Determination of sunscreen agents in cosmetic products by supercritical fluid extraction and high-performance liquid chromatography

A rapid supercritical fluid extraction (SFE) procedure for the isolation of five of the most common sunscreen agents (2-ethylhexyl-p-dimethylaminobenzoate, 2-hydroxy-4-methoxybenzophenone, 2-ethylhexyl-p-methoxycinnamate, 4-methylbenzylidene camphor and 4-tert.-butyl-4′-methoxydibenzoylmethane) from cosmetic products is described. Investigation of the factors affecting the extraction efficiency in SFE indicated that sunscreen recoveries were affected mainly by the supercritical CO₂ pressure and by the trapping method. The sunscreens were analyzed by reversed-phase high-performance liquid chromatography after a 10-min extraction of the cosmetic product with CO₂ at 250 bar and 40°C, using sequential glass surface and C₁₈ sorbent as collection system. A quantitative comparison of SFE with a liquid extraction procedure was performed on commercial cosmetics. The SFE method yielded recoveries higher than 94.8% compared with conventional liquid extraction and exhibited a precision better than 5.3% relative standard deviation. Moreover, SFE minimized sample handling, reduced the consumption of harmful solvents and afforded a more effective purification of the cosmetic matrices.     

Laser-induced oxidation reactions in supercritical ethane---O2 mixtures

The laser-induced oxidation of ethane by O₂ at 318 K was investigated with varying the pressure between 12–91 atm. The reaction condition was regarded as the supercritical phase above 50–60 atm, depending on the O₂ fraction. Ethanol, acetaldehyde, and CO₂ were mainly produced at any reaction conditions, together with small amounts of C₁ compounds and formic esters. The kinetic discussion for the time dependence indicated that the consecutive photolysis of primary products takes place during the subsequent laser irradiation period. The branching ratio to CO₂ formation in the primary process in the supercritical phase is much smaller than that in the gas phase, and the selectivities for ethanol and acetaldehyde show a discontinuous change near the critical point. These facts show that the supercritical phase affects this complex radical reaction system. The primary photoabsorption process is also discussed.     

Investigation of carbon dioxide modified supercritical and near supercritical carrier streams for flow injection systems

Since flow injection (FI) is a dilution technique, efforts have been undertaken to minimize online dilution or dispersion. Solutes in supercritical fluids exhibit increased diffusion coefficients which have been shown to decrease dispersion of the sample zone. This work investigates the use of supercritical fluids (or CO₂ modified fluids) as carrier streams for FI. Both a non-reacting tracer and an online chemical reaction were employed to investigate the behavior of solutes in supercritical and near critical systems. Further, these results are compared to those obtained in the system studied with a conventional carrier stream. Plots of peak response vs% CO₂ modifier increase with a sharp break at moderate modifier composition (20–30%). Plots of peak variance vs% CO₂ modifier show decreased variance with increasing % modifier. The system was also optimized with regards to temperature and pressure. The optimized system displayed improved limits of detection and decreased variance relative to 0% CO₂ modifier carrier streams.     

Thermophysical properties of supercritical fluids with special consideration of aqueous systems

Selected thermophysical properties of polar, dense supercritical fluids are discussed. The static dielectric constant of water and the freon R22 (CHClF₂) is shown in some detail. Examples of critical curves for binary systems with water and methanol are given. New experimental data of excess volumes up to 400 °C and 2000 bar are shown for water combined with H₂, CH₄ and benzene. Excess Gibbs energies and activity coefficients for water-benzene are also shown. Results of the solubility of anthracene in ten different high pressure fluids, obtained by UV-spectroscopy, are presented. The PVT-data of concentrated supercritical aqueous NaCl-solutions and the ion product of pure water to 1000 °C are discussed.     

Formation of cellulose acetate membranes using a supercritical fluid assisted process

Microporous cellulose acetate membranes have been prepared from polymer–acetone solutions using a supercritical fluid phase inversion process in which CO₂ acts as the non-solvent. Series of experiments were performed at various polymer concentrations, temperatures and pressures. The structure of the resulting membranes was analysed using scanning electron microscopy. We operated with polymer concentrations ranging between 5 and 40% (w/w) in acetone obtaining different pore dimensions and membrane structures. Increasing the percentage of polymer in the solution, the structure of the membranes changed from beads-like structure to cellular structure. Polymer concentration also influenced the mean diameter of the pores that ranged from 2 to 50 μm for polymer concentrations from 40 to 5% (w/w). We also tested membrane formation pressures between 100 and 200 bar and at temperature between 45 and 65 °C. Pressure influences the change in membrane structure from cellular to beads-like, whereas temperature has a minor influence on pore size: both the effects can be partially related to CO₂ density. Cellulose acetate membrane formation mechanisms have also been discussed.     

A new strategy for supercritical fluid extraction of copper ions

Complexation combined with supercritical fluid extraction was used to extract Cu²⁺. The effects of pressure, temperature, and total volume of CO₂ on the efficiency of extraction were systematically investigated. The extraction recovery was low (57.32%) only by pure supercritical CO₂. Addition of a suitable amount of methanol (v/v=5%) to supercritical CO₂ could enhance the extraction of Cu²⁺ (72.69%, relative standard deviation (R.S.D.)=2.12%, n=3), and the recovery increased largely (90.52%, R.S.D.=2.20%, n=3) in the presence of nonionic surfactant Triton X-100. Reverse micelle formation is presented as a new strategy of improving the extraction of metal ions with supercritical CO₂ in this paper.     

Surface modification of γ-alumina membranes by silane coupling for CO2 separation

Top layers of γ-Al₂O₃ composite membranes have been modified by the silane coupling technique using phenyltriethoxysilane for improving the separation factor of CO₂ to N₂. The separation efficiency of the modified membranes was strongly dependent upon the hydroxylation tendency of the support materials and the amount of the special functional group (i.e. phenyl radical) which was coupled onto a top layer. The separation factor through the TiO₂ supported γ-Al₂O₃ membrane was found to be fairly enhanced by silane coupling, but in case of the -Al₂O₃ supported membrane was not. The CO₂/N₂ separation factor through the modified γ-Al₂O₃/TiO₂ composite membrane is 1.7 at 90°C and ΔP = 2 × 10⁵ Pa for the binary mixture containing 50 vol% CO₂. The separation factor is proportional to the CO₂ concentration in the gas mixture, and the modified membrane is stable up to 100°C. The main mechanism of the CO₂ transport through the modified γ-Al₂O₃ layer is known to be a surface diffusion.     

Supported carbon molecular sieve membranes based on a phenolic resin

The preparation of a composite carbon membrane for separation of gas mixtures is described. The membrane is formed by a thin microporous carbon layer (thickness, 2 μm) obtained by pyrolysis of a phenolic resin film supported over a macroporous carbon substrate (pore size, 1 μm; porosity, 30%). The microporous carbon layer exhibits molecular sieving properties and it allows the separation of gases depending on their molecular size. The micropore size was estimated to be around 4.2 Å. Single and mixed gas permeation experiments were performed at different temperatures between 25°C and 150°C, and pressures between 1 and 3.5 bar. The carbon membrane shows high selectivities for the separation of permanent gases like O₂/N₂ system (selectivity≈10 at 25°C). Gas mixtures like CO₂/N₂ and CO₂/CH₄ are successfully separated by means of prepared membranes. For example, the membrane prepared by carbonization at 700°C shows at 25°C the following separation factors: CO₂/N₂≈45 and CO₂/CH₄≈160.     

生物油超临界CO_2酯化反应研究

将超临界CO2萃取与酯化反应耦合,研究了萃取酯化提质生物油过程。乙酸(AC)、丙酸(PA)和丙烯酸(AR)在超临界CO2(scCO2)条件下酯化时的平衡转化率显著高于常压酯化时的平衡转化率,表明scCO2对酯化反应具有明显的促进作用。这主要是由于生成的酯不断被萃入scCO2相。在恒温下scCO2的密度随压力升高而增大,因而酯化率随着CO2压力的升高而增加,与有机酸单独酯化时相比,混酸(AC、PA和AR)酯化后各种酸的转化率却比较接近,表明酯化过程中存在着酯交换机制。真实生物油的酯化结果表明,在80℃和28.0MPa下酯化3.0h,总酸的转化率可达86.78%。酯化后生物油的pH值从3.78提高到5.11,萃出生物油在140℃下挥发率接近100%,表明油品质量得到显著提升。     

超临界水中钾对甲醛降解过程影响的研究

为掌握生物质中钾对生物质超临界水降解过程的影响,选择生物质气化转化过程中生成的重要小分子中间产物甲醛作为研究对象,研究不同工艺条件下(反应温度400～650℃、压力23～29 MPa、停留时间4～12 s),单一钾成分(KHCO₃/K₂CO₃/KCl)或混合钾成分(KHCO₃、K₂CO₃、KCl)对甲醛超临界水降解气体产物的影响。结果表明,KHCO₃、K₂CO₃、KCl、混合钾均降低了气体产物中CO的体积分数,提高了CO₂的体积分数,但KCl的影响程度弱于其他三种钾成分。此外,由于不同钾成分均不利于气体产物中CO和H₂体积分数的提高,从而使得气体产物的热值降低。KHCO₃、K₂CO₃、KCl、混合钾均降低了H₂、CO、CO₂的产率以及气化率,其对H₂产率以及气化率的抑制程度从大到小依次为:混合钾、KHCO₃、K₂CO₃、KCl,且提高反应温度、延长反应停留时间时抑制气体生成的作用相对越明显。而当反应压力改变时,钾成分对H₂产率及气化率的影响程度变化较小。较高反应温度、较高反应压力、较长停留时间时,混合钾中各成分出现协同作用,明显抑制了气体产物的生成。     

Palladium-catalyzed Heck coupling reactions using different fluorinated phosphine ligands in compressed carbon dioxide and conventional organic solvents

Palladium-catalyzed Heck reaction of iodobenzene and styrene was investigated in compressed CO₂ using different fluorinated phosphine compounds as ligands at a temperature of 70 °C. The reaction mixture is a single phase at 12 MPa but biphasic at 8 MPa, a little higher than the critical pressure of pure CO₂ under the reaction conditions used. Although the solubility of fluorinated ligands is very high in dense CO₂, they have marginal improvements in Heck conversion in this medium compared with a non-fluorinated ligand of triphenylphosphine. The activity of palladium complexes strongly depends on the kind of phosphine compound used, in the order of bis(pentafluorophenyl)phenylphosphine (III)>triphenylphosphine (I), tris(pentafluorophenyl)phosphine (IV)>diphenyl(pentafluorophenyl)phosphine (II), tris(p-fluorophenyl)phosphine (V)>tris(p-trifluoromethyl phenyl)phosphine (VI), 1,2-bis[bis(pentafluorophenyl)phosphino]ethane (VII), for the homogeneous reaction at 12 MPa. This order of effectiveness of these ligands is different from those obtained in conventional organic solvents. Hexane, toluene, ethanol, and N-methylpyrrolidone (NMP) showed maximum conversions with the ligands VI, IV, V and VII, respectively. The conversion in CO₂ with the ligand III is comparable with those in polar solvents of ethanol and NMP, and larger than those in hexane and toluene in the presence of the best ligands. The dense CO₂ may affect the specific activity of palladium complex catalysts and/or the reactivity of reacting species. Small quantities of fluorinated products were observed to form at high pressure of CO₂ and this is direct evidence of P–C bond cleavage during Heck reaction in dense CO₂. The activity of palladium complexes with those ligands is higher in more polar solvent.     

Some aspects of calcium sulphite reduction with carbon monoxide

The non-isothermal reductive decomposition reaction of crystalline CaSO₃·0.5H₂O and anhydrous CaSO₃ under CO, CO₂ and CO-CO₂ gas mixtures at the two heating rates of 25°C min⁻¹ and 6°C min⁻¹ up to 900°C, respectively, was investigated employing thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and continuous SO₂ measurement by on-line fluorescence spectroscopy. During the heating process the reaction involved a multistage weight loss, in both cases, with a corresponding multistage SO₂ release. The multistage weight loss and the corresponding SO₂ release were presumed to be the consequence of different sequential reactions taking place along with the direct reduction of CaSO₃ to CaS, including the formation and decomposition of CaCO₃ and CaSO₄, respectively. The corresponding SO₂ evolution was found to be considerably lower at slow heating rates. In the presence of additional CO₂, the SO₂ release was increased and the highest SO₂ concentration was found for a feed-gas mixture of 70% CO₂ and 30% CO, and also in pure CO₂. The CaCO₃ product also increased with increasing CO₂ concentration. The possible reaction pathway is discussed.     

Evidence for the importance of intermolecular coupling in the OD band''s vibrational structure in deeply supercooled liquid D2O

We present the Raman spectrum of pure liquid D₂O at −27.0°C, 17°C lower than any previously reported Raman spectrum of liquid D₂O. The liquid's OD stretch band at −27.0°C displays a prominent feature which is clearly analogous to the ν₁ in-phase mode in D₂O ice Ih providing strong evidence that the structure of cold liquid D₂O's OD band is principally due to strong intermolecular coupling. Deeply supercooled liquid D₂O displays this ν₁ in-phase feature more clearly than deeply supercooled liquid H₂O due to the smaller disparity in the D/O mass ratio compared to that of H/O which enhances this coupling.     

Resolution studies on counter-current chromatography using supercritical fluid carbon dioxide

Counter-current chromatography (CCC) is a form of liquid–liquid partition chromatography. It requires two immiscible solvent phases; the stationary phase is retained in the separation column, generally by centrifugal force, while the mobile phase is eluted. We recently replaced the mobile phase with supercritical fluid carbon dioxide (SF CO₂). Since the solvent strength of SF CO₂ can be varied by changing the temperature and pressure of the system, separation adjustments are thus more versatile. We investigated the pressure and temperature effects on resolution using water and low-carbon alcohol mixtures as the stationary phases. It was demonstrated that these special properties of SF CO₂ were indeed beneficial to the optimization of separations. In addition, the phase retention ratio was examined in terms of separation resolution. The results appeared very similar to those obtained from conventional traditional CCC. This study should be helpful for the future development of SF applications in CCC.     

Extraction of arsenic as the diethyl dithiophosphate complex with supercritical fluid and quantitation by cathodic stripping voltammetry

The separation of arsenic based on in situ chelation with ammonium diethyl dithiophosphate (ADDTP) has been carried out using methanol-modified supercritical CO₂. Aliquots of extract were added to an electroanalytical cell and arsenic was determined by square wave cathodic stripping voltammetry (SWCSV) at a hanging mercury drop electrode (HMDE). Quantitative extractions of As(DDTP)₃ were achieved when the experiments were carried out at a pressure of 2500 psi, a temperature of 90 °C, 2.0 mL of methanol, 20.0 min of static extraction and 5.0 min of dynamic extraction in the presence of 18 mg of ADDTP. Analysis of arsenic was made using 150 mg L⁻¹ of Cu(II) in 1 M HCl solution as supporting electrolyte in the presence of ADDTP as ligand. Preconcentration was carried out by deposition at a potential of −0.50 V and the intermetallic compound Cu_xAs_y was reduced at a potential of −0.77 to −0.82 V, depending on ligand concentration. The results showed that the presence of ligand plays an important role, increasing the method's sensitivity and preventing the oxidation of As(III). The calibration graph of the As(DDTP)₃ solution was linear from 0.8 to 12.5 μg L⁻¹ of arsenic (LOD 0.5 μg L⁻¹, R = 0.9992, t_acc = 60 s). The method was validated using carrot pulp spiked with arsenic solution. This method was applied to the determination of arsenic in samples of carrots, beets and irrigation water. Arsenic in beets was: skin 4.10 ± 0.18 mg kg⁻¹; pulp 3.83 ± 0.19 mg kg⁻¹ and juice 0.71 ± 0.09 mg L⁻¹; arsenic in carrots was: skin 2.15 ± 0.09 mg kg⁻¹; pulp 0.59 ± 0.11 mg kg⁻¹ and juice 0.71 ± 0.03 mg L⁻¹. Arsenic in water were: Chiu-Chiu 0.08 mg L⁻¹, Inacaliri 1.12 mg L⁻¹, and Salado river 0.17 ± 0.07 mg L⁻¹.     

一种新型CO2/原油助混剂CAA8-X的应用与助混机理

CO₂驱是一种具有广阔前景的提高油藏采收率的方法。其中,降低CO₂与原油的最低混相压力以实现混相驱是增强CO₂驱效果的重要手段。由此我们设计了由亲油基团十六烷基和亲CO₂基团全乙酰蔗糖酯基结合的新型“亲油-亲CO₂助混分子”十六酸全乙酰基蔗糖酯CAA8-X,研究发现,CAA8-X对超临界CO₂流体和不同油相的煤油、白油以及长庆原油有优异的助混效果,界面张力消失法和细管实验法测定结果表明,CAA8-X可以将超临界CO₂/长庆原油的最低混相压力降低20.5%。用分子动力学模拟计算了CO₂分子与全乙酰蔗糖酯基的亲和能力,研究了这类新型“亲油-亲CO₂助混分子”通过多酯头基降低与CO₂亲和势能而降低油/CO₂界面能的助混机理。     

超临界水中甲酸降解过程实验研究

在550℃~650℃,24 MPa~30 MPa,反应停留16 s~46 s的条件下,对初始浓度0.05 mol/L~0.70 mol/L的甲酸溶液在超临界水中的降解过程进行实验研究。结果表明,甲酸降解的气体产物为H2、CO2和CO,其中H2、CO2为主要产物。高温有利于甲酸降解和H2生成。温度较高(600℃)时,压力变化对甲酸降解无明显影响。在一定范围内延长反应时间可提高气体产物中H2的体积分数和碳气化率。甲酸初始浓度对甲酸降解机理有重要影响,浓度较低(0.1 mol/L)时,甲酸降解主要包含脱羧反应和脱羰反应两条反应路径,其中脱羧反应为主反应路径;浓度较高时则有许多副反应发生。碱性添加剂不利于甲酸降解生成H2。     

Study of self-association of water in supercritical CO2 by Monte Carlo simulation: Does water have a specific interaction with CO2?

The extent of the self-association of water in supercritical CO₂ has been investigated in a wide range of density and temperature by the test particle insertion technique. The results show that the association constant for water decreases with temperature and weakly depends on CO₂ density. This weak density dependence provides evidence for the lack of a strong specific CO₂–water interaction. Comparing calculated association constants with its gas-phase values shows that the association constant is at most ca. 38% lower than its gas-phase value in the high density–low temperature region. Inspection of the simulated radial distribution functions revealed that forming modest water–CO₂ complexes does not result in substantial interference in H-bonding of water molecules.     

Systematic investigation of the effects of temperature and pressure on gas transport through polyurethane/poly(methylmethacrylate) phase-separated blends

Polyurethane (PU) and polyurethane–poly(methylmethacrylate) (PMMA) blend membranes were used in gas separation studies. The effects of blend composition, temperature, and pressure on the permeability, diffusivity, and solubility of CO₂, H₂, O₂, CH₄, and N₂ were investigated. The separation factors of some gas pairs were also evaluated. Positron annihilation lifetime spectroscopy was applied to assess free volume changes as a function of blend composition and temperature. Free volume size increases by approximately 30% with increasing temperature from 10 to 40 °C for all blends studied. The permeability of all gases decreases by approximately 55% with the addition of 30 wt% of PMMA. The permeation process is governed by diffusion, except that of CO₂. In relation to the behavior of gas transport as a function of temperature, some important observations are (i) CO₂ presents the lowest permeation activation energy value (28 kJ/mol), and (ii) gas pair selectivity increases at low temperatures and is high for gas pairs that present differences in permeation activation energies as high as 15 kJ/mol for the CO₂/CH₄ gas pair. Furthermore, the study with pressure variations shows that: (i) at elevated pressure, the PU and the blend membrane permeability to CO₂ and H₂ increases by approximately 35%, and (ii) oxygen-to-nitrogen selectivity increases with pressure as a consequence of the decrease in the permeability to nitrogen in the case of the 30%-PMMA blend.