibenzofuran system are reported. The built in-house static view cell apparatus used in these measurements is described. The solubility of naphthalene in supercritical CO₂ and the CO₂ + naphthalene SLV line are also determined in order to assess the reliability and accuracy of the measurement technique. The solubility of dibenzofuran in carbon dioxide is determined at 301.3, 309.0, 319.2, 328.7 and 338.2 K in the 6–30 MPa pressure range. Solubility data are correlated using the Chrastil model and the Peng–Robinson equation of state. This equation is also used to predict the CO₂ + dibenzofuran SLV line. Results show the feasibility of using supercritical CO₂ to extract dibenzofuran.     

Effect of maltodextrin concentration and inlet temperature during spray drying on physicochemical and antioxidant properties of amla (Emblica officinalis) juice powder

The effects of inlet temperatures of 125, 150, 175 and 200 °C and maltodextrin levels at 3, 5, 7 and 9% on the physicochemical properties, total phenolic content (TPC) and 2,2-diphenyl picryl hydrazile (DPPH) scavenging activity of spray dried amla juice powder were studied. Moisture content and hygroscopicity of powder were significantly affected by inlet temperature and maltodextrin level. However, an increase in the level of maltodextrin did not significantly affect the bulk density and water solubility index (WSI). An increase in drying temperature and maltodextrin concentration decreased the free radical scavenging activity of the powder. Morphological study revealed that at higher inlet temperatures the spray dried powder had small sized particles that were densely packed. Spray dried amla juice powder made with 7% maltodextrin and processed at 175 °C inlet temperature had less hygroscopicity, acceptable color and potent free radical scavenging activity.     

Impact of carboxylated styrene–butadiene copolymer on the hydration kinetics of OPC and OPC/CAC/AH: The effect of Ca2 + sequestration from pore solution

It was found that carboxylated styrene–butadiene latex copolymer retards OPC and accelerates a ternary binder system based on OPC/CAC/anhydrite. The reason behind both effects is the sequestration of Ca^2 + ions from the pore solution. In the case of OPC, the depletion of Ca^2 + hinders the formation of cement hydrates and thus retards hydration of OPC, whereas for the ternary binder system, the depletion of Ca^2 + shifts the solubility equilibrium of CaSO₄ in favor of sulfate. As a result, the dissolution of anhydrite is accelerated and ettringite formation is enhanced. The consequence of these processes is earlier strength development, which is highly desirable in drymix mortar applications. The results explain why anionic SB latex performs particularly well in ternary binder systems.     

Effect of operating parameters on PVP/tadalafil solid dispersions prepared using supercritical anti-solvent process

Supercritical anti-solvent (SAS) process was employed to produce tadalafil solid dispersion sub-micron particles. Three independent variables for the SAS process (temperature, pressure, and drug concentration) were varied in order to investigate the effects on particle size and morphology of PVP/tadalafil solid dispersion (drug to polymer ratio 1:4). The mean particle size decreased with decreasing temperature (50 → 40 °C) and concentration (15 → 5 mg/mL) and increasing pressure (90 → 150 bar). Depending on the experimental variable, the mean particle size varied from 200 nm to 900 nm, and the dominant experimental variable was determined to be the drug concentration. Moreover, at a concentration of 15 mg/mL with any other process conditions, tadalafil tended to partially aggregate in crystalline form with irregular particle shapes. The results of in vitro dissolution experiments showed good correlation with mean particle size and crystallinity of the SAS-processed particles, in that the highest drug concentration showed the least dissolution rate and vice versa. Therefore, among the three variables studied, the drug concentration is the major factor that produces sub-micron particles in the SAS process.     

Formulation of a new generic density-based model for modeling solubility of polyphenols in supercritical carbon dioxide and ethanol

The aim of this work is to present a first approach in formulating a generic model for polyphenols solubility in ternary mixtures (polyphenol + ethanol + sc-CO₂). Solubility data of six polyphenols were collected from the literature, and six different groups of parameters were proposed for the new generic model in order to evaluate their effects and find the best set for each polyphenol. Likewise, four dimensional groups of factors were proposed to evaluate the effect of dimensions on solubility data calculation. The results show that the originally formulated model and its modifications are particularly useful in calculating polyphenols solubility data; for instance, when resveratrol solubility data was fitted, the AARD decreased from a value of 38.52 to 14.03, upon changing from a simple to a complex model. Additionally, this generic model with a specific modification can estimate solubility maxima occurring in the ternary resveratrol + ethanol + sc-CO₂ system.     

Representing experimental solubility of phenylephrine hydrochloride in supercritical carbon dioxide and modeling solute solubility using semi-empirical correlations

Phenylephrine is used as a decongestant sold as an oral medicine, as a nasal spray, or as eye drops. Phenylephrine is now the most common over-the-counter decongestant in the United States. In this regard, measuring the solubility of phenylephrine hydrochloride seems applicable in supercritical carbon dioxide-based processes dealing with this drug. The obtained solubility data obtained by a static method coupled with gravimetric method were in the range of 1.01 × 10⁻⁴ to 2.89 × 10⁻³ based on the mole fraction at the different temperature and pressure ranges of 308.15–338.15 K and 160–400 bar, respectively. In addition, the solubility data were used to obtain the adjusting parameters of semi-empirical correlations namely Kumar and Johnston, Bartle et al., Chrastil and Mendez-Santiago-Teja using a simple data regression.