Structure determination of gas-phase niobium and tantalum carbide nanocrystals via infrared spectroscopy

Niobium and tantalum carbide clusters have been isolated in the gas phase and irradiated with intense tunable infrared (IR) light. Stable neutral clusters are selectively ionized and subsequently detected in a mass spectrometer. By tuning the IR frequency, infrared multiphoton absorption spectra are obtained for a whole range of clusters. These mass-selective IR spectra lead to insights into the structures of small niobium and tantalum carbide clusters and nanocrystals.     

Microcionamides A and B, bioactive peptides from the philippine sponge Clathria (Thalysias) abietina

Microcionamides A (1) and B (2) have been isolated from the Philippine marine sponge Clathria (Thalysias) abietina. These new linear peptides are cyclized via a cystine moiety and have their C-terminus blocked by a 2-phenylethylenamine group. Their total structures, including absolute stereochemistry, were determined by a combination of spectral and chemical methods. Compound 1 was shown to slowly isomerize about the C-36/C-37 double bond when stored in DMSO. Microcionamides A (1) and B (2) exhibited significant cytotoxicity against the human breast tumor cells lines MCF-7 and SKBR-3 and displayed inhibitory activity against Mycobacterium tuberculosis H(37)Ra.     

Proton source size measurements in the eA-->e'ppX reaction

Two-proton correlations at small relative momentum q were studied in the eA(3He,4He,C,Fe)-->e(')ppX reaction at E(0)=4.46 GeV using the CLAS detector at Jefferson Lab. The enhancement of the correlation function at small q was found to be in accordance with theoretical expectations. Sizes of the emission region were extracted, and proved to be dependent on A and on the proton momentum. The size of the two-proton emission region for He was measured in eA reactions for the first time.     

Poly(p‐phenylene methylene)‐based block copolymers by mechanistic transformation

The synthesis of poly(p‐phenylene methylene) (PPM)‐based block copolymers such as poly(p‐phenylene methylene)‐b‐poly(ε‐caprolactone) and poly(p‐phenylene methylene)‐b‐polytetrahydrofuran by mechanistic transformation was described. First, precursor PPM was synthesized by acid‐catalyzed polymerization of tribenzylborate at 16 °C. Then, this polymer was used as macroinitiators in either ring‐opening polymerization of ε‐caprolactone or cationic ring‐opening polymerization of tetrahydrofuran to yield respective block copolymers. The structures of the prepolymer and block copolymers were characterized by GPC and ¹H NMR investigations. The composition of block copolymers as determined by ¹H NMR and TGA analysis was found to be in very good agreement. The thermal behavior and surface morphology of the copolymers were also investigated, respectively, by differential scanning calorimetry and atomic force microscopy measurements, and the contribution of the major soft segment has been observed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

On the ionic conductivity of polymer electrolytes in terms of hole fraction

A theoretical model to interpret the conductivity of ions through polymer electrolytes is established in terms of the temperature and pressure‐dependent hole fraction computed from Simha‐Somcynsky hole theory. The model successfully linearizes the logarithm of PPG and PEG conductivity data with NaCF₃SO₃ in a 20:1 ratio for a broad range of temperature and pressure. The conductivity parameter and transmission coefficient with an additive hole fraction constant are discussed and compared for both species. The derivative of the logarithm of conductivity with respect to the hole fraction decreases inversely with the hole fraction and saturates at about 0.08 and 0.12 hole fractions for PPG and PEG, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2249–2254, 2008     

Linear and Nonlinear Optical Properties in Spherical Quantum Dots

We calculate the energy eigenvalues and the sate functions of one-electron Quantum Dot （QD） by using a combination of Quantum Genetic Algorithm （QGA） and Hartre-Fock-Roothaan （HFR） method. The linear and the third-order nonlinear optical absorption coefficients for the 1s-1p, 1p-1d, and 1d-1f transitions are examined as a function of the incident photon energy for three different values of the stoichiometric ratio. The results show that the stoichiometric ratio, impurity, relaxation time, and dot size have great influence on the optical absorption coefficients of QDs.     

Cloning of the Orange Light‐Producing Luciferase from Photinus scintillans—A New Proposal on how Bioluminescence Color is Determined

Unlike the enchanting yellow‐green flashes of light produced on warm summer evenings by Photinus pyralis, the most common firefly species in North America, the orange lights of Photinus scintillans are infrequently observed. These Photinus species, and likely all bioluminescent beetles, use the same substrates beetle luciferin, ATP and oxygen to produce light. It is the structure of the particular luciferase enzyme that is the key to determining the color of the emitted light. We report here the molecular cloning of the P. scintillans luc gene and the expression and characterization of the corresponding novel recombinant luciferase enzyme. A comparison of the amino acid sequence with that of the highly similar P. pyralis enzyme and subsequent mutagenesis studies revealed that the single conservative amino acid change tyrosine to phenylalanine at position 255 accounted for the entire emission color difference. Additional mutagenesis and crystallographic studies were performed on a H‐bond network, which includes the position 255 residue and five other stringently conserved beetle luciferase residues, that is proximal to the substrate/emitter binding site. The results are interpreted in the context of a speculative proposal that this network is key to the understanding of bioluminescence color determination.     

Ring‐opening metathesis polymerization of fatty acid derived monomers

The ring‐opening metathesis polymerization (ROMP) of fatty acid functionalized norbornenes was explored in the presence of dichloro[1,3‐bis(2,4,6‐trimethylphenyl)‐2‐imidazolidinylidene](benzylidene)bis(3‐bromopyridine)ruthenium(II) ( C3 ) at room temperature. The investigated monomers were derived from fatty acids with different chain lengths (C₆, C₈, C₁₀, C₁₂, C₁₄, C₁₆, and C₁₈) and can therefore contribute to the development of more sustainable, bio‐based polymeric materials. The polymerizations initiated by C3 proceeded in a living fashion with good initiation efficiency, and thus the synthesis of well‐defined polymers with narrow polydispersities was accomplished. All prepared polymers were fully characterized (GPC, DSC, TGA, NMR) and the results of these investigations are discussed within this contribution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Optically implemented broadband blueshift switch in the terahertz regime

We experimentally demonstrate, for the first time, an optically implemented blueshift tunable metamaterial in the terahertz (THz) regime. The design implies two potential resonance states, and the photoconductive semiconductor (silicon) settled in the critical region plays the role of intermediary for switching the resonator from mode 1 to mode 2. The observed tuning range of the fabricated device is as high as 26% (from 0.76 THz to 0.96 THz) through optical control to silicon. The realization of broadband blueshift tunable metamaterial offers opportunities for achieving switchable metamaterials with simultaneous redshift and blueshift tunability and cascade tunable devices. Our experimental approach is compatible with semiconductor technologies and can be used for other applications in the THz regime.