Resonant amplification of frustrated evanescent waves by single dielectric coating

Resonant amplification and enhancement of evanescent wave’s frustration across an optical barrier by using single dielectric coating is numerically demonstrated in this article. With further tuning of the thickness values of the second and the third medium (optical barrier) of the proposed stratified four-media configuration, it is shown that it may be possible to achieve unity transmittance at discrete, but closely spaced incident angles within the full range defined by the theoretical cut-off limit. The designed configuration may have other potential applications than lithography and waveguide design is one such example.     

Characterization of structural irregularities in highly birefringent photonic crystal fiber using torsional acoustic polarization coupling

We demonstrate a novel method to characterize structural irregularities in a highly birefringent photonic crystal fiber (HB PCF) with high accuracy based on polarization coupling by torsional acoustic wave. Birefringence variation induced by the irregularities of air-hole structure in the fiber cross-section is analyzed via the transmission spectra of the acousto-optic coupling between two orthogonal polarization modes propagating along the fiber. The estimated maximum birefringence variation of two sections in the same batch of the HB PCF is 3 × 10^− 6 and 10^− 5, respectively, from nominal birefringence value of 4.86 × 10^− 4. The comparison between the experimental results and the numerical simulation resulted in the estimation of few tens of nm variation in the air-hole structure in the PCF.     

Nanohybridization of Low-Dimensional Nanomaterials: Synthesis,Classification, and Application

Nanomaterials have attracted much attention from academic to industrial research. General methodologies are needed to impose architectural order in low-dimensional nanomaterials composed of nanoobjects of various shapes and sizes, such as spherical particles, rods, wires, combs, horns, and other non specified geometrical architectures. These nanomaterials are the building blocks for nanohybrid materials, whose applications have improved and will continuously enhance the quality of the daily life of mankind. In this article, we present a comprehensive review on the synthesis, dimension, properties, and present and potential future applications of nanomaterials and nanohybrids. Due to the large number of review articles on specific dimension, morphology, or application of nanomaterials, we will focus on different forms of nanomaterials, such as, linear, particulate, and miscellaneous forms. We believe that almost all the nanomaterials and nanohybrids will come under these three categories. Every form or dimension or morphology has its own significant properties and advantages. These low-dimensional nanomaterials can be integrated to create novel nano-composite material applications for next-generation devices needed to address the current energy crisis, environmental sustainability, and better performance requirements. We discuss the synthesis, properties, and morphology of different forms of nanomaterials (building blocks). Moreover, we elaborate on the synthesis, modification, and application of nanohybrids. The applications of these nanomaterials and nanohybrids in sensors, solar cells, lithium batteries, electronic, catalysis, photocatalysis, electrocatalysis, and bio-based applications will be detailed. The time is now ripe to explore new nanohybrids that use individual nanomaterial components as basic building blocks, potentially affording additionally novel behavior and leading to new, useful applications. In this regard, the combination or integration of linear nanorods/nanowires and spherical nanoparticles to produce mixed-dimensionality, higher-level nanocomposites of greater complexity is an interesting theme, which we explore in this review article.     

Iridium-catalyzed carbonyl group-directed oxidative coupling of arenes with alkenes

The iridium complex [Cp¹IrCl₂]₂ is a good catalyst for the directed oxidative coupling of arenes with alkenes; a wide range of carbonyl functionalities (NHCOR, CONH₂ and COR) can be employed as the directing group.     

The rate enhancement for prolyl cis-to-trans isomerization of cyclic CPFC peptide is caused by an increase in the vibrational entropy of the transition state

The conformational preferences and prolyl cis-trans isomerization of oxidized and reduced Ac-Cys-Pro-Phe-Cys-NH2 (CPFC peptides) have been carried out using the ab initio HF/6-31+G(d) and hybrid density functional B3LYP/6-311++G(d,p) levels of theory. The most preferred conformations of oxidized and reduced CPFC peptides with the trans prolyl peptide bond have a type-I beta-turn for the Pro-Phe sequence in common. In particular, the transition states for both forms are stabilized by the intramolecular hydrogen bonds between the prolyl nitrogen and the N-H group of the Phe3 residue. The rotational barrier DeltaGct to the cis-to-trans isomerization for the oxidized CPFC peptide is calculated to be 19.37 kcal/mol at the B3LYP/6-311++G(d,p)//HF/6-31+G(d) level of theory, which is lower by 0.88 kcal/mol than that of the reduced CPFC peptide. This may indicate that the rate constant kc-->t of the prolyl cis-to-trans isomerization for the oxidized form is about 4 times larger than that of the reduced form, which is reasonably consistent with the value deduced from NMR experiments. In particular, the increase in vibrational entropy for the transition state of the oxidized form over that of the reduced form contributes to enhance the rate constant for the prolyl cis-to-trans isomerization of the oxidized form.     

Synthesis and excited-state photodynamics of a chlorin-bacteriochlorin dyad--through-space versus through-bond energy transfer in tetrapyrrole arrays.

Understanding energy transfer among hydroporphyrins is of fundamental interest and essential for a wide variety of photochemical applications. Toward this goal, a synthetic free base ethynylphenylchlorin has been coupled with a synthetic free base bromobacteriochlorin to give a phenylethyne-linked chlorin-bacteriochlorin dyad (FbC-pe-FbB). The chlorin and bacteriochlorin are each stable toward adventitious oxidation because of the presence of a geminal dimethyl group in each reduced pyrrole ring. A combination of static and transient optical spectroscopic studies indicate that excitation into the Qy band of the chlorin constituent (675 nm) of FbC-pe-FbB in toluene results in rapid energy transfer to the bacteriochlorin constituent with a rate of approximately (5 ps)(-1) and efficiency of >99%. The excited bacteriochlorin resulting from the energy-transfer process in FbC-pe-FbB has essentially the same fluorescence characteristics as an isolated monomeric reference compound, namely a narrow (12 nm fwhm) fluorescence emission band at 760 nm and a long-lived (5.4 ns) Qy excited state that exhibits a significant fluorescence quantum yield (Phif=0.19). F?rster calculations are consistent with energy transfer in FbC-pe-FbB occurring predominantly by a through-space mechanism. The energy-transfer characteristics of FbC-pe-FbB are compared with those previously obtained for analogous phenylethyne-linked dyads consisting of two porphyrins or two oxochlorins. The comparisons among the sets of dyads are facilitated by density functional theory calculations that elucidate the molecular-orbital characteristics of the energy donor and acceptor constituents. The electron-density distributions in the frontier molecular orbitals provide insights into the through-bond electronic interactions that can also contribute to the energy-transfer process in the different types of dyads.     

Novel approach to microwave-assisted extraction and micro-solid-phase extraction from soil using graphite fibers as sorbent

A single-step extraction-cleanup procedure involving microwave-assisted extraction (MAE) and micro-solid-phase extraction (micro-SPE) has been developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) from soil samples. Micro-SPE is a relatively new extraction procedure that makes use of a sorbent enclosed within a sealed polypropylene membrane envelope. In the present work, for the first time, graphite fiber was used as a sorbent material for extraction. MAE-micro-SPE was used to cleanup sediment samples and to extract and preconcentrate five PAHs in sediment samples prepared as slurries with addition of water. The best extraction conditions comprised of microwave heating at 50 degrees C for a duration of 20 min, and an elution (desorption) time of 5 min using acetonitrile with sonication. Using gas chromatography (GC)-flame ionization detection (FID), the limits of detection (LODs) of the PAHs ranged between 2.2 and 3.6 ng/g. With GC-mass spectrometry (MS), LODs were between 0.0017 and 0.0057 ng/g. The linear ranges were between 0.1 and 50 or 100 microg/g for GC-FID analysis, and 1 and 500 or 1000 ng/g for GC-MS analysis. Granular activated carbon was also used for the micro-SPE device but was found to be not as efficient in the PAH extraction. The MAE-micro-SPE method was successfully used for the extraction of PAHs in river and marine sediments, demonstrating its applicability to real environmental solid matrixes.     

Extraction of lead ions by electromembrane isolation

A new microextraction approach namely electromembrane isolation (EMI) coupled with capillary electrophoresis (CE) and ultraviolet (UV) detection for determining lead (Pb) ions was developed. The EMI technique involved the use of a polypropylene hollow fiber whose channel was filled with a sodium dihydrogen phosphate/sodium tetraborate buffer solution of pH 8.1, immersed in 10 mL of an aqueous sample solution. A voltage of 300 V was applied across the hollow fiber wall for 15 min to extract Pb ions. The extract was then complexed with ethylenediamminetetracetic acid (20 mM EDTA solution, at pH 3.4) for CE analysis. Satisfactory linear dynamic ranges (0.1-10 mg L(-1)), limits of detection (0.019 mg L(-1)) and good repeatability (ranging from 4.9 to 15.6%, n=3) were obtained. EMI exhibits good linearity with a correlation coefficient of 0.9935. The optimized EMI procedure was applied to determine the concentration of Pb(2+) in various matrices, such as amniotic fluid, blood serum, lipstick and urine samples.     

The deposition of osmium carbonyl clusters onto inorganic oxide surfaces: a ToF-SIMS and IR spectroscopic study of the surface species

The interaction between the osmium clusters [Os3(CO)12], [Os3(CO)10(mu-H)2], [Os3(CO)10(mu-H)(mu-OH)], and a series containing a free functional group, viz., [Os3(CO)10(mu-H)(mu-S--EH)] (where -- =alkylwedge chain or an aromatic ring, E=COO, S or O), with SiO2, ZnO and In2O3, was examined by ToF-SIMS and IR spectroscopy. While the interaction with the silica surface is mostly via an O atom or the functional group, the interaction with the ZnO and In2O3 surfaces is more complex.     

Photophysical characterization of imidazolium-substituted Pd(II), In(III), and Zn(II) porphyrins as photosensitizers for photodynamic therapy

The photophysical properties of four imidazolium-substituted metalloporphyrins have been assessed to gain insights into the relative efficacy of the compounds for photodynamic therapy (PDT). A set of zinc(II), palladium(II), and chloro-indium(III) porphyrins all bear a net positive charge owing to the diethylimidazolium unit; one zinc chelate bears a negative charge owing to a bis(sulfobutyl)imidazolium unit. The photophysical properties of the cationic and anionic zinc porphyrins are very similar to one another in organic solvents, phosphate-buffered saline, and in the presence of bovine serum albumin. The properties of the zinc and palladium porphyrins bearing charged peripheral groups are generally similar to those of neutral analogs in organic solvents. The palladium porphyrin shows an essentially quantitative yield (≥0.99) of the triplet excited state compared to the zinc porphyrins (0.9), and all are quantitatively quenched (at the diffusion limit) by molecular oxygen in air-saturated fluid solution. If the rate constant and yield of quenching of the triplet excited state by energy or electron transfer to molecular oxygen is the same in the cellular environment as in solution, then these processes combined with the triplet yield contribute only a factor of 1.3 to the higher PDT activity of analogous palladium versus zinc porphyrins, which is much smaller than what is observed. Therefore, other factors such as transient reduction of the excited porphyrin or delivery to the target site must predominantly underlie the difference in PDT efficacy of these sensitizers.