Microwave enhanced Akabori reaction for peptide analysis

The Akabori reaction, devised in 1952 for the identification of C-terminus amino acids, involves the heating of a linear peptide in the presence of anhydrous hydrazine in a sealed tube for several hours. We report here a modified Akabori reaction that rapidly identifies the C-terminus amino acid in a polypeptide including its amino acid sequence information at both the C-terminus and the N-terminus. This modified methodology demonstrates the fundamentals of microwave chemistry applied to bioanalytical problems. In this modified process, hydrazinolysis has been accelerated by the application of microwave irradiation. In our reaction, the linear peptide and hydrazine solution, contained in a loosely covered conical flask, was exposed to a few minutes of irradiation using an unmodified domestic microwave oven. While the classical Akabori reaction required several hours, the microwave assisted reaction takes just minutes. If dimethyl sulfoxide is added to dilute the reaction mixture, the process is retarded enough to allow aliquots of the reaction mixture to be drawn every few minutes over a period of about an hour in order to study the progress of hydrazinolysis. Reaction products were monitored by mass spectrometry-primarily FAB-MS. In addition to providing sequence information, the microwave enhanced Akabori reaction quickly detects the presence of arginine (Arg) by converting each Arg to ornithine (Orn). Furthermore, certain amino acids, containing beta-SH, CO2H, and CONH2 groups in their side chain, are susceptible to modification by hydrazine, thereby, providing rapid confirmation of the presence of these amino acid residues. In these preliminary studies, the following oligopeptides were analyzed to demonstrate the effectiveness of our approach; the dipeptide (Trp-Phe), the tripeptide (Tyr-Gly-Gly), the tetrapeptide (Pro-Phe-Gly-Lys), the heptapeptide (Ala-Pro-Arg-Leu-Arg-Phe-Tyr), and a N-terminal blocked tripeptide (N-acetyl-Met-Leu-Phe).     

Anion Cluster: Assembly of Dihydrogen Phosphates for the Formation of a Cyclic Anion Octamer

Structural characterization of a dihydrogen phosphate complex of triprotonated tris[2-(2-thienylmethylamino)ethyl] amine shows that eight dihydrogen phosphate anions are assembled around the host by strong interactions of H-bond donors and acceptors to form a new type of cyclic anion octamer as (H(2)PO(4) (-))(8), an analogy of cyclic water octamer. The presence of an anion cluster has also been identified by electrospray ionization mass spectrometry and (31)P NMR experiments.     

Study of effective parameters on wear behavior of rubbers based on statistical methods

This study investigates the wear, surface roughness, and temperature buildup (TBU) of styrene butadiene rubber (SBR), natural rubber (NR), and nitrile butadiene rubber (NBR) while sliding over abrasives of different sizes with the variation of normal load. Rubber properties such as tensile strength (s) and elongation at break (e) were considered as input parameters. Individual, as well as interacting effects of different parameters, were analyzed in‐depth by using statistical methods. Overall wear of rubber depends not only on the tribological system but also on mechanical properties that contribute different wear mechanisms in addition to abrasion. The abrasive particle size and 1/(se) are the first and second most significant contributing factors, respectively, to all output parameters except the wear rate where the second contributing factor is the applied load and abrasive size is the highest contributor. Larger abrasive particles deepen ploughing marks, which is enhanced by the higher load, and lead to higher surface roughness. The effect of load on TBU is negligible because of the soft nature of the rubber material.     

Convergence of two-dimensional weighted integrals

A two-dimensional weighted integral in is proposed as a tool for analyzing higher-dimensional unweighted integrals, and a necessary and sufficient condition for the finiteness of the weighted integral is obtained.

     

Nanoparticle decoration with surfactants: Molecular interactions,assembly, and applications

Nanostructures of diverse chemical nature are used as biomarkers, therapeutics, catalysts, and structural reinforcements. The decoration with surfactants has a long history and is essential to introduce specific functions. The definition of surfactants in this review is very broad, following its lexical meaning “surface active agents”, and therefore includes traditional alkyl modifiers, biological ligands, polymers, and other surface active molecules. The review systematically covers covalent and non-covalent interactions of such surfactants with various types of nanomaterials, including metals, oxides, layered materials, and polymers as well as their applications. The major themes are (i) molecular recognition and noncovalent assembly mechanisms of surfactants on the nanoparticle and nanocrystal surfaces, (ii) covalent grafting techniques and multi-step surface modification, (iii) dispersion properties and surface reactions, (iv) the use of surfactants to influence crystal growth, as well as (v) the incorporation of biorecognition and other material-targeting functionality. For the diverse materials classes, similarities and differences in surfactant assembly, function, as well as materials performance in specific applications are described in a comparative way. Major factors that lead to differentiation are the surface energy, surface chemistry and pH sensitivity, as well as the degree of surface regularity and defects in the nanoparticle cores and in the surfactant shell. The review covers a broad range of surface modifications and applications in biological recognition and therapeutics, sensors, nanomaterials for catalysis, energy conversion and storage, the dispersion properties of nanoparticles in structural composites and cement, as well as purification systems and classical detergents. Design principles for surfactants to optimize the performance of specific nanostructures are discussed. The review concludes with challenges and opportunities.     

A tighter steering criterion using the Robertson–Schrödinger uncertainty relation

We consider quantum steering by non-Gausssian entangled states. The Reid steering criterion based on the Heisenberg uncertainty relation fails to detect steerability for many categories of such states. Here, we derive a tighter steering criterion using the Robertson–Schrödinger uncertainty relation. We show that our steering condition is able to detect steerability of several classes of non-Gaussian states such as entangled eigenstates of the two-dimensional harmonic oscillator, the photon subtracted squeezed vacuum state and the NOON state.     

Levels in doubly odd 138Pr

The band structures of the doubly odd ¹³⁸Pr nucleus have been investigated using the ¹²⁸Te(¹⁴N, 4n)¹³⁸Pr reaction at a beam energy of 55-65 MeV. Altogether six distinct structures have been established, of which the lower part of the yrast band and two side bands were known from earlier works. The observed level properties of the members of the yrast band have been compared with theoretical calculations performed within the Particle Rotor Model (PRM) with axially symmetric core. The experimental branching ratios and B(M1)/B(E2) values when compared with the theoretical results of the PRM, suggest an oblate core.     

Photoneutron cross sections for unstable neutron-rich oxygen isotopes.

The dipole response of stable and unstable neutron-rich oxygen nuclei of masses A = 17 to A = 22 has been investigated experimentally utilizing electromagnetic excitation in heavy-ion collisions at beam energies about 600 MeV/nucleon. A kinematically complete measurement of the neutron decay channel in inelastic scattering of the secondary beam projectiles from a Pb target was performed. Differential electromagnetic excitation cross sections d sigma/dE were derived up to 30 MeV excitation energy. In contrast to stable nuclei, the deduced dipole strength distribution appears to be strongly fragmented and systematically exhibits a considerable fraction of low-lying strength.     

An efficient phosphate sensor: tripodal quinoline excimer transduction

A novel quinoline based tripodal receptor that shows intermolecular excimer emission has been designed and synthesized. The excimer emission has been used to confirm the selective recognition of phosphate ion. It combines three different types of N-donor with the elegant fluorescent signaling properties.