Regenerating Spent Solutions of Vanadium‐containing Heteropoly Acids in the Presence of Additives

Vanadium‐containing heteropoly acid solutions of Keggin H_3+xPMo_12–xV_xO₄₀ and modified H_aP_zMo_yV_xO_b types (P‐Mo‐V HPAs) are promising nanosized inorganic metal‐oxygen cluster compounds with the property of reversible oxidability (V^V ↔ V^IV). The oxidation of reduced P‐Mo‐V HPAs at a temperature of 130–170 °C and an oxygen pressure of 4 atm is a convenient method for their regeneration, but results in regeneration degree of only 75–88 %. Various materials with electron transfer or oxidative properties, such as nitrogen doped carbon nanofibers (N‐CNFs), Sibunit‐4, HNO₃, and MoO₂, were investigated as additives to facilitate and accelerate the regeneration of HPA solutions. Among the studied additives HNO₃ was found to show the best efficiency, resulting in regeneration degree of higher 95 %. Rapid and efficient regeneration of spent HPA catalysts is an important criterion for achieving high productivity and sustainability of oxidative processes on their basis.     

肽类药物口服剂型材料及控制释放性能研究──Ⅱ.含有添加剂的壳聚糖-海藻酸盐微囊对胰岛素的控释作用

应用壳聚糖－海藻酸盐微囊技术制备了一系列含有添加剂的胰岛素微囊,并研究了在添力。剂存在下,不同反应条件对微囊的胰岛素包封率及其释放性能的影响．结果表明,在添加剂存在下,海藻酸钠浓度越高,微囊在胃液中释放率越大,在模拟小肠液中释放速率越低,并且微球的韧性很强,不易破裂;海藻酸钠与添加剂的质量比越大,微囊的包封率越大,胃液中释放率减小;胰岛素含量越高,包封率越小,胃液中释放率越大;明胶和牛血清白蛋白的加入使微囊在胃液中释放率显著增大,微球的强度和韧性大大增强,尤其明胶的加入使微囊在模拟小肠液中释放率显著降低,释放达到最大值的时间延长．     

A study on the degradation of polylactic acid in the presence of phosphonium ionic liquids

In this overview study, two ionic liquids (IL) with different anions (decanoate, tetrafluoroborate) but with the same phosphonium-based cation that showed promising plasticizing/lubricating behavior in polylactic acid (PLA) were screened for their effects on the polymer degradation under thermomechanical, thermo-oxidative (at 160 °C), hydrolytic (100% humidity, 60 °C), conditions, and during soil immersion. Depending on the particular medium and conditions used, degradation was followed by changes in molecular weight, melt viscosity, sample weight and appearance, morphology, crystallinity, acid number, and pH. The effects of the IL containing a decanoate anion were more pronounced on lubrication and also on degradation as evidenced by reduced melt viscosities and accelerated thermomechanical, isothermal, hydrolytic, and soil degradation. The IL containing the tetrafluoroborate anion showed higher thermal stability compared with the IL containing decanoate anion as also confirmed from thermal degradation rate constants which were calculated from random chain scission statistics. Accelerated hydrolytic degradation was observed in PLA containing the tetrafluoroborate based IL but to a lesser extent than the decanoate based IL. The catalytic role of the decanoate anion in hydrolytic degradation was confirmed through experiments with model compounds. X-ray diffraction (XRD) data on the materials exposed to soil degradation provided evidence that the initially amorphous polymer attained a certain degree of crystallinity as a result of the significant MW reduction.     

Formamide as an organic modifier in MEKC with SDS

The effect of formamide (FA) as a modifier on the retention in MEKC with SDS as the detergent was investigated. The mobility of a series of alkylphenones and of a zwitterionic fluorescent compound as a function of the FA and the SDS concentration was determined for this purpose. Buffering electrolyte was borate, pH 9.23, with total ionic strength of 50 mM. The dependence of the mobility on the FA content – up to 63% w/w – of the BGE (at 10 mM SDS) allows the conclusion that the micelles are destabilized, and the CMC is shifted to higher values. In the system containing 33% FA or more no micelles are present anymore, and the retention factors of all compounds tend to zero. In an MEKC system with 27% v/v FA the CMC of SDS is increased from 2.4 mM in the aqueous BGE with the same buffer composition to 9.7 mM, a behavior that is in contrast to electrolyte‐free FA–water systems. The partition constants of free analytes and the formation constants of the adduct between analyte and detergent monomer (assuming 1:1 stoichiometry) were derived from the dependence of the mobility on the SDS concentration. In addition, the involved equilibria were extended by that from the distribution of the analyte–monomer adduct between aqueous and micellar phase, and the according partition constants were derived as well. A selective change in the extent of partitioning was observed for the zwitterionic compound. In general, all binding constants were decreased upon addition of FA, though to a different extent. Although the binding constants of the analyte–monomer associate were only slightly influenced, the most pronounced decrease is found for their partitioning into the micelles.     

原子荧光光谱法测定饲料添加剂中的汞

建立了原子荧光光谱法测定硫酸盐型饲料添加剂中汞的方法,讨论了共存离子的干扰情况。在最佳实验条件下.方法的检出限达到了0.0096ng/mL,加标回收率在97.2%—109.7%之间,相对标准偏差为1.03%,被分析的硫酸盐型饲料添加剂中的共存离子对汞的测定基本无干扰。方法可用于硫酸盐型饲料添加剂中的汞的测定。     

乙醛酸化学镀铜的电化学研究

以乙醛酸作还原剂,Na2EDTA.2H2O为络合剂,亚铁氰化钾和2,2'-联吡啶为添加剂组成化学镀铜液体系,应用线性扫描伏安法研究分析了络合剂、添加剂对该镀铜体系电化学性能的影响.结果表明,络合剂Na2EDTA对乙醛酸的氧化和铜的还原有阻碍作用.亚铁氰化钾和过量(20 mg/L)的2,2'-联吡啶对乙醛酸的氧化起较明显的抑制作用.     

Repeated migration of additives from a polymeric article in food simulants

The migration of three additives from polypropylene samples into a series of five liquid food simulants was investigated at 60 °C in a repeated migration regime. This regime was simulated by 20 migration periods each of 8 h and using initially additive free food simulants. Between these migration periods the bare samples were stored in an air conditioned room at around 23 °C for 16 h at working days and for 64 h during weekends. An asymptotic decrease of the additive level in the food simulants in the successive migration periods, from a maximum values towards zero, was observed when the additives easily solve in the food simulants. In contrast when the additives solve poorly in the food simulants this additive level decrease is almost linear and shows a slow decrease rate. In the first case the leaching/migration of the additives is controlled mainly by their diffusion in the matrix of the polymer. In the latter case this process is controlled mainly by the partitioning of the additives between the polymer and food simulants. Two approaches were used to model theoretically these results.In the first approach the mass transport equation was solved by using as input parameters overestimated diffusion and partitioning coefficients as estimated for polypropylene homopolymer, the used food simulants and the three additives according to the recommendations of a practical guidance document in support of migration modelling as stipulated in the Regulation (EU) 10/2011. As expected the results of these calculations overestimate the vast majority of the migration levels determined experimentally. However there are also situations in which this approach leads to underestimations of the real migration levels.In the second approach numerical fitting was applied with the same equation and using the diffusion and partition coefficients as adjustable parameters to obtain a best-fit between experimental and calculated results. It was found that the so obtained “realistic” diffusion coefficients are all lower than the overestimated ones mentioned above. Moreover these “realistic” coefficients depend not only on the nature of the additive but also on the nature of the food simulant in contact with the polymer. This suggests that interaction of food simulants with the polypropylene occurs, which changes the properties of the polymer and thus the mobility of the additive molecules in its matrix. For the “realistic” partition coefficients it was found that they all are higher than the conservative ones mentioned above. Using these “realistic” parameters a good fit between calculated and experimental migration results was found.     

The compatibility of (natural) polyols with heavy metal- and zinc-free poly(vinyl chloride): Their effect on rheology and implications for plate-out

This paper describes the rheological effects observed after addition of (natural) polyols to several different types of heavy metal-free PVC formulations. It is found that addition of natural polyols, such as sorbitol, leads to changes in the rheology of the system comparable to the addition of external lubricants. Hence as suggested previously, addition of (natural) polyols may lead to the occurrence of undesirable plate-out phenomena. The magnitude of the effect on the rheology depends on the number of hydroxyl groups in the polyol and its propensity to undergo intramolecular cyclodehydration reactions. It is established that the undesirable rheological effects, which coincide with plate-out phenomena, can be suppressed by the addition of various types of inorganic as well as organic substances, most of which are known PVC additives. This will allow for the use of (natural) polyols as efficient and benign co-stabilisers in next generation stabiliser systems.     

Separation techniques for the analysis of artists' acrylic emulsion paints

Emulsion paints are complex chemical systems. The main problems in their characterization are related to the similarities in polymer composition and to the presence of many different types of additives. Thus high resolution separations, sensitivity, and response specificity are required to identify simultaneously the polymer matrix and the minor components. Especially surfactants and pigments are thought to affect significantly the properties of the paint layers during ageing and their identification is the first step in evaluating the behaviour of these products in working conditions. Representative samples of acrylic emulsion paints for artists have been investigated by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and size exclusion chromatography-Fourier transform infrared spectroscopy (SEC-FTIR), and the results have been compared. All the analysed samples were bound in ethyl acrylate-methyl methacrylate, poly(EA-co-MMA), or n-butyl acrylate-methyl methacrylate, poly(nBA-co-MMA), copolymers. Two types of nonionic surfactants, ethoxylated fatty alcohols and alkylaryl polyethoxylates, commonly used as emulsifiers and dispersive agents have been identified, together with a number of organic pigments.     

添加剂的吸附行为及其对Ni沉积层性能的影响

采用电化学及X射线衍射等方法研究有机添加剂苯磺酸钠、苯亚磺酸钠和糖精的吸附作用及其对Ni电沉积层的电化学活性、晶粒尺寸、织构及显微硬度的影响．结果表明，苯亚磺酸钠和糖精使Ni沉积层的电化学活性提高，（111）晶面的织构系数明显增大，而使（200）晶面的织构系数减小，还导致沉积层的晶粒尺寸显著减小和显微硬度提高；然而，苯磺酸钠对沉积层的活性及织构影响很小．讨论了上述添加剂的作用．