Hydrophilic Alcohols Research Articles

Water‐free two‐phase systems: phase equilibria and partitioning of vitamins from tomatoes (Solanum lycopersicum)

AbstractBACKGROUNDThe present work provides diagrams for water‐free two‐phase systems based on polypropylene glycol 2000 (PPG 2000) + [C2mim][OAc] + alcohols (primary: methanol, ethanol, 1‐propanol and 1‐butanol; secondary: 2‐propanol and 2‐butanol; and tertiary: 2‐methyl‐2‐propanol) at 298.15 ± 1.00 K and 0.10 ± 0.01 MPa. As a proof of concept, the systems were applied to study the selective partitioning of vitamins, namely β‐carotene and α‐tocopherol.RESULTSThe hydrophilic/hydrophobic balance is the driving force for phase separation. The more hydrophilic alcohols are responsible for the wider biphasic area, and branching increases hydrophilicity and the biphasic area compared to linear alcohols. Additionally, it was verified that the mathematical determination of the tie‐lines satisfactorily describes the positioning in the phase diagram when compared with the analytical determination. In the proposed systems, pure biomolecules partitioned selectively: α‐tocopherol migrated to the PPG 2000 phase (top phase) while β‐carotene to the [C2mim][OAc] phase (bottom phase). For the study with real biomolecules, solid–liquid extraction was performed using 1‐butanol (more selective alcohol) in a solid–liquid ratio of 1:10 at 200 rpm for 60 min. The partitioning trend followed the behavior of systems using pure biomolecules. The highest selectivity (5.3) was observed for the system composed of PPG 2000 + [C2mim][OAc] + 1‐butanol or 2‐butanol. The partition system did not impair the antioxidant potential expressed as DPPH inhibition.CONCLUSIONSWater‐free two‐phase systems can be formed and applied to partitioning vitamins from tomatoes. © 2023 Society of Chemical Industry (SCI).

Enhanced Activity and Stability of an Acetyl Xylan Esterase in Hydrophilic Alcohols through Site-Directed Mutagenesis.

Current demands for the development of suitable biocatalysts showing high process performance is stimulated by the need to replace current chemical synthesis with cleaner alternatives. A drawback to the use of biocatalysts for unique applications is their low performance in industrial conditions. Hence, enzymes with improved performance are needed to achieve innovative and sustainable biocatalysis. In this study, we report the improved performance of an engineered acetyl xylan esterase (BaAXE) in a hydrophilic organic solvent. The structure of BaAXE was partitioned into a substrate-binding region and a solvent-affecting region. Using a rational design approach, charged residues were introduced at protein surfaces in the solvent-affecting region. Two sites present in the solvent-affecting region, A12D and Q143E, were selected for site-directed mutagenesis, which generated the mutants MUT12, MUT143 and MUT12-143. The mutants MUT12 and MUT143 reported lower Km (0.29 mM and 0.27 mM, respectively) compared to the wildtype (0.41 mM). The performance of the mutants in organic solvents was assessed after enzyme incubation in various strengths of alcohols. The mutants showed improved activity and stability compared to the wild type in low strengths of ethanol and methanol. However, the activity of MUT143 was lost in 40% methanol while MUT12 and MUT12-143 retained over 70% residual activity in this environment. Computational analysis links the improved performance of MUT12 and MUT12-143 to novel intermolecular interactions that are absent in MUT143. This work supports the rationale for protein engineering to augment the characteristics of wild-type proteins and provides more insight into the role of charged residues in conferring stability.

In Situ Product Recovery of Bio-Based Industrial Platform Chemicals: A Guideline to Solvent Selection

In situ product recovery (ISPR), in the form of an extractive fermentation process, can increase productivity and product titers in the sustainable production of platform chemicals. To establish a guideline for the development of industrially relevant production processes for such bio-based compounds, a wide screening was performed, mapping the potential of an extensive range of solvents and solvent mixtures. Besides solvent biocompatibility with Saccharomyces cerevisiae, distribution coefficients of three organic acids (protocatechuic acid, adipic acid and para-aminobenzoic acid) and four fragrance compounds (2-phenylethanol, geraniol, trans-cinnamaldehyde and β-ionone) were determined. While for highly hydrophobic fragrance compounds, multiple pure solvents were identified that were able to extract more than 98%, reactive extraction mixtures were proven effective for more challenging compounds including organic acids and hydrophilic alcohols. For example, a reactive mixture consisting of 12.5% of the extractant CYTOP 503 in canola oil was found to be biocompatible and showed superior extraction efficiency for the challenging compounds as compared to any biocompatible single solvent. This mapping of biocompatible solvents and solvent mixtures for the extraction of various classes of industrial platform chemicals can be a tremendous step forward in the development of extractive fermentations.

Alcohol solvent treatment of PEDOT:PSS hole transport layer for optimized inverted perovskite solar cells

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is widely used as a hole transport materials in perovskite solar cells, due to a variety of suitable properties. However, the existence of the insulated PSS chain leads to the low electrical conductivity, which should be improved for the further development of inverted perovskite solar cells. In this study, three alcohol solvents were proposed for post-treatment of PEDOT:PSS thin films, which utilized the electrostatic shielding effect of alcohol molecules to promote phase separation of the PEDOT chain and the PSS chain. At the same time, The insulated PSS chain was removed by dissolving in highly hydrophilic alcohols. In the end, we successfully improved the conductivity of PEDOT:PSS thin films. By ethanol solvent treatment, the short-circuit current density of the perovskite solar cell based on glass/ITO/PEDOT:PSS was increased from 15.64 to 17.45 mA/cm2, the power conversion efficiency (PCE) reached 11.36%, which was 25% higher than the traditional structure. For flexible devices, a preliminary PCE of 9.20% was achieved.

Study of excipients influence on the noopept releasing from the nasal dosage form

Разработка средств быстрой доставки лекарственных средств – актуальное направление современной фармации. В связи с этим перспективным является назальный путь введения лекарственных веществ, характеризующийся рядом преимуществ. Большая проницаемость назальной слизистой вместе со значительной площадью поверхности способствует быстрому достижению терапевтического эффекта. Назальный путь минует пресистемный метаболизм в печени, характерный для орального введения, легок в применении и удобен для пациента. Для разработки новой лекарственной формы с ноотропными и нейропротективными свойствами выбран ноопепт. Это вещество малотоксично, не проявляет побочных эффектов, характеризуется проявлениями антиоксидантных и противовоспалительных свойств, снижает проявления нейротоксичности кальция и глутамата, улучшает реологические характеристики крови. Цель работы – определить влияние вспомогательных веществ на высвобождение ноопепта из назальной лекарственной формы. Материалы и методы . Для исследования выбраны основные группы вспомогательных веществ при разработке назальной лекарственной формы: мукоадгезивные и регуляторы вязкости (полимеры) и увлажнители (спирты). Определяли высвобождение ноопепта методом равновесного диализа по Крувчинскому при 37,0 ± 0,5 °С через полупроницаемую мембрану – целлофановую пленку «Купрофан». Концентрацию ноопепта после 30 минут определяли методом УФ-спектрофотометрии при длине волны 258 нм. Результаты . В результате дисперсионного анализа установлено, что F эксперим. > F табл. для обоих факторов, таким образом, полимеры и спирты имеют значимое влияние на высвобождение ноопепта из назальных лекарственных форм. После проверки различия средних значений результатов с помощью множественного рангового критерия Дункана построены следующие ряды преимуществ: натрий карбоксиметилцеллюлоза (хитозан) > альгинат натрия (гиалуронат натрия); глицерин > сорбит > D-пантенол (без спирта). Выводы . Установили, что вид полимеров гидрофильных основ и спирты для увлажнения слизистой значимо влияют на высвобождение ноопета из назальных лекарственных форм. Оптимальное высвобождение ноопепта обеспечивают натрий карбоксиметилцеллюлоза и хитозан с добавлением глицерина.

Synthesis and characterization of butylamine-functionalized Cr(III)–MOF–SO3H: Synergistic effect of the hydrophobic moiety on Cr(III)–MOF–SO3H in esterification reactions

Mesoporous solid acid catalysts with partially hydrophobic moieties, [Cr3O(BDC–SO3H)3−x(BDC–SO3NH3Bu)x]n, were prepared from [Cr3O(BDC–SO3H)3]n (MIL-101(Cr)–SO3H) and BuNH2 for the first time and then characterized by the Brunauer–Emmet–Teller (BET) technique, powder X-ray diffraction, field emission electron microscopy, Fourier transform infrared spectroscopy, and thermal and elemental analyses. The nitrogen adsorption–desorption study showed that the specific surface area and total pore volume of MIL-101(Cr)–SO3H decreased after the reaction with butylamine and formation of [Cr3O(BDC–SO3H)3−x(BDC–SO3NH3Bu)x]n. The prepared materials were used as catalysts to investigate the impact of hydrophobic moieties in esterification yields of phthalic anhydride with several alcohols as a probe reaction. The presence of butylamine as a hydrophobic group on MIL-101(Cr)–SO3H increases the esterification yield significantly for hydrophilic alcohols under solvent-free conditions. Moreover, results showed that [Cr3O(BDC–SO3H)3−x(BDC–SO3NH3Bu)x]n can be recovered and reused for several consecutive reactions without significant loss in catalyst activity.

Salts and 1‐propanol induced aqueous two‐phase systems: phase separation and application

AbstractBACKGROUNDToday there is a resurgence of interest in using short‐chain hydrophilic alcohols and salts to recover stronger polar bio‐based chemicals and fuels for use as platform chemicals and renewable alternative transportation fuels. How to reduce the extractant depletion during the recovery of other bio‐based chemicals from the fermentation broths is a problem of concern to researchers.RESULTSThe present work investigated a 1‐propanol salt aqueous two‐phase system and its application to recover bio‐based acetoin. The water + 1‐propanol + K4P2O7 system was preferred for recovering bio‐based acetoin according to the recovery of 1‐propanol in the 1‐propanol salt aqueous two‐phase ternary system and after extraction of acetoin, and the salt content in the organic phase so as to avoid the losses of salt and 1‐propanol.CONCLUSIONSubsequently, almost 100% of acetoin can be recovered from the aqueous solution; almost all of the salt was retained in the aqueous phase and more than 99% of 1‐propanol was recovered. © 2019 Society of Chemical Industry

THE IMPROVEMENT OF BETULIN-3, 28-DIPHOSPHATE WATER-SOLUBILITY BY COMPLEXATION WITH AMINES–MEGLUMINE AND XYMEDON

Objective: To study betulin-3,28-diphosphate (BDP) water solubility improved by forming salt complexes with hydrophilic amino alcohols: meglumine as acidosis corrector and xymedon as the water-soluble antioxidant.
 Methods: We used 13C-, 31P-NMR, UV-spectroscopy and potentiometric titration to study the BDP-amine salt complexes formation and their solubility using HPLC-analysis.
 Results: The participation of xymedon in the proton transfer reaction with BDP in aqueous solutions was confirmed by the bathochromic shift of the carbonyl band from 299.1 nm to 304.2 nm, and by a hyperchromic effect (molar extinction ε from 8508 to 10 441 l·mol-1·cm-1) in UV-spectra. BDP complexation with meglumine was estimated by UV-spectral molar ratio method at 256 nm. Molar ratio of BDP-amine complexes (1:4) was proved by 31P-NMR. The chemical shift of phosphorus at C-3 atom of BDP (δ =-0.58 ppm) changed to+3.39 ppm, and at C-28 atom (δ =+0.28 ppm)–to+4.60 ppm. BDP solubility increased 100-600 fold according to HPLC-analysis.
 Conclusion: BDP interaction with amine in an aqueous solution was shown to proceed via a proton transfer due to relatively weak forces such as London forces, hydrogen bonding, electrostatic and hydrophobic interactions. In general, the formation of BDP salt complexes with amines in solution determines BDP water solubility. Water-soluble BDP enables to develop hydrophilic dosage forms.

Study of phase behavior and Congo red dye partitioning in aqueous two-phase systems composed of hydrophilic alcohols (1-propanol/ 1-butanol) and sodium salts

ABSTRACTThe partitioning of the Congo red dye in ATPSs formed by alcohols (1-butanol, 1-propanol)/sodium salts was considered. Binodal and the LLE data were experimentally determined at 298.15 K. The salting-out abilities of the salts follow the order Na3C6H5O7 > NaH2PO4 > C2H3 O2Na. The phase-forming abilities of the alcohols follow the order: 1-butanol > 1-propanol. The four-parameter equation was applied to correlate the binodal curves data. Therefore, The Bancroft and Othmer-Tobias equations were used to prove the reliability of the corresponding LLE data. ATPS composed of 6.5% of 1-butanol and 20% of Na3C6H5O7 had the highest values of extraction by the yield of 98.54%.

Impact of polyphenols on the headspace concentration of aroma compounds in apple cider.

To study the effect of polyphenols on the release of aroma compounds in apple cider, the impact of (-)-epicatechin, hydrocaffeic acid and phloridzin on volatility of 12 typical aroma compounds was investigated by headspace solid phase microextraction and gas chromatography-mass spectrometry. Analysis of variance results showed that increased concentrations of the phenolic compounds significantly affected the headspace concentration of most aroma compounds. The three polyphenols induced a volatility decrease for the majority of hydrophobic aroma compounds, while they exhibited an opposite behavior by salting out some hydrophilic alcohols. (-)-Epicatechin and hydrocaffeic acid showed a higher retention effect on most hydrophobic aroma compounds than phloridzin did. This study showed that the polyphenols had varying effects on aroma compound volatility in apple cider. The physicochemical characteristics and spatial conformation of polyphenols and aroma compounds influenced the magnitude of aroma-polyphenol interaction in apple cider. Understanding the effects of polyphenols on aroma release can improve the prediction of aroma profiles through chemical analysis, which assists cidermakers in improving the aroma quality of apple cider. © 2018 Society of Chemical Industry.

Liquid–Liquid Equilibrium of Hydrophilic Alcohols with Three Different Salts of Chloride: Experiment and Correlation

Ternary liquid–liquid phase equilibria were investigated at 298.15 K for hydrophilic alcohols (2-propanol/1-propanol) + different salts of chloride (KCl/NaCl/CaCl2) + water systems. The phase-forming and salting-out capabilities of the mentioned salts were discussed by determination of both excluded effective volume and salting-out coefficient. The results showed that the salting-out capabilities of the studied salts are as follows: CaCl2 > NaCl > KCl. The phase-forming capability of the investigated hydrophilic alcohols was discussed by using the dielectric constant and the boiling point of the alcohols. The four-parameter equation was used to fit the binodal curves data, and also the Bancroft and Othmer–Tobias equations were successfully used to correlate the tie-lines data. Correlation of the data demonstrates that the calculated method and experimental data are in good accord.

Effects of cytoplasm and reactant polarities on acid-catalyzed lipid transesterification in wet microalgal cells subjected to microwave irradiation

The polarities of the cytoplasm and reactants were measured through dielectric spectroscopy, contact angle test, NMR, and FTIR to investigate the mechanisms underlying acid-catalyzed lipid transesterification in wet microalgal cells subjected to microwave irradiation. Organics with apolar functional groups in the cytoplasm decreased the contact angle of methanol against triglyceride by 13.92°, which subsequently increased transesterification efficiency by 2.4 times. The microalgal biomass, given its higher hydrophilicity index of 1.96 than lipids, was more accessible to hydrophilic alcohols, which subsequently promoted transesterification. Water in the cytoplasm promoted the dielectric constant of methanol and increased the contact angle of methanol against triglyceride by 20.51°, which subsequently decreased transesterification efficiency by 72.6%. The inhibitory effect of water on transesterification weakened with the prolonged carbon lengths of the alcohols because of decreased polarity. Microwave decreased the electric constants of alcohols and reduced the polarity difference between alcohols and lipids, thereby improving transesterification efficiency.

Partition behavior of hydrophilic diols in an ethanol/ammonium sulfate salting‐out extraction system

It is important to investigate the partition behavior of hydrophilic alcohols at different process parameters in order to have a deep understanding of the salting‐out extraction technique and to design suitable downstream processes. First, phase diagram data of ethanol/ammonium sulfate at 293.15 K were obtained, and the reliability of binodal curve and tie line data were proved by Merchuk, Othmer–Tobias, and Bancroft equations, respectively. Then, the partition behavior of five short‐chain diols was studied. For different tie lines, the partition coefficient changed linearly with an increase in tie line length. The concentration of diols also had a significant effect on the partition behavior due to the similarity between diols and ethanol. Further, the effect of temperature was increased as the hydrophobicity of the diols increased, and the partition behavior of diols was correlated with their hydrophobicity, implying that the solutes with higher hydrophobicity could be extracted more effectively. These findings are useful for designing an economic and efficient salting‐out extraction process for diverse products.

Aqueous Two-Phase Extraction Combined with Chromatography: New Strategies for Preparative Separation and Purification of Capsaicin from Capsicum Oleoresin

Capsaicin was preparatively separated and purified from capsicum oleoresin with a new method combined with aqueous two-phase extraction (ATPE) and chromatography. Screening experiments of ATPE systems containing salts and hydrophilic alcohols showed that potassium carbonate/ethanol system was the most suitable system for capsaicin recovery among the systems considered. Response surface methodology was used to determine an optimized aqueous two-phase system for the extraction of capsaicin from capsaicin oleoresin. In a 20 % (w/w) ethanol/22.3 % (w/w) potassium carbonate system, 85.4 % of the capsaicin was recovered in the top ethanol-rich phase while most oil and capsanthin ester were removed in the interphase. The capsaicinoid extract was then subjected to two chromatographic steps using D101 macroporous resin and inexpensive SKP-10-4300 reverse-phase resin first applied for the purification of capsaicin. After simple optimization of loading/elution conditions for D101 macroporous resin chromatography and SKP-10-4300 reverse-phase resin chromatography, the purities of capsaicin were improved from 7 to 85 %. In the two chromatography processes, the recoveries of capsaicin were 93 and 80 % respectively; the productivities of capsaicin were 1.86 and 4.2 (g capsaicin/L resin) per day respectively. It is worth mentioning that a by-product of capsaicin production was also obtained with a high purity (90 %).

Liquid–liquid equilibria of hydrophilic alcohol + sodium hydroxide + water systems: Experimental and correlation

Binodal data for ethanol, 2-propanol and 1-propanol+sodium hydroxide (NaOH)+water systems were experimentally determined at 283.15, 298.15 and 313.15K, respectively. An empirical equation was used to correlate the binodal data. On the basis of the empirical equation with binodal data and the lever rule, the tie-lines data for the investigated systems at 298.15K were obtained via the MATLAB and then correlated by Othmer-Tobias and Bancroft equations. Temperature and salting-out effects on this type of ATPS were investigated. It was found that an increase in temperature leads to an expansion of the two-phase area. The salting-out ability of NaF is stronger than that of NaOH. Additionally, the phase-forming abilities of the investigated hydrophilic alcohols were discussed by both the effective excluded volume (EEV) of the investigated salt and the location of the binodal curves of the investigated systems. The phase-forming abilities of the investigated hydrophilic alcohols follow the order: 1-propanol>2-propanol>ethanol.

Isolation of caffeine from aqueous media with solvents of homologous structure and its determination by spectrophotometry

The extraction of caffeine by hydrophilic and hydrophobic aliphatic alcohols of linear and branched structure is studied, also by water-soluble alkyl acetates. A correlation between the distribution ratios of caffeine (logD) and the molecular weight of alcohol (logM) is found. The concentration of caffeine in the aqueous phase is determined by UV spectrophotometry. The distribution ratios and recovery of caffeine are calculated.

Liquid–liquid equilibrium of aqueous two-phase systems composed of hydrophilic alcohols (ethanol/2-propanol/1-propanol) and MgSO4/ZnSO4 at (303.15 and 313.15) K and correlation

Binodal data for ethanol, 2-propanol and 1-propanol+magnesium sulfate/zinc sulfate+water systems were experimentally determined at (303.15 and 313.15)K, respectively. An empirical equation was used to correlate binodal data. The liquid–liquid equilibrium data for part of the investigated systems were obtained via the MATLAB. In order to evaluate the dependability of the calculation method and the tie-line data, the liquid–liquid equilibrium data were correlated by the Othmer–Tobias and Bancroft equations. The salting-out abilities of the investigated salts and the phase-forming abilities of the investigated hydrophilic alcohols were discussed by the effective excluded volume (EEV) of salt. The salting-out abilities of the investigated salts follow the order ZnSO4>MgSO4, which can be indicated by the location of the binodal curves plotted in molality and the salting-out coefficient. In addition, the phase-forming abilities of the investigated hydrophilic alcohols follow the order: 1-propanol>2-propanol>ethanol.

Solvent-Driven Room-Temperature Synthesis of Nanoparticles BiPO4:Eu3+

In this work, a novel solvent-driven room-temperature synthesis of BiPO(4):Eu(3+) nanoparticles was presented. By virtue of 11 solvents with different properties and function groups, phase structure and composition of BiPO(4):Eu(3+) can be systematically tailored. Hexagonal phase (HP) of BiPO(4):Eu(3+) was obtained in water and hydrophobic organic solvents such as arenes and cyclohexane, while low-temperature monoclinic phase (LTMP) was prepared in hydrophilic alcohols. In other solvents (i.e., hydrophilic ethers, aldehydes, ketones, and carboxylic acids), a mixture of HP and LTMP was formed, in which the relative content of LTMP gradually increased following the above solvent sequence. It is also found that particle sizes of BiPO(4):Eu(3+) nanoparticles were closely related to the phase structure: HP exhibited a comparatively larger particle size. The phase evolution processes for both polymorphs with varying solvents were investigated in details. Photoluminescence (PL) properties were sensitive to the phase structure and compositions of the final products. With increasing the phase content of LTMP, the lifetimes and quantum yields both increased. The methodology reported here is fundamentally important, which may give a novel insight into the polymorph-controlled synthesis for further optimized materials performance.

Aqueous Two Phase Extraction for the Recovery of 1,3-Propanediol from Its Aqueous Solutions

As the biodiesel production is rapidly enhanced, the crude glycerol, which is by-product of biodiesel processes, is state of surplus. 1,3-PDO (1,3-propanediol), a valuable monomer of poly(trimethylene terephthalate) (PTT), can be produced from the fermentation process using crude glycerin as a carbon source. For the economic biological production of 1,3-PDO, the low cost and high efficient separation processes is essential. In this study, aqueous two-phase system composed of various hydrophilic alcohols and salt was used as a primary separation step for 1,3-PDO. It was found that the aqueous two-phase systems are easily formed with decreasing of the polarity of alcohols. The extraction efficiency is proportional to the polarity of alcohols. In case of methanol or ethanol/K2HPO4, the extraction efficiency was more than 90%. It was concluded that the aqueous two-phase extraction using methanol or ethanol/K2HPO4 can be applied for the primary separation of 1,3-PDO as an alternative to a conventional primary separation processes.

Miniemulsion as efficient system for enzymatic synthesis of acid alkyl esters

The aim of this work is to devise an efficient enzymatic process for the production of linear alkyl esters in aqueous miniemulsion systems. The esterification reactions of linear alcohols and carboxylic acids were performed with three different enzymes, commercial Amano lipase PS from Pseudomonas cepacia, Lipase type VII from Candida rugosa, and lyophilized Fusarium solani pisi cutinase expressed in Saccharomyces cerevisiae SU50. The miniemulsion system shows a high potential for the synthesis of linear alkyl esters, for example, hexyl octanoate, which could be synthesized with an ester yield of 94% using Amano lipase PS. Even with hydrophilic alcohols as ethanol, ethyl decanoate could be obtained with a concentration of 0.45 M and a yield of 62% using F. s. pisi cutinase as catalyst. High esterification rates for ethyl- and hexyloleate in miniemulsion showed a significant shift in cutinase selectivity towards longer chain length carboxylic acids. The stepwise addition of the alcohol led to an increase of the esterification yield. Moreover, increasing the amount of dispersed organic phase, mainly consisting of the substrates, led to a significant increase of the final ester concentration (e.g., concentration of 1.4 M for ethyl decanoate for the esterification with Amano Lipase PS).