Theoretical Simulation of Vibrational Sum‐Frequency Generation Spectra from Density Functional Theory: Application to p‐Nitrothiophenol and 2,4‐Dinitroaniline

The molecular orientation of adsorbed molecules forming self‐assembled monolayers can be determined by combining vibrational sum‐frequency generation (SFG) measurements with quantum chemical calculations. Herein, we present a theoretical methodology used to simulate the SFG spectra for different combinations of polarizations. These simulations are based on calculations of the IR vectors and Raman tensors, which are obtained from density functional theory computations. The dependency of the SFG vibrational signature with respect to the molecular orientation is presented for the molecules p‐nitrothiophenol and 2,4‐dinitroaniline. It is found that a suitable choice of basis set as well as of exchange‐correlation (XC) functional is mandatory to correctly simulate the SFG intensities and consequently provide an accurate estimation of the adsorbed molecule orientation. Comparison with experimental data shows that calculations performed at the B3LYP/6‐311++G(d,p) level of approximation provide good agreement with experimental frequencies, and with IR and Raman intensities. In particular, it is demonstrated that polarization and diffuse functions are compulsory for reproducing the IR and Raman spectra, and consequently vibrational SFG spectra, of systems such as p‐nitrothiophenol. Moreover, the investigated XC functionals reveal their influence on the relative intensities, which show rather systematic variations with the amount of Hartree–Fock exchange. Finally, further aspects of the modeling are revealed by considering the frequency dependence of the Raman tensors.     

Amphiphilic Multi‐Arm Block Copolymer Based on Hyperbranched Polyester,Poly(L‐lactide) and Poly(ethylene glycol) as a Drug Delivery Carrier

A novel type of biodegradable/biocompatible amphiphilic hyperbranched copolymer (H40‐PLA‐b‐MPEG) was synthesized. Its micellar properties were studied by DLS, fluorescence spectroscopy and TEM. The drug release profile showed that the H40‐PLA‐b‐MPEG micelles provide an initial burst release, followed by a sustained release of the entrapped hydrophobic model drug over a period of 4 to 58 h. The copolymer degraded hydrolytically within 6 weeks under physiological conditions. The MTT assay showed no obvious cytotoxicity against a human endothelial cell line at a concentration range of 0–400 µg · mL⁻¹. These results indicate that the H40‐PLA‐b‐MPEG micelles have great potential as hydrophobic drug delivery carriers.

     

A heuristic application of Integer Goal Programming and Taguchi Method for planning cable cutting process in power plant projects

The Optimization utilization of raw material and components is one of the main challenges in production and project management success. Executives usually face with waste and shortage of raw material which cause delay and cost, however the material and required components are usually provided more than needed. Therefore planning to provide these components from existing spools of material is one of these challenges especially when the number of the needed material pieces and the existing spools are high. For instance, in power plant projects cables are usually provided in form of spools which later cut down to required pieces in the project location. Extraction of each needed piece of cable from specific existing spool is a decision to be made. In this paper, a heuristic method based on integrating Integer Goal Programming and Taguchi Method is suggested to optimize cutting down process of these materials.     

The Shape Invariance in <Emphasis Type="Italic">S</Emphasis><Superscript>2</Superscript> Space with Electromagnetic Field

In this paper, we use the Laplace equation in curvature space S ² with electromagnetic field, and write the Schrödinger equation in S ²space. By comparing this equation with well known polynomial we obtain the wave function and energy spectrum. In that case we face with two values of λ which guarantee the stability of system. On the other hand, we take advantage from factorization method, and factorize the second order equation in terms of first order equations. These first orders operators lead us to investigate the potential and super-potential which are satisfied by shape invariance condition. We show that, in order to have such condition the λ must be zero, the energy spectrum also obtained by this condition. Finally we show that these corresponding operators will be generators of algebra.     

Not So Innocent After All: Interfacial Chemistry Determines Charge-Transport Efficiency in Single-Molecule Junctions

Most studies in molecular electronics focus on altering the molecular wire backbone to tune the electrical properties of the whole junction. However, it is often overlooked that the chemical structure of the groups anchoring the molecule to the metallic electrodes influences the electronic structure of the whole system and, therefore, its conductance. We synthesised electron-accepting dithienophosphole oxide derivatives and fabricated their single-molecule junctions. We found that the anchor group has a dramatic effect on charge-transport efficiency: in our case, electron-deficient 4-pyridyl contacts suppress conductance, while electron-rich 4-thioanisole termini promote efficient transport. Our calculations show that this is due to minute changes in charge distribution, probed at the electrode interface. Our findings provide a framework for efficient molecular junction design, especially valuable for compounds with strong electron withdrawing/donating backbones.     

Studies on the lattice match and strain in the epitaxial growth of III – V alloys on inas and GaSb substrates

The compositional conditions to deposit the epitaxial films of III – V materials lattice matched to InAs and GaSb substrates have been investigated and the results are presented in the form of charts. The validity of our theoretical predictions has been tested by comparing with the available experimental results. Strain in the Ga_xIn_{1 − x}As_ySb_{1 − y} quaternary alloy has been visualised as three-dimensional perspective plots.     

Making an H $H$-free graph k $k$-colorable

We study the following question: How few edges can we delete from any $H$-free graph on $n$ vertices to make the resulting graph $k$-colorable? It turns out that various classical problems in extremal graph theory are special cases of this question. For $H$ any fixed odd cycle, we determine the answer up to a constant factor when $n$ is sufficiently large. We also prove an upper bound when $H$ is a fixed clique that we conjecture is tight up to a constant factor, and prove upper bounds for more general families of graphs. We apply our results to get a new bound on the maximum cut of graphs with a forbidden odd cycle in terms of the number of edges.     

Leveraging Torsional and Steric Strains: A Pre-macrocyclization Strategy Enables Conformation-Specific Fullerene Binding in m-Cyclophanes

Though the chemistry of resorcinarenes is half a century old, the conformationally-locked resorcinarene crowns are generally constructed using hydrogen bonds or covalent tethers. Often, covalent tethering involves extra post-macrocyclization steps involving upper-rim functionalities. We have leveraged the torsional and steric strains through α-substituents of the lower-rim C-alkyl chains and accomplished conformationally-rigid fluorescent m-cyclophane deep-crowns in a predetermined way. The strategy offers a pre-macrocyclization route conserving upper-rim functionalities, an aspect overlooked in resorcinarene chemistry. X-ray structural and computational analyses unveil the cause for conformational rigidity in m-cyclophanes due to α-branching in C-alkyls (linear vs. α-/β-branched). The conformationally-locked fluorescent deep-crown with a preorganized cavity captures hydrophobic spherical guest C₆₀ in both solution and solid states specifically, when compared to conformationally-dynamic boats, enabling conformation-specific binding.