Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study

We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent.     

Two-stage data segmentation permitting multiscale change points,heavy tails and dependence

Annals of the Institute of Statistical Mathematics - The segmentation of a time series into piecewise stationary segments is an important problem both in time series analysis and signal processing....     

Light and heat control over secondary structure and amyloid-like fiber formation in an overcrowded-alkene-modified Trp zipper

The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils.     

Guanidine‐Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases

Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2‐hydroxypropyl para‐nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts.     

Logarithmic temperature dependence of the conductivity of the two-dimensional metal

We report on the first observation and studies of a weak delocalizing logarithmic temperature dependence of the conductivity, which causes the conductivity of the 2D metal to increase as T decreases down to 16 mK. The prefactor of the logarithmic dependence is found to decrease gradually with density, to vanish at a critical density n _c , 2∼2×10¹² cm⁻², and then to have the opposite sign at n>n _c ,2. The second critical density sets the upper limit on the existence region of the 2D metal, whereas the conductivity at the critical point, G _c ,2∼120e ²/h, sets an upper (low-temperature) limit on its conductivity. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 6, 497–501 (25 September 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Carbon precipitation and diffusion in SiGeC alloys under silicon self-interstitial injection

In this work we investigate the diffusion and precipitation of supersaturated substitutional carbon in 200-nm-thick SiGeC layers buried under a silicon cap layer of 40 nm. The samples were annealed in either inert (N₂) or oxidizing (O₂) ambient at 850 °C for times ranging from 2 to 10 h. The silicon self-interstitial (I) flux coming from the surface under oxidation enhances the C diffusion with respect to the N₂-annealed samples. In the early stages of the oxidation process, the loss of C from the SiGeC layer by diffusion across the layer/cap interface dominates. This phenomenon saturates after an initial period (2–4 h), which depends on the C concentration. This saturation is due to the formation and growth of C-containing precipitates that are promoted by the I injection and act as a sink for mobile C atoms. The influence of carbon concentration on the competition between precipitation and diffusion is discussed. Received: 19 October 2001 / Accepted: 19 December 2001 / Published online: 20 March 2002 / Published online: 20 March 2002