An Efficient Labelling Approach to Harness Backbone and Side‐Chain Protons in 1H‐Detected Solid‐State NMR Spectroscopy

¹H‐detection can greatly improve spectral sensitivity in biological solid‐state NMR (ssNMR), thus allowing the study of larger and more complex proteins. However, the general requirement to perdeuterate proteins critically curtails the potential of ¹H‐detection by the loss of aliphatic side‐chain protons, which are important probes for protein structure and function. Introduced herein is a labelling scheme for ¹H‐detected ssNMR, and it gives high quality spectra for both side‐chain and backbone protons, and allows quantitative assignments and aids in probing interresidual contacts. Excellent ¹H resolution in membrane proteins is obtained, the topology and dynamics of an ion channel were studied. This labelling scheme will open new avenues for the study of challenging proteins by ssNMR.     

Comparison of stabilization modes of a symmetrical third-order non-linear oscillatory unit

The possibility of constructing symmetrical stabilized oscillator models that operate in several phases instead of operating in two phases, as is more usual, is considered in the present paper. In particular, symmetrical oscillator models operating in three phases are discussed comprehensively. An interesting feature of their dynamic behaviour, e.g. the appearance of limit cycles which are regionally stable and not orbitally stable, as is the case in the two phase counterpart, is suggested and dealt with.     

Functionalization of Silk Fibroin with NeutrAvidin and Biotin

New methods are needed to modify silk biomaterials with bioactive molecules for tissue engineering and drug delivery. In the present study, silk fibroin in solution or in microsphere format was coupled with NeutrAvidin via carbodiimide chemistry. Silk fibroin retained its self‐assembly features after reaction. It was found that more than four NeutrAvidin molecules bound to one silk molecule. Non‐specific binding of biotin or NeutrAvidin to silk microspheres could be reduced by pre‐treatment of the microspheres with BSA or post‐treatment with detergent. The NeutrAvidin‐coupled silk microspheres were coupled with biotinylated anti‐CD3 antibody and the functionalized microspheres were able to specifically bind to the CD3 positive T‐lymphocytic cell line Jurkat.

     

An algorithm to compute <Emphasis Type="Italic">ω</Emphasis>-primality in a numerical monoid

Let M be a commutative, cancellative, atomic monoid and x a nonunit in M. We define ω(x)=n if n is the smallest positive integer with the property that whenever x∣a ₁???a _t , where each a _i is an atom, there is a T?{1,2,…,t} with |T|≤n such that x∣∏_k∈T a _k . The ω-function measures how far x is from being prime in M. In this paper, we give an algorithm for computing ω(x) in any numerical monoid. Simple formulas for ω(x) are given for numerical monoids of the form 〈n,n+1,…,2n?1〉, where n≥3, and 〈n,n+1,…,2n?2〉, where n≥4. The paper then focuses on the special case of 2-generator numerical monoids. We give a formula for computing ω(x) in this case and also necessary and sufficient conditions for determining when x is an atom. Finally, we analyze the asymptotic behavior of ω(x) by computing \(\lim_{x\rightarrow \infty}\frac{\omega(x)}{x}\).     

Artin-Schreier extensions in NIP and simple fields

We show that NIP fields have no Artin-Schreier extension, and that simple fields have only a finite number of them.     

Elaboration of hybrid nanocluster materials by solution chemistry

The [(M₆L₁₂ⁱ)L₆^a]ⁿ⁻ and [(M₆L₈ⁱ)L₆^a] units (a = apical, i = inner) constitute the basic building blocks in the octahedral cluster chemistry. Nano-sized metallic clusters are easily obtained by solid state synthesis with transition elements associated with halogen or chalcogen. The intrinsic properties of M₆ cluster units—one or two electron reversible redox process, magnetism and luminescence—depend on the nature of the metal and ligands. The solubilisation of M₆ solid state compounds provides [(M₆L₁₂ⁱ)L₆^a]ⁿ⁻ or [(M₆L₈ⁱ)L₆^a]ⁿ⁻ building blocks with individual properties that can be further used for the design of hybrid organic/inorganic materials. Several examples of solid state precursors are presented as well as substitution reactions of apical ligands in solution. Indeed, hexacyano M₆ clusters are obtained by direct reaction of solid state precursors in aqueous KCN solutions. Low dimensional frameworks are subsequently obtained by recrystallisation of hexacyano M₆ clusters with transition elements. The functionalisation of cluster proceeds in two steps. The first one consists in the replacement of apical halogens of cluster unit precursors by labile groups as CF₃SO₃ (triflate) or solvent molecules after solution reaction. The second one consists in the substitution of the labile groups by functionalised phenolate or pyridine ligands.     

Solution behavior of synthetic silk peptides and modified recombinant silk proteins

Spider dragline silk from Nephila clavipes possesses impressive mechanical properties derived in part from repetitive primary sequence containing polyalanine regions that self-assemble into crystalline β-sheets. In the present study, we have sought to understand more details of redox responses related to conformational transitions of modified silk peptides and a recombinant protein containing encoded methionine triggers. Regardless of the position of the methionine trigger relative to the polyalanine domain, chemical oxidation was rapid and slight increases in the α-helical structure and decreases in the β-sheet and random coil content were observed by CD and FTIR in the assembled silk-like peptides and the recombinant protein. CD results indicated that the decrease in β-sheet and random coil conformations, coupled with the increase in helical content during oxidation, occurred during the first 30 min of the reaction. No further conformational changes occurred after this time and the response was independent of methionine trigger location relative to the penta-alanine domain. These results were confirmed with fluorescence studies. The design, processing and utility of these modified redox triggered silk-like peptides and proteins suggest a range of potential utility, from biomaterials to engineered surface coatings with chemically alterable secondary structure and, thus, properties. PACS 87.14.Ee; 87.64.-t; 87.6.+2.