본 연구에서는 친유성기의 크기는 같으면서 친수성기의 크기가 다른 계면활성제를 이용한 베타카로틴이 탑재된 에멀션을 제조하여, 에멀션의 계면특성과 산화방지제의 물리적 위치가 베타카로틴의 화학적 안정성에 미치는 영향 을 평가하였다. 계면활성제의 혼합은 에멀션에 탑재된 베타카로틴의 분해속도에 영향을 주었다. 에멀션을 Brij™ 계 면활성제 중 친수성기가 가장 작은 계면활성제(Brij™ S10)와 가장 큰 계면활성제(Brij™ S100)를 몰 비율 1:1로 각 각 3.17 mM의 농도와 1.00 mM의 농도로 제조하였을 때, 에멀션에 탑재된 베타카로틴은 계면활성제를 3.17 mM 농 도로 제조된 에멀션에서 1.00 mM 농도로 제조된 에멀션에 비해 더 급격하게 감소하였다. 친유성 산화방지제 (tert-butylhydroquinone (TBHQ))와 양친매성(lauryl gallate) 산화방지제 모두 에멀션에 포집된 베타카로틴의 화학적 안 정성을 향상시켰으며, 에멀션의 계면활성제의 농도와 계면 조성과는 무관하게 TBHQ가 lauryl gallate 보다 베타카로 틴의 분해를 지연시키는데 더 효과적이었다.
수용성 비이온고분자인 Polyvinylalcohol (PVA), Polyvinylpyrrolidone (PVP), Hydroxypropyl cellusoe (HPC)와 iodine과의 착물 형성에 대한 계면활성제의 영향을 알아보기 위해 Sodiumdodecylsulfate을 포함하는 수용액에서 이들 사이의 반응을 수행하였다. PVP와 HPC에서 tri-iodide band의 적색 이동에 의하여 착물이 만들어졌다는 것을 알게되었고, PVA-iodine 착물에서는 500 nm 부근에서 고유의 특색있는 띠를 나타내었다. SDS 계면활성제의 존재는 PVA-iodine 착물의 파괴를 가져왔고, 고유의 푸른색도 사라지게 만들었다. 그러나 SDS 단량체는 PVP, HPC와 iodine의 착물 형성을 도와주는 경향을 나타내었다. 고분자 용액에서 겔이 만들어지는 것을 방해하는 n-propanol은 고 분자-iodine 착물이 형성되는 것을 도와주었다. SDS가 있을 때와 없을 경우의 영향을 알아보기 위해 순 수한 HPC와 HPC-iodine 착물을 만들고 이들의 성질을 조사하였다.
여러 종류의 양이온성, 비이온성 및 혼합성 계면활성제 수용액에서 4-클로로벤조산의 가용화현상을 UV/Vis 분광광도법을 이용하여 연구하였다. 또한 온도의 변화에 따른 가용화상수값(Ks)의 변화를 측정함으로써 열역학적 함수값들을 계산하고 분석하였다. 그 결과 모든 계면활성제의 용액에서 4-클로로벤조산의 가용화에 대한 △Gos 값은 측정범위 내에서 모두 음의 값을 나타내었으며, △Hos 값과 △Sos 값은 모두 양의 값을 나타내었다. 계면활성제 종류와 계면활성제분자의 알킬-그룹 길이에 따라 Ks값이 큰 폭으로 변하였으며, 그런 결과로부터 4-클로로벤조산이 미셀 내에서 가용화되는 위치와 미셀과의 상호작용의 정도를 예측할 수 있었다.
4-클로로벤조산의 가용화현상을 이용하여 순수양이온성 계면활성제(DTAB, TTAB, CTAB), 비이온성 계면활성제(Tween-20, Tween-40, Tween-80) 및 이들 혼합계면활성제(TTAB/Tween-20, TTAB/Tween-40, TTAB/Tween-80)의 임계미셀농도(CMC)값과 반대이온 결합상수값(B)를 온도 284 K에서 312 K 까지 변화를 주면서 UV/Vis 분광광도법과 전도도법으로 측정하였다. 온도에 따른 CMC와 B값의 변화를 측정하여 미셀화현상에 대한 여러 가지 열역학 함수값(△G˚m, △H˚m, 및 △S˚m)을 계산하고 분석 하였다. 그 결과 측정범위 내에서 △G˚m 값은 모두 음의 값을 나타내었다. 그러나 △H˚m 과 △S˚m값은 계면활성제의 종류와 계면활성제분자에서 탄소사슬의 길이에 따라 양의 값 혹은 음의 값을 나타내었다.
본 연구에서는 계면활성제 분석법의 개발을 위하여 High performance liquid chromatography-evaporative light scattering detection(HPLC-ELSD) 기기를 이용하여 음이온 및 비이온 계면활성제 중 다소비 계면활성제인 Alkyl polyglucoside(APG)와 Alpha olefin sulfonate(AOS)를 분석하였다. 실험 결과 APG와 AOS 모두 직선성의 상관관계 계수(R2)가 0.99 이상으로 직선성이 양호하였으며, 검출한계는 APG가 2.29 mg/L, AOS가 16.55 mg/L로 나타났고, 정량한계는 APG가 7.63 mg/L, AOS가 55.16 mg/L로 나타났다. 또한, 회수율 검증을 실시한 결과 APG는 99.29%, AOS는 96.11%로 나타나 회수율 100±10% 이내의 검증기준을 모두 만족하였다. 정밀성 및 정확성을 판단한 결과 APG의 정밀성은 상대표준편차 0.30%, 정확성은 0.26-0.52%로 분석되었으며, AOS의 정밀성은 상대표준편차 0.10%, 정확성은 0.01-0.52%로 분석되어 모두 상대표준편차 1.0% 이하의 검증기준에 적합하였다. 확립된 분석법을 주방세제에 적용하여 분석한 결과 샘플 3종 모두에서 APG와 AOS가 각각 검출되었으며, 표준사용량을 기준으로 APG, AOS의 평균 함유량은 각각의 LD50에 크게 미치지 못하는 것으로 나타났다. 따라서 본 연구를 통하여 확립된 음이온 및 비이온 계면활성제의 분석법은 모든 성분에 대해 감응함으로 한가지 검출기를 이용하여 여러성분을 동시에 측정할 수 있어 식기 등의 잔류물질 혹은 식품 중 혼입되어 있는 다양한 계면활성제 함유량 분석에 적용하여 계면활성제의 관리를 위한 기초자료로 활용될 것으로 본다.
Substantial efforts have been made to manipulate ruminal environment in a hope to enhance ruminal fermentation efficiency for better ruminant productivity. Some of examples are methane inhibitors, antibiotics, microbial enzymes, fatty acids and/or lipid feeding, buffering agents, ionophores and probiotics. Of these efforts, the non-ionic surfactant (NIS) has been known for its stimulation to release enzymes from a range of anaerobic microbes. A series of studies were conducted 1) to evaluate NIS diluted with water and ethanol on in vitro ruminal fermentation and 2) to determine the influence of diluted NIS on digestibility of feedstuffs. In first experiment (Exp. 1), NIS was diluted with water or ethanol to measure its effects on in vitro microbial growth, ruminal enzyme activities and gas production by mixed ruminal microbial culture. The NIS was diluted with water or ethanol separately in a 1:5 ratio (w/v). Water and ethanol-diluted NIS with wheat flour were added with rice straw-based mixed ruminal microbial cultures at the rate of 2 ㎎ NIS/16 ㎖ McDougall buffer plus 4 ml ruminal fluid solution. The mixed ruminal microbial culture was run without any NIS addition as control. Addition of NIS either diluted with water or ethanol has significantly reduced the gas production in mixed ruminal microbial culture at 12 and 24 h of incubation. At 48 h post incubation, gas production was the highest with the addition of ethanol diluted NIS followed by water-diluted NIS and control. Carboxy methyl cellulase activity in rice straw-based mixed ruminal bacterial culture was significantly higher with the addition of ethanol-diluted NIS compared with the addition of water-diluted NIS and control at 24 and 72 h post incubation. In second in vitro experiment (Exp. 2), effects of addition of ethanol diluted NIS on dry matter (DM) digestibility of alfalfa hay, gas production, pH and cellular growth in mixed ruminal microbial culture were examined. Alfalfa hay based mixed ruminal microbial culture without any NIS addition was run as a control. The pH of mixed ruminal microbial culture was significantly lower than control at all post incubation sampling hours. In vitro DM digestibility of alfalfa hay was significantly higher with the addition of NIS compared with control. Gas production was significantly less with NIS addition compared with control at all post incubation sampling hours. Microbial growth in mixed ruminal microbial culture was significantly increased with the addition of NIS compared to control.
The transformation of the liquid crystal complex made by binding of anionic surfactant, sodium dodecyl sulfate (SDS), into high charge density cationic polymer, the homopolymer of diallyldimethylammonium chloride (PDADMAC) was induced by adding of nonionic surfactants and investigated by means of microscopy and FE.SEM. Among nonionic surfactants in this experiments polyethylene glycol (3 mol) ether of lauryl alcohol (laureth-3) made variation in the complex. The laureth-3 transformed the complex into spherulite vesicle with the size of ca.100μm. This change increased the viscosity and the turbidity of the solution phase separated originally. Microscope showed that they are spherulite particles and polarized microscope suggested they are multi.lamellar liquid crystals. FE-SEM also proved that explicitly.
The rheological properties and surface tensions of polymer solutions and polymer-surfactant mixed solutions were investigated. The polymers used in this study were a homopolymer of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose, or an allyl ether of propylene (CARBOMER), acylate/C10-30 alkyl acylate crosspolymer (AAAC), and ammonium acryloydimethyltaurate/VP copolymer (ADTV). A solubilizing agent PEG-40 hydrogenated castor oil (HCO-40) and an emulsifying agent polyoxyethylene (20) sorbitan monostearate (POLYSORBATE 60) made the micelles intervening between AAAC polymers, resulting in the increase of viscosity. However, HCO-40 made this behavior over the wider range of surfactant concentration than POLYSORBATE 60. From the view point of surface tensions in the same range of surfactant concentration, AAAC/HCO-40 solution showed the area of increasing surface tension with surfactant concentration in contrast to the AAAC/POLYSORBATE 60 solution showing no increasing area.
A proposed method of determining the composition of mixed micelles in equilibrium with monomer of known composition is described. The systems were sodium α-sulfonated dodecanoyl ethyl esther (α-SR12Et) or sodium dodecyl sulfate(SDS)-polyoxyethylene 23 lauryl ether (Brij 35) un water and in 0.1M sodium chloride solution at 25℃. This technique applies the Gibbs-Duhem equation to the mixed micelles, which is treated as a pseudophase. This proposed methodology, which needs only critical micelle concentration data as a function of monomer composition, is applied to an anionic/nonionic surfactant pair. The calculated monomer-micelle equilibrium is found to be very similar to the much-used regular solution for nonideal systems.
The synthesis and solution properties of polyglycerol alkyl ether(R12Gn) are described. The phase behavior, surface tension, cloud point and HLB value of polyglycerol dodecyl ether in aqueous solution and in mixed solution of surfactant /water /oil have been investigated and compared with values of polyoxyethylene dodecyl ether. The surface tension showed that R12Gn have sufficiently low values of surface tension and cmc to serve as useful polyoxyethylene alkyl ether. The mesophases appearing in the R12Gn systems were more stable in a high temperature range than the mesophases of polyoxyethylene alkyl ether systems. The cloud point and HLB data indicated that addition of one glycerol group was equivalent to the addition of three oxyethylene group units, as far as the hydrophilic property was concerned. The phase diagrams of the polyglycerol alkyl ether /dodecane /water systems showed that the solubilizing and emulsifying powers of R12Gn were greater than those of polyoxyethylene alkyl ether. It is concluded that the polyglycerol chain can be even more useful as hydrophilic group of nonionic surfactants than the polyoxyethylene chain.
본 연구에서는 인지질-비이온계면활성제의 혼합계면활성제를 이용하여 옥틸도데실미리스테이트를 조성상전이 유화법으로 O/W 타입 나노에멀젼을 제조하였다. 혼합 계면활성제와 오일의 농도 비가 1 : 1 정도의 매우 좁은 영역에서 나노에멀젼이 형성되었다. 비이온계면활성제로만 제조된 나노에멀젼과는 달리 전상점 이후에 수용액상을 첨가함에 따라 에멀젼의 입자 크기가 감소하였다. 제조된 나노에멀젼은 실온에서 한 달 이상 안정하였다. 인지질을 함유하고 저에너지 유화법으로 제조된 나노에멀젼 제형은 화장품의 기재로서 널리 사용될 수 있다.
The environmental behaviors of polycyclic aromatic hydrocarbons (PAHs) are mainly governed by their solubility and partitioning properties on soil media in a subsurface system. In surfactant-enhanced remediation (SER) systems, surfactant plays a critical role in remediation. In this study, sorptive behaviors and partitioning of naphthalene in soils in the presence of surfactants were investigated. Silica and kaolin with low organic carbon contents and a natural soil with relatively higher organic carbon content were used as model sorbents. A nonionic surfactant, Triton X-100, was used to enhance dissolution of naphthalene. Sorption kinetics of naphthalene onto silica, kaolin and natural soil were investigated and analyzed using several kinetic models. The two compartment first-order kinetic model (TCFOKM) was fitted better than the other models. From the results of TCFOKM, the fast sorption coefficient of naphthalene (k1) was in the order of silica > kaolin > natural soil, whereas the slow sorbing fraction (k2) was in the reverse order. Sorption isotherms of naphthalene were linear with organic carbon content (foc) in soils, while those of Triton X-100 were nonlinear and correlated with CEC and BET surface area. Sorption of Triton X-100 was higher than that of naphthalene in all soils. The effectiveness of a SER system depends on the distribution coefficient (KD) of naphthalene between mobile and immobile phases. In surfactant-sorbed soils, naphthalene was adsorbed onto the soil surface and also partitioned onto the sorbed surfactant. The partition coefficient (KD) of naphthalene increased with surfactant concentration. However, the KD decreased as the surfactant concentration increased above CMC in all soils. This indicates that naphthalene was partitioned competitively onto both sorbed surfactants (immobile phase) and micelles (mobile phase). For the mineral soils such as silica and kaolin, naphthalene removal by mobile phase would be better than that by immobile phase because the distribution of naphthalene onto the micelles (Kmic) increased with the nonionic surfactant concentration (Triton X-100). For the natural soil with relatively higher organic carbon content, however, the naphthalene removal by immobile phase would be better than that by mobile phase, because a high amount of Triton X-100 could be sorbed onto the natural soil and the sorbed surfactant also could sorb the relatively higher amount of naphthalene.
Ultrasound and Surfactant aided soil washing process has been shown to be an effective method to remove diesel from soils. The use of surfactants can improve the mobility of diesel in soil-water systems by increasing solubility of adsorbed diesel into surfactant micelles. However, a large amount of surfactant is required for treatment. In addition, synthetic surfactants, specially anionic, are more toxic and the surfactant wastewater is hard to treat by conventional wastewater treatments even by AOPs. Ultrasound improves desorption of the diesel adsorbed on to soil. The mechanisms are based on physical breakage of bonds by hot spot, directly impact onto soil particle surface, the fragmentation of long-chain hydrocarbons by micro-jet and microstreaming in the soil pores. The use of ultrasound as an enhancement method in both anionic and nonionic surfactant aided soil-washing processes were studied. And all experiments were examined proceeded under CMC surfactant concentration, frequency 35 khz, power 400 W, Soil-water ratio 1:3(wt%), particle size 0.24 ~ 2mm and initial diesel concentration. 20,000 mg/kg. Combination with ultrasound showed significant enhancements on all the processes. Especially, nonionic surfactant Triton-X100 with ultrasound showed remarkable enhancements and diesel removal rate enhanced by ultrasound helps desorpting of surfactant adsorbed onto soils which prevented decreasing surfactant activity.
The adsorption of the anionic surfactants, sodium lauryl sulfate (SLS) and sodium dodecylbenzene sulfonate (SDBS) anion surfactants from aqueous solutions with nonionic resins, Amberlite XAD-2, XAD-4 and XAD-7 at temperatures in 15∼45℃ range was studied. Several adsorption isotherm models were used to fit the experimental data. The best results were obtained with the Redlich-Peterson equation and the Freundlich model provided remarkably good fits. For a particular resin at a particular temperature, SDBS was more extensively adsorbed than SLS. The highest adsorption were obtained with XAD-4 resin and the specific surface area of the resins plays a major role in adsorption of the surfactants. Estimations of the isosteric heat of adsorption were indicative of an exothermic process, and their magnitudes manifested a physisorption process.
On the basis of the principle of Bratch`s electronegativity equalization, we calculated group partial charges and group electronegativities for nonionic surfactants with Pauling`s electronegativity parameters by using numerical calculation method. From calculated output, we have investigated structural stability of micelle, characteristics of hydrophilic and hydrophobic groups, and relation between CMC(Critical Micelle Concentraion) and group partial charge and group electronegativity of hydrophilic and hydrophobic groups for nonionic surfactants. We have known that CMC by micelle formation depends upon group partial charge and group electronegativity of hydrophilic and hydrophobic groups for surfactants. Also, the structural stability of micelle in H_2O solution is related to the electric double layer by the hydrophilic group of nonionic surfactants with H atoms in water. CMC is diminished by the decrease of repeating units in hydrophilic group at constant hydrophobic group and is diminished by the increments of alkyl chains in hydrophobic group at constant hydrophilic group for nonionic surfactants. In conclusion, CMC is diminished because there is no electrostatic repulsion and is diminished of Debye length by the increments of partial charge of hydrophobic group.