Rapid Autoxidation Forms Highly Oxidized RO2 Radicals in the Atmosphere

Gas‐phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α‐pinene) form highly oxidized RO₂ radicals with up to 12 O atoms, along with related closed‐shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O₂ addition generating a next R′OO radical, is similar to the well‐known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well‐known reaction principle of autoxidation is also applicable to the atmospheric gas‐phase oxidation of hydrocarbons leading to extremely low‐volatility products which contribute to organic aerosol mass and hence influence the aerosol–cloud–climate system.     

A Novel Chronoimpedimetric Glucose Sensor in Real Blood Samples Modified by Glucose‐imprinted Pyrrole‐Aminophenylboronic Acid Modified Screen Printed Electrode

In this study, a molecularly imprinted sensor technology is engineered to detect glucose in real blood samples by chronoimpedimetrically. The imprinting process of glucose (Glc) was carried out by electrochemical polymerization of aminophenylboronic acid (APBA) and pyrrole (Py) by performing cyclic voltammetry (CV). Afterwards, glucose molecule was removed from imprinted surface by 5 % acetic acid to reveal glucose imprinted cavities. Electrochemical Impedance Spectroscopy (EIS) was used to characterize sensor modification steps and glucose removal. Glucose monitoring process was carried out chronoimpedimetrically(CI) for the first time in real blood samples. Calibration curve was prepared between 20–800 mg/dL. The standard deviations of the 18 calibration curves R² were calculated as 0.9866±0.0066 to assess reproducibility. Recovery was calculated by using 105 mg/dL Glc Serum Sample, which was monitored by auto analyzer and into this sample 50 mg/dL Glc added and our sensor response was 147.92±2.43 mg/dL, 98.6±1.62 % (n=5). Non‐imprinted (NIP) sensor gave no signal for the glucose concentration.     

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     

Carleman estimates and unique continuation property for the anisotropic differential-operator equations

The unique continuation theorems for the anisotropic partial differential-operator equations with variable coeffcients in Banach-valued Lp-spaces are studied.To obtain the uniform maximal regularity and the Carleman type estimates for parameter depended differential-operator equations,the suffcient conditions are founded.By using these facts,the unique continuation properties are established.In the application part,the unique continuation properties and Carleman estimates for finite or infinite systems of quasielliptic partial differential equations are studied.     

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     

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.     

Cystic fibrosis: a label-free detection approach based on thermally modulated electrochemical impedance spectroscopy

Cystic fibrosis is one of the most common genetically inherited diseases in northern Europe, with the DF508 mutation being the most common, and among the Caucasian population being responsible for almost 70% of cases. In this work, we report on the use of thermally modulated electrochemical impedance spectroscopy for the discrimination of the DF508 mutation from the wild-type sequence. DNA probes (15 and 21 bases long) were immobilised on the surface of gold electrodes and the variation of the charge-transfer resistance was monitored as a function of hybridisation. Two sets of targets were used in this work: synthetic 15-mer sequences and two single-stranded synthetic analogues of PCR products 82 (mutant) and 85 (wild type) bases long. Hybridisation with short targets resulted in very sequence specific charge-transfer-resistance variation with a discrimination factor at room temperature between fully complementary and mismatched sequences of approximately fivefold. However, in the case of the single-stranded synthetic PCR product analogues, a lower discrimination factor was recorded (1.5-fold). The effect of temperature was investigated to improve discrimination and the use of a posthybridisation wash at elevated temperature resulted in a fivefold improvement in the discrimination factor. Using an electrode array with probes immobilised against each of the mutant and wild-type sequences, we achieved an unequivocal detection of the DF508 mutation.