Operator spaces with prescribed sets of completely bounded maps

Suppose A is a dual Banach algebra, and a representation π:A→B(?₂) is unital, weak* continuous, and contractive. We use a “Hilbert-Schmidt version” of Arveson distance formula to construct an operator space X, isometric to ?₂⊗?₂, such that the space of completely bounded maps on X consists of Hilbert-Schmidt perturbations of π(A)⊗I_?2. This allows us to establish the existence of operator spaces with various interesting properties. For instance, we construct an operator space X for which the group K₁(CB(X)) contains Z₂ as a subgroup, and a completely indecomposable operator space containing an infinite dimensional homogeneous Hilbertian subspace.     

Isomerization of 5-(2H-Azirin-2-yl)oxazoles: An Atom-Economic Approach to 4H-Pyrrolo[2,3-d]oxazoles

An atom economical method for the preparation of variously substituted 4H-pyrrolo[2,3-d]oxazoles was developed on the basis of thermal isomerization of 5-(2H-azirin-2-yl)oxazoles. The latter were prepared by Rh₂(oct)₄ catalyzed reaction of 2-(3-aryl/heteroaryl)-2-diazoacetyl-2H-azirines with a set of substituted acetonitriles, benzonitriles, acrylonitrile and fumaronitrile. According to DFT calculations the transformation of 5-(2H-azirin-2-yl)oxazole to 4H-pyrrolo[2,3-d]oxazole occurs through the nitrenoid-like transition state to give a 3aH-pyrrolo[2,3-d]oxazole intermediate, followed by 1,5-H-shift.     

A novel theranostic nanobioconjugate: 125/131I labeled phenylalanine conjugated boron nitride nanotubes

Journal of Radioanalytical and Nuclear Chemistry - Here we report the synthesis of boron nitride nanotubes (BNNTs) via a chemical vapor deposition method, as potential agents for boron neutron...     

Planarity takes over in the C(x)H(x)P(6-x) (x = 0-6) series at x = 4

In this work we examine a structural transition from non-planar three-dimensional structures to planar benzene-like structures in the C(x)H(x)P(6-x) (x = 0-6) series. The global minima of P(6), CHP(5), and C(2)H(2)P(4) species are benzvalene-like structures. The benzvalene and benzene-like structures of C(3)H(3)P(3) are close in energy with the former being slightly more stable at our best level of theory. The transition occurs at x = 4 (C(4)H(4)P(2)), where the benzene-like structures become significantly more stable than the benzvalene-like structures. We show that the pseudo Jahn-Teller effect, which is responsible for the deformation of planar P(6), CHP(5), and C(2)H(2)P(4) structures, is completely suppressed at x = 3 (benzene-like structures of C(3)H(3)P(3)). We present NICS(zz) values of all the benzene-like isomers in the series.     

Electrochemical sensor for blood deoxyribonucleases: design and application to the diagnosis of autoimmune thyroiditis

We designed an electrochemical sensor based on a carbon nanotube modified electrode (ME) to analyze DNA-cleaving activity. The cleavage of high molecular weight DNA resulted in an increase in the oxidation current from DNA guanine nucleotides due to a change in DNA adsorptive behavior on the surface of the ME. DNA digestion with DNAse I was accompanied by a linear increase in the DNA signal in proportion to the enzyme activity. We then proposed an assay based on the sensor for the direct assessment of the total deoxyribonuclease activity of blood serum as well as the separate detection of DNAse I and DNA abzymes. The assay was applied to analyze deoxyribonucleases in sera from 21 healthy donors and 17 patients with autoimmune thyroiditis. Our results show that the response of the sensor to DNA cleavage by blood deoxyribonucleases is a promising diagnostic criterion for autoimmune thyroiditis. This sensor can be implemented in a disposable screen-printed electrode format for application in clinical laboratories.     

Concurrent simulation of multibody systems coupled with stress–strain and heat transfer solvers

In the present work multibody 3-axis truck vehicle model coupled with submodels of suspension bodies is considered. Coupling the main model with submodels allows to perform simulation of multibody dynamics and non-stationary heat conduction and stress distribution processes in bodies simultaneously. High efficiency of parallel simulation on computer cluster is achieved using developed software based on MPI library.     

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Amino‐functionalized zirconium‐based metal‐organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non‐functionalized analogues for hydrolysis of organophosphonate‐based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO‐66‐NH₂, where the amino groups reside near the node, compared to UiO‐67‐m‐NH₂, where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate‐based nerve agents. The generality of the observed amine‐proximity‐dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr₆‐node active site and therefore increase the overall catalytic rates.     

Pore Aperture Control Toward Size-Exclusion-Based Hydrocarbon Separations

Metal–organic frameworks (MOFs) have been proposed as a promising material for non-thermal chemical separations owing to their high structural diversity and tunability. Here, we report the synthesis of a zinc-based MOF containing a three-dimensional (3D) linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, with high thermal stability towards the separation of hexane isomers. The incorporation of the 3D linker enhances the structural stability and provides well-defined pore apertures/channels with sub-Ångstrom precision. This precision allowed for the separation of similarly sized hexane isomers based on subtle differences in their kinetic diameters. Multi-component liquid phase batch experiments confirmed the separation of hexanes mixture into linear, monobranched, and dibranched isomers. This work represents a significant milestone in the construction of stable Zn-based MOFs and the incorporation of 3D linkers as a potential solution to challenging separations.     

Probing the Raman scattering tensors of individual molecules

Single-molecule experiments provide new views into the mechanisms behind surface-enhanced Raman scattering. It was shown previously that spectra of individual rhodamine 6G molecules adsorbed on silver nanocrystal aggregates present stronger fluctuations in two low-frequency bending modes, at 614 and 773 cm(-1). Here we use polarization spectroscopy to show that these bands are enhanced by a resonant process whose transition dipole is rotated by 15+/-10 degrees with respect to the molecular transition dipole. We also show that the polarization function remains stable over the whole time scale of a measurement, indicating that molecular reorientation with respect to the surface is unlikely. Together these findings provide further support to the involvement of a charge-transfer resonance in the enhancement of the low-frequency bands and allow us to suggest a model for the orientation of rhodamine 6G molecules at Raman hot spots.