Elucidating the Stereochemistry of Enzymatic Benzylsuccinate Synthesis with Chirally Labeled Toluene

Benzylsuccinate synthase is a glycyl radical enzyme that initiates anaerobic toluene metabolism by adding fumarate to the methyl group of toluene to yield (R)‐benzylsuccinate. To investigate whether the reaction occurs with retention or inversion of configuration at the methyl group of toluene, we synthesized both enantiomers of chiral toluene with all three H isotopes in their methyl groups. The chiral toluenes were converted into benzylsuccinates preferentially containing ²H and ³H at their benzylic C atoms, owing to a kinetic isotope effect favoring hydrogen abstraction from the methyl groups. The configuration of the products was analyzed by enzymatic CoA‐thioester synthesis and stereospecific oxidation using enzymes involved in benzylsuccinate degradation. Assessment of the configurations of the benzylsuccinate isomers based on loss or retention of tritium showed that inversion of configuration at the methyl group occurs when the chiral toluenes react with fumarate.     

Synthesis, NMR conformational analysis and pharmacological evaluation of 7,7a,13,14-tetrahydro-6H-cyclobuta[b]pyrimido[1,2-a:3,4-a']diindole analogues as melatonin receptor ligands

A structure for the self-condensation product of 2-(1H-indol-2-yl)ethyl tosylate 2a, previously proposed as 6,7,14,15-tetrahydro-15aH-azocino[1,2-a:6,5-b]diindole 3a, was revised based on the (13)C-2D-INADEQUATE experiment, and proved to be 7,7a,13,14-tetrahydro-6H-cyclobuta[b]pyrimido[1,2-a:3,4-a']diindole 4a. A mechanism for the unexpected formation of this novel hexacyclic heterocycle was proposed and its NMR solution structure was elucidated. Five derivatives of the title ring skeleton 12-16 designed as melatonin receptor ligands were synthesized and their affinities for the human MT(1) and MT(2) receptors were determined. Both butyramides 13 and 15, as well as the non-methoxy acetamide 12 exhibited micromolar binding affinities for both receptors being slightly MT(2) selective. The methoxy acetamide 14 showed the best pharmacological profile exhibiting a five times higher affinity for MT(1) (K(i) = 49 nM) than for MT(2) (K(i) = 246 nM) receptor.     

Comparison of the Optoelectronic Performance of Neutral and Cationic Forms of Riboflavin

The riboflavin dye 2,3,4,5-tetra-O-acetyl-1-[3-(6-bromohexyl)-7,8-dimethyl-2,4-dioxo-3,4-dihydrobenzo[g]pteridin-10(2H)-yl]-1-deoxypentitol and its pyridinium salt were synthesized, and studied by absorption and fluorescence spectroscopy in solutions and on thin film states. The first absorption band of riboflavin-pyridinium salt derivative is red-shifted by 10 nm compared to neutral one on film. Cationic riboflavin derivative shows significant wavelength changes on its fluorescence emission spectrum in the excited state depending on the solvent polarity and the electronic environment. The fluorescence quantum yields of cationic riboflavin gave much higher values as compared to that of its neutral form. The fluorescence lifetimes were found to be in the range of 5.5–6.6 ns with mono ? exponential behavior. These dyes possess low-lying HOMO energy levels which are suitable to be able to inject holes to donor polymers so that they can be used as acceptor component in the active layer of bulk heterojunction solar cells (BHJ-SCs). Photovoltaic responses are reported for P3HT:riboflavin active layer wherein the synthesized dyes are used as acceptor component. Also, neutral riboflavin shows greater electron mobility value of 1.3 × 10^?3 cm²/V?s compared to its cationic derivative.     

Gold nanoparticles having dipicolinic acid imprinted nanoshell for Bacillus cereus spores recognition

Taking into account the recognition element for sensors linked to molecular imprinted polymers (MIPs), a proliferation of interest has been witnessed by those who are interested in this subject. Indeed, MIP nanoparticles are theme which recently has come to light in the literature. In this study, we have proposed a novel thiol ligand-capping method with polymerizable methacryloylamidocysteine (MAC) attached to gold nanoparticles, reminiscent of a self-assembled monolayer. Furthermore, a surface shell by synthetic host polymers based on molecular imprinting method for recognition has been reconstructed. In this method, methacryloyl iminodiacetic acid-chrome (MAIDA–Cr(III)) has been used as a new metal-chelating monomer via metal coordination–chelation interactions and dipicolinic acid (DPA) which is the main participant of Bacillus cereus spores has been used as a template. Nanoshell sensors with templates produce a cavity that is selective for DPA. The DPA can simultaneously chelate to Cr(III) metal ion and fit into the shape-selective cavity. Thus, the interaction between Cr(III) ion and free coordination spheres has an effect on the binding ability of the gold nanoparticles nanosensor. The interactions between DPA and MIP particles were studied observing fluorescence measurements. DPA addition caused significant decreases in fluorescence intensity because they induced photoluminescence emission from Au nanoparticles through the specific binding to the recognition sites of the crosslinked nanoshell polymer matrix. The binding affinity of the DPA imprinted nanoparticles has been explored by using the Langmuir and Scatchard methods and the analysis of the quenching results has been performed in terms of the Stern–Volmer equation.     

Diffusion-weighted magnetic resonance imaging in differentiation of postobstructive consolidation from central lung carcinoma

Purpose

To prospectively evaluate diffusion-weighted (DW) magnetic resonance (MR) imaging for differentiation of postobstructive consolidation from centrally located lung carcinomas by using apparent diffusion coefficients (ADCs).

Materials and Methods

An institutional review board approved this study; informed consent was obtained from patients. Forty-nine consecutive patients (3 women, 46 men; mean age, 63.6 years; age range, 42–85 years) with lung carcinoma underwent DW MR imaging. Forty patients had central and nine patients had peripheral lung carcinomas. ADC of each lung carcinoma was calculated from DW MR images obtained with two different b values (0, 1000 s/mm²).In the final study group including 27 patients with central lung carcinoma accompanying distal lung consolidation (mean age, 67.2 years; 3 women, 24 men), ADCs of lung carcinomas were statistically compared among cytologic/histologic types and accompanying postobstructive consolidations. Unpaired t test was used for measurable variables with normal distribution, and Kruskal–Wallis variance analysis and Mann–Whitney U tests were used for the measurable variables without normal distribution.

Results

There was no significant difference between mean ADC values of all types of carcinomas (P=.302) and also between mean ADC values of central (1.91 ± 0.7×10⁻³ mm²/s) and peripheral carcinomas (1.58 ± 0. 6×10⁻³ mm²/s) (P=.224). The mean ADC value for the masses of central lung carcinoma with postobstructive consolidations was 1.83 ± 0.75×10⁻³ mm²/s, and for consolidation was 2.50 ± 0.76×10⁻³ mm²/s. ADC of central carcinoma masses was significantly lower than that of postobstructive consolidations (P=.003).

Conclusions

ADC values of central lung carcinoma masses appear to be lower than accompanying postobstructive consolidations. ADC values could be considered useful as a differentiating parameter among central lung carcinomas and accompanying postobstructive consolidations.     

The neutron-proton pairing and the moments of inertia of the rare earth even-even nuclei

In this study, the possible effect of the neutron-proton pairing interaction in the heavy nuclei has been investigated in the framework of the BCS model by making a simple approximation. This effect has been searched realistically by calculating the moments of inertia of deformed even-even nuclei. Calculations show that the moments of inertia of rare earth nuclei changed dramatically and approached the experimental values.     

Use of ionic liquid based chitosan as sorbent for preconcentration of fluoroquinolones in milk,egg, fish,bovine, and chicken meat samples by solid phase extraction prior to HPLC determination

The possibility of using ionic liquid based chitosan sorbent for the separation and preconcentration of fluoroquinolone antibiotics (marbofloxacin, enoxacin, ofloxacin, ciprofloxacin, and enrofloxacin) has been studied. For this reason, different ionic liquids were prepared and coated on the chitosan sorbent. The conditions of the preconcentration of fluoroquinolones on a microcolumn have been optimized and the extraction efficiencies of the prepared sorbents have been compared. The compounds were eluted with 5 mL of 20% NH₃ (v/v, MeOH) solution and determined by HPLC with diode array and fluorescence detector. The limits of detection were found as 4.23 µ g L^?1 for marbofloxacin, and 1.09 µg L^?1 for enoxacin; 3.23 × 10^?3 µg L^?1 for ofloxacin; 8.39 × 10^?3 µg L^?1 for ciprofloxacin; and 19.50 × 10^?3 µg L^?1 for enrofloxacin. The developed method was applied for the analysis of fluoroquinolone in milk, egg, fish, bovine, and chicken samples and the recoveries were obtained in the range 70–100%.     

Synthesis,characterization and catalytic properties of cationic N-heterocyclic carbene silver complexes

Three new dibenzimidazolium salts bridged by 2-methylenepropane-1,3-diyl group were synthesized. Their dinuclear N-heterocyclic carbene Ag(I) complexes were prepared by the reactions of these salts with Ag₂O. The structures of the synthesized compounds were defined by nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), elemental analysis, and LC-MSMS (for complexes) techniques. Stability of the silver complexes was confirmed by ¹H NMR spectroscopy. Catalytic activities of Ag(I) compounds were tested for three-component coupling reaction of some aldehydes, amines, and phenylacetylene.     

Thermal entanglement in the mixed three-spin XXZ Heisenberg model on a triangular cell

We numerically investigate the thermal entanglements of spins （1/2, 1） and spins （1/2, 1/2） in the three-mixed （1/2, 1, 1/2） anisotropic Heisenberg XXZ spin system on a simple triangular cell under an inhomogeneous magnetic field. We show that the external magnetic field induces strong plateau formation in the pairwise thermal entanglement for fixed parame-ters of the Hamiltonian in the cases of ferromagnetic and antiferromagnetic interactions. We also .observe an unexpected critical point at finite temperature in the thermal entanglement of spins （1/2, 1） for the antiferromagnetic case, while the entanglement of spins （1/2, 1） in the ferromagnetic case and the entanglement of spins （1/2, 1/2） in both ferromagnetic and antiferromagnetic cases almost decay exponentially to zero with increasing temperature. The critical point in the en-tanglement of spins （1/2, 1） in the antiferromagnetic case may be a signature of the quantum phase transition at finite temperature.     

Indium phosphide nanofibers prepared by electrospinning method: Synthesis and characterization

Nine sets of (3 × 3) InP nanofiber samples have been successfully prepared at three different voltages (20, 25, 30 kV) and at three separate heights (5, 7, 10 cm) by electrospinning with a constant precursor flow rate of 0.3 mLh⁻¹. The crystalline structure, thermal, morphologies and nanostructure, electrical, and optical properties of the samples are characterized by X‐ray powder diffractometer (XRD) and thermal gravity‐differential scanning calorimeter (TG‐DSC), scanning electron microscopy (SEM), by Four‐Point Probe Technique (FPPT,) and ultraviolet/visible spectrometry (UV/VIS), respectively. From these measurements, we have found the formation of stoichiometric nanostructured InP with zinc‐blende structure and having lattice parameter of a = 5.874 Å, weight loss of 64.59% and crystallization temperature of 500°C, average fiber diameter of 65.82 nm, the activation energies, E_a, of the samples, and band gap energy, E_g, of the nanofibers developed at constant applied voltage 30 kV. The band gap energies determined at different distances 5, 7, and 10 cm are found to be as 1.29, 1.37, and 1.30 eV, respectively.