Manganese and iron flavonolates as flavonol 2,4-dioxygenase mimics

Mononuclear manganese(II) and iron(III) flavonolates were synthesized as synthetic enzyme-substrate complexes, and their oxygenation reactions as biomimetic functional models with relevance to flavonol 2,4-dioxygenases are briefly described.     

Assessment of Oxidative Stress in Patients with an Isolated Traumatic Brain Injury Using Disposable Electrochemical Test Strips

The barriers to using plasma redox potential as a measure of oxidative stress in patients are the use of specialized equipment, necessity of sterilization between tests, and inconsistent electrode surfaces and cell geometry. These problems are resolved using disposable test strips with built in electrochemical cells. Measuring the electrode potential at a small current yields a stable value that is ～50 mV higher for isolated traumatic brain injury (ITBI) patients than for healthy individuals. Even with natural variations within blood chemistry, this simple method may be clinically useful for assessing the degree of oxidative stress and injury severity in ITBI patients.     

Vibrational spectra of α-glucose, β-glucose, and sucrose: anharmonic calculations and experiment

The anharmonic vibrational spectra of α-D-glucose, β-D-glucose, and sucrose are computed by the vibrational self-consistent field (VSCF) method, using potential energy surfaces from electronic structure theory, for the lowest energy conformers that correspond to the gas phase and to the crystalline phase, respectively. The results are compared with ultraviolet-infrared (UV-IR) spectra of phenyl β-D-glucopyranoside in a molecular beam, with literature results for sugars in matrices and with new experimental data for the crystalline state. Car-Parrinello dynamics simulations are also used to study temperature effects on the spectra of α-D-glucose and β-D-glucose and to predict their vibrational spectra at 50, 150, and 300 K. The effects of temperature on the spectral features are analyzed and compared with results of the VSCF calculations conducted at 0 K. The main results include: (i) new potential surfaces, constructed from Hartree-Fock, adjusted to fit harmonic frequencies from M?ller-Plesset (MP2) calculations, that give very good agreement with gas phase, matrix, and solid state spectra; (ii) computed infrared spectra of the crystalline solid of α-glucose, which are substantially improved by including mimic groups that represent the effect of the solid environment on the sugar; and (iii) identification of a small number of combination-mode transitions, which are predicted to be strong enough for experimental observation. The results are used to assess the role of anharmonic effects in the spectra of the sugars in isolation and in the solid state and to discuss the spectroscopic accuracy of potentials from different electronic structure methods.     

Solution-phase synthesis of silver nanodiscs in HPMC-matrix and simulation of UV-vis extinction spectra using DDA based method

Present investigation demonstrates a very simple seed-mediated route, using hydroxypropyl methyl cellulose (HPMC) as stabilizing agent, for the synthesis of silver nanodiscs in aqueous solution. Central to the concept of seed-mediated growth of nanoparticles is that small nanoparticle seeds serve as nucleation centres to grow nanoparticles to a desired size and shape. It is found that the additional citrate ions in the growth solution play the pivotal role in controlling the size of silver nanodiscs. Similar to the polymers in the solution, citrate ions could be likewise dynamically adsorbed on the growing silver nanoparticles and promote the two-dimensional (2D) growth of nanoparticles. Morphological, structural, and spectral changes associated with the seed-mediated growth of the nanoparticles in the presence of HPMC are characterized using UV–vis and TEM spectroscopic studies. Metal nanoparticles have received increasing attention for their peculiar capability to control local surface plasmon resonance (LSPR) when interacting with incident light waves. Extensive simulation study of the UV–vis extinction spectra of our synthesized silver nanodiscs has been carried out using discrete dipole approximation (DDA) methodology.     

Detection of explosives and latent fingerprint residues utilizing laser pointer–based Raman spectroscopy

A modular, compact Raman spectrometer, based on a green laser pointer, an air cooled intensified charged coupled device and a x, y motorized translation stage was developed and applied for point detection. Its performance was tested for measurements of Raman spectra of liquids, trace amounts of explosives and individual particles, as well as for locating individual particles of interest and for chemical imaging of residues of latent human fingerprints. This system was found to be highly sensitive, identifying masses as low as ~1 ng in short times. The point and real-time detection capabilities of the spectrometer, together with the portability that it offers, make it a potential candidate for replacing existing Raman microscopes and for field applications.     

Facial Nonrepetitive Vertex Coloring of Plane Graphs

A sequence is a repetition. A sequence S is nonrepetitive, if no subsequence of consecutive terms of S is a repetition. Let G be a plane graph. That is, a planar graph with a fixed embedding in the plane. A facial path consists of consecutive vertices on the boundary of a face. A facial nonrepetitive vertex coloring of a plane graph G is a vertex coloring such that the colors assigned to the vertices of any facial path form a nonrepetitive sequence. Let denote the minimum number of colors of a facial nonrepetitive vertex coloring of G. Harant and Jendrol’ conjectured that can be bounded from above by a constant. We prove that for any plane graph G.     

Antimicrobial and antiquorum-sensing activity of Ricinus communis extracts and ricinine derivatives

Ricinine (1), a known major alkaloid in Ricinus communis plant, was used as a starting compound for the synthesis of six ricinine derivatives; two new and four known compounds. The new derivatives; 3-amino-5-methyl-1H-pyrazolo[4,3-c]pyridin-4(5H)-one (2), and 3-amino-5-methyl-1-(phenylsulfonyl)-1H-pyrazolo[4,3-c]pyridin-4(5H)-one (3), as well as the previously prepared derivatives (4–7) were subjected for antimicrobial and antiquorum-sensing evaluation in comparison to different R. communis extracts. Acetyl ricininic acid derivative (5) showed the highest antimicrobial activity among all tested derivatives against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeuroginosa and Candida albicans. However, compound 7 (4-methoxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxamide) showed the highest antiquorum-sensing activity among all tested compounds and extracts. These findings proved the usefulness of ricinine as a good scaffold for the synthesis of new antimicrobial and antiquorum-sensing derivatives in spite of its poor contribution to the antimicrobial activity of the plant extracts.     

Competitive adsorption of anionic dyes onto DMOA modified MCM-41

Research on Chemical Intermediates - The single and binary adsorption of two anionic dyes Acid Yellow 17 (AY17) and Naphtol Green B (NGB) onto N–N–Dimethyl-n-octylamine (DMOA) modified...     

An exploration of social identity: The structure of the BBC news‐sharing community on Twitter

Online social media influence the flow of news and other information, potentially altering collective social action while generating a large volume of data useful to researchers. Mapping these networks may make it possible to predict the course of social and political movements, technology adoption, and economic behavior. Here, we map the network formed by Twitter users sharing British Broadcasting Corporation (BBC) articles. The global audience of the BBC is primarily organized by language with the largest linguistic groups receiving news in English, Spanish, Russian, and Arabic. Members of the network primarily “follow” members sharing articles in the same language, and these audiences are primarily located in geographical regions where the languages are native. The one exception to this rule is a cluster interested in Middle East news which includes both Arabic and English speakers. We further analyze English‐speaking users, which differentiate themselves into four clusters: one interested in sports, two interested in United Kingdom (UK) news—with word usage suggesting this reflects political polarization into Conservative and Labour party leanings—and a fourth group that is the English speaking part of the group interested in Middle East news. Unlike the previously studied New York Times news sharing network the largest scale structure of the BBC network does not include a densely connected group of globally interested and globally distributed users. The political polarization is similar to what was found for liberal and conservative groups in the New York Times study. The observation of a primary organization of the BBC audience around languages is consistent with the BBC's unique role in history as an alternative source of local news in regions outside the UK where high quality uncensored news was not available. © 2014 Wiley Periodicals, Inc. Complexity 19: 55–63, 2014     

Glucose‐ and Cellulose‐Derived Ni/C‐SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual‐functional Ni catalysts supported on sulfonated carbon (Ni/C‐SO₃H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C‐SO₃H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C‐SO₃H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3–5 nm grafted Ni particles was analysed by in situ X‐ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C‐SO₃H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C‐SO₃H with the Ni/C‐SO₃H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C‐SO₃H to the most active of the Ni/C‐SO₃H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90 %) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.