Differential geometric analysis of alterations in MH α‐helices

Antigen presenting cells present processed peptides via their major histocompatibility (MH) complex to the T cell receptors (TRs) of T cells. If a peptide is immunogenic, a signaling cascade can be triggered within the T cell. However, the binding of different peptides and/or different TRs to MH is also known to influence the spatial arrangement of the MH α‐helices which could itself be an additional level of T cell regulation. In this study, we introduce a new methodology based on differential geometric parameters to describe MH deformations in a detailed and comparable way. For this purpose, we represent MH α‐helices by curves. On the basis of these curves, we calculate in a first step the curvature and torsion to describe each α‐helix independently. In a second step, we calculate the distribution parameter and the conical curvature of the ruled surface to describe the relative orientation of the two α‐helices. On the basis of four different test sets, we show how these differential geometric parameters can be used to describe changes in the spatial arrangement of the MH α‐helices for different biological challenges. In the first test set, we illustrate on the basis of all available crystal structures for (TR)/pMH complexes how the binding of TRs influences the MH helices. In the second test set, we show a cross evaluation of different MH alleles with the same peptide and the same MH allele with different peptides. In the third test set, we present the spatial effects of different TRs on the same peptide/MH complex. In the fourth test set, we illustrate how a severe conformational change in an α‐helix can be described quantitatively. Taken together, we provide a novel structural methodology to numerically describe subtle and severe alterations in MH α‐helices for a broad range of applications. © 2013 Wiley Periodicals, Inc.     

Synthesis of structurally diverse diarylketones through the diarylmethyl sp CH oxidation

Under open-flask conditions, an efficient method to assemble a series of diversely functionalized diarylketones in the presence of commercially available NBS has been developed. Yields of up to 99% have been achieved employing diarylmethanes as starting material. Based on ¹⁸O-labeled experiment, the addition of stoichiometric water eventually leads to excellent yields in all carbonylation cases.     

A turn-on and reversible fluorescence sensor with high affinity to Zn in aqueous solution

A new simple receptor 1 based on aminosalicylimine was prepared. It exhibited an ‘off–on fluorescence type’ mode with high sensitivity in the presence of Zn²⁺. In particular, this chemosensor could clearly distinguish Zn²⁺ from Cd²⁺. Also, it could be a reusable chemosensor because the addition of EDTA quenched the fluorescence of the Zn²⁺-2·1 complex. Furthermore, receptor 1 had a sufficiently low detection limit (68 nM) in aqueous solutions, which implies that 1 could sense the nanomolar concentration of Zn²⁺. Therefore, this sensor has the ability to be a practical system for the monitoring of Zn²⁺ concentrations in aqueous samples.     

BF3·OEt2-catalyzed synthesis of 1-(tetrahydropyran-3-yl)-1,3-dihydroisobenzofuran and trans-fused hexahydropyrano[3,2-c]chromene derivatives

A novel intramolecular Prins cyclization of (E)-5-(2-(hydroxymethyl)phenyl)pent-4-en-1-ol with aldehydes has been achieved using 10 mol % BF₃·Et₂O to produce 1-(tetrahydropyran-3-yl)-1,3-dihydroisobenzofuran derivatives in good to excellent yields with high selectivity. Similar type of coupling with salicylaldehydes provides the trans-fused hexahydropyrano[3,2-c]chromene derivatives in excellent yields.     

Identification of stiffness, dissipation and input parameters of randomly excited non-linear systems: Capability of restricted potential models (RPM)

A dynamic identification technique in the time domain for time invariant systems under random external forces is presented. This technique is based on the use of the class of restricted potential models (RPM), which are characterized by a non-linear stiffness and a special form of damping, that is a product of the input power spectral density (PSD) matrix and the velocity gradient of a non-linear function of the total mechanical energy. By applying stochastic differential calculus and by specific analytical manipulations, some algebraic equations, depending on the response statistics and on the mechanic parameters that characterize RPM, are obtained. These equations can be used for the dynamic identification of the above mechanic parameters once the response statistics of the system to be identified are evaluated. The proposed technique allows one to identify single-degree-of-freedom or multi-degrees-of-freedom systems in the case of unmeasurable input. Further, the probabilistic characteristics of the external forces can be completely estimated in terms of PSD matrix.     

（FeCp2）0．65FNi（C3S7）2]的合成及表征

合成了一种新型的导电配位型化合物（FeCp2）0．65FNi（C3S7）2].通过元素分析（EA），电感耦合等离子体原子发射光谱（ICP—AES），核磁共振（^1HNMR），紫外光谱（UV）对该化合物进行了表征。