Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes. I. C60, C59N+, and C48N12: theory and experiment

Low-energy excitations and optical absorption spectrum of C(60) are computed by using time-dependent (TD) Hartree-Fock, TD-density functional theory (TD-DFT), TD DFT-based tight-binding (TD-DFT-TB), and a semiempirical Zerner intermediate neglect of diatomic differential overlap method. A detailed comparison of experiment and theory for the excitation energies, optical gap, and absorption spectrum of C(60) is presented. It is found that electron correlations and correlation of excitations play important roles in accurately assigning the spectral features of C(60), and that the TD-DFT method with nonhybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C(60) justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C(59)N(+), to serve as a spectroscopy reference for the characterization of carborane anion salts. Although it is an isoelectronic analogue to C(60), C(59)N(+) exhibits distinguishing spectral features different from C(60): (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C(59)N(+) characterize and explain well the measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C(59)N][Ag(CB(11)H(6)Cl(6))(2)] [Kim et al., J. Am. Chem. Soc. 125, 4024 (2003)]. For the most stable isomer of C(48)N(12), we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C(60), and optical absorption maxima occur at 585, 528, 443, 363, 340, 314, and 303 nm. We point out that the characterization of the UV-vis and transient absorption spectra of C(48)N(12) isomers is helpful in distinguishing the isomer structures required for applications in molecular electronics. For C(59)N(+) and C(48)N(12) as well as C(60), TD-DFT-TB yields reasonable agreement with TD-DFT calculations at a highly reduced cost. Our study suggests that C(60), C(59)N(+), and C(48)N(12), which differ in their optical gaps, have potential applications in polymer science, biology, and medicine as single-molecule fluorescent probes, in photovoltaics as the n-type emitter and/or p-type base of a p-n junction solar cell, and in nanoelectronics as fluorescence-based sensors and switches.     

Chain transfer polymerisation of poly-N-alkylacrylamides in superheated methanol and by microwave induction

The chain transfer polymerisation (telomerisation) of poly-N-isopropylacrylamide (PNIPAM), poly-N,N-dimethylacrylamide (PNDMAM) and poly-N-{3-(dimethylamino)propyl}acrylamide (PN3DMAPAM) as well as of co-polymers of PNIPAM and PNDMAM were studied. Reactions in superheated yet subcritical methanol (80-170 °C) and—under solvent free conditions—induced by microwave irradiation were compared in terms of product yield and quality to those obtained under standard reflux conditions (methanol reflux, ∼65 °C, ambient pressure). In superheated methanol the reaction time was reduced by 66%, the average molar mass and the yield (monomer conversion) remain largely unchanged. Dielectric heating reduces the reaction time even further, i.e. to the minute range. Surprisingly, the average molar mass of the polymers dropped by 30% in these experiments, an effect that is most likely caused by the higher polarity of the reaction mixture under solvent-free conditions.     

Preparative three-dimensional GC and nuclear magnetic resonance for the isolation and identification of two sesquiterpene ethers from Dictyota Dichotoma

Separation science plays a crucial role in the isolation of novel compounds contained in complex matrices. Yet their rationale employment needs preliminary structure elucidation, which usually requires sufficient aliquots of grade substances to characterize the molecule by nuclear magnetic resonance experiments. In this study, two peculiar oxa-tricycloundecane ethers were isolated by means of preparative multidimensional gas chromatography from the brown alga species Dictyota dichotoma (Huds.) Lam., aiming to assign their 3D structures. Density functional theory simulations were carried out to select the correct configurational species matching the experimental NMR data (in terms of enantiomeric couples). In this case, the theoretical approach was crucial as the protonic signal overlap and spectral overcrowding were preventing any other unambiguous structural information. Just after the identification through the density functional theory data matching of the correct relative configuration it was possible to verify an enhanced self-consistency with the experimental data, confirming the stereochemistry. The results obtained further pave the way toward structure elucidation of highly asymmetric molecules, whose configuration cannot be inferred by other means or strategies.     

Testing the applicability of artificial intelligence techniques to the subject of erythemal ultraviolet solar radiation. Part two: an intelligent system based on multi-classifier technique

The problem we address here describes the on-going research effort that takes place to shed light on the applicability of using artificial intelligence techniques to predict the local noon erythemal UV irradiance in the plain areas of Egypt. In light of this fact, we use the bootstrap aggregating (bagging) algorithm to improve the prediction accuracy reported by a multi-layer perceptron (MLP) network. The results showed that, the overall prediction accuracy for the MLP network was only 80.9%. When bagging algorithm is used, the accuracy reached 94.8%; an improvement of about 13.9% was achieved. These improvements demonstrate the efficiency of the bagging procedure, and may be used as a promising tool at least for the plain areas of Egypt.     

Flash ignition and initiation of explosives-nanotubes mixture

Optical ignition and initiation of energetic materials could thus far be only accomplished through lasers, with specific characteristics of high power, pulse length, wavelength, and a small target area that greatly inhibit their applications. Here, we report that an ignition and an initiation process, further leading to actual detonation, does occur for energetic materials in lax contact with carbon nanotubes that are prone to opto-thermal activity via a conventional flashbulb. Our results show that, for the first time, optical initiation of energetic materials is possible on a large surface area and using ordinary light intensity of several W/cm2. The implication is that energetic materials mixed with optically active nanotubes could be new ideal candidates for safety apparatus, such as the firing of bolts on space shuttle rockets and aircraft exit doors.     

Wideband omnidirectional infrared absorber with a patchwork of plasmonic nanoantennas

In this Letter, we demonstrate experimentally that a patchwork of four metal-insulator-metal patches leads to an unpolarized wideband omnidirectional infrared absorption. Our structure absorbs 70% of the incident light on a 2.5 μm bandwidth at 8.5 μm. It paves the way to the design of wideband efficient plasmonic absorbers in the infrared spectrum.     

Antimalarial activity of sesquiterpene lactones from Vernonia cinerea

Two new sesquiterpene lactones, vernolides C and D as well as six known ones were isolated from the dichloromethane fraction of an aqueous extract from Vernonia cinerea. Their structures were elucidated by spectroscopic methods. Among the known sesquiterpene lactones, three of them were described in this plant for the first time. In vitro antiplasmodial evaluation showed that the three major compounds 1, 7 and 8 were active against chloroquine resistant Plasmodium falciparum strain (W2) with IC(50) 3.9, 3.7 and 3.5 microM, respectively.     

Investigation on the mechanical properties of sintered porous copper compacts

In line with recent attention on porous metals having low and medium porosities in the range of 20-50%, this paper studies the effect of porosity on the mechanical properties of sintered copper compacts. Experiments were designed to investigate the effect of porosity, applied stress and sliding velocity on the wear rate of copper compacts, leading to the finding that the effects of both porosity and applied stress of the wear test on the wear rate are approximately similar and higher than that of sliding velocity. The investigation concerning the effect of porosity on compressive strength indicated that the stress-strain curve of high-porosity compact exhibited identifiable ultimate strength points, though low-porosity compact showed distinct stages of elastic plastic behavior.