Extended Reaction Scope of Thiamine Diphosphate Dependent Cyclohexane‐1,2‐dione Hydrolase: From C?C Bond Cleavage to C?C Bond Ligation

ThDP‐dependent cyclohexane‐1,2‐dione hydrolase (CDH) catalyzes the C C bond cleavage of cyclohexane‐1,2‐dione to 6‐oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH‐H28A is much less able to catalyze the C C bond formation, while the ability for C C bond cleavage is still intact. The double variant CDH‐H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane‐1,2‐dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54–94 % enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane‐2,3‐dione are alternative donor substrates for C C bond formation. Thus, the very rare aldehyde–ketone cross‐benzoin reaction has been solved by design of an enzyme variant.     

Scalable production of magnetic fluorescent cellulose microparticles

Cellulose - Fluorescent and magnetic nano- and microparticles have already been used for wide range of (bio)applications. Multimodal imaging as well as simultaneous control and monitoring of...     

Multiplexed Discrimination of Single Amino Acid Residues in Polypeptides in a Single SERS Hot Spot

The SERS-based detection of protein sequences with single-residue sensitivity suffers from signal dominance of aromatic amino acid residues and backbones, impeding detection of non-aromatic amino acid residues. Herein, we trap a gold nanoparticle in a plasmonic nanohole to generate a single SERS hot spot for single-molecule detection of 2 similar polypeptides (vasopressin and oxytocin) and 10 distinct amino acids that constitute the 2 polypeptides. Significantly, both aromatic and non-aromatic amino acids are detected and discriminated at the single-molecule level either at individual amino acid molecules or within the polypeptide chains. Correlated with molecular dynamics simulations, our results suggest that the signal dominance due to large spatial occupancy of aromatic rings of the polypeptide sidechains on gold surfaces can be overcome by the high localization of the single hot spot. The superior spectral and spatial discriminative power of our approach can be applied to single-protein analysis, fingerprinting, and sequencing.     

Study of a plane‐free jet exhausting from a channel by vortex‐in‐cell method

A two‐dimensional simulation of a plane jet exhausting from a channel has been performed using the vortex in cell algorithm in the Reynolds number range of 100–900. The vorticity is generated on the wall of the entrance channel whose length has been fixed in order to obtain a fully developed velocity profile at the entry of the jet. The transient behaviour of the velocity field starting from rest has been observed until reaching a quasi steady regime. The mean value of the velocity field is compared with the results of a finite volume computation on the same mesh. The velocity fluctuations obtained using this method are analysed. Their effect on the mean flow is estimated to be smaller than the viscous effect. Copyright © 2006 John Wiley & Sons, Ltd.     

Sub-ppbv nitric oxide concentration measurements using cw thermoelectrically cooled quantum cascade laser-based integrated cavity output spectroscopy

A nitric oxide (NO) gas sensor based on a thermoelectrically cooled, continuous-wave, distributed feedback quantum cascade laser operating at 5.45 μm (1835 cm^-1) and off-axis integrated cavity output spectroscopy combined with a wavelength-modulation technique was developed to determine NO concentrations at the sub-ppbv levels that are essential for a number of applications, such as medical diagnostics, environmental monitoring, and industrial process control. The sensor employs a 50-cm-long high-finesse optical cavity that provides an effective path length of ∼700 m. A noise equivalent (SNR=1) minimum detection limit of 0.7 ppbv with a 1-s observation time was achieved. PACS 07.07.Df; 33.20.Ea; 42.62.Fi; 87.64.Je     

Mid-infrared single-photon counting

We report a procedure to detect mid-infrared single photons at 4.65 microm by means of a two-stage scheme based on sum-frequency generation, by using a periodically poled lithium niobate nonlinear crystal and a silicon avalanche photodiode. An experimental investigation shows that, in addition to a high timing resolution, this technique yields a detection sensitivity of 1.24 pW with 63 mW of net pump power.     

Texture analysis of bronze age axes by neutron diffraction

Neutron diffraction has been utilised as a non-invasive diagnostic tool to gain insight into the ancient metallurgic and manufacturing techniques employed for the production of three bronze age axes from archaic to late bronze age (20th to 13th Century BC). The analysed bronze artefacts are from the “Terramare” and other bronze age settlements near Modena, Italy. Neutron diffraction provides the alloy and phase compositions in a totally non destructive approach, without interference from surface alteration and corrosion layers. Furthermore, neutron based texture analysis, with the advantage of large grain statistics deep into the bulk, provides details of the production techniques that can complement traditional metallographic examinations, and may provide unique information for samples that cannot suffer invasive treatments. PACS 61.12.Ld; 81.05.Bx     

Invariance operator groups for a charged particle in an external electromagnetic field

In this paper a general group theoretical approach is given for the problem of a charged particle moving in an external electromagnetic field F. From a knowledge of the symmetry transformations of the field (Galilean or Poincaré), it is possible to explicitly construct groups of operators which commute with the operators of the equations of motion (classical, quantum mechanical, Klein-Gordon or Dirac) using the concept of compensating gauge transformations together with a uniquely chosen map π: F → A fixing the gauge of the potential A. Other choices of gauges give rise to isomorphic operator groups. The general structure of the possible symmetry groups of the fields is discussed and the corresponding invariance operator groups are explicitly given for (almost) arbitrary fields. The structure of these groups is then investigated and it is shown in particular that a large class of fields give rise to non-Type I groups, i.e. to groups which have (unitary continuous) representations whose corresponding von Neumann algebras have non-discrete factors. A general criterion for these pathological cases is given. As an application, we study the problem of a Bloch electron in arbitrary constant uniform electric and magnetic fields.     

Correlation length and fluctuations in inhomogeneous superconductors

The correlation length and the effect of fluctuations of the grains are calculated for weakly coupled granular superconductors, using a two order parameter Ginzburg-Landau-Wilson functional. The main effect of fluctuations is shown to be a shift of the coherent transition temperature, and the correlation length is compared to the corresponding expression in strongly coupled granular superconductors.