Design and optimization of a new self-nanoemulsifying drug delivery system

To improve the dissolution rate of ibuprofen, a model poorly water soluble drug, self-nanoemulsifying drug delivery systems (SNEDDS) were developed. Various surfactants and oils were screened as candidates for SNEDDS on the basis of droplet size of the resulting emulsions. The influence of the constituent structure, concentration and the composition of SNEDDS formulations, and the emulsifier HLB value, on the properties of the resulting emulsions was systematically investigated. Several SNEDDS formulations were employed to study the relationship between the emulsion droplet size and the dissolution rate of ibuprofen. The dissolution rate was accelerated by decreasing the nanoemulsion droplet size, and was significantly faster than that from a conventional tablet. The optimal SNEDDS formulation had a mean nanoemulsion droplet diameters of 58 nm in phosphate buffer, pH 6.8 (simulated intestinal fluid), and released ibuprofen more than 95% within 30 min. Therefore, these novel SNEDDS carriers appear to be useful for controlling the release rate of poorly water soluble drugs.     

Formation of water-in-oil (W/O) nano-emulsions in a water/mixed non-ionic surfactant/oil systems prepared by a low-energy emulsification method

W/O nano-emulsion formation by a low-energy emulsification method is described for the first time. The nano-emulsions have been formed in water/mixed Cremophor EL:Cremophor WO7 surfactant/isopropyl myristate systems at Cremophor EL:Cremophor WO7 ratios between 1:2 and 1:9, by slow addition of isopropyl myristate to surfactant/water mixtures. Phase behaviour studies have showed that the compositions giving rise to W/O nano-emulsions belong to multiphase regions, one of the phases being a lamellar liquid crystalline phase. The droplet size of the nano-emulsions at a fixed oil concentration of 85% and mixed surfactants/water ratio of 70/30 ranged from 60 to 160 nm as Cremophor EL:Cremophor WO7 ratio increased from 1:8 to 1:2. These nano-emulsions showed high kinetic stability. No phase separation was observed during 5 months in nano-emulsions of the water/Cremophor EL:Cremophor WO7 1:8/isopropyl myristate system with 85% oil concentration, although droplet size experienced an increase with time.     

Branched non-ionic oligo-oxyethylene V-amphiphiles effect of molecular geometry on LC-phase behavior 2

A homologous series of double-chain non-ionic surfactants with the general formula (C_n)₂ GE_mM, where C_n denotes an alkyl chain, G a triglyceryl, and E_mM an oligo-oxyethylene mono-methyl ether are synthesized withn=6–8 andm=6, 8, 10. The branched hydrophobic part of the surfactants introduces a large cross-section of the lipophilic surfactant moiety that is directly reflected in the shape of the micelles and the LC phase behavior in aqueous solution. The phase behavior of these V-amphiphiles is investigated with polarizing microscopy and x-ray diffraction and reveals that the branched lipophilic part strongly stabilizes the lamellar mesophase. This is in agreement with established packing models.     

茶叶中多种有机磷农药残留量测定不确定度的评定

利用实验室内部方法《茶叶中多种有机磷农药残留量检验方法》测定茶叶中甲胺磷、乐果和三唑磷的质量分数，从而评定其不确定度。     

非离子表面活性剂Tween-20胶束体系流体室温燐光法测定色氨酸

提出了一种以非离子表面活性剂Tween 2 0为胶束介质、I-作重原子微扰剂、Na2 SO3 为除氧剂的胶束增稳室温光测定色氨酸的方法。详细研究了各种实验条件的影响。线性范围 8.0× 1 0 -8～ 8.0× 1 0 -6mol L ,检出限达 1 .4×1 0 -9mol L。直接用于大米、花生、大豆及竹笋中色氨酸的测定 ,相对标准偏差2 4%～ 3.3% ,与荧光法比较 ,相对误差 - 3.1 %～ 4.2 %。     

Flame atomic absorption determination of manganese(II) in natural water after cloud point extraction

The possibility to use 4-(2-pyridylazo)resorcinol (PAR) and 1-(2-pyridylazo)-2-naphthol (PAN) for manganese(II) concentrating by the micellar extraction at cloud point (CP) temperature and subsequent atomic absorption spectrometry (AAS) determination was investigated. Under the optimum conditions, preconcentration of 100 ml of water sample in the presence of 1% non-ionic surfactant (NS) OP-7, 1×10⁻⁴ M 1-(2-pyridylazo)-2-naphthol permitted the detection 5 μg l⁻¹ manganese. The proposed method has been applied to the AAS determination of manganese in water samples after cloud point extraction.     

Small angle X-ray scattering from lamellar phase for β-3,7-dimethyloctylglucoside/water system: comparison with β-n-alkylglucosides

Small angle X-ray scattering (SAXS) is measured for the lamellar phase in aqueous systems of 1-o-β-3,7-dimethyoctyl-D-glucopyranoside (β-Glc(Ger)), which has recently been prepared by us, 1-o-β-decyl-D-glucopyranoside (β-GlcC₁₀), and 1-o-β-octyl-D-glucopyranoside (β-GlcC₈). The repeat distance d obtained from the position of the diffraction peak does not follow the swelling law d = 2δ_hc/_hc, where δ_hc and _hc are the thickness and the volume fraction of the hydrophobic layer, respectively. This may result from the fact that δ_hc increases and, equivalently, the surface area per surfactant molecule (a_s) decreases with increasing concentration. So we calculate δ_hc and a_s from the observed d value at each concentration using the above swelling law. The half-thickness δ_hc increases in the order β-GlcC₈ < β-Glc(Ger) < β-GlcC₁₀ at a fixed concentration. On the other hand, the data on a_s for β-GlcC₁₀ and β-GlcC₈ lie on the same line and the data for β-Glc(Ger) lies above this line. These results suggest that the cross-sectional area of the geranyl chain is larger than that of the glucose headgroup. Existence of water filled defects in bilayer sheets is also discussed based on the SAXS pattern and the concentration dependence of d.     

Effect of β-cyclodextrin on the aggregation of the non-ionic surfactant Igepal CO-630 in water as studied by 1D and 2D NMR spectroscopy

The micellization process of the non-ionic surfactant, Igepal CO-630, and its inclusion complexes with β-cyclodextrin (β-CD) have been investigated by NMR spectroscopy. The critical micelle concentration of Igepal was determined by measuring the chemical shifts of different resonances. The structure and binding of the inclusion complexes between the Igepal and the β-CD have been studied by 1D proton NMR and ROESY experiments. The stoichiometry of the inclusion complex is mainly 1:1, with a slight contribution of 2:1. At high concentrations of surfactant, the plots of the chemical shifts in the absence and presence of β-CD coalesce, which indicates that the complexes do not take part into the micelles. The ROESY spectrum displays strong correlations between the internal cavity protons of the CD and the aromatic and aliphatic regions of the Igepal, suggesting the formation of a 2:1 primary face-to-face inclusion complex at high concentrations of β-CD.     

Synthesis of new 4,6-diaryl-2-(arylthio)nicotinonitriles in Triton X-100 aqueous micellar media

In this communication,we report four component condensations of acetophenone,arylaldehydes,arylthiol,and malononitrile in the presence of Triton X-100（5 mol%） aqueous micelles.This reaction led to the formation of 4,6-diaryl-2-（arylthio）nicotinonitrile new derivatives in good yields.The FT-IR,¹⁹F NMR,¹H NMR,¹³C NMR spectra and elemental analysis confirm the structure of compounds.     

超高效液相色谱-串联质谱测定多种食品中抑霉唑、嘧霉胺、克百威、三唑磷、多菌灵的残留量

建立了超高效液相色谱-串联质谱法同时测定苦瓜、木瓜、菠萝、绿茶饮料等4种食品基体中抑霉唑、嘧霉胺、克百威、三唑磷、多菌灵的方法,对提取条件、净化条件、流动相、质谱条件进行了研究.待测样品直接用含1%冰乙酸的乙腈提取,乙二胺-N-丙基硅烷(PSA)吸附剂除杂,采用电喷雾离子源(ESI)、多反应监测正离子模式扫描,外标法定...     

环境因素对正负表面活性剂体系相行为的影响

在1:1正负离子表面活性剂混合体系(十二烷基硫酸钠/辛基三甲基溴化铵 SDS-C8NM3Br; 十二烷基硫酸钠/十二烷基三甲基溴化铵,SDS-C12NM3Br)中加入短链脂肪醇 (乙醇,正丙醇,正丁醇),正负离子表面活性剂沉淀溶解,出现表面活性剂双水相.上相有液晶存在,下相有囊泡自发形成.折光率数据和电镜结果表明:上相为表面活性剂富集相,下相表面活性剂浓度较低.混合体系中,出现表面活性剂双水相所需短链脂肪醇的体积百分数,随短链脂肪醇的链长增加而降低.温度升高,出现表面活性剂双水相所需短链脂肪醇的体积百分数降低.对SDS/C8NM3Br/H2O体系的研究结果表明:超声处理,可使混合体系中沉淀向囊泡转化,与短链脂肪醇的加入后的作用类似.     

Physicochemical investigations of anionic–nonionic mixed surfactant microemulsions in nonaqueous polar solvents: I. Phase behavior

Phase behaviors of AOT/heptane (Hp)/formamide (FA), ethylene glycol (EG), propylene glycol (PG), triethylene glycol (TEG) and glycerol (GLY) have been investigated in the absence and presence of a nonionic surfactant, polyoxyethylene(2) cetyl ether (Brij-52) at 303 K. The phase characteristics of (AOT+Brij-52)/Hp/(EG or PG or TEG) have been found to be different from that of AOT/Hp/FA systems in respect of both the area of monophasic domain and the appearance of other mesophases. The area of monophasic domain of (AOT+Brij-52)/Hp/EG depends on the content of Brij-52 (X _Brij-52) and shows a maximum at X _Brij-52=0.4. A negligible effect on the area of the monophasic domain has been shown by more hydrophobic surfactants, polyoxyethylene(2) stearyl ether (Brij-72) and polyoxyethylene(2) oleyl ether (Brij-92). The effect of oils (dodecane and hexadecane) on the mixed systems stabilized by (AOT+Brij-52) in EG has been investigated. The area of monophasic domain has been found to be dependent on the type of nonaqueous solvents and follows the order GLY>EG>PG>TG. A systematic investigation on the measurement of phase volumes of mixed surfactant systems [AOT+nonionic surfactant(s)] stabilized in oils of different chain lengths (heptane, dodecane and hexadecane) and polar solvent (EG) has been carried out at different compositions of the ingredients to identify the phase transitions of these systems as a function of X _Brij-52. The threshold point of phase transition (both W I→W IV and W IV→W II transitions) has been found to be a function of the configuration of added nonionic surfactant, nature of the polar solvent and oil. The conversion of the initial oil/EG droplets into EG/oil droplets with increasing X _nonionic has been facilitated for hydrophobic surfactants polyoxyethylene(4) lauryl ether (Brij-30), Brij-52, and Brij-72 in comparison to the hydrophilic surfactants polyoxyethylene(10) cetyl ether (Brij-56) and polyoxyethylene(20) cetyl ether (Brij-58).     

pH-Dependent Aggregation Behavior and Emulsion Stability of Comb-Like Surfactant Containing PEO Grafts

The aggregation behavior of the comb-like surfactant, poly(styrene-co-maleic anhydride)-g-(poly(ethylene glycol) monomethyl ether) (SMA-M), prepared via the one-pot method, at surface and in solution, was investigated by equilibrium surface tension, rheological technology, and transmission electron microscopy (TEM). The emulsion prepared from n-decane/water/C₁₃E₇ was used as a model system to determine the influence of SMA-M on the stability of the emulsion. The equilibrium surface tensions of SMA-M solution with various pH were measured. The adsorption data, that is, the saturation surface excess concentration (Γ_max) and the minimum area (A _min) were evaluated using the average monomeric molecular weight (M _nA ). The results showed that Γ_max decreased with the increase of pH, but the A _min enlarged with the increase of pH. The results of the steady-state shear experiment indicated that the aggregate structure of the as-prepared comb-like surfactant SMA-M in aqueous solution evolved from interlinked micelle-like aggregates to isolated inflated micelle-like aggregates, then to rod-like aggregates with the increasing pH, which were confirmed by the TEM images. The investigation of the stabilization of n-decane/water/C₁₃E₇/SMA-M emulsion system indicated that SMA-M obviously slows down the phase separation, and the most effectively stabilized sample was obtained at pH 5.0. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Dispersion Science and Technology to view the free supplemental file.     

Determination of Prometryne in water and soil by HPLC-UV using cloud-point extraction

A CPE-HPLC (UV) method has been developed for the determination of Prometryne. In this method, non-ionic surfactant Triton X-114 was first used to extract and pre-concentrate Prometryne from water and soil samples. The separation and determination of Prometryne were then carried out in an HPLC-UV system with isocratic elution using a detector set at 254 nm wavelength. The parameters and variables that affected the extraction were also investigated and the optimal conditions were found to be 0.5% of Triton X-114 (w/v), 3% of NaCl (w/v) and heat-assisted at 50 °C for 30 min. Using these conditions, the recovery rates of Prometryne ranged from 92.84% to 99.23% in water and 85.48% to 93.67% in soil, respectively, with all the relative standard deviations less than 3.05%. Limit of detection (LOD) and limit of quantification (LOQ) were 3.5 μg L⁻¹ and 11.0 μg L⁻¹ in water and 4.0 μg kg⁻¹ and 13.0 μg kg⁻¹ in soil, respectively. Thus, we developed a method that has proven to be an efficient, green, rapid and inexpensive approach for extraction and determination of Prometryne from soil samples.     

Determination of estrogens in water by HPLC-UV using cloud point extraction

A method based on cloud point extraction was developed to determine four kinds of estrogens: estriol (E3), estradiol (E2), estrone (E1), and progesterone (P) in water by high performance liquid chromatography separation and ultraviolet detection (HPLC-UV). The non-ionic surfactant Triton X-114 was chosen as extractant solvent. The parameters affecting extraction efficiency, such as concentrations of Triton X-114 and Na₂SO₄, equilibration temperature, equilibration time and centrifugation time were evaluated and optimized. Under the optimum conditions, preconcentration factors of 99 for E3, 73 for E2, 152 for E1 and 86 for P were obtained for 10 mL water sample. The detection of limitation was 0.23 ng mL⁻¹ for E3, 0.32 ng mL⁻¹ for E2, 0.25 ng mL⁻¹ for E1 and 5.0 ng mL⁻¹ for P. The proposed method was successfully applied to the determination of trace amount of estrogens in wastewater treatment plant (WWTP) effluent water and exposure water with 10 ng mL⁻¹ E2 for toxicological study in our lab. For the case of WWTP effluent water samples, no estrogen was found. The accuracy of the proposed method was tested by recovery measurements of spiked samples and good recoveries of 81.2-99.5% were obtained.     

聚乙烯吡咯啉酮对稀土变色酸双偶氮类试剂显色反应的褪色作用

研究了非离子型表面活性剂聚乙烯吡咯啉酮（ＰＶＰ）、（ＮＨ４）２ＳＯ４对ＲＥ（Ⅲ）、Ｆｅ（Ⅲ）、Ｚｒ（Ⅳ）、Ｔｈ（Ⅳ）、Ｃｕ（Ⅱ）等离子与变色酸双偶氮类试剂显色反应的影响。建立了大量稀土存在下测定微量Ｆｅ（Ⅲ）的新方法。纯稀土中Ｆｅ（Ⅲ）的测定，回收率在９８．０％～１０１．０％；对矿样测定，６次测定ＲＳＤ为１．７９％。     

Phase behavior of binary system of bromobenzene–chlorobenzene confined in SBA-15 and MCM-41

Phase behavior of binary system of bromobenzene-chlorobenzene（C6H₅Br-C₆H₅Cl） confined in SBA-15 and MCM-41（pore diameter 8 nm,3.8 nm,respectively） has been investigated by means of differential scanning calorimetry（DSC）.Phase diagram of C₆H₅Br-C₆H₅Cl system confined in SBA-15 is a type of the complete miscible both in liquid and solid state,the same phase behavior as the bulk system.However,the phase diagram comprises only one boundary line,which is shifted down 22-36 K with respect to the bulk system.C₆H₅Br,C₆H₅Cl or the mixture within nanopores of MCM-41 is nonfreezing.The different phase behavior of the system confined in SBA-15 and MCM-41 is thought mainly due to the relative size of pore to molecule.     

Phase behavior, interfacial composition and thermodynamic properties of mixed surfactant (CTAB and Brij-58) derived w/o microemulsions with 1-butanol and 1-pentanol as cosurfactants and n-heptane and n-decane as oils

Phase diagrams of pseudo-quaternary systems of cetyltrimethylammonium bromide (CTAB)/polyoxyethylene(20)cetyl ether (Brij-58)/water/1-butanol (or 1-pentanol)/n-heptane (or n-decane) at fixed omega (=[water]/[surfactant]) of 55.6 were constructed at different temperatures (293, 303, 313, and 323 K) and different mole fraction compositions of Brij-58 (X(Brij-58)=0, 0.5, and 1.0 in CTAB + Brij-58 mixture). Pure CTAB stabilized systems produced larger single-phase domains than pure Brij-58 stabilized systems. Increasing temperature increased the single-phase domain in the Brij-58 stabilized systems, whereas the domain decreased in the CTAB stabilized systems. For mixed surfactant systems (with X(Brij)=0.5) negligible influence of temperature in the studied range of 293 to 323 K on the phase behavior was observed. Interfacial compositions of the mixed microemulsion systems at different temperature and different compositions were evaluated by the dilution method. The n(a)(i) (number of moles of alcohol at the interface) and n(a)(o) (number of moles of alcohol in the oil phase) determined from dilution experiments were found to decrease and increase respectively for CTAB stabilized systems, whereas an opposite trend was witnessed for Brij-58 stabilized systems. The energetics of transfer of cosurfactants from oil to the interface were found to be exothermic and endothermic for CTAB and Brij-58 stabilized systems, respectively. At equimolar composition of CTAB and Brij-58, the phase diagrams were temperature insensitive, so that the enthalpy of the aforesaid transfer process was zero.     

原子吸收光谱法测定水中微量PEO非离子型表面活性剂的研究

叙述了原子吸收光谱法间接测定水中微量非离子型表面活性剂的分析原理、条件和方法。该法主要是根据聚氧乙烯（ＰＥＯ）型表面活性剂能与钡盐和磷钼酸铵定量生成络盐沉淀，且络盐中Ｍｏ与ＰＥＯ有较大的摩尔比，因而在试样的萃取液中沉淀表面活性剂，然后通过原子吸收光谱法测定沉淀中Ｍｏ的含量，能间接测定表面活性剂含量。回收实验表明，该法灵敏度、选择性和重现性均较好，适宜测定水中微量非离子型表面活性剂。     

Solubilization of oil in a mixed cationic liquid crystal

The mixing fraction of didodecyldimethylammonium bromide (DDAB) in dodecyltrimethylammonium bromide + DDAB to produce a lamellar liquid crystal (L _α) abruptly decreases upon addition of a small amount of m-xylene, whereas the mixing fraction becomes constant at high m-xylene content. Similar results were obtained in saturated hydrocarbon systems. It is considered that oil molecules in the surfactant palisade layer increases the effective cross-sectional area per surfactant head group, a_s, whereas a_s is constant if the oil molecules are solubilized in the core of the liquid crystal. The volume fraction of penetrating oil in the total solubilized oil is defined as a penetration parameter, Pe, which is calculated from small-angle X-ray scattering data. Pe is high in the m-xylene system, whereas it is low in the n-decane system. Even in the same oil system, Pe decreases dramatically with increasing solubilization. Hence, most of the oil added penetrates into a palisade layer at an early stage of oil addition. This causes a change in the mixing fraction of surfactant in the L _α phase. Thereafter the oil is solubilized in the core of the bilayer with further addition of oil. Received: 20 April 1998 Accepted: 16 July 1998