An exploration of ferrocenyl ureas as enantioselective electrochemical sensors for chiral carboxylate anions

The syntheses of a series of chiral ureas containing the redox-active ferrocene group are described. Each of these bind chiral carboxylates in organic solvents through hydrogen-bonding interactions, as evidenced by spectroscopic and cyclic voltammetry measurements, the latter allowing these guests to be electrochemically sensed in solution. The enantioselectivity in the complexation of the protected amino acid N-benzenesulfonylproline by a ferrocenylbenzyl host is high enough to allow opposite enantiomers to be distinguished by electrochemical means.     

微塑料:生物效应、分析和降解方法综述

微塑料(MPs)的出现引起了全球的广泛关注,它们遍布海洋和陆地的各个环境介质中,造成了严重的环境污染。微塑料通常被定义为粒径小于5 mm的塑料纤维、颗粒或者薄膜,可被生物吸收积累,产生生态风险和健康风险。实际上很多微塑料可达微米乃至纳米级别,肉眼是不可见的,因此也被形象地比作海洋中的“PM2.5”。作为目前学术界和社会各界争论的热点问题,本篇综述旨在系统地介绍环境中微塑料的来源与分布、生物效应以及分析鉴定方法,并重点介绍了微塑料污染的降解策略和研究成果,为今后微塑料降解方法的研究提供了参考。     

Elucidation of the decomposition pathways of protonated and deprotonated estrone ions: application to the identification of photolysis products

With the future aim of elucidating the unknown structures of estrogen degradation products, we characterized the dissociation pathways of protonated estrone (E1) under collisional activation in liquid chromatography/tandem mass spectrometry (LC/MS/MS) experiments employing a quadrupole time‐of‐flight mass spectrometer. Positive ion and negative ion modes give information on the protonated and deprotonated molecules and their product ions. The mass spectra of estrone methyl ether (CH₃‐E1) and estrone‐d₄ (E1‐d₄) were compared with that of E1 in order (i) to elucidate the dissociation mechanisms of protonated and deprotonated molecules and (ii) to propose likely structures for each product ions. The positive ion acquisition mode yielded more fragmentation. The mass spectra of E1 were compared with those of estradiol (E2), estriol (E3) and 17‐ethynylestradiol (EE2). This comparison allowed the identification of marker ions for each ring of the estrogenic structure. Accurate mass measurements have been carried out for all the identified ions. The resulting ions revealed to be useful for the characterization of structural modifications induced by photolysis on each ring of the estrone molecule. These results are very promising for the determination of new metabolites in the environment. Copyright © 2010 John Wiley & Sons, Ltd.     

Design of 1D and 2D molecule-based magnets with the ligand 4,5-dimethyl-1,2-phenylenebis(oxamato)

Three new bimetallic oxamato-based magnets with the proligand 4,5-dimethyl-1,2-phenylenebis(oxamato) (dmopba) were synthesized using water or dimethylsulfoxide (DMSO) as solvents. Single crystal X-ray diffraction provided structures for two of them: [MnCu(dmopba)(H(2)O)(3)](n)·4nH(2)O (1) and [MnCu(dmopba)(DMSO)(3)](n)·nDMSO (2). The crystalline structures for both 1 and 2 consist of linearly ordered oxamato-bridged Mn(II)Cu(II) bimetallic chains. The magnetic characterization revealed a typical behaviour of ferrimagnetic chains for 1 and 2. Least-squares fits of the experimental magnetic data performed in the 300-20 K temperature range led to J(MnCu) = -27.9 cm(-1), g(Cu) = 2.09 and g(Mn) = 1.98 for 1 and J(MnCu) = -30.5 cm(-1), g(Cu) = 2.09 and g(Mn) = 2.02 for 2 (H = -J(MnCu)∑S(Mn),(i)(S(Cu,i) + S(Cu),(i-1))). The two-dimensional ferrimagnetic system [Me(4)N](2n){Co(2)[Cu(dmopba)](3)}(n)·4nDMSO·nH(2)O (3) was prepared by reaction of Co(II) ions and an excess of [Cu(dmopba)](2-) in DMSO. The study of the temperature dependence of the magnetic susceptibility as well as the temperature and field dependences of the magnetization revealed a cluster glass-like behaviour for 3.     

Block Arnoldi-based methods for large scale discrete-time algebraic Riccati equations

In the present paper, we present block Arnoldi-based methods for the computation of low rank approximate solutions of large discrete-time algebraic Riccati equations (DARE). The proposed methods are projection methods onto block or extended block Krylov subspaces. We give new upper bounds for the norm of the error obtained by applying these block Arnoldi-based processes. We also introduce the Newton method combined with the block Arnoldi algorithm and present some numerical experiments with comparisons between these methods.     

Structural modifications induced in Bayfol polycarbonate due to heavy highly energetic ions irradiations

The effects of 28 GeV ⁵⁶Fe and 13.72 GeV ²⁸Si ion irradiation on the structural properties of two types of Bayfol, namely DPF 5023 and CR 1–4 polycarbonates, have been investigated. It is worth mentioning that this report is almost the first one dealing with the topic of material changes in such a high energy range. Samples from each type of Bayfol were classified into two groups. The first group has been exposed to Fe ion fluences at levels between 2000 and 8000 ion/cm². The second group has been exposed to Si ions with similar fluences. The total energy deposited is between 27.44 and 224 E12 eV. The modifications induced in Bayfol samples due to ion irradiation have been studied using X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy. The results indicate that the Fe ion irradiation causes crosslinking in Bayfol DPF 5023, reflected as a decrease in the ordering character. Also, the tendency of Bayfol CR 1–4 to crosslinking due to Fe ion irradiation is lower than that of Bayfol DPF 5023. On the other hand, the Si ion irradiation causes mainly chain scission at the carbonate site of both types of Bayfol associated with the formation of hydroxyl group.     

Nanovesicle encapsulation of antimicrobial peptide P34: physicochemical characterization and mode of action on <Emphasis Type="Italic">Listeria monocytogenes</Emphasis>

Antimicrobial peptide P34, a substance showing antibacterial activity against pathogenic and food spoilage bacteria, was encapsulated in liposomes prepared from partially purified soybean phosphatidylcholine, and their physicochemical characteristics were evaluated. The antimicrobial activity was estimated by agar diffusion assay using Listeria monocytogenes ATCC 7644 as indicator strain. A concentration of 3,200 AU/mL of P34 was encapsulated in nanovesicles and stocked at 4 °C. No significant difference (p > 0.05) in the biological activity of free and encapsulated P34 was observed through 24 days. Size and PDI of liposomes, investigated by light scattering analysis, were on average 150 nm and 0.22 respectively. Zeta potential was −27.42 mV. There was no significant change (p > 0.05) in the physicochemical properties of liposomes during the time of evaluation. The liposomes presented closed spherical morphology as visualized by transmission electron microscopy (TEM). The mode of action of liposome-encapsulated P34 under L. monocytogenes cells was investigated by TEM. Liposomes appeared to adhere but not fuse with the bacterial cell wall, suggesting that the antimicrobial is released from nanovesicles to act against the microorganism. The effect of free and encapsulated P34 was tested against L. monocytogenes, showing that free bacteriocin inhibited the pathogen more quickly than the encapsulated P34. Liposomes prepared with low-cost lipid showed high encapsulation efficiency for a new antimicrobial peptide and were stable during storage. The mode of action against the pathogen L. monocytogenes was characterized.     

Methyl-Induced Polarization Destabilizes the Noncovalent Interactions of N-Methylated Lysines

Lysine methylation can modify noncovalent interactions by altering lysine's hydrophobicity as well as its electronic structure. Although the ramifications of the former are documented, the effects of the latter remain largely unknown. Understanding the electronic structure is important for determining how biological methylation modulates protein−protein binding, and the impact of artificial methylation experiments in which methylated lysines are used as spectroscopic probes and protein crystallization facilitators. The benchmarked first-principles calculations undertaken here reveal that methyl-induced polarization weakens the electrostatic attraction of amines with protein functional groups – salt bridges, hydrogen bonds and cation-π interactions weaken by as much as 10.3, 7.9 and 3.5 kT, respectively. Multipole analysis shows that weakened electrostatics is due to the altered inductive effects, which overcome increased attraction from methyl-enhanced polarizability and dispersion. Due to their fundamental nature, these effects are expected to be present in many cases. A survey of methylated lysines in protein structures reveals several cases in which methyl-induced polarization is the primary driver of altered noncovalent interactions; in these cases, destabilizations are found to be in the 0.6–4.7 kT range. The clearest case of where methyl-induced polarization plays a dominant role in regulating biological function is that of the PHD1-PHD2 domain, which recognizes lysine-methylated states on histones. These results broaden our understanding of how methylation modulates noncovalent interactions.     

Pupils,tools and the Zone of Proximal Development

In this article, I use the Vygotskian concept of the Zone of Proximal Development (ZPD) to examine the learning experience of two grade seven pupils as they attempted to solve an addition of fractions problem using fraction strips. The aim is to highlight how tools can facilitate the enactment of a ZPD, within which the tool provides the guidance. Viewing the ZPD as a zone that allows for the emergence of various forms of guided talk and actions, I present a detailed analysis of a short video-recording of the pupils’ participation in a tool-mediated problem-solving activity. I show how their knowing of the concept of fractions and their perceptions of the affordances of the fraction strips marked what they said and did. I conclude by suggesting that the ZPD emerges through participation and interaction, not only between individuals but also between individuals and tools.