Membrane Proteins Have Distinct Fast Internal Motion and Residual Conformational Entropy

The internal motions of integral membrane proteins have largely eluded comprehensive experimental characterization. Here the fast side‐chain dynamics of the α‐helical sensory rhodopsin II and the β‐barrel outer membrane protein W have been investigated in lipid bilayers and detergent micelles by solution NMR relaxation techniques. Despite their differing topologies, both proteins have a similar distribution of methyl‐bearing side‐chain motion that is largely independent of membrane mimetic. The methyl‐bearing side chains of both proteins are, on average, more dynamic in the ps–ns timescale than any soluble protein characterized to date. Accordingly, both proteins retain an extraordinary residual conformational entropy in the folded state, which provides a counterbalance to the absence of the hydrophobic effect. Furthermore, the high conformational entropy could greatly influence the thermodynamics underlying membrane‐protein functions, including ligand binding, allostery, and signaling.     

Probing the Brønsted Acidity of the External Surface of Faujasite-Type Zeolites

We outline two methodologies to selectively characterize the Brønsted acidity of the external surface of FAU-type zeolites by IR and NMR spectroscopy of adsorbed basic probe molecules. The challenge and goal are to develop reliable and quantitative IR and NMR methodologies to investigate the accessibility of acidic sites in the large pore FAU-type zeolite Y and its mesoporous derivatives often referred to as ultra-stable Y (USY). The accessibility of their Brønsted acid sites to probe molecules (n-alkylamines, n-alkylpyridines, n-alkylphosphine- and phenylphosphine-oxides) of different molecular sizes is quantitatively monitored either by IR or ³¹P NMR spectroscopy. It is now possible, for the first time to quantitatively discriminate between the Brønsted acidity located in the microporosity and on the external surface of large pore zeolites. For instance, the number of external acid sites on a Y (LZY-64) zeolite represents 2 % of its total acid sites while that of a USY (CBV760) represents 4 % while the latter has a much lower framework Si/Al ratio.     

Equilibrium Formation of Stable All‐Silicon Versions of 1,3‐Cyclobutanediyl

Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si₃Tip₄ (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR₂CH₂)(NtBu)₂]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)₂(NtBu)₂Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate.     

Light-induced cis/trans isomerization of cis-[Pd(L-S,O)2] and cis-[Pt(L-S,O)2] complexes of chelating N,N-dialkyl-N′-acylthioureas: key to the formation and isolation of trans isomers

Irradiation cis-[M(Lⁿ-S,O)₂] complexes (M = Pt^II, Pd^II) derived from N,N-dialkyl-N′-benzoylthioureas (HLⁿ) with various sources of intense visible polychromatic or monochromatic light with λ < 500 nm leads to light-induced cis?→?trans isomerization in organic solvents. In all cases, white light derived from several sources or monochromatic blue-violet laser 405 nm light, efficiently results in substantial amounts of the trans isomer appearing in solution, as shown by ¹H NMR and/or reversed-phase HPLC separation in dilute solutions at room temperature. The extent and relative rates of cis/trans isomerization induced by in situ laser light (λ = 405 nm) of cis-[Pd(L²-S,O)₂] was directly monitored by ¹H NMR and ¹⁹⁵Pt NMR spectroscopy of selected cis-[Pt(L-S,O)₂] compounds in chloroform-d; both with and without light irradiation allows the δ(¹⁹⁵Pt) chemical shifts cis/trans isomer pairs to be recorded. The cis/trans isomers appear to be in a photo-thermal equilibrium between the thermodynamically favored cis isomer and its trans counterpart. In the dark, the trans isomer reverts back to the cis complex in what is probably a thermal process. The light-induced cis/trans process is the key to preparing and isolating the rare trans complexes which cannot be prepared by conventional synthesis as confirmed by the first example of trans-[Pd(L-S,O)₂] characterized by single-crystal X-ray diffraction, deliberately prepared after photo-induced isomerization in acetonitrile solution.     

Efficient synthesis of phosphorus-containing dendrimers capped with isosteric functions of amino-bismethylene phosphonic acids

An efficient synthetic strategy to synthesize phosphorus-containing dendrimers capped with isosteric acid functions derived from tyramine is described. The method is demonstrated on a first generation dendrimer that can be easily capped with 12 amino(bismethylene) sulfonic acids and amino(bismethylene) carboxylic acids that are strict analogs of the corresponding amino(bismethylene) phosphonic acids.     

Weighted irregular Gabor tight frames and dual systems using windows in the Schwartz class

We give a characterization for the weighted irregular Gabor tight frames or dual systems in L²(Rn) in terms of the distributional symplectic Fourier transform of a positive Borel measure on R2n naturally associated with the system and the short-time Fourier transform of the windows in the case where the window (or at least one of the windows in the case of dual systems) belongs to S(Rn). This result implies that, for certain classes of windows such as generalized Gaussians or “extreme-value” windows, the only weighted irregular Gabor tight frames (or even dual systems with both windows in the same class) that can be constructed with these windows are the trivial ones, corresponding to the measure μ=1 on R2n. Furthermore, we show that, if a such Gabor system admits a dual which is of Gabor type, then the Beurling density of the associated measure exists and is equal to one.     

A double-sided multiunit combinatorial auction for substitutes: Theory and algorithms

Combinatorial exchanges have existed for a long time in securities markets. In these auctions buyers and sellers can place orders on combinations, or bundles of different securities. These orders are conjunctive: they are matched only if the full bundle is available. On business-to-business (B2B) exchanges, buyers have the choice to receive the same product with different attributes; for instance the same product can be produced by different sellers. A buyer indicates his preference by submitting a disjunctive order, where he specifies the quantity he wants of each particular good and what limit price he is willing to pay for each good, thus providing a subjective valuation of each attribute. Only the goods with the best prices will be traded. This article considers a doubled-sided multiunit combinatorial auction for substitutes, that is, a uniform price auction where buyers and sellers place both types of orders, conjunctive (AND orders) and disjunctive (XOR orders). We show that linear competitive prices exist. We also propose an algorithm to clear the market, which is particularly efficient when the number of traders is large, and the goods are divisible.     

A chaotic secure communication scheme using fractional chaotic systems based on an extended fractional Kalman filter

In recent years chaotic secure communication and chaos synchronization have received ever increasing attention. In this paper, for the first time, a fractional chaotic communication method using an extended fractional Kalman filter is presented. The chaotic synchronization is implemented by the EFKF design in the presence of channel additive noise and processing noise. Encoding chaotic communication achieves a satisfactory, typical secure communication scheme. In the proposed system, security is enhanced based on spreading the signal in frequency and encrypting it in time domain. In this paper, the main advantages of using fractional order systems, increasing nonlinearity and spreading the power spectrum are highlighted. To illustrate the effectiveness of the proposed scheme, a numerical example based on the fractional Lorenz dynamical system is presented and the results are compared to the integer Lorenz system.     

Multiplurifunctionalized Phosphorus Dendrimers: Selective Functionalization of P(X)CL2 Terminal Groups

Abstract

Dendrimers are hyperbranched macromolecules constituted of repetitive branched units. They are synthesized step-by-step, a method which ensures a perfectly defined structure. This mini-review reports examples of rare “multiplurifunctionalized” dendrimers that have several types of functional groups precisely located on each terminal branching point. They are obtained thanks to the specificity of the reactivity of each Cl of P(X)Cl₂ (X = generally S, but also O) terminal groups on the surface of poly(phosphorhydrazone) dendrimers.