Chemoenzymatic dynamic kinetic resolution of primary amines catalyzed by CAL-B at 38-40 °C

The (R)-selective chemoenzymatic dynamic kinetic resolution of primary amines was performed at 38-40 °C in MTBE, in good to high yields and with high enantiomeric excesses. These reactions associating CAL-B to octanethiol as radical racemizing agent were carried out in the presence of methyl β-methoxy propanoate as acyl donor, under photochemical irradiation at 350 nm in glassware.     

The use of electrothermal vaporizer coupled to the inductively coupled plasma mass spectrometry for the determination of arsenic,selenium and transition metals in biological samples treated with formic acid

A fast method for the determination of As, Co, Cu, Fe, Mn, Ni, Se and V in biological samples by ETV-ICP-MS, after a simple sample treatment with formic acid, is proposed. Approximately 75 mg of each sample is mixed with 5 mL of formic acid, kept at 90 °C for 1 h and then diluted with nitric acid aqueous solution to a 5% (v/v) formic acid and 1% (v/v) nitric acid final concentrations. A palladium solution was used as a chemical modifier. The instrumental conditions, such as carrier gas flow rate, RF power, pyrolysis and vaporization temperatures and argon internal flow rate during vaporization were optimized. The formic acid causes a slight decrease of the analytes signal intensities, but does not increase the signal of the mainly polyatomic ions (¹⁴N³⁵Cl⁺, ¹⁴N¹²C⁺, ⁴⁰Ar¹²C⁺, ¹³C³⁷Cl⁺, ⁴⁰Ar³⁶Ar⁺, ⁴⁰Ar³⁵Cl⁺, ³⁵Cl¹⁶O⁺, ⁴⁰Ar¹⁸O⁺) that affect the analytes signals. The effect of charge transfer reactions, that could increase the ionization efficiency of some elements with high ionization potentials was not observed due to the elimination of most of the organic compounds during the pyrolysis step. External calibration with aqueous standard solutions containing 5% (v/v) formic acid allows the simultaneous determination of all analytes with high accuracy. The detection limits in the samples were between 0.01 (Co) and 850 μg kg⁻¹ (Fe and Se) and the precision expressed by the relative standard deviations (RSD) were between 0.1% (Mn) and 10% (Ni). Accuracy was validated by the analysis of four certified reference biological materials of animal tissues (lobster hepatopancreas, dogfish muscle, oyster tissue and bovine liver). The recommended procedure avoids plasma instability, carbon deposit on the cones and does not require sample digestion.     

Colorimetric and fluorescent signaling of Au3+ by desulfurization of thiocoumarin

We investigated the chemosignaling of Au(3+) by the selective desulfurization of thiocoumarin. In the presence of a heavy metal ion chelator N,N,N',N'-tetrakis-(2-pyridylmethyl)ethylenediamine, thiocoumarin was selectively converted to its oxo analogue by reaction with Au(3+), resulting in a pronounced chromogenic and fluorescent signaling. Selective signaling of Au(3+) was possible in the presence of common alkali, alkaline earth, and transition metal ions, as well as Au(+) in a mixed aqueous environment. The colorimetric determination of Au(3+) was possible by the color change from pink to yellowish green of the designed probe. The detection limit for the determination of Au(3+) in 50% aqueous acetonitrile was 1.1 × 10(-7) M.     

Enantioselective organocatalytic intramolecular Diels-Alder reactions: a computational study

The diastereo- and enantioselectivity obtained experimentally by Christmann in the amine-catalyzed intramolecular Diels-Alder reaction of α,β-unsaturated carbonylic compounds were fully rationalized using density functional theory methods at the PBE1PBE/6-311+G** level. A polarizable continuum model was used to describe solvent effects. The selectivity is induced in the cyclization step, and while the enantioselectivity results from the syn/anti orientation around the C-N enamine bond, the diastereoselectivity mainly results from the syn/anti configuration of the substituents in the forming cyclopentane ring. The remarkable reaction rate experimentally observed when an external protic acid is used is attributed to the strong decrease in the activation energy of all steps needed for the enamine formation, while the external acid marginally influences the cyclization step. When hydrogen-bond-donor catalysts are used, the formation of one hydrogen bond in the cyclization step inverts the configuration and reduces the selectivity. The different behavior between dialdehydes and ketoaldehydes is suggested to be resulting from different reaction rates in the catalyst elimination step.     

Gold nanoparticle-paper as a three-dimensional surface enhanced Raman scattering substrate

This work investigates the effect of gold nanoparticle (AuNP) addition to paper substrate and examines the ability of these composite materials to amplify the surface enhanced Raman scattering (SERS) signal of a dye adsorbed. Paper has a three-dimensional (3D), porous, and heterogeneous morphology. The manner in which paper adsorbs the nanoparticles is crucial to its SERS properties, particularly with regards to aggregation. In this work, we sought to maintain the same degree of aggregation, while changing the concentration of nanoparticles deposited on paper. We achieved this by dipping paper into AuNP solutions of different, known concentration and found that the initial packing density of AuNPs in solutions was retained on paper with the same degree of aggregation. The surface coverage of AuNPs on paper was found to scale linearly to their concentration profile in solutions. The SERS performances of the AuNP-treated papers were evaluated with 4-aminothiophenol (4-ATP) as the Raman molecule, and their SERS intensities increased linearly with the AuNPs' concentration. Compared to AuNP-treated silicon, the Raman enhancement factor (EF) from paper was relatively higher due to a more uniform and greater degree of adsorption of AuNPs. The effect of the spatial distribution of AuNPs in their substrates on SERS activity was also investigated. In this experiment, the number of AuNPs was kept constant (a 1 μL droplet of AuNPs was deposited on all substrates), and the distribution profile of AuNPs was controlled by the nature of the substrate: paper, silicon, and hydrophobized paper. The AuNP droplet on paper showed the most reproducible and sensitive SERS signal. This highlighted the role of the z-distribution (through film) of AuNPs within the bulk of the paper, producing a 3D multilayer structure to allow inter- and intralayer plasmon coupling, and hence amplifying the SERS signal. The SERS performance of nanoparticle-functionalized paper can thus be optimized by controlling the 3D distribution of the metallic nanoparticles, and such control is critical if these systems are to be implemented as a low-cost and highly sensitive bioassay platform.     

Antimicrobial Hydantoin‐Containing Polyesters

A new N‐hydantoin‐containing biocompatible and enzymatically degradable polyester with antibacterial properties is presented. Different polyesters of dimethyl succinate, 1,4‐butanediol, and 3‐[N,N‐di(β‐hydroxyethyl)aminoethyl]‐5,5‐dimethylhydantoin in varying molar ratios are prepared via two‐step melt polycondensation. The antibacterially active N‐halamine form is obtained by subsequent chlorination of the polyesters with sodium hypochlorite. Chemical structures, thermal properties, and spherulitic morphologies of the copolymers are studied adopting FT‐IR, NMR, TGA, DSC, WAXD, and POM. The polyesters exhibit antibacterial activity against Escherichia coli. The adopted synthetic approach can be transferred to other polyesters in a straightforward manner.

     

Integral geometry of complex space forms

We show how Alesker’s theory of valuations on manifolds gives rise to an algebraic picture of the integral geometry of any Riemannian isotropic space. We then apply this method to give a thorough account of the integral geometry of the complex space forms, i.e. complex projective space, complex hyperbolic space and complex Euclidean space. In particular, we compute the family of kinematic formulas for invariant valuations and invariant curvature measures in these spaces. In addition to new and more efficient framings of the tube formulas of Gray and the kinematic formulas of Shifrin, this approach yields a new formula expressing the volumes of the tubes about a totally real submanifold in terms of its intrinsic Riemannian structure. We also show by direct calculation that the Lipschitz-Killing valuations stabilize the subspace of invariant angular curvature measures, suggesting the possibility that a similar phenomenon holds for all Riemannian manifolds. We conclude with a number of open questions and conjectures.     

Study of the cosmic rays transport problems using second order parabolic type partial differential equation

It has been exactly 100 years since Hess’s historical discovery: an extraterrestrial origin of cosmic rays [1]. Galactic cosmic rays (GCR) being charged particles, penetrate the heliosphere and are modulated by the solar magnetic field. The propagation of cosmic rays is described by Parker’s transport equation [2], which is a second order parabolic type partial differential equation. It is time dependent 4-variables (with r, θ, φ, R, meaning: distance from the Sun, heliolatitudes, heliolongitudes and particles’ rigidity, respectively) equation which is a well known tool for studying problems connected with solar modulation of cosmic rays. Transport equation contains all fundamental processes taking place in the heliosphere: convection, diffusion, energy changes of the GCR particles owing to the interaction with solar wind’s inhomogeneities, drift due to the gradient and curvature of the regular interplanetary magnetic field and on the heliospheric current sheet.     

Seasonal Evaluation of Phlorotannin-Enriched Extracts from Brown Macroalgae Fucus spiralis

Fucus spiralis that was collected in the four seasons was submitted to an extraction with ethanol:water (crude extracts Et80), followed by a liquid–liquid fractionation with organic solvents (fraction He from n-hexane; aqueous fractions AQ1, AQ2, AQ3 and AQ4; ethyl acetate fraction EA), with the aim of obtaining phlorotannin-enriched extracts. All the extracts (Et80, He, AQ1, AQ2, AQ3, AQ4 and EA) that were obtained for the F. spiralis of the four seasons were evaluated for their antioxidant capacity and total phenolic compounds. The summer extracts presented the highest contents in polyphenols (TPC), as well as the highest ferric reducing antioxidant power (FRAP), when compared to the samples from the other seasons. The reductive percentage of the DPPH (2,2-diphenyl-1-picryl-hydrazyl-hydrate) compound was similar between the seasons. For all the seasons, the EA extract showed the highest polyphenol content (TPC), and the highest antioxidant capacity (highest ferric reducing power (FRAP) and lowest concentration needed to reduce 50% of the DPPH compound), which is in agreement with a phlorotannin-enriched fraction. This study revealed that the polyphenol content and antioxidant power of the F. spiralis extracts are influenced by the time of harvest, as well as by the solvents used for their extraction.     

Diagnostic value of breast MRI for predicting metastatic axillary lymph nodes in breast cancer patients: diffusion-weighted MRI and conventional MRI

Purposes

To evaluate the diagnostic value of diffusion-weighted MRI (DWI) and combination of conventional MRI and DWI to predict metastatic axillary lymph nodes in breast cancer.

Materials and methods

Two hundred fifty-two breast cancer patients with 253 axillae were included. The morphological parameters on axial T2-weighted images without fat saturation and apparent diffusion coefficient (ADC) values were retrospectively analyzed. An independent t-test/chi-square test and receiver operating characteristics (ROC) curve analysis were used.

Results

On conventional MRI, short and long axis length, maximal cortical thickness, relative T2 value, loss of fatty hilum (p < 0.001 for each), and eccentric cortical thickening (p < 0.003) were statistically significantly different between the metastatic and nonmetastatic groups. The short axis to long axis ratio was not a statistically significant parameter. The ADC value was significantly different between the 2 groups, with an AUC that was higher than that of conventional MR parameters (AUC, 0.815; threshold, ≤ 0.986 × 10–3 mm²/sec; sensitivity, 75.8%; specificity, 83.9%). Using the adopted thresholds for each parameter, a total number of findings suggesting malignancy of 4 or higher was determined as the threshold, with high specificity (90.1%).

Conclusion

Using conventional MRI and DWI, we can evaluate the axilla in breast cancer with high specificity.