Tools to discover anionic and nonionic polyfluorinated alkyl surfactants by liquid chromatography electrospray ionisation mass spectrometry

A tiered approach is proposed for the discovery of unknown anionic and nonionic polyfluorinated alkyl surfactants (PFASs) by reversed phase ultra high performance liquid chromatography (UHPLC)--negative electrospray ionisation--quadrupole time of flight mass spectrometry (UHPLC-ESI(-)-QTOF-MS). The chromatographic separation, ionisation and detection of PFASs mixtures, was achieved at high pH (pH=9.7) with NH(4)OH as additive. To distinguish PFASs from other chemicals we used the characteristic negative mass defects of PFASs, their specific losses of 20 Da (HF) and the presence of series of chromatographic peaks, belonging to homologues series with m/z of n×50 Da (CF(2)) or n×100 Da (CF(2)CF(2)). The elemental composition of the precursor ions were deducted from the accurate m/z values of the deprotonated molecules [M-H](-). In case of in-source fragmentation, the presence of dimers, e.g. [M(2)-H](-) and adduct ions such as [M-H+solvent](-) and [(M-H)(M-H+Na)(n)](-) were used to confirm the identity of the precursor ions. In relation to quantification of PFASs, we discuss how their surfactancy influence the ESI processes, challenge their handling in solution and choices of precursor-to-product ions for MSMS of e.g., structural PFAS isomers. The method has been used to discover PFASs in industrial blends and in extracts from food contact materials.     

Effect of several variables in the polymer toys additive migration to saliva

Capacity to migrate of a representative group of polymeric additives, dyes, antioxidants, hindered amine light stabilizers (HALS) or antistatics, from plastic toys to saliva was analyzed to protect children in their habits of sucking and biting. Most of target additives appear no-regulated in toys normative but adverse effects on human health of some of them have been demonstrated and their presence in others commercial articles normative has been included.In order to offer an effective and easy tool to perform these controls, migration tests by dynamic and static contact, followed by a preconcentration step by liquid-liquid extraction (LLE) and ultra performance liquid chromatographic analysis with ultraviolet-visible and evaporative light scattering detections (UPLC-UV/Vis-ELSD) have been optimized to evaluate the migrated amounts of the additives in saliva simulant. The detection limits of the migration methodologies were ranged from 8.68 × 10⁻² to 1.30 × 10⁻³ mg migrated (L simulant)⁻¹.Influence of several variables on this mass transport, as time, temperature and friction, was also analyzed to achieve the most aggressive methodology to protect consumers.Migration of several studied additives, whose presence has been demonstrated in several purchased commercial toys, has been observed.     

压电管堆式宽带换能器*

研究了一种具有管状叠堆结构的圆管换能器,其敏感元件是由纵向极化压电陶瓷单元组成的薄壁管状压电叠堆,探讨利用管状叠堆纵向和径向振动耦合实现宽带发射。利用压电柱壳振动理论推导了管堆的频率方程,分析了换能器的纵向和径向模态的振动耦合特性。在理论分析的基础上利用有限元方法对换能器的带宽和发射电压响应进行优化并研制换能器样机。测试结果表明,纵向极化的管状压电叠堆结构具有良好的发射电压响应和宽带特性,与理论及仿真结果相符。     

ICP-MS法测定仿真饰品中11种重金属迁移量

模拟配戴环境,研究了酸性汗液浸萃样品,建立了ICP-MS同时测定仿真饰品中11种重金属迁移量。优化了实验条件,讨论了内标选择、干扰和消除等。方法对仿真饰品进行了测定,相对标准偏差为2.4%～11%,回收率为84.5%～113.5%。     

Evolutionary dynamics of nationalism and migration

I present a dynamic evolutionary game model to address the relation between nationalism against immigrants and assimilation of the latter into the host country culture. I assume a country composed of two different large polymorphic populations, one of native citizens and the other of immigrants. A native citizen may behave nationalistically or may welcome immigrants. Immigrants may have an interest in learning the host country language or not. Evolution is modeled using replicator dynamics (RD). I also account for the presence of an enclave of immigrants in the host country. In the RD, the latter represents the immigrants’ own population effect, which contribution to fitness is controlled using a parameter ρ$\rho$, 0≤ρ≤1$0\le \rho \le 1$, that represents the enclave size. In line with the empirical literature on migration, the existence of an enclave of immigrants makes assimilation less likely to occur. For large values of ρ$\rho$, complete assimilation may not occur even if immigrants and natives share very close cultures and norms. Government policy regarding nationalism is modeled both exogenously and endogenously. A single or multiple asymptotically stable states exist for all cases studied but one in which the dynamics is similar to that found in the predator–prey model of Lotka–Volterra for competing species.     

受体型酪氨酸激酶变异体对结肠癌细胞侵袭能力影响的研究

目的研究受体型酪氨酸激酶变异体RON△160表达对结肠癌细胞迁移、浸润能力的影响.方法将携有受体型酪氨酸激酶RON变异体RON△160 cDNA的质粒转染入结肠癌细胞株RKO细胞,挑选稳定转染克隆,以过河实验和Transwel 趋化运动实验检测细胞迁移能力;Matrigel基质浸润实验检测细胞浸润能力,Western blot检测E-钙粘连蛋白(E-cadherin)表达的变化.结果转染RON△160后RKO细胞的过河时间为(38.00±1.63)h,明显短于未转染组与载体对照组的(69.50±2.52)h与(72.00±1.63)h,差异均有统计学意义(均P<0.05).转染后RKO细胞的穿膜能力显著增强,穿膜细胞数为(59.22±6.67)个/HP、未转染组为(25.90±4.56)个/HP、载体对照组为(28.33±6.75)个/HP,差异均有统计学意义(均P<0.05).转染RON△160后,RKO细胞中E-cadherin表达降低(P<0.05).结论 RON△160转染可以降低E-cadherin表达,降低肿瘤细胞间的黏附性,增加结肠癌细胞RKO的移动、浸润能力.RON△160的表达可能是结肠癌浸润、转移的机制之一.     

Representability of Hilbert Schemes and Hilbert Stacks of Points

We show that the Hilbert functor of points on an arbitrary separated algebraic stack is an algebraic space. We also show the algebraicity of the Hilbert stack of points on an algebraic stack and the algebraicity of the Weil restriction of an algebraic stack along a finite flat morphism. For the latter two results, no separation assumptions are necessary.     

Ultra-high pressure LC determination of glucosamine in shrimp by-products and migration tests of chitosan films

Chitosan, a multiple applications molecule, was isolated from shrimp by-products by fermentation. The amount of chitosan in the solid fraction of the fermented extract was measured after its conversion in the respective glucosamine units. The procedure includes an acid hydrolysis (110 °C, 4 h with HCl 8 M) and a derivatization with 9-fluorenylmethyl chloroformate (Fmoc-Cl). Ultra-high-pressure liquid chromatography method was developed and optimized. Excellent peaks resolution was achieved in just 10 min. The method was evaluated in what concerns to validation parameters such as linearity, repeatability, quantification limit, and recovery. Migration tests of films prepared with chitosan were carried out in two simulants: ultrapure water and ethanol 95% (v/v).     

The electrical properties of dielectric stacks of SiO2 and Al2O3 prepared by atomic layer deposition method

We produced dielectric stacks composed of ALD SiO₂ and ALD Al₂O₃, such as SiO₂/Al₂O₃, Al₂O₃/SiO₂, and SiO₂/Al₂O₃/SiO₂, and measured the leakage currents through the stacks in comparison with those of the single oxide layers. SiO₂/Al₂O₃ shows lowest leakage current for negative bias region below 6.4 V, and Al₂O₃/SiO₂ showed highest current under negative biases below 4.5 V. Two distinct electron conduction regimes are observed for Al₂O₃ and SiO₂/Al₂O₃. Poole-Frenkel emission is dominant at the high-voltage regime for both dielectrics, whereas the direct tunneling through the dielectric is dominant at the low-voltage regime. The calculated transition voltage between two regimes for SiO₂ (6.5 nm)/Al₂O₃ (12.6 nm) is −6.4 V, which agrees well with the experimental observation (−6.1 V). For the same EOT of entire dielectric stack, the transition voltage between two regimes decreases with thinner SiO₂ layer.