An investigation of the dissolution of acetylsalicylic acid in supercritical carbon dioxide

The dissolution of acetylsalicylic acid in supercritical carbon dioxide (SC–CO₂) is investigated using Fourier transform IR spectroscopy. Temporal dependences of integrated intensities of the absorption band of acetylsalicylic acid (ASA) near 1199 cm^–1 are measured for various ASA charges placed into a cuvette. Molar fractions of ASA in the saturated solution in SC–CO₂ are determined at a temperature of 40°C and pressures of 10.0 and 15.0 MPa, and the components are 2.10 ± 0.25 × 10^–4 and 11.0 ± 1.5 × 10^–4, respectively.     

Simultaneous Determination of Acetylsalicylic Acid and Caffeine in Pharmaceutical Formulation by First Derivative Synchronous Fluorimetric Method

A sensitive, rapid, and specific assay has been developed for the simultaneous determination of acetylsalicylic acid and caffeine in commercial tablets based on their natural fluorescence. The mixture of these drugs was resolved by first derivative synchronous fluorimetric technique using two scans. At Δλ=106 nm, using first derivative synchronous scanning, only acetylsalicylic acid yields a detectable signal at 316 nm (peak to zero method) which is unaffected by caffeine. At Δλ=30 nm, the signal of caffeine at 288 nm (peak to zero method) is not affected by acetylsalicylic acid. The range of application is between 0.021 and 41.62 μg ml⁻¹ (correlation coefficient, R=0.9995) for acetylsalicylic acid and between 0.4486 and 44.86 μg ml⁻¹ (correlation coefficient, R=0.99786) for caffeine. The recovery range of 98.40–102% for acetylsalicylic acid and 90–100.5% for caffeine from their synthetic mixture was reported. Overall recovery of both compounds about 97–99% for acetylsalicylic acid and 97–98% for caffeine was obtained from real sample analysis. The detection limits are 0.0013 μg ml⁻¹ and 0.0306 μg ml⁻¹ for acetylsalicylic acid and caffeine, respectively. The relative standard deviation (n=10) for 20 μg ml⁻¹ of acetylsalicylic acid is 2.75% and for 2.2 μg ml⁻¹of caffeine is 1.7%.     

Determination of three analgesics in pharmaceutical and urine sample on nano poly (3, 4-ethylenedioxythiophene) modified electrode

Three analgesics, acetaminophen, acetylsalicylic acid, and dipyrone were determined by stripping voltammetry using nanosized poly(3,4-ethylenedioxythiophene)-modified glassy carbon electrode . The cyclic voltammetric behavior of the three analgesics was studied in aqueous acid, neutral, and alkaline conditions. One well-defined oxidation peak each for acetaminophen and acetylsalicylic acid and three oxidation peaks for dipyrone were observed in the cyclic voltammograms. The influence of pH, scan rate, and concentration revealed irreversible diffusion controlled reaction. A systematic study of the experimental parameters that affect the differential pulse stripping voltammetric response was carried out. Calibration was made under maximum peak current conditions. The scanning electron microscope analysis confirmed good accumulation of the drugs on the electrode surface. The range of study for both acetaminophen, acetylsalicylic acid were 0.015–0.4 and dipyrone was 0.025–0.4 μg/ml. The lower limit of determination for both acetaminophen, acetylsalicylic acid was 0.01 μg/mL and for dipyrone was 0.02 μg/mL. The suitability of the method for the determination of the three analgesics in pharmaceutical preparations and urine samples was also ascertained.     

Electrogenerated chemiluminescence quenching of Ru(bpy)3 2+ (bpy=2,2′-bipyridine) in the presence of acetaminophen,salicylic acid and their metabolites

Quenching of Ru(bpy) ₃²⁺ (bpy=2,2′-bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV–vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the ^?Ru(bpy)₃²⁺ excited state or (ii) highly energetic coreactant radicals.     

双波长比值光谱法测定复方乙酰水杨酸片中三组分含量

应用双波长比值光谱法测定了复方乙酰水杨酸片中三组分的含量。依据复方乙酰水杨酸片中三组分的比值光谱特征, 选择213,227,245和265 nm作为测定三个组分的波长。结果显示乙酰水杨酸在5～20 μg·mL-1, 非那西丁在2～10 μg·mL-1, 咖啡因在2～20 μg·mL-1浓度范围内线性关系良好,平均回收率分别为100.03%,100.23%和99.96%。样品测定结果与部颁标准方法一致(P＞0.05)。本法具有测定波长少、计算简单、光谱“分离”能力强以及能在低档分光光度计上实现, 易于推广等特点。     

The effect of acids on fluorescence of coumarin-6 in organic solvents

The effect of acids (HCl, HClO₄, HNO₃, and CH₃COOH) on the fluorescence of coumarin-6 in organic solvents (acetonitrile, acetone, butanol-1, and ethanol) is studied. The regions of acid (HCl, HClO₄, HNO₃) concentrations that lead to a change in the fluorescence spectra are determined for each of the solvents. It is shown that, for all the solvents studied, acetic acid with a concentration within the region 10^?1–10^?6 M causes no significant changes in the fluorescence spectrum of coumarin-6. A mechanism of the coumarin-6 protonation is proposed.     

荧光光谱法研究乙酰水杨酸和牛血清蛋白的相互作用

应用荧光光谱法研究了乙酰水杨酸和牛血清蛋白(BSA)分子间的相互作用。研究表明乙酰水杨酸可猝灭BSA的荧光,同时自身的荧光增强并存在一个等发射点,表明两者之间形成稳定的复合物并发生能量转移。乙酰水杨酸和BSA分子间的结合常数为1.35×103,结合数0.87,静电引力是结合反应的主要的作用力。同时观察了乙酰水杨酸的加入对BSA构象的影响。     

13C NMR of tunnelling methyl groups

The dipolar interactions between the protons and the central ¹³C nucleus of a ¹³CH₃ group are used to study rotational tunnelling and incoherent dynamics of such groups in molecular solids. Single-crystal ¹³C NMR spectra are derived for arbitrary values of the tunnel frequency ν_t. Similarities to ESR and ²H NMR are pointed out. The method is applied to three different materials. In the hydroquinone/acetonitrile clathrate, the unique features in the ¹³C NMR spectra which arise from tunnelling with a tunnel frequency that is much larger than the dipolar coupling between the methyl protons and the ¹³C nucleus are demonstrated, and the effects of incoherent dynamics are studied. The broadening of the ¹³C resonances is related to the width of the quasi-elastic line in neutron scattering. Selective magnetization transfer experiments for studying slow incoherent dynamics are proposed. For the strongly hindered methyl groups of L-alanine, an upper limit for ν_t is derived from the ¹³C NMR spectrum. In aspirin? (acetylsalicylic acid), incoherent reorientations dominate the spectra down to the lowest temperatures studied; their rate apparently increases with decreasing temperature below 25 K.     

复方乙酰水杨酸片中有效成分的DOSY技术分析

复方乙酰水杨酸片是临床常用的解热镇痛消炎药物,目前其有效成分的分析方法存在操作繁琐而分析速度慢等不足.该文利用二甲基硅油(PDMS)辅助的扩散排序(DOSY)技术以及扩散排序-同核相关(DOSY-COSY)联用技术,成功地对复方乙酰水杨酸片中三种有效成分的分子结构进行了快速定性分析,并且利用核磁共振氢谱(~1H NMR)技术进行了相对定量分析.该方法具有方便、快捷等特点,可作为借鉴和参考用于药物的质量评价.     

The influence of the structural characteristics of the substrate and the medium on the stability of triflusal and acetylsalicylic acid in micellar systems

A spectrophotometric study of the alkaline hydrolysis of two salicylic acid (SA) derived drugs, performed on acetylsalicylic acid (ASA) and triflusal, both in the absence and presence of cationic micelles. In the absence of micelles, a catalytic effect is produced by the favoured OH⁻ ion in the molecule of triflusal, due to the presence of the trifluoromethyl group. The surfactants used were: hexadecyltrimethylammonium hydroxide (HDTAOH), hexadecyltrimethylammonium chloride (HDTACl), hexadecyltrimethylammonium bromide (HDTABr), hexadecylethyldimethylammonium bromide (HDEDABr) and tetradecyltrimethylammonium bromide (TDTABr). In micelles with reactive counterions, the pseudo-first-order rate constant (k_obs) increases with the increase in surfactant concentration, while in micelles with non-reactive counterions, the rate constant increased with surfactant concentration at low concentration, reaching a maximum, and decreased at high surfactant concentration, even to below the value found in the absence of micelle. The micellar binding constant of both drugs (K_S), the micellar rate constant (k_M) and the ion-exchange constant (K_X^OH) were determined according to variation in k_obs in relation to surfactant concentration, through the application of the pseudophase ion-exchange model (PPIE) proposed. The empirical parameters obtained were found to depend on the substrate and the surfactant structure, these parameters were: the counterion of the micelle, the size of the headgroup and the chain length of the hydrophobic tail of the surfactant.     

The study on the interaction between Tb(III) and ligand in Tb–acetylsalicylic acid complex and fluorescence mechanism

In this paper, a luminescent complex of terbium–acetylsalicylic acid (Tb-ASA) was studied for the first time using combination of the quantum chemical calculation, fluorescence spectroscopic method and X-ray photoelectron spectroscopy (XPS). The results from the quantum chemical calculation indicated that it is possible for the energy-transfer from ASA to Tb (III); Fluorescence spectroscopy demonstrated that there is an intramolecular energy-transfer from ASA to Tb with the efficiency (III) of about 87.9% under an excitation at 308 nm. The XPS indicated that the coordinate covalent bond between Tb and O existed in the complex of Tb-ASA leads to the effective energy transfer from ASA to Tb (III) because the energy transfer rate may be improved with reducing the distance between the ligand and Tb (III). The results will have important values for the studies of this type of complexes.     

Polyurea Dendrimer‐Perylene Self‐Imprinted Nanoshells for Trace Explosive Detection

Polyurea dendrimer‐perylene nanoshells are found to accurately discriminate structurally closely related nitroaromatics. Both studied systems, PURE_G1‐PER₆ and PURE_G4‐PER₄₈ , present high sensitivity (detection limits between 5 × 10^?6 and 20 × 10^?6m ) and selectivity for 2,4,6‐trinitrotoluene (TNT) collected from a powdered military grenade and picric acid. The selectivity is highly dependent on the dendrimer generation. A conformationally restricted 3D arrangement in PURE_G4‐PER₄₈ , which is favored by shell π‐π stacking and core urea‐assisted hydrogen bonding, supports the formation of self‐imprinted channels with molecular recognition for picric acid and TNT in complex mixtures of nitroaromatics.     

热解法制备KY3F10: Yb, RE(RE=Er, Ho, Tm)纳米晶及其特性研究

有机染料和量子点等荧光标记材料存在发射光谱宽、 光热稳定性差和细胞毒性等缺陷, 限制了其在生物学研究中的应用. 镧系掺杂上转换发光材料不存在"自发荧光"和"光漂白"现象, 灵敏度高, 长期稳定性好, 利于活体检测. 论文首次采用热解法, 以油酸和十八烯为表面活性剂和溶剂, 制备了KY₃F₁₀: Yb, RE(RE=Er, Ho, Tm) 纳米晶. 研究了油酸含量对产物形貌和粒径尺寸的影响, 当油酸与十八烯的比例为3:1时, 为制备类球形单分散纳米晶体的最佳工艺条件, 在980 nm半导体激光器激发下, 样品KY₃F₁₀: Yb, RE(RE=Er, Ho, Tm) 分别发射出较强的黄绿、 绿色和蓝色光, 这些结果显示KY₃F₁₀: Yb, RE(RE=Er, Ho, Tm) 纳米粒子作为生物探针在多重荧光标记方面具有优异的特性.     

克里奇中间体CH2OO与CF3CF=CF2反应的动力学研究

本文使用OH激光诱导荧光方法研究了结构最简单的克里奇中间体CH₂OO和CF₃CF=CF₂的反应动力学. 在压强为10 Torr条件下,测量了温度在283,298,308和318 K的反应速率常数,分别为(1.45±0.14)×10^-13,(1.18±0.11)×10^-13,(1.11±0.08)×10^-13和(1.04±0.08)×10^-13 cm³·molecule^-1·s^-1. 根据阿伦尼乌斯方程,获得该反应的活化能为(-1.66±0.21) kcal/mol. 在6.3∽70 torr压力范围内,未观察到该反应的速率常数存在压力相关.     

PEG crosslinked poly(vinylbenzene boronic acid) polymer electrolytes for Li-ion batteries

Poly(4-vinylbenzeneboronic acid), PVBBA was synthesized via free-radical polymerization of 4-vinylbenzeneboronic acid (4-VBBA) and followed by crosslinking with polyethylene glycol (PEG) with different molecular weights to produce boron containing crosslinked polymers. Prior to crosslinking, the materials were doped with CF₃SO₃Li at several stoichiometric ratios to get PVBBAPEGX-Y where X is the molecular weight of PEG and Y is the EO/Li ratio. The materials were characterized by using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC). The ionic conductivity of these novel crosslinked electrolytes was studied by dielectric-impedance spectroscopy. Li-ion conductivity of these polymer electrolytes depends on the length of the side units as well as the doping ratio. PVBBAPEG200-10 illustrated a satisfactory ionic conductivity of 3.1 × 10^?5 S/cm at 20 °C and 1.8 × 10^?3 S/cm at 100 °C.     

Thermally induced nonlinear optical response and optical power limiting of acid blue 40 dye

We report the investigations of thermally induced third-order nonlinear optical and optical limiting characterizations for various concentrations of acid blue 40 dye in N,N-Dimethyl Formamide, studied by employing z-scan technique under cw He–Ne laser irradiation at 633 nm wavelength. The samples exhibited nonlinear absorption and nonlinear refraction under the experimental conditions. For lower concentration, the samples display both saturable absorption (SA) and reverse saturable absorption (RSA); whereas with increase in concentration, RSA behaviour prevails. The estimated values of the effective coefficients of nonlinear absorption β_eff, nonlinear refraction n₂ and third-order nonlinear susceptibility χ⁽³⁾ were found to be of the order of 10^?2 cm/W, 10^?4 esu and 10^?6 esu respectively. Multiple diffraction rings were observed when the samples were exposed to laser beam due to refractive index change and thermal lensing. The effect of concentration and the laser intensity on the self-diffraction ring patterns was studied experimentally. The acid blue 40 dye also exhibited strong optical limiting properties under cw excitation and reverse saturable absorption is found to be the dominant nonlinear optical process leading to the observed nonlinear behaviour.     

Adsorption and decomposition of formic acid on the NiO(111)-p(2 × 2) surface: TPD and steady state kinetics studies

The adsorption and decomposition of formic acid on NiO(111)-p(2 × 2) films grown on Ni(111) single crystal surface were studied by temperature-programmed desorption (TPD) spectroscopy. Exposure of formic acid at 163 K resulted in both molecular adsorption and dissociation to formate. The adsorbed formate underwent further dissociation to H₂, CO₂ and CO. H₂ and CO₂ desorbed at the same temperatures of 340, 390 and 520 K, while CO desorbed at 415 and 520 K. The desorption features varied with the formic acid exposure. Two reaction channels were identified for the decomposition of formate under equilibrium with gas-phase formic acid with a pressure of 2.5 × 10⁻⁴Pa, one preferentially producing H₂ and CO₂ with an activation energy of 22 ± 2 kJ mol⁻¹ and the other preferentially producing CO and H₂O with an activation energy of 16 ± 2 kJ mol⁻¹. The order of both reaction paths was 0.5 with respect to the pressure of formic acid.     

Structural and electrical properties of pure and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> doped (PVA)<Subscript>0.7</Subscript>(NaI)<Subscript>0.3</Subscript> solid polymer electrolyte

Solid polymer electrolytes (SPE) based on poly-(vinyl alcohol) (PVA)_0.7 and sodium iodide (NaI)_0.3 complexed with sulfuric acid (SA) at different concentrations were prepared using solution casting technique. The structural properties of these electrolyte films were examined by X-ray diffraction (XRD) studies. The XRD data revealed that sulfuric acid disrupt the semi-crystalline nature of (PVA)_0.7(NaI)_0.3 and convert it into an amorphous phase. The proton conductivity and impedance of the electrolyte were studied with changing sulfuric acid concentration from 0 to 5.1 mol/liter (M). The highest conductivity of (PVA)_0.7(NaI)_0.3 matrix at room temperature was 10⁻⁵ S cm⁻¹ and this increased to 10⁻³ S cm⁻¹ with doping by 5.1 M sulfuric acid. The electrical conductivity (σ) and dielectric permittivity (ε′) of the solid polymer electrolyte in frequency range (500 Hz–1 MHz) and temperature range (300–400) K were carried out. The electrolyte with the highest electrical conductivity was used in the fabrication of a sodium battery with the configuration Na/SPE/MnO₂. The fabricated cells give open circuit voltage of 3.34 V and have an internal resistance of 4.5 kΩ.     

Lasing action of rhodamine B in polyacrylic acid films

 Rhodamine B (Rh-B) has been embedded in PolyAcrylic acid (PAA) films. The materials are studied for the laser action with nitrogen laser excitation. The lasing efficiency of Rh-B/PAA films is comparable to that of rhodamine 6G in methanol. There is a 50% reduction in the laser intensity of the films with 2600 pulses from the N₂ laser (2 Hz). The photostability of these materials is far superior to that of other polymeric materials and is comparable to that of sol–gel materials. Received: 22 May 1996 /Revised version: 10 July 1996     

Optical anisotropy of Langmuir-Blodgett films of long-chain acetylenic acids

The optical anisotropy of Langmuir-Blodgett films, along with its variation in the course of polymerization under UV radiation, is studied by ellipsometry at a fixed wavelength of 632.8 nm for several angles of incidence of light. Films of the Cd and Pb salts of acetylenic acids with internal and terminal triple bonds—HC≡ C(CH₂)₂₁COOH (I) and CH₃(CH₂)₁₈C≡CCOOH (II)—are studied. The refractive indices and thicknesses of the films are determined on the basis of a model of a biaxial anisotropic film. It is found that the films of the Pb salt of acid II are biaxial, while the films of the Cd salt of acid II and of the Cd and Pb salts of acid I have nearly uniaxial anisotropy. The calculated thicknesses of monolayers coincide with the thicknesses determined from small-angle x-ray scattering. The anisotropy of the films is shown to vary under UV irradiation. After polymerization of the films, the anisotropy in the plane of the layer virtually vanishes, while that in the direction perpendicular to the interface is retained.