Contact angle hysteresis in multiphase systems

Contact angle (CA) hysteresis is the difference between the maximum (advancing) and minimum (receding) water CA. Hysteresis is caused by adhesion hysteresis in the solid–water contact area (2D effect) and by pinning of the solid–water–air triple line due to the surface roughness (1D effect). In this work, we show that CA hysteresis is present also in more complex systems, such as an organic liquid (oil) in contact with a solid immersed in water. In order to decouple the 1D and 2D effects, we study CA hysteresis in solid–water–air (droplet), solid–air–water (bubble), solid–water–oil, and solid–water–air–oil systems involving rough and microstructured surfaces. The comparative analysis of these systems allows decoupling the 1D and 2D effects as well as hydrogen bonding and entropic forces (water–air tension) and dispersion forces (oil–air tension).     

Intrinsic viscosities of polymers in mixed solvents

The intrinsic viscosity of a polymer in a solvent mixture is related to the excess free energy of the solvents. Intrinsic viscosities at different temperatures are obtained for poly-2-vinylpyridine–chloroform–ethyl alcohol, poly(methyl methacrylate)–chloroform–ethyl alcohol, polystyrene–cyclohexane–benzene, polystyrene–dioxane–chloroform, and polystyrene–cyclohexane–ethanol. Qualitative, but not quantitative, agreement is found between theory and experiment.     

Seasonal changes in arsenic speciation in Fucus species

Arsenic speciation in a brown alga, Fucus gardneri, collected in Vancouver, B.C., Canada, was carried out by using high-performance liquid chromatography–inductively coupled plasma–mass spectrometry (HPLC–ICP–MS). Hydride generation–atomic absorption spectrometry (HG–AAS) was used for total arsenic determination. The relative amounts of some arsenosugars 1 in growing tips are found to be different in comparison with the remainder of the plant. Fucus samples collected in summer contain 9 ppm of total arsenic. Most of the arsenic species are extractable. Fucus samples collected in winter contain relatively higher amounts of arsenic, 16–22 ppm, but only low amounts of this are extractable. © 1998 John Wiley & Sons, Ltd.     

Thermodynamische Berechnungen zum Wolframtransport in fluorhaltigen Systemen

Thermodynamic Calculations on the Transport of Tungsten in Systems Containing Fluorine Compounds Information on the transport behaviour of tungsten in systems containing fluorine is obtained by a thermodynamic analysis of the systems W_(s)–F, W_(s)–F–O, W_(s)–F–Br, W_(s)–F–Br–O, W_(s)–Si–F, W_(s)–B–F, W_(s)–Si–F–Br, and W_(s)–B–F–Br. The results are compared with experimental findings. The influence of bromine, oxygen, silicon, and boron on the transport of tungsten is investigated. The nonblackening condition (dλ_W/dT < 0) is fulfilled in systems containing fluorine as well as bromine.     

Mineral element content in prized matsutake mushroom (Tricholoma matsutake) collected in China

The contents of Ca, Cu, Fe, K, Mg, Mn, Na, and Zn in fruiting bodies of the highly-prized matsutake mushroom (Tricholoma matsutake) from twelve widely separated sites in Southwest China were determined using AAS. The results for dried mushrooms showed that the mean contents (mg kg^?1) of the determined elements decreased in the following order: K (440–2000), Na (150–740), Ca (90–850), Mg (90–680), Zn (20–180), Fe (13–78), Cu (0.34–45), Mn (0.09–7.6).     

铬天青S–盐酸氯丙嗪–溴化十六烷基三甲铵光度法测定水样中的铁

采用铁(Ⅲ)–铬天青S–盐酸氯丙嗪–溴化十六烷基三甲铵(CTMAB)四元配合物光度法测定水样中铁的含量。在pH 5.50的HAc–NaAc缓冲介质中,在铁(Ⅲ)–铬天青S–盐酸氯丙嗪显色反应中,加入CTMAB,四元配合物的表观摩尔吸光系数为9.85×10~4 L/(mol·cm),是三元配合物灵敏度的两倍。结果表明,配合物在657nm波长处有最大吸收,Fe(Ⅲ)的质量浓度在0~20μg/(25 mL)范围内与吸光度呈良好的线性关系,线性相关系数为0.999 6,方法的检出限为1.84×10~(–3) mg/L。样品加标回收率为97.3%~98.8%,测定结果的相对标准偏差为1.9%~3.2%(n=5)。该方法灵敏度高,精密度与准确度好,便于在实验室推广应用。     

Heavy metals contamination in roadside soil near different traffic signals in Dubai,United Arab Emirates

The present research was conducted to study heavy metal contamination in roadside soil viz. (i) at sites having more than two traffic signals (ii) roads having only one traffic signal and (iii) roads having no traffic signals. The samples were collected and analyzed for seven heavy metals i.e. cadmium (Cd), lead (Pb), copper (Cu), nickel (Ni), iron (Fe), manganese (Mn) and zinc (Zn) by Atomic Absorption Spectroscopy (AAS) following the acid digestion of the respective soil samples. The range of the metals observed in soil having more than two traffic signals were Cd (0.17–1.01), Pb (259.66–2784.45), Cu (15.51–65.90), Ni (13.31–98.13), Fe (325.64–5136.37), Mn (57.95–166.43), and Zn (91.34–166.43) mg kg^?1 respectively. Similarly, the range of metals analyzed in samples collected from the roadside having only one traffic signal were Cd (nd–0.80), Pb (145.95–308.09), Cu (0.82–18.04), Ni (18.29–59.36), Fe (88.51–3649.42), Mn (25.88–147.34) and Zn (8.97–106.11 mg kg ^?1) respectively. However, the range of metals at roads having no traffic signals were Cd (0.0–0.57), Pb (8.34–58.20), Cu (2.88–5.81), Ni (3.34–73.80), Fe (55.34–332.81), Mn (2.98–98.73) and Zn (1.23–46.6 mg kg^?1) respectively. Cd, Cu, Ni, Fe, Mn and Zn in soil were present within the normal range of background levels, whereas lead was reported in high concentration. The level of lead had a correlation with the traffic density attributing its origin to vehicular exhaust. The values from three different sites of monitoring suggest that automobiles are a major source of the studied metals for the roadside environment.     

Role of the Bridge in Photoinduced Electron Transfer in Porphyrin–Fullerene Dyads

The role of π‐conjugated molecular bridges in through‐space and through‐bond electron transfer is studied by comparing two porphyrin–fullerene donor–acceptor (D–A) dyads. One dyad, ZnP–Ph–C₆₀ (ZnP=zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP–EDOTV–C₆₀, introduces an additional 3,4‐ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster charge recombination, which indicates enhanced electronic coupling between the charge‐separated and ground electronic states; and 2) the disappearance of the intramolecular exciplex, which mediates photoinduced charge separation in the ZnP–Ph–C₆₀ dyad. The latter can be interpreted as a gradual decrease in electronic coupling between locally excited singlet states of D and A when introducing the EDOTV unit into the D–A bridge.     

Jasmonic acid changes the composition of essential oil isolated from narrow-leaved lavender propagated in in vitro cultures

The aim of the present study was to determine the effect of jasmonic acid added to the culture medium on composition of Lavandula angustifolia essential oils. The chemical composition was determined by gas chromatography coupled to mass detector (GC/MS). The experiment was conducted with the use of MS medium supplemented with increasing concentration of JA (0.2, 0.5, 1, 1.5 mg?dm^?3). It was found that the analysed essential oils varied in terms of chemical composition depending on the content of JA in the medium. All obtained essential oils were characterised by a high content of σ-cadinene (17.06–29.64%), borneol (6.66–17.47%), caryophyllene oxide (8.30–14.01%), τ-cadinol (4.87–9.16%), beta-caryophyllene (3.54–6.57%), 1.8-cineole (1.94–5.87%), β-pinene (1.48–3.05%), geranyl acetate (0.56–2.14%) and myrtenal (0.65–2.14%).     

Cooperativity in a cycloalkane-1,2/1,3-polyol corona: Topological hydrogen bonding in 1,2-diol motifs

A corona, consisting of 18 carbon atoms bearing 12 hydroxy groups in a continuous hydrogen-bonded chain, is built up by alternating degenerate conformations of alternating alkane-1,2-diol and 1,3-diol motifs. Geometries, proton nuclear magnetic resonance shifts and interaction energies for the dodecahydroxycyclo-octadecane and selected fragments are determined by density functional calculations at the B3LYP/6-311+G(d,p) level. Cooperative effects of O–H⋯O–H bonding are evident from the simple juxtaposition of these two motifs with a common OH group in butane-1,2,4-triol conformers. Bracketing a 1,2-diol motif with two 1,3-diol motifs in hexane-1,3,4,6-tetrol leads to a structure in which the 1,2-diol motif displays a bond critical point for hydrogen bonding. This is associated with enhancement of the shift of the hydrogen-bonded OH proton and of the corresponding H⋯O interaction energy. The full corona has a complete outer ring of O–H⋯O–H bond paths, and an inner ring of bond paths, due to C–H⋯H–C hydrogen–hydrogen bonding, which result in a central ring critical point. The topological O–H⋯O–H hydrogen bond, never seen in simple alkane-1,2-diols, is associated with cooperative enhancement of the H⋯O interaction energy, but this is not a necessary condition for a bond path: values for topological C–H⋯H–C hydrogen–hydrogen bonds can be as low as −0.4 kcal mol⁻¹.     

离子色谱法测定纯净水中F~-,BrO_3~-等6种阴离子

建立阴离子分离柱离子色谱法测定纯净水中F~-,BrO_3~-,Cl~-,NO_2~-,Br~-,NO_3~- 6种微量阴离子的方法。以SH-AC-1型阴离子柱为分离柱,柱箱温度为35℃,以1.0 mmol/L Na_2CO_3为淋洗液,流量为1.5 mL/min。F~-,BrO_3~-,Cl~-,NO_2~-,Br~-,NO_3~-的线性范围分别为20~320,40~800,40~640,10~200,50~1 000,50~1 000μg/L,线性相关系数均大于0.999,检出限为0.7~7.5μg/L,加标回收率在95.0%~106.3%之间,测定结果的相对标准偏差为1.41%~4.27%(n=5)。该方法测定结果准确、可靠,操作简便、快速,适用于纯净水中BrO_3~-,F~-,Cl~-,NO_2~-,Br~-,NO_3~- 6种阴离子的测定。     

Electrical double layer in surface-inactive electrolyte solution and adsorption of halide ions from 0.1 M solutions on liquid Cd–Ga and In–Ga alloys in gamma-butyrolactone

The double-layer characteristics of liquid renewable Cd–Ga (0.3 at % Cd) and In–Ga (14.2 at % In) electrodes in the gamma-butyrolactone (GBL) solutions of various electrolytes are studied by measuring the differential capacitance and using the method of open-circuit jet electrode. For the (Cd–Ga)/GBL and (In–Ga)/GBL interfaces, the zero-charge potentials, which are not distorted by the specific adsorption of ions, and the chemisorption potential drops of solvent are determined. It is shown that, in spite of the fact that the work function decreases as we pass from (In–Ga) to (Cd–Ga), the chemisorption potential drops of solvent on both electrodes are close. This behavior is explained by a closer approach of GBL dipoles to the surface of (Cd-Ga) electrode providing more effective overlapping of donor–acceptor levels of metal and solvent. It is shown that, in GBL, the adsorption parameters of halide ions and their surface activity series depend on the metal nature. On the (Cd–Ga) and (In–Ga) electrodes, the reversed surface activity series of halide ions is observed: on the Hg electrode in various solvents, the surface activity increases in the series Cl^– < Br^– < I^–, whereas on the (Cd–Ga) and (In–Ga) electrodes in GBL, it varies in the reverse series I^– < Br^– < Cl^–.     

Comparison of membrane assisted solvent extraction,stir bar sorptive extraction,and solid phase microextraction in analysis of tetramine in food

Three environmentally friendly extraction techniques, membrane assisted solvent extraction (MASE), stir bar sorptive extraction (SBSE), and headspace solid phase microextraction (HS‐SPME), were compared for the direct analysis of the highly toxic rodenticide tetramine in food. The optimized MASE method was applied to seven foods fortified with tetramine and compared to previously reported SBSE and HS‐SPME results. Parameters such as the standard addition linearity (MASE (0.964–0.999), SBSE (0.966–0.999), HS‐SPME (0.955–0.999)), recovery (MASE (12–86%), SBSE (36–130%), HS‐SPME (50–200%)), reproducibility (MASE (3.0–30%), SBSE (4.4–9.6%), HS‐SPME (1–12%)), and LOD (MASE (1.6–6.4 ng/g), SBSE (0.2–2.1 ng/g), HS‐SPME (0.9–4.3 ng/g)) were compared.     

Thermodynamic characteristics of praseodymium in the gallium–aluminum eutectic melt

The Ga–Al eutectic melt saturated with praseodymium was studied in the temperature range 572–1076 K by electromotive force (emf) method relative to the reference electrode (In_L + PrIn₃, where L is the liquid phase) in a LiCl–KCl–CsCl eutectic electrolyte. The partial molar thermodynamic functions (enthalpy, entropy, and Gibbs energy) of praseo dymium in a Ga–Al eutectic melt were calculated. According to the emf measurements of the two-phase Pr–Ga–Al_L + intermetallic compound alloys equilibrated with the Ga–Al eutectic melt saturated with praseodymium, there are intermetallic compounds PrGa₆, PrGa₄, and Pr_0.22Ga_0.78(PrGa₂) in the temperature ranges 572–741, 741–883, and 883–1076 K, respectively.     

XAFS analysis of coprecipitation of zinc by sulfide ions in an acidic solution

The fluorescence XAFS (X–ray absorption fine structure) technique using synchrotron radiation was applied to characterize zinc in the Hg–Zn, Cd–Zn, and Bi–Zn coprecipitates, and to elucidate the reaction mechanism of the coprecipitation of zinc from a strong acidic solution. Hg L_II–, Cd K–, and Bi L_III–edge XAFS spectra suggested that the respective host materials of the coprecipitates listed above are metacinnabar (HgS), greenockite (CdS), and bismuthinite (Bi₂S₃) and that existence of zinc has not affected the local structure of the host metal sulfides in each system. On the other hand, the Zn K–edge XAFS spectra of each coprecipitate indicated that the chemical forms of zinc compounds are controlled by the crystal structure of the host sulfides.The shapes of the Zn K–XAFS spectra of the Hg–Zn and Cd–Zn coprecipitates showed a strong resemblance to those of crystalline standards ZnS, wurtzite and spharelite. It was suggested that the two coprecipitated phases (HgS, ZnS) and (CdS, ZnS) may form a solid solution in the Hg–Zn and Cd–Zn coprecipitates. The local structure around the zinc(II) ion in the Bi–Zn coprecipitate is the same as that around hexaaqua–zinc(II) ions, and adsorption of soluble ions or mechanical occlusion from the mother liquor is regarded as a driving force of coprecipitation in the Bi–Zn system.     

Phase equilibrium in the system water–acetonitrile–cyclohexene–cyclohexanone

Phase equilibrium in the water–acetonitrile–cyclohexene–cyclohexanone quaternary system and in its binary and ternary constituents was studied using experimental and calculation methods. The parameters were determined for the NRTL equation that adequately describes liquid–vapor, liquid–liquid–vapor, and liquid–liquid–liquid equilibria. The evolution of the three-phase splitting region inside the concentration tetrahedron was studied on the basis of the obtained model, and its transformation into the two-phase region through the critical node was shown. Thermodynamic analysis involving topological representation for the diagram of the phase equilibrium in a quaternary system was performed, and schemes for the complete separation of the reaction mixture were proposed.     

Stepwise Self-assembly of a Tripeptide from Molecular Dimers to Supramolecular β-sheets in Crystals and Amyloid-like Fibrils in the Solid State

The terminally protected tripeptide Boc–Ala(1)–Leu(2)–Ala(3)–OMe 1 forms antiparallel hydrogen-bonded dimers of two different conformers in the asymmetric unit and the individual dimers then self-associate to form supramolecular β-sheet structures in crystals and amyloid-like fibrils in the solid state.     

Changes in Time Spent Outdoors During the Daytime in Rural Populations in Four Geographically Distinct Regions in China: A Retrospective Study

Changes in time‐activity patterns may influence personal exposure to various environmental factors and affect individual health. However, few studies have investigated the changes in patterns of time spent outdoors. To investigate the trends in outdoor activity in recent decades in China, a retrospective questionnaire was used to examine the amount and pattern of time spent outdoors during the day by 2076 subjects in four geographically distinct rural regions of China. Rural Chinese people spent less time outdoors than they used to because of the economic development, increase in education and changes in working conditions that occurred over time. Outdoor time was the shortest during the school stage of life (Sanya: 3.24–3.61; Shaoxing: 3.35–3.68; Lhasa: 4.37–4.54; Xiuyan: 2.94–3.26 h per day). Subjects in wealthy regions spent less time outdoors during their working stage of life. In the four regions in this study, the average daily times spent outdoors were 3–13% lower for subjects aged 40–59 years and 20–38% lower for those under 40 years compared to subjects aged 60 years and over. Certain health‐related issues, such as vitamin D deficiency, will become more prominent in China if this trend continues.     

Exploratory analysis in thermodynamics of equilibria. Classification and prediction of benzoic acid strength in aqueous-organic solvents

Decisive rule for classification and prediction of benzoic acid strength from dielectric constant and Kamlet–Taft parameter of the mixed solvents (water–methanol, water–ethanol, and water–2-propanol) has been elaborated basing on the results of multivariate exploratory analysis. The rule has been verified using the independent experimental data on dissociation constant of benzoic acid in water–dioxane and water–dimethylsulfoxide mixtures. Two-parameter linear regression model of the Gibbs energy of benzoic acid dissociation as a function of the properties of aqueous-alcoholic solvents has been built, and the contributions of dielectric and cohesion medium properties to the decrease in the acid strength have been shown.     

离子色谱法测定核电站一回路冷却剂中痕量F~-,Cl~-和SO_4~(2-)

建立离子色谱法测定核电站一回路冷却剂中痕量氟离子F~-,氯离子Cl~-,硫酸根离子SO_4~(2-)的方法。采用80 mmol/L硼酸溶液配合氢氧化钾淋洗液发生器在线生成淋洗液,梯度洗脱,淋洗液流量为1.2 mL/min,在选定的分析条件下,NO_2~-,NO_3~-,PO_4~(3-)和CO_3~(2-)不干扰F~-,Cl~-,SO_4~(2-)的测定。F~-,Cl~-,SO_4~(2-)的质量浓度与其色谱峰面积呈良好的线性关系,线性相关系数分别为0.999 8,0.999 5,0.999 7,线性范围分别为0.85~30.0,2.65~30.0,2.00~30.0μg/L。F~-,Cl~-,SO_4~(2-)测定结果的相对标准偏差分别为0.56%~1.58%,0.85%~3.62%,1.21%~4.60%(n=7)。F~-,Cl~-,SO_4~(2-)的加标回收率分别为98%~104%,98%~108%,93%~108%。该方法快速、准确,满足核电站一回路冷却剂中痕量F~-,Cl~-,SO_4~(2-)的检测要求。