Stereospecific Synthesis of D -Glycero- D -ido-oct-2-ulose

 D-Glycero-D-gulo-heptose reacted with 2,2-dimethoxypropane to give its 2,3:6,7-di-O-isopropylidene derivative. Its base-catalyzed addition to formaldehyde resulted in the formation of 2,3:6,7-di-O-isopropylidene-2-C-(hydroxymethyl)-D-glycero-D-gulo-heptofuranose. After acid hydrolysis of this aldolization product, a new branched-chain aldose, 2-C-(hydroxymethyl)-D-glycero-D-gulo-heptose, was obtained, which was stereospecifically rearranged under the catalytic action of molybdic acid to D-glycero-D-ido-oct-2-ulose.     

Compression resilience and impact resistance of fiber‐reinforced sandwich composites

This paper presents an experimental investigation on the compression behavior of fiber‐reinforced sandwich composites. In this study, five different types of sandwich composites were prepared with warp knitted spacer fabric as middle layer. Four different types of woven Kevlar fabric structures were used as outer layers (skin) along with one sample of woven basalt fabric. The middle layer used is 100% polyester spacer fabric. Sandwich composites were fabricated using epoxy resin by wet lay‐up method under vacuum bagging technique. Compression behavior, ball burst, and knife penetration were tested for all samples. The effect of outer layer of these composites on the mechanical performance was studied using the compression stress‐strain curves. It is known that spacers have excellent compression elasticity and cushioning. Maximum knife penetration resistance is obtained with twill weave on surface because of maximum yarn cohesion and resin impregnation. Higher amount of cohesive friction results in higher resistance against penetration of sharp objects like the knife edge. Plain and twill fabrics offer sufficient resistance again ball burst. The yarn deformation allows formation of dome shape after ball impact. Maximum impact resistance in ball burst is obtained for plain weave because of highest level of interyarn binding. The results provide new understanding of knitted spacer fabric‐based sandwich composites under compression and impact loading condition.     

Aqueous chemistry of transition metals in oxidation state (I) in Nanodroplets

"Nanodroplets" consisting of a central ion surrounded by a solvation shell of water molecules provide an interesting medium for studies of aqueous transition-metal chemistry in the unusual oxidation state (I). While VI undergoes efficient, solvent shell dependent redox reactions to VII and VIII, the absence of any similar reactivity in aqueous CrI, Mn1, FeI, CoI, NiI, and CuI clusters is explained by a rapid precipitation of the corresponding single monochloride molecules from the nanosolutions.     

Multiple solutions for Neumann and periodic problems with singular ?-Laplacian

We use the critical point theory for convex, lower semicontinuous perturbations of C¹-functionals to establish existence of multiple radial solutions for some one parameter Neumann problems involving the operator . Similar results for periodic problems are also provided.     

Closely embedded Kre?n spaces and applications to Dirac operators

Motivated by energy space representation of Dirac operators, in the sense of K. Friedrichs, we recently introduced the notion of closely embedded Kre?n spaces. These spaces are associated to unbounded selfadjoint operators that play the role of kernel operators, in the sense of L. Schwartz, and they are special representations of induced Kre?n spaces. In this article we present a canonical representation of closely embedded Kre?n spaces in terms of a generalization of the notion of operator range and obtain a characterization of uniqueness. When applied to Dirac operators, the results differ according to a mass or a massless particle in a dramatic way: in the case of a particle with a nontrivial mass we obtain a dual of a Sobolev type space and we have uniqueness, while in the case of a massless particle we obtain a dual of a homogenous Sobolev type space and we lose uniqueness.     

Crown ethers at the aqueous solution-air interface: 1. Assignments and surface spectroscopy

The surface of aqueous solutions of 4-Nitro Benzo-15-Crown-5 (NB15C5) and Benzo-15-Crown-5 (B15C5) has been studied using the surface sensitive technique vibrational sum frequency spectroscopy (VSFS). The NO, CN, COC and CH vibrational modes of these compounds at the air-water interface as well as OH vibrational modes of the surface water hydrating this compound have been targeted in order to obtain molecular information about arrangement and conformation of the adsorbed crown ether molecules at the air-water interface. The CH(2) vibrational modes of crown ethers have been identified and found to be split due to interaction with ether oxygen. The spectra provide evidence for the existence of a protonated crown complex moiety at the surface leading to the appearance of strongly ordered water species. The interfacial water species are influenced by the resulting charged interface and by the strong Zundel polarizability due to tunneling of the proton species between equivalent sites within the crown ring.     

Analysis of human blood plasma and hen egg white by chiroptical spectroscopic methods (ECD, VCD, ROA)

Chiroptical methods are widely used in structural and conformational analyses of biopolymers. The application of these methods to investigations of biofluids would provide new avenues for the molecular diagnosis of protein-misfolding diseases. In this work, samples of human blood plasma and hen egg white were analyzed using a combination of conventional and chiroptical methods: ultraviolet absorption/electronic circular dichroism (UV/ECD), Fourier transform infrared absorption/vibrational circular dichroism (FTIR/VCD), and Raman scattering/Raman optical activity (Raman/ROA). For comparison, the main components of these substances—human serum albumin (HSA) and ovalbumin (Ova)—were also analyzed by these methods. The ultraviolet region of the ECD spectrum was analyzed using the CDNN CD software package to evaluate the secondary structures of the proteins. The UV/ECD, FTIR/VCD, and Raman/ROA spectra of the substances were quite similar to those of the corresponding major proteins, while some differences were also detected and explained. The conclusions drawn from the FTIR/VCD and Raman/ROA data were in good agreement with the secondary structures calculated from ECD. The results obtained in this work demonstrate that the chiroptical methods used here can be applied to analyze not only pure protein solutions but also more complex systems, such as biological fluids.

A metrological approach for the assessment of selenium status in human serum

This work addresses a metrological approach for the assessment of Se status in humans in terms of serum selenomethionine (SeMet). The quantification of SeMet was carried out using a primary method of chemical analysis, namely species-specific isotope dilution (SSID) in combination with HPLC coupled to collision/reaction cell inductively coupled plasma-mass spectrometry. SeMet was released from the serum selenoalbumin (a seleno-containing protein where SeMet is randomly incorporated) by enzymatic hydrolysis of the whole serum. This study is a follow-up of the analytical method development reported previously, and it focuses primarily on the evaluation of the uncertainty budget and the main uncertainty sources for SeMet determination in three commercial serums, namely BCR-637 (certified for total Se) and two serum standards, SERONORM level 1 (SERO-L1) and 2 (SERO-L2) (with indicative concentrations of total Se). The metrological approach reported here could be considered as a pilot study in terms of metrological determination of SeMet in human serum, hence being suitable for method validation and inter-laboratory comparison.