Characterization of the terminal iron(IV) imides [[PhBP(t)(Bu)2(pz')]Fe(IV)NAd]+

New hybrid bis(phosphine)(pyrazole)borate tripodal ligands ([PhBPtBu2(pz')]-) are reported that support pseudotetrahedral iron in the oxidation states +1, +2, +3, and +4. The higher oxidation states are stabilized by a terminal FeNR linkage. Of particular interest is the generation and thorough characterization of an S = 1 FeIVNR+ imide cation using this new ligand system. The latter species can be observed electrochemically and spectroscopically, and its solid-state crystal structure is reported.     

Nucleophilic-alkylation-reoxidation: a functionalization sequence for single-wall carbon nanotubes

A new reaction sequence for the chemical functionalization of single-wall carbon nanotubes (SWNTs) consisting of the nucleophilic addition of t-BuLi to the sidewalls of the tubes and the subsequent reoxidation of the intermediates t-Bu(n)SWNT(n-) leading to t-Bu(n)SWNT was developed. During the formation of the t-Bu(n)SWNT(n-), a homogeneous dispersion in benzene was formed due to the electrostatic repulsion of the negatively charged intermediates causing debundling. The entire reaction sequence can be repeated, and the degree of functionalization of the products (t-Bu(n))(m)SWNT (m = 1-3) increases with increasing m. Degrees of functionalization expressed as the carbon-to-addend ratio of up to 31 were reached. The reaction was studied in detail by photoelectron spectroscopy, Raman spectroscopy, and scanning tunneling microscopy (STM). The C 1s core level spectra reveal that the nucleophilic attack of the t-BuLi leads to negatively charged SWNTs. Upon oxidation, this negative charge is removed. The valence band spectra of the functionalized samples exhibit a significant reduction in the pi-derived density of states. In STM, the covalently bonded t-butyl groups attached to the sidewalls have been visualized. Raman spectroscopy reveals that addition of the nucleophile to metallic tubes is preferred over the addition to semiconducting tubes.     

Sample pretreatment on a microchip with an integrated electrospray emitter

This study presents a microbead-packed PDMS microchip with an integrated electrospray emitter for sample pretreatment prior to sheathless ESI-MS. We prove the concept of analytical functions integrated onto a cm-sized area of a single bulk material. The microchip consists of two PDMS substrates replicated from SU-8 fabricated silicon wafer masters, bonded together after oxidation by corona discharge treatment. The channel within the microchip contains a grid structure that was used to trap 5 microm hypercross-linked polystyrene beads. The beads acted as a medium for sample desalting and enrichment. Electrical contact for the sheathless ESI process was achieved by coating the integrated emitter with conductive graphite powder after applying a thin layer of PDMS as glue. The coating as well as the bond of the PDMS structures showed excellent durability. A continuous spray was obtained from the microchip for over 800 h in a long-term electrospray stability experiment. Desalting and enrichment of neuropeptides from a physiological salt solution was successful by loading the sample onto the packed beads, followed by a washing and an eluting step. The results were obtained and evaluated using a TOF MS. An LOD of approximately 20 fmol (loaded onto the beads) for angiotensin II was obtained from a sample of neuropeptides dissolved in physiological salt solution.     

Surface treatment and characterization: perspectives to electrophoresis and lab-on-chips

The control and modification of surface state is a major challenge in bioanalytical sciences, and in particular in electrokinetic separation methods, due to the importance of electroosmosis. This topic has gained recently a renewed interest, associated with the development of "lab-on-chips" systems that extend the range of materials in which separation channels are fabricated. The surface science community has developed through the years a large toolbox of characterization tools and surface modification protocols, which is not yet fully exploited in the bioanalytical world. In this paper, we try and present an overview of these tools, in order to stimulate new ideas for improved and more controlled surface treatment strategies for separations in capillaries and microchannels. We briefly describe some physical and chemical aspects of electroosmosis (global and spatially resolved), streaming current, and streaming potential. We also review the main strategies for surface coating, and compare the advantages of physisorption, well-organized thin self-assembled monolayers, or conversely thick polymer "brushes". Examples of existing applications to electrophoresis in microchannel are also given.     

A projection method to solve linear systems in tensor format

In this paper, we propose a method for the numerical solution of linear systems of equations in low rank tensor format. Such systems may arise from the discretisation of PDEs in high dimensions, but our method is not limited to this type of application. We present an iterative scheme, which is based on the projection of the residual to a low dimensional subspace. The subspace is spanned by vectors in low rank tensor format which—similarly to Krylov subspace methods—stem from the subsequent (approximate) application of the given matrix to the residual. All calculations are performed in hierarchical Tucker format, which allows for applications in high dimensions. The mode size dependency is treated by a multilevel method. We present numerical examples that include high‐dimensional convection–diffusion equations.Copyright © 2012 John Wiley & Sons, Ltd.     

Microwave‐Promoted Palladium(II)‐Catalyzed C?P Bond Formation by Using Arylboronic Acids or Aryltrifluoroborates

The first Pd^II‐catalyzed P arylation has been performed by using palladium acetate, the rigid bidentate ligand dmphen (dmphen=2,9‐dimethyl‐1,10‐phenanthroline), and without the addition of base or acid. Couplings of arylboronic acids or aryl trifluoroborates with H‐phosphonate dialkyl esters were conducted in 30 min with controlled microwave (MW) heating under non‐inert conditions. Aryl phosphites were also synthesized at room temperature with atmospheric air as the sole reoxidant. The arylated phosphonates were isolated in 44–90 % yields. The excellent chemoselectivity of the method was illustrated in the synthesis of a Mycobacterium tuberculosis glutamine synthetase (MTB‐GS) inhibitor. Online ESIMS was used to detect cationic palladium species in ongoing reactions directly, and a catalytic cycle has been proposed based on these results.     

A Different Approach to Enantioselective Organic Synthesis: Absolute Asymmetric Synthesis of Organometallic Reagents

Voilà, optical activity : Both enantiomers of 1‐chloroindene have been synthesized in high selectivity from solely achiral starting materials, and without using optically active catalysts (see scheme). These symmetry‐breaking syntheses provide a proof‐of‐concept for a new approach to asymmetric synthesis. NCS=N‐chlorosuccinimide.

     

On small tension p-branes

This Letter deals with p-branes with small but non-zero tension. We prove the existence of canonical transformations, within a perturbation theory, that link specific geometries of p  -branes to solvable theories, namely string-like and particle-like theories. The specific shapes correspond to stretched configurations. For configurations linked to string-like theories one will upon quantization get a critical dimension of (25+p$25+p$).