The laser polarization as control parameter in the formation of laser-induced periodic surface structures: Comparison of numerical and experimental results

Considering self-organized surface pattering upon multi-pulse femtosecond laser irradiation, in particularly the strong dependence of ripples orientation on the laser polarization, we present numerical simulations from an adopted surface erosion model and compare the result to our experimental data on laser-induced nanostructures formation. We present the surface morphologies obtained by this model for different polarizations of the incident laser electric field and show good agreement with ripple formation produced by laser ablation experiments. The correlation of ripples orientation with laser polarization can be described within a model where the polarization causes a breaking of symmetry at the surface. Further we discuss a time evolution of pattern formation. Our results support the non-linear self-organization mechanism of pattern formation on the surface of solids.     

Effect of Alkali Metal Cations on Length and Strength of Hydrogen Bonds in DNA Base Pairs

For many years, non-covalently bonded complexes of nucleobases have attracted considerable interest. However, there is a lack of information about the nature of hydrogen bonding between nucleobases when the bonding is affected by metal coordination to one of the nucleobases, and how the individual hydrogen bonds and aromaticity of nucleobases respond to the presence of the metal cation. Here we report a DFT computational study of nucleobase pairs interacting with alkali metal cations. The metal cations contribute to the stabilization of the base pairs to varying degrees depending on their position. The energy decomposition analysis revealed that the nature of bonding between nucleobases does not change much upon metal coordination. The effect of the cations on individual hydrogen bonds were described by changes in VDD charges on frontier atoms, H-bond length, bond energy from NBO analysis, and the delocalization index from QTAIM calculations. The aromaticity changes were determined by a HOMA index.     

Novel K/Mn phosphate hydrates,K2Mn3(H2O)2[P2O7]2 and KMn(H2O)2[Al2(PO4)3]: hydrothermal synthesis and crystal chemistry

Two novel K/Mn phosphate hydrates, namely, dipotassium trimanganese dipyrophosphate dihydrate, K₂Mn₃(H₂O)₂[P₂O₇]₂, (I), and potassium manganese dialuminium triphosphate dihydrate, KMn(H₂O)₂[Al₂(PO₄)₃], (II), were obtained in the form of single crystals during a single hydrothermal synthesis experiment. Their crystal structures were studied by X‐ray diffraction. Both new compounds are members of the morphotropic series of phosphates with the following formulae: A₂M₃(H₂O)₂[P₂O₇]₂, where A = K, NH₄, Rb or Na and M = Mn, Fe, Co or Ni, and AM²⁺(H₂O)₂[M³⁺₂(PO₄)₃], where A = Cs, Rb, K, NH₄ or (H₃O); M²⁺ = Mn, Fe, Co or Ni; and M³⁺ = Al, Ga or Fe. A detailed crystal chemical analysis revealed correlations between the unit‐cell parameters of the members of the series, their structural features and the sizes of the cations. It has been shown that a mixed type anionic framework is formed in (II) by aluminophosphate [(AlO₂)₂(PO₄)₂]_∞ layers, with a cationic topology similar to the Si/Al‐topology of the crystal structures of feldspars. A study of the magnetic susceptibility of (II) demonstrates a paramagnetic behaviour of the compound.     

Effective PHIP Labeling of Bioactive Peptides Boosts the Intensity of the NMR Signal

A series of novel bioactive derivatives of the sunflower trypsin inhibitor‐1 (SFTI‐1) suitable for hyperpolarization by parahydrogen‐induced polarization (PHIP) was developed. The PHIP activity was achieved by labeling with L ‐propargylglycine, O‐propargyl‐L ‐tyrosine, or 4‐pentynoic acid. ¹H NMR signal enhancements (SE) of up to a factor of 70 were achieved in aqueous solution. We found that an isolated spatial location of the triple bond within the respective label and its accessibility for the hydrogenation catalyst are essential factors for the degree of signal enhancement.     

Single‐Step Gas‐Phase Polyperfluoroalkylation of Naphthalene Leads to Thermodynamic Products

High‐temperature gas‐phase, solvent‐ and catalyst‐free reaction of naphthalene with an excess of R_FI reagent (R_F?CF₃, C₂F₅, n‐C₃F₇, and n‐C₄F₉) was used for the first time to produce a series of highly perfluoroalkylated naphthalene products NAPH(R_F)_n with n=2–5. Four 95+ % pure 1,3,5,7‐NAPH(R_F)₄ with R_F?CF₃, C₂F₅, n‐C₃F₇, and n‐C₄F₉ were isolated using a simple chromatography‐free procedure. These new compounds were fully characterized by ¹⁹F and ¹H NMR spectroscopy, X‐ray crystallography (for R_F?CF₃ and C₂F₅), atmospheric‐pressure chemical ionization mass spectrometry, and cyclic and square‐wave voltammetry. DFT calculations confirm that the proposed synthesis yields the most stable isomers that have not been accessed by alternative preparation techniques.     

A homogeneous quenching resonance energy transfer assay for the kinetic analysis of the GTPase nucleotide exchange reaction

A quenching resonance energy transfer (QRET) assay for small GTPase nucleotide exchange kinetic monitoring is demonstrated using nanomolar protein concentrations. Small GTPases are central signaling proteins in all eukaryotic cells acting as a “molecular switches” that are active in the GTP-state and inactive in the GDP-state. GTP-loading is highly regulated by guanine nucleotide exchange factors (GEFs). In several diseases, most prominently cancer, this process in misregulated. The kinetics of the nucleotide exchange reaction reports on the enzymatic activity of the GEF reaction system and is, therefore, of special interest. We determined the nucleotide exchange kinetics using europium-labeled GTP (Eu-GTP) in the QRET assay for small GTPases. After GEF catalyzed GTP-loading of a GTPase, a high time-resolved luminescence signal was found to be associated with GTPase bound Eu-GTP, whereas the non-bound Eu-GTP fraction was quenched by soluble quencher. The association kinetics of the Eu-GTP was measured after GEF addition, whereas the dissociation kinetics could be determined after addition of unlabeled GTP. The resulting association and dissociation rates were in agreement with previously published values for H-Ras^Wt, H-Ras^Q61G, and K-Ras^Wt, respectively. The broader applicability of the QRET assay for small GTPases was demonstrated by determining the kinetics of the Ect2 catalyzed RhoA^Wt GTP-loading. The QRET assay allows the use of nanomolar protein concentrations, as more than 3-fold signal-to-background ratio was achieved with 50 nM GTPase and GEF proteins. Thus, small GTPase exchange kinetics can be efficiently determined in a HTS compatible 384-well plate format.

Synthesis of Nitroxide Paramagnetic Ketones from Nitroxide Acid Chlorides and Anhydrides by Fiedel-Crafts Acylation

Friedel-Crafts acylation of benzene or toluene with 5- and 6-membered nitroxide acid chloride, anhydrides derivatives (symmetrical or mixed) and aluminium chloride to aryl nitroxide ketones is described.     

Disposable amperometric biosensor for the determination of tyramine using plasma amino oxidase

We have developed screen–printed carbon electrodes for the determination of tyramine (Tyr) via plasma amine oxidase. The enzyme was immobilized on the carbon working electrode by cross–linking it with bovine serum albumin using glutaraldehyde. The employment of the mediator hydroxymethylferrocene lowers the working potential to +260 mV (vs. a screen–printed Ag/AgCl reference electrode). The effects of pH, potential and mediator concentration were optimized and resulted in reproducibility and repeatability values of 8.6 % and 8.7 %, respectively. Response is linear in the range from 2 to 164 μM, and the limit of detection is 2.0?±?0.18 μM. The effects of potentially interfering biogenic amines such as putrescine, cadaverine, histamine, spermine, spermidine and tryptamine were also evaluated. The biosensor was successfully applied to the determination of Tyr in cheese.

Ultrasound-Promoted Dimerization of Benzylic Halides

Simple and straightforward coupling of benzylic compounds was achieved by sonicating benzylic halides in the presence of magnesium.     

Asymptotics of Intersection Local Time for Diffusion Processes

In the paper, we investigate the intersection local time for two correlated Brownian motions on the plane that form a diffusion process in ?⁴ associated with a divergence-form generator. Using Gaussian heat kernel bounds, we prove the existence of intersection local time for these Brownian motions, obtain estimates of its moments, and establish the law of iterated logarithm for it.