Application of Non-Destructive X-Ray Fluorescence Spectrometry to the Analysis of Suspended Matter in Sea Water

Abstract

In the framework of remote sensing studies concerning coastal transport of pollution in the Northern Adriatic Sea, a method has been developed for the quantitative determination of sulphur, iron, titanium, calcium, phosphorus, silicon, aluminium, magnesium in suspended matter of sea water.

The suspended material was collected by filtering on millipore membrane filters with pore width of 0.45 μ and directly analysed by X-ray spectroscopy. For calibration dried solution and particulate standard samples were used. Limits of sensitivity and precision of the method are reported.

Correlations between the concentration of these elements and the total suspended matter/chlorophyll are discussed.

The aim is to study the geochemical composition of particulate matter and its variations within the geographical site of the sea basin and the seasonal conditions. The approach is to consider aluminium and the other elements normalized on Al. On the basis of a matrix correlation analyses of some sets of data chosen in the restricted area for investigation, some hypothesis on superficial distribution of clay, carbonate, iron hydrous oxides and other mineral detrites, are taken into account. The results confirm the complex situation existing in the offshore area of the Venice lagoon from a geochemical point of view.

The suspended matter seem to be argillaceous in the Southern part of the investigated area and semi-argillaceous with hydrous oxides and carbonates in the Northern part which is influenced by the Piave river.     

Fredholm boundary value problems for perturbed systems of dynamic equations on time scales

This paper offers conditions ensuring the existence of solutions of linear boundary value problems for systems of dynamic equations on time scales. Utilizing a method of Moore–Penrose pseudo‐inverse matrices leads to an analytical form of a criterion for the existence of solutions in a relevant space and, moreover, to the construction of a family of linearly independent solutions of such problems in a general case with the number of boundary conditions (defined by a linear vector functional) not coinciding with the number of unknowns of a system of dynamic equations. As an example of an application of the presented results, the problem of bifurcation of solutions of boundary value problems for systems of dynamic equations on time scales with a small parameter is considered.     

Efficient partial hydrogenation of trichloromethyl to gem-dichloromethyl groups in platinum on carbon-catalyzed system

While gem-dichloromethyl groups can be directly synthesized by the mono-dechlorination of the corresponding trichloromethyl groups, the suppression control of the over-reduction to form chloromethyl or methyl functionalities is quite difficult. We have established the efficient and widely applicable mono-dechlorination method of the trichloromethyl groups to form the corresponding gem-dichloromethyl groups using platinum on carbon in dimethylacetamide as a specific solvent at 25 °C under a hydrogen atmosphere. The mono-dechlorination of the α,α,α-trichloromethylcarbonyl groups smoothly proceeded by the use of platinum on carbon as a catalyst in a highly chemoselective manner, while the efficient mono-dechlorination of the alkyl- and aryl-trichloromethyl groups required the combined use of Bu₃SnH.     

基于创新能力培养的化学专业本科实验教学新体系的构建与实践

课程体系是人才培养的载体。为了更好地培养拔尖创新人才,南京大学化学国家级实验教学示范中心依据化学学科的特点和发展趋势,以科学内容的内在联系和研究规律为主线构建了“化学实验基础?化学合成与表征+化学原理与测量?化学功能分子实验+化学生物学综合实验+基于项目的研究实验”实验课程新体系,按照一流课程建设要求(高阶性、创新性和挑战度)对实验教学内容进行了优化,并建立起与之相适应的实验教学平台。新课程体系综合考虑了化学一级学科的整体性和关联学科的交叉性,在南京大学化学化工学院“拔尖计划”和“强基计划”学生中实施,教学效果显著。     

A Spectroscopic Overview of Intramolecular Hydrogen Bonds of NH…O,S,N Type

Intramolecular NH…O,S,N interactions in non-tautomeric systems are reviewed in a broad range of compounds covering a variety of NH donors and hydrogen bond acceptors. ¹H chemical shifts of NH donors are good tools to study intramolecular hydrogen bonding. However in some cases they have to be corrected for ring current effects. Deuterium isotope effects on ¹³C and ¹⁵N chemical shifts and primary isotope effects are usually used to judge the strength of hydrogen bonds. Primary isotope effects are investigated in a new range of magnitudes. Isotope ratios of NH stretching frequencies, νNH/ND, are revisited. Hydrogen bond energies are reviewed and two-bond deuterium isotope effects on ¹³C chemical shifts are investigated as a possible means of estimating hydrogen bond energies.     

Scale-Up Preparation of Crocins I and II from Gardenia jasminoides by a Two-Step Chromatographic Approach and Their Inhibitory Activity Against ATP Citrate Lyase

Crocins are highly valuable natural compounds for treating human disorders, and they are also high-end spices and colorants in the food industry. Due to the limitation of obtaining this type of highly polar compound, the commercial prices of crocins I and II are expensive. In this study, macroporous resin column chromatography combined with high-speed counter-current chromatography (HSCCC) was used to purify crocins I and II from natural sources. With only two chromatographic steps, both compounds were simultaneously isolated from the dry fruit of Gardenia jasminoides, which is a cheap herbal medicine distributed in a number of countries. In an effort to shorten the isolation time and reduce solvent usage, forward and reverse rotations were successively utilized in the HSCCC isolation procedure. Crocins I and II were simultaneously obtained from a herbal resource with high recoveries of 0.5% and 0.1%, respectively, and high purities of 98.7% and 99.1%, respectively, by HPLC analysis. The optimized preparation method was proven to be highly efficient, convenient, and cost-effective. Crocins I and II exhibited inhibitory activity against ATP citrate lyase, and their IC₅₀ values were determined to be 36.3 ± 6.24 and 29.7 ± 7.41 μM, respectively.     

Using the full Raman depolarisation in the determination of the order parameters in liquid crystal systems

The depolarisation ratio for the Raman-active phenyl stretching mode has been measured over the whole of the mesophase range, and the orientational order parameters deduced, in the uniaxial nematic liquid crystal octylcyanobiphenyl (8CB). Linearly polarised light was incident normally on a homogeneously aligned sample and a χ² minimisation routine performed on the 360^° depolarisation ratio profile. The order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 , together with the differential polarisability ratio, r , are used as fitting parameters and measured as a function of temperature. Interestingly, we show that the value for r , conventionally measured in the isotropic phase and assumed to remain constant, has a clear temperature dependence, ranging from -0.032±0.008 in the isotropic phase through to -0.245±0.015 at the nematic-to-smectic A phase transition. The measured order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 varied from 0.35- 0.55±0.02 and 0.180- 0.245±0.02 , respectively, across the 8 ^° C wide nematic phase range. The values of both 〈P ₂₀₀〉 and 〈P ₄₀₀〉 are in excellent agreement with theory, but it is noteworthy that 〈P ₄₀₀〉 shows a much better quantitative match than has been reported in previous work. Crucially the temperature dependence of r is shown to be a contributing factor in the low 〈P ₄₀₀〉 values that have been conventionally reported from Raman scattering measurements. The potential for fitting the entire angular depolarisation ratio distribution in liquid crystalline systems that are described by more order parameters, specifically biaxial materials, is discussed.     

Field-temperature phase diagrams in chiral tilted smectics,evidencing ferroelectric and ferrielectric phases

Usual ferroelectric compounds undergo a paraelectric-to-ferroelectric phase transition when the susceptibility of the electric polarization density changes its sign. The temperature is the only thermodynamic field that governs the phase transition. Chiral tilted smectics may also present an improper ferroelectricity when there is a tilt angle between the average long axis direction and the layer normal. The tilt angle is the order parameter of the phase transition which is governed by the temperature. Although the electric susceptibility remains positive, a polarization proportional to the tilt appears due to their linear coupling allowed by the chiral symmetry. Further complications come in when the chirality increases, as new phases are encountered with the same tilt inside the layers but a distribution of the azimuthal direction which is periodic with a unit cell of two (SmC(A)*, three (SmC(Fi1)*, four (SmC(Fi2)* or more (SmC(alpha)* layers. In most of these phases, the layer normal is a symmetry axis so there is no macroscopic polarization except for the SmC(Fi1)* in which the average long axis is tilted so the phase is ferrielectric. By studying a particular compound with only a SmC(Fi2)* and a SmC(alpha)* phase, we show that we recover the uniformly tilted ferroelectric SmC* when applying an electric field. We are thus led to build field-temperature phase diagrams for this class of compounds by combining different experimental techniques described here.