Longer Backbone Research Articles

B2 N2 -Embedded Polycyclic Aromatic Hydrocarbons with Furan and Thiophene Derivatives Functionalized in Crossed Directions.

A series of polycyclic aromatic hydrocarbons (PAHs), consisting of two pairs of BN units, have been designed and their synthesis has been achieved by electrophilic C-H borylation. Two conjugation extension directions can be found in these B2 N2 -embedded PAHs. The B2 N2 -containing backbone with shorter effective conjugation length is isoelectronic with diaryl-fused anthracene, whereas the second derivative, with longer effective conjugation length, is isoelectronic with bis(trans-arylvinyl)benzene. By incorporating different aryl groups, i.e., furyl, thienyl, benzo[b]furyl, and benzo[b]thienyl groups, into the two crossed directions of the B2 N2 -embedded PAHs, their electronic and optical properties have been comparatively investigated by photophysical, electrochemical, and theoretical approaches. It is found that both the substituents and their conjugation extension directions have significant effects on the aromatic and photophysical properties of the B2 N2 -embedded PAHs. The conjugation extension in the shorter backbone is more pronounced on the effective conjugation length than the longer backbone. Moreover, all the B2 N2 -embedded PAHs behave as both Lewis acids and Lewis bases, and reversible photoluminescence switching can be observed by simply neutralizing the added Lewis acid or Lewis base.

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N′,N′-tetraacetic acid (TMDTA) was investigated over the pH range 5.50–8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4–5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2− and FeII(H)L− to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2−. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation rates at higher pH. Finally, this work demonstrates that the rate of FeII oxidation is very sensitive to the identity and structure of the polyaminocarboxylate chelating agent, which has implications for any metal or organic chemical that reacts either directly or indirectly with iron.

Fundamental aspects in surface self-assembly: theoretical implications of molecular polarity and shape.

We investigate fundamental aspects of structure formation in molecular self-assembly, by examining the emergence of order upon adsorption of a series of model molecules. It is known that strongly polar diatomic molecules form three-dimensional crystals in the absence of a substrate. This tendency can be disrupted upon assembly on a solid surface, and various other types of order may arise. Depending on the relative strength of the interactions, disordered phases, two-dimensional crystals commensurate to the surface, and unmodified crystals were observed upon adsorption of simple dipoles in the present work. Introduction of steric features, in the form of a longer backbone or substituents external to the polar pair, led to even richer phase diagrams. The formation of two-dimensional phases with nematic (parallel) or antiparallel alignment was accomplished by altering the polarity of the end groups on needle-like molecules, whereas embedded charged groups made two-dimensional structure unstable for even very long molecules. These molecules preferred to align in long, often desorbed, molecular wires. The wealth of phases observed here parallel the results of experimental systematic or incidental studies of the relationships between molecular interactions and self-assembled patterns, and provide some insight into the molecular handles that self-assembly researchers can wield to guide the process towards a desired structural outcome.

Cationic Peptides that Increase the Thermal Stabilities of 2′‐O‐MeRNA/RNA Duplexes but Do Not Affect DNA/DNA Melting

Several different cationic nonapeptides have been synthesized and investigated with respect to how they can influence the thermal melting of 2'-O-methylRNA/RNA and DNA/DNA duplexes. Each peptide has a C-terminal L-phenylalanine unit and is otherwise uniformly composed of a sequence of a specific basic D-amino acid that in most cases will be largely charged at neutral pH. These N-terminal octamer stretches are composed variously of the amino acids D-lysine, D-diaminobutyric acid (D-Dab), D-diaminopropionic acid (D-Dap), or D-histidine. None of the peptides substantially affected the thermal melting of DNA/DNA duplexes, which was in sharp contrast with their effects on 2'-O-methylRNA/RNA duplexes. In particular, the peptides based on diaminopropionic and diaminobutyric acid units had strong positive effects on the melting temperatures of the 2'-O-methylRNA duplexes (up to 16 °C higher with 1 equivalent of peptide) at pH 7, whereas at pH 6 the effect was even more drastic (ΔT(m) up to +25 °C). The shorter R groups of the Dap and Dab groups appear to have a better length than lysine for enhancement of the thermal melting of the 2'-O-methylRNA/RNA duplex, an effect that is more pronounced at lower pH but substantial even at pH 7, although the Dap derivative is not likely to be fully protonated. The dramatic difference between the influence, or lack thereof, on the 2'-O-methylRNA/RNA and the DNA/DNA thermal meltings suggest that, although electrostatic interactions probably play a role, there is another major and structurally dependent component influencing the properties of the duplexes. This is also seen in the observation that the oligo-Dap and oligo-Dab peptides give greater melting point enhancements than both the lysine peptide (with a longer side chain) and a β-linked Dap peptide with a shorter side chain and a longer backbone.

Elastic behavior of comb-like polymer chains

Three-dimensional Monte Carlo simulations of comb-like polymer chains with various backbone lengths N b, arm lengths N a and arm densities m are carried out to study the elastic behavior of comb-like polymer chains. The radius of gyration, the shape factors and bond length in different cases during elastic process are calculated, and it is found that the comb-like polymer molecules with longer backbone or shorter arm are more close to linear chains. But the arm density m affects the chain conformation non-monotonously. Some thermodynamic properties are also studied. Average Helmholtz free energy and elastic force f all increase with elongation ratio λ for all chains.