Seven-coordinate anion complex with a tren-based urea: binding discrepancy of hydrogen sulfate in solid and solution states

Structural characterization of a hydrogen sulfate complex with a tren-based urea suggests that the anion is coordinated with six NH···O bonds (d(N···O) = 2.857 (3) to 3.092 (3) ?) and one OH···O bond (d(O···O) = 2.57 (2) ?) from three receptors; however, in solution the anion is bound within the pseudo-cavity of one receptor.     

DNA tetraplex structure formation from human telomeric repeat motif (TTAGGG):(CCCTAA) in nanocavity water pools of reverse micelles

In an equimolar ratio the human telomeric oligonucleotides d[AGGG(TTAGGG)(3)] and d[(CCCTAA)(3)CCCT] formed mixed structures of duplex and tetraplex in bis(2-ethylhexyl)sulfosuccinate reverse micelles; only the duplex was observed in aqueous buffer. This finding suggests that heterogeneous confined media in the cell nucleus might induce a significant fraction of the telomeric region of genomic DNA to adopt non-canonical tetraplex structure.     

An improved synthesis of pentacene: rapid access to a benchmark organic semiconductor

Pentacene is an organic semiconductor used in a variety of thin-film organic electronic devices. Although at least six separate syntheses of pentacene are known (two from dihydropentacenes, two from 6,13-pentacenedione and two from 6,13-dihydro-6,13-dihydroxypentacene), none is ideal and several utilize elevated temperatures that may facilitate the oxidation of pentacene as it is produced. Here, we present a fast (-2 min of reaction time), simple, high-yielding (≥ 90%), low temperature synthesis of pentacene from readily available 6,13-dihydro-6,13-dihydroxypentacene. Further, we discuss the mechanism of this highly efficient reaction. With this improved synthesis, researchers gain rapid, affordable access to high purity pentacene in excellent yield and without the need for a time consuming sublimation.     

Self-assembly of ordered water tetramers in an encapsulated [Br(H2O)12]- complex

An unanticipated anion-water cluster is assembled by one bromide and three highly-ordered "water tetramers" within the cavity of a receptor, providing a perfect C(3) symmetric propeller-shaped bromide-water cluster of [Br(H(2)O)(12)](-).     

Spectroscopic, structural, and theoretical studies of halide complexes with a urea-based tripodal receptor

A urea-based tripodal receptor L substituted with p-cyanophenyl groups has been studied for halide anions using (1)H NMR spectroscopy, density functional theory (DFT) calculations, and X-ray crystallography. The (1)H NMR titration studies suggest that the receptor forms a 1:1 complex with an anion, showing a binding trend in the order of fluoride > chloride > bromide > iodide. The interaction of a fluoride anion with the receptor was further confirmed by 2D NOESY and (19)F NMR spectroscopy in DMSO-d(6). DFT calculations indicate that the internal halide anion is held by six NH···X interactions with L, showing the highest binding energy for the fluoride complex. Structural characterization of the chloride, bromide, and silicon hexafluoride complexes of [LH(+)] reveals that the anion is externally located via hydrogen bonding interactions. For the bromide or chloride complex, two anions are bridged with two receptors to form a centrosymmetric dimer, while for the silicon hexafluoride complex, the anion is located within a cage formed by six ligands and two water molecules.     

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.     

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.