Porphyrin‐Ryleneimide Hybrids: Low‐Bandgap Acceptors in Energy‐Transfer Cassettes

Energy‐transfer cassettes consisting of naphthaleneimide‐fused metalloporphyrin acceptors (M=Zn and Pd) and BODIPY donors have been designed and synthesized. These systems have rigid pseudo‐tetrahedral structures with a donor‐acceptor separation of ca. 17.5 Å. Spectroscopic investigations, including femtosecond transient absorption measurements, showed efficient excitation energy transfer (EET) occurring according to the Förster mechanism. Strong fluorescence of the donor units and significant spectral overlap of the donor and acceptor subunits are prerequisites for the efficient EET in these systems.     

New Insight on Carbon Dioxide-Mediated Hydrogen Production**

A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7–8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO₂ under UV-C, the hydrogen production amounted to 0.6 μmol h⁻¹ during 24 h of radiation.     

Ab initio optical rotatory dispersion and electronic circular dichroism spectra of (S)-2-chloropropionitrile

Coupled-cluster and density-functional methods have been used to determine specific rotations and electronic circular dichroism (ECD) rotational strengths for (S)-2-chloropropionitrile. Coupled-cluster specific rotations using both the length- and velocity-gauge representations of the electric-dipole operator, computed with basis sets of triple-zeta quality containing up to 326 functions, compare very well with recently reported gas-phase cavity-ring-down polarimetry data. ECD rotational strengths for the six lowest-lying excited states are found to vary in sign, and the second excited state, which has a larger rotational strength than the first by a factor of 4, was found to yield a much larger contribution (by a factor of 10) to the overall negative specific rotation observed both experimentally and theoretically. However, both valence and Rydberg states appear to make substantial contributions to the total rotation, often of opposite sign from the converged/linear-response result. Furthermore, the sum-over-states approach was found to be inadequate for reproducing the specific rotations derived from the linear-response approach, even when 100 excited states (well beyond the estimated ionization limit) were included in the summation. Density-functional specific rotations using the B3LYP functional with basis sets of quadruple-zeta quality containing up to 588 functions are found to be too large compared to experiment by approximately a factor of 2. This error appears to be related to both the underestimation of the electronic excitation energies, as well as concomitant overestimation of the corresponding ECD rotational strengths. Although earlier studies reported good agreement between density-functional specific rotations and experiment when electric-field-dependent functions were used in conjunction with a double-zeta-quality basis set, the results reported here, which are near the basis-set limit, suggest that this agreement may be fortuitous.     

The investigation of femoroacetabular impingement using motion capture,FEM and multi-body simulations

In recent years, femoroacetabular impingement (FAI) has become increasingly common. As published in the literature, FAI is caused by an unphysiological contact between the proximal femur and the acetabular rim, which may lead to pain, limitation of movement, and damage of cartilage. In this paper, patient-specific finite element simulations of the movement of the hip based on gait motion data and MRI segmentation were conducted to check stresses of the acetabulum and femur, and additionally whether a bony contact is present or not. The study's findings show no bony contact between femur and acetabulum, which may lead to the hypothesis that the labrum and its deformation and/or the articular capsule are involved in the mechanism of FAI. In order to verify this hypothesis more simulations including labrum and capsule must be performed. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Certification of reference materials for inorganic trace analysis: the INCT approach

This paper presents the work done by the Institute of Nuclear Chemistry and Technology (INCT), Warsaw on a procedure of the certification of matrix reference materials (CRMs) for inorganic trace analysis. The INCT has been involved in preparation and certification of that type of CRMs since 1986 till now. The certification of CRMs is performed on the basis of statistical evaluation of the data obtained from the worldwide interlaboratory comparison. The initially adopted certification procedure has been developed, and the final shape is presented and discussed. The modifications are connected with the new demands of the international standards. The results of analysis of candidate CRMs obtained by the potentially primary procedures based on radiochemical neutron activation analysis (RNAA) and results of analysis of CRM accompanying candidate RMs are applied in the certification process for quality assurance purpose.     

Synthesis of unsymmetrical alkyl acetals via addition of primary alcohols to allyl ethers mediated by ruthenium complexes

Abstract  

Ru-catalyzed synthesis of mixed alkyl–alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl₂(PPh₃)₃ and [RuCl₂(1,5-COD)]_x and phosphines [PPh₃ or P(p-chlorophenyl)₃] or SbPh₃. Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers––subsequent addition of ROH to vinyl ethers.     

The E(4) Πu state in K2 and its perturbations

The E(4) ¹Π_u←X ¹Σ⁺_g band system of the K₂ molecule is investigated by the technique of Doppler-free optical–optical double resonance polarization spectroscopy. The observed vibrational levels v=0 to 9 of the E state are subject to numerous rotational perturbations by the neighboring 4 ³Π_u, 4 ¹Σ⁺_u, and 5 ³Σ⁺_u electronic states. By using deperturbation methods, the potential curves of the 4 ¹Π_u and 4 ³Π_u states are determined as well as some properties of the 4 ¹Σ⁺_u and 5 ³Σ⁺_u state potentials. The results are compared with predictions of ab initio calculations.     

Mechanical model of lung parenchyma as a two-phase porous medium

The anatomy and geometry of the lung at the micro- and macroscopic level have been described briefly. A notion of lung parenchyma — a macroscopically continuous medium whose mechanical properties result from those of microstructural components — has been adapted. Simplifying assumptions propounded in the constitutive model have been discussed. Two phases have been distinguished in the medium: the solid phase — a highly deformable, nonlinearly elastic skeleton in the form of a thin-walled tissue structure on the micro-scale — and the fluid phase — perfect gas (air) filterating through the structure. General constitutive relations for both phases and their mechanical interactions have ben formulated. Further, the fundamental set of differential equations of the quasi-static coupled problem has been developed. Large deformations, material nonlinearities, and dependence of permeability on skeleton deformation have been included. Matrix formulation of the problem has been presented from the point of view of the finite element method. An implicit iterative time integration scheme has been proposed. The algorithm has been illustrated with results of simple numerical tests.     

NKT cell-dependent glycolipid–peptide vaccines with potent anti-tumour activity

It is known that T cells can eliminate tumour cells through recognition of unique or aberrantly expressed antigens presented as peptide epitopes by major histocompatibility complex (MHC) molecules on the tumour cell surface. With recent advances in defining tumour-associated antigens, it should now be possible to devise therapeutic vaccines that expand specific populations of anti-tumour T cells. However there remains a need to develop simpler efficacious synthetic vaccines that possess clinical utility. We present here the synthesis and analysis of vaccines based on conjugation of MHC-binding peptide epitopes to α-galactosylceramide, a glycolipid presented by the nonpolymorphic antigen-presenting molecule CD1d to provoke the stimulatory activity of type I natural killer T (NKT) cells. The chemical design incorporates an enzymatically cleavable linker that effects controlled release of the active components in vivo. Chemical and biological analysis of different linkages with different enzymatic targets enabled selection of a synthetic vaccine construct with potent therapeutic anti-tumour activity in mice, and marked in vitro activity in human blood.     

Design,synthesis and application of new bile acid ligands with 1,2,3-triazole ring

New dimers have been obtained from propargyl ester of bile acids and α,α′-diazide-m-xylene by intermolecular 1,3-dipolar cycloaddition. These compounds have been used as ligands to form intermolecular hydrogen bonds with various aromatic acids. The structures of all products were confirmed by spectroscopic (¹H NMR, ¹³C NMR and FT-IR) analysis, mass spectrometry (ESI, MALDI) and PM5 semiempirical methods.