Reversible Phosphaalkene Formation Frol'i Iminodi-Phosphines

Abstract

Addition of variousnucleophiles to phosphaalkenes is considered to be irreversible. As an example, the quantitative formation of iminodiphosphine III from phosphinous amide and phosphaalkene was recently reported (1).     

Multicriteria mapping of stakeholder preferences in regulating nanotechnology

In order to facilitate stakeholder discussions on how to regulate nanotechnology, the opensource program multicriteria mapping (MCM) was used to structure 26 interviews with stakeholders in the USA. MCM offers a systematic part quantitative, part qualitative approach to clarify why some regulatory options (bans, moratoriums, voluntary measures, etc.) were deemed to be acceptable/unacceptable by various stakeholders and which criteria stakeholders used to evaluate the different regulatory options. Adopting an incremental approach and implementing a new regulatory framework was evaluated as the best options whereas a complete ban and no additional regulation of nanotechnology were found to be the least favorable. Criteria applied differed substantially among stakeholders and included social, ethical, regulatory, environmental, and health issues. Opinions on future regulation seem far less polarized than expected and it seems that stakeholders would welcome a combination of voluntary measures, an incremental approach and forming of a new regulatory framework.     

Molecular and crystal structure of 2-(2-p-tolyloxyethoxy)ethylchloroacetate

2-(2-p-Tolyloxyethoxy)ethylchloroacetate is synthesized and its single crystal X-ray diffraction analysis is performed.     

Comments on: Polling: past,present and perspective

In their exposé on the past, present and perspective of the analysis of polling systems, professors Borst and Boxma give a first-hand account on the advancement of this particular research field. As any good historical account, the paper highlights some of the key turning points in the advancement of our current understanding of the dynamics of polling systems. Their paper, however, goes far beyond a classical literature review, as it also emphasises recent developments and points to many open problems. In the first section of this present note, we give some introductory comments on polling systems and queueing systems in general, followed by a discussion of Borst and Boxma’s survey of the past and the present in Sect. 2. Finally, we discuss some of their suggestions for further research in Sect. 3.     

Structural elucidation by 1D and 2D NMR of three isomers of a carotenoid lysophosphocholine and its synthetic precursors

A carotenoic acid was used to obtain a long-chain unsaturated lysophosphocholine. The carotenoid lysophosphocholine was synthesized by two methods. The first method resulted in mixtures of regioisomers for each step in the synthetic route. Homo- and heteronuclear 1D and 2D NMR methods were employed to elucidate the structures of the individual isomers and their intermediates. The pure regioisomer [1-(beta-apo-8'-carotenoyl)-2-lyso-glycero-3-phosphocholine] was obtained by a second method, but in low yield. The 1D 1H NMR subtraction spectrum of the mixture and the pure regioisomer was used to interpret the 1H shifts of the unsaturated acyl moieties. The 1H and 13C signals of the acyl chain show characteristic shifts depending on the positions of the choline and the acyl group attached to the glycerol backbone. Therefore, the unsaturated acyl chain signals have diagnostic values for the identification of isomers of unsaturated (lyso)phosphocholines. Chemical shifts and indirect coupling constants are reported for each of the major components of the mixtures. The methods used were 1D (1H, 13C and 31P) and 2D (H,H-COSY, HMBC, HSQC and HETCOR) NMR.     

Multilayer chitosan-based open tubular capillary anion exchange column with integrated monolithic capillary suppressor

We describe a multilayered open tubular anion exchange column fabricated by alternately pumping solutions of chitosan and glutaraldehyde. The column is terminated in an integrally bonded monolithic suppressor cast around a mandrel of a tungsten wire, composed of an acrylic acid (AA)-ethylene dimethacrylate (EDMA) monolith that is made with sufficient porogen for the monolith to function as a membrane. For a 4.5m long 75 μm bore column coated with 24 successive layers of the condensation polymer (estimated to contain ~72 molecular layers) and coupled to 1cm length of a suppressor fabricated with 55-60% AA, effective separation of several common anions (F(-), Cl(-), NO(2)(-), Br(-), NO(3)(-), average number of theoretical plates ~12,000) and adequate suppression of 1 mM KOH used as eluent was observed at a flow rate of 800 nL min(-1) to obtain sub-picomol detection limits at an operating pressure of ~1 bar. The separation is not time efficient but the system can be meritorious in unique niche applications where a small form factor is desired and liquid volume and power consumption are more important than separation speed.     

Flavin Derivatives with Tailored Redox Properties: Synthesis,Characterization, and Electrochemical Behavior

This study establishes structure–property relationships for four synthetic flavin molecules as bioinspired redox mediators in electro‐ and photocatalysis applications. The studied flavin compounds were disubstituted with polar substituents at the N1 and N3 positions (alloxazine) or at the N3 and N10 positions (isoalloxazines). The electrochemical behavior of one such synthetic flavin analogue was examined in detail in aqueous solutions of varying pH in the range from 1 to 10. Cyclic voltammetry, used in conjunction with hydrodynamic (rotating disk electrode) voltammetry, showed quasi‐reversible behavior consistent with freely diffusing molecules and an overall global 2e^?, 2H⁺ proton‐coupled electron transfer scheme. UV/Vis spectroelectrochemical data was also employed to study the pH‐dependent electrochemical behavior of this derivative. Substituent effects on the redox behavior were compared and contrasted for all the four compounds, and visualized within a scatter plot framework to afford comparison with prior knowledge on mostly natural flavins in aqueous media. Finally, a preliminary assessment of one of the synthetic flavins was performed of its electrocatalytic activity toward dioxygen reduction as a prelude to further (quantitative) studies of both freely diffusing and tethered molecules on various electrode surfaces.     

A computer controlled,finite duration “steady” flow facility

A novel and relatively simple flow facility was designed and fabricated to study the instability characteristics of a slit-jet flow field. The performance of the flow facility has been found to be statisfactory. The operation of this gravity driven, finite duration, steady flow facility was based upon an inviscid flow model. This technique to establish a finite duration steady flow field is quite general in nature and can be easily adapted to other flow fields of interest.The authors are pleased to acknowledge the support of the National Science Foundation grant MEA-8216946. Efforts of Irwin Lawson, John Joyce and Richard Haw are also acknowledged; they provided help on various aspects of the flow facility.