Human Group IIA Phospholipase A2—Three Decades on from Its Discovery

Phospholipase A₂ (PLA₂) enzymes were first recognized as an enzyme activity class in 1961. The secreted (sPLA₂) enzymes were the first of the five major classes of human PLA₂s to be identified and now number nine catalytically-active structurally homologous proteins. The best-studied of these, group IIA sPLA₂, has a clear role in the physiological response to infection and minor injury and acts as an amplifier of pathological inflammation. The enzyme has been a target for anti-inflammatory drug development in multiple disorders where chronic inflammation is a driver of pathology since its cloning in 1989. Despite intensive effort, no clinically approved medicines targeting the enzyme activity have yet been developed. This review catalogues the major discoveries in the human group IIA sPLA₂ field, focusing on features of enzyme function that may explain this lack of success and discusses future research that may assist in realizing the potential benefit of targeting this enzyme. Functionally-selective inhibitors together with isoform-selective inhibitors are necessary to limit the apparent toxicity of previous drugs. There is also a need to define the relevance of the catalytic function of hGIIA to human inflammatory pathology relative to its recently-discovered catalysis-independent function.     

First-principles study of electron dynamics with explicit treatment of momentum dispersion on Si nanowires along different directions

ABSTRACT

In this research, ground-state electronic structure and optical properties along with photoinduced electron dynamics of Si nanowires oriented in various directions are reviewed. These nanowires are significant functional units of future nano-electronic devices. All observables are computed for a distribution of wave vectors at ambient temperature. Optical properties are computed under the approximation of momentum conservation. The total absorption is composed of partial contributions from fixed values of momentum. The on-the-fly non-adiabatic couplings obtained along the ab initio molecular dynamics nuclear trajectories are used as parameters for Redfield density matrix equation of motion. The main outcomes of this study are transition energies, light absorption spectra, electron and hole relaxation rates, and electron transport properties. The results of these calculations would contribute to the understanding of the mechanism of electron transfer process on the Si nanowires for optoelectronic applications.     

Shahidine, a novel and highly labile oxazoline from Aegle marmelos: the parent compound of aegeline and related amides

A rare alkaloid, shahidine (1), having an unstable oxazoline core has been isolated as a major constituent from the fresh leaves of Aegle marmelos. It is moisture-sensitive, and found to be the parent compound of aegeline and other amides, however, it is stable in dimethyl sulfoxide. Its structure was established by spectroscopic analysis. Biogenetically, oxazolines may be considered as the precursor of hydroxy amides and oxazoles found in plants. Shahidine (1) showed activity against a few Gram-positive bacteria.     

Preparation of activated carbon from date pits: Effect of the activation agent and liquid phase oxidation

Two series of activated carbons have been prepared from date pits; series C, using carbon dioxide as activating agent, and series S, prepared by activation with steam under the same experimental conditions. The obtained samples were oxidized with nitric acid in order to introduce more oxygen surface groups. The surface area and porosity of the parent and oxidized activated carbons were studied by N₂ adsorption at 77 K and CO₂ adsorption at 273 K. The oxygen surface complexes were characterized by temperature-programmed decomposition (TPD). The results show that carbon dioxide and steam activations produce microporous carbons with an increasing amount of CO evolving groups when increasing the burn-off. On the other hand, oxidation with nitric acid increases the amount of CO and CO₂ evolved by the decomposition of surface oxygen groups, this increase being related to the development of porosity in the carbon with the degree of activation and to the activating agent used (CO₂ versus steam).     

High-dimensional mixed-valence copper cyanide complexes: Syntheses,structural characterizations and magnetism

Reactions of CuCl₂ with different CN complexes in presence of a neutral ancillary ligand lead to two novel mixed-valence Cu complexes [Cu^II(bpy)Cu^I(CN)₃]_n, 1 (bpy = 2,2′-bipyridine) and {[Cu^II(tn)₂][Cu^I₄(CN)₆]}_n2 (tn = 1,3-diaminopropane). For compound 1, the asymmetric unit involves two Cu ions Cu1 and Cu2 (Cu^I and Cu^II centres, respectively) which strongly differ in their environments. The Cu1 ion presents a CuC₄ pseudo-tetrahedral geometry, while the Cu2 ion presents a CuN₅ slightly distorted square-pyramidal geometry. The extended structure of 1 is generated by three cyano ligands which differ in their coordination modes. One CN group has a μ₃ coordination mode and bridges two Cu^I and one Cu^II ion, while the two other CN groups act as μ₂ bridges leading to a sophisticated 3-D structure. As for 1, the asymmetric unit of 2 involves three crystallographically different Cu ions (Cu1A and Cu1B, presumably Cu^I centres, and Cu2 presumably Cu^II centres). The Cu2 ion presents centrosymmetric CuN₄ coordination environments involving four nitrogen atoms from two bidentate tn ligands; while the Cu1A and Cu1B ions are three coordinated to cyano groups. The structure can be described as formed by 18-membered “[Cu^I(CN)]₆” planar metallocycles that are connected to their six neighbors to generate 2-D sheets; these sheets stack forming infinite hexagonal channels in which the [Cu(tn)₂]²⁺ units are located. Magnetic measurements show an unexpected weak ferromagnetic coupling (θ = 0.239(1) K) of the Cu^II ions through the long and “a priori diamagnetic” –NC–Cu^I–CN– bridges in compound 1 and an essentially paramagnetic behavior in compound 2.     

The electronic gas-phase spectrum of B3 radical revisited

The gas-phase electronic spectrum of cyclic-B₃ (D_3h) radical has been remeasured in a supersonic molecular beam using a mass-selective resonant 2-color 2-photon technique, leading to a revision of previously reported spectroscopic constants. The species was prepared by ablation of a boron nitride rod in the presence of helium. Ab intio calculations on the geometries and vertical electronic excitation energies, as well as mass identification, indicate that the detected band, centered at 21848.77(2) cm⁻¹, is the origin of the cyclic-¹¹B₃ system. A spectral fit yields the rotational constants as B″ = 1.2246(45) and C″ = 0.62131(72) cm⁻¹ in the ground state, and B′ = 1.1914(44) and C′ = 0.61173(69) cm⁻¹ in the excited 2 ²E′ state.     

Evolving timetabling heuristics using a grammar-based genetic programming hyper-heuristic framework

This paper introduces a Grammar-based Genetic Programming Hyper-Heuristic framework (GPHH) for evolving constructive heuristics for timetabling. In this application GP is used as an online learning method which evolves heuristics while solving the problem. In other words, the system keeps on evolving heuristics for a problem instance until a good solution is found. The framework is tested on some of the most widely used benchmarks in the field of exam timetabling and compared with the best state-of-the-art approaches. Results show that the framework is very competitive with other constructive techniques, and did outperform other hyper-heuristic frameworks on many occasions.     

Hydrogen adsorption in an interpenetrated dynamic metal-organic framework

A metal-organic framework Zn(NDC)(4,4'-Bpe)(0.5).xG [NDC = 2,6-naphthalenedicarboxylate; 4,4'-Bpe = 4,4'-trans-bis(4-pyridyl)ethylene; G = guest molecules] has been synthesized, structurally characterized, and rationalized to be a two-interpenetrated elongated primitive cubic net. Powder X-ray diffraction and adsorption studies reveal the dynamic feature of the framework, which can take up hydrogen of about 2.0 wt % at 77 K and 40 bar and 0.3 wt % at 298 K and 65 bar.     

Quantum Corrections for Regular Black Holes with Charge and Coupling Constant

In this paper, we use semi-classical tunneling approach to calculate the quantum corrections to the Hawking temperature as well as entropy of the Kehagias-Sftesos asymptotically flat black hole solution and charged regular black hole with Fermi-Dirac distribution. For this purpose, we apply the first law of black hole thermodynamics to investigate the semi-classical entropy of both black holes having mass as well as charge or coupling constant. For both black holes, the entropy corrections contain the logarithmic term as a leading order correction term. For Kehagias-Sftesos asymptotically flat black hole, the semi-classical Hawking temperature and black hole entropy will behave asymptotically by considering the vanishing coupling constant b = 0. We have obtained the same analysis for the corrected thermodynamical quantities for this BH. For charged regular black hole with Fermi-Dirac distribution, if we neglect the charged effects in our analysis, i.e., q = 0, then these corrections approximately leads to the Schwarzschild black hole which is already given in the literature.