抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com.

Multiwfn: a multifunctional wavefunction analyzer.

https://zenodo.org/record/1258475/files/article.pdf

Electron transfers in chemistry and biology

The surface science of titanium dioxide

Copper is an essential trace element in living systems, present in the parts per million concentration range. It is a key cofactor in a diverse array of biological oxidation-reduction reactions. These involve either outer-sphere electron transfer, as in the blue copper proteins and the Cu{sub A} site of cytochrome oxidase and nitrous oxide redutase, or inner-sphere electron transfer in the binding, activation, and reduction of dioxygen, superoxide, nitrite, and nitrous oxide. Copper sites have historically been divided into three classes based on their spectroscopic features, which reflect the geometric and electronic structure of the active site: type 1 (T1) or blue copper, type 2 (T2) or normal copper, and type 3 (T3) or coupled binuclear copper centers. 428 refs.

Multicopper Oxidases and Oxygenases

Spectroscopic and chemical studies of the ascorbate oxidase trinuclear copper active site: comparison to laccase

List of Contributors. Series Preface. Volume Preface. Part 1: Methods. Calculation of Bonding Properties (Gernot Frenking and Moritz von Hopffgarden). Determining Transition States in Bioinorganic Reactions (Marcus Lundberg and Keiji Morokuma). Quantum Mechanical/Molecular Mechanical (QM/MM) Methods and Applications in Bioinorganic Chemistry (Ulf Ryde). Ab initio and Semiempirical Methods (Serge I. Gorelsky). Spectroscopic Properties of Proten-Bound Cofactors: Calculation by Combined Quantum Mechanical/Molecular Mechanical (QM/MM) Approaches (Mahesh Sundararajan, Christoph Riplinger, Maylis Orio, Frank Wennmohs and Frank Neese). Spectroscopic Properties Obtained from Time-Dependent Density Functional Theory (TD-DFT) (Jochen Autschbach). Nuclear Magnetic Resonance (NMR) Parameters of Transition Metal Complexes: Methods and Applications (Martin Kaupp and Michael Buhl). Calculation of Reduction Potential and pK a . Quantum-Chemistry-Centered Normal Coordinate Analysis (QCC-NCA): Application of NCA for the Simulation of the Vibrational Spectra of Large Molecules (Nicolai Lehnert). Molecular Mechanics in Bioinorganic Chemistry (Robert J. Deeth). Multiconfigurational Quantum Mechanics (QM) for Heavy Element Compounds (Bjorn O. Roos). Approximate Density Functionals: Which Should I Choose? (Dmitrij Rappoport, Nathan R. M. Crawford, Filipp Furche and Kieron Burke). Spin Contamination in Inorganic Chemistry Calculations (Jason L. Sonnerberg, H. Bernhard Schlegel and Hrant P. Hratchian). Gaussian Basis Sets for Quantum Mechanical (QM) Calculations (Kirk A. Peterson). Part 2: Case Studies - Bioinorganic. Modeling Metalloenzymes with Density Functional and Mixed Quantum Mechanical/Molecular Mechanical (QM/MM) Calculations: Progress and Challenges (Richard A. Friesner). Broken Symmetry States of Iron-Sulfur Clusters (Louis Noodleman and David A. Case). Water Oxidation by the Manganese Cluster in Photosynthesis (Per E. M. Siegbahn). Nature of the Catecholate-Fe(III) Bond: High Affinity Binding and Substrate Activation in Bioinorganic Chemistry (Edward I. Solomon, Monita Y. M. Pau and Rosalie K. Hocking). Computational Studies: B 12 Cofactors and Their Interaction with Enzyme Active Sites (Thomas C. Brunold). Reaction Coordinate of Pyranopterin Molybdenum Enzymes (Martin L. Kirk, Sushilla Knottenbelt and Abebe Habtegabre). Electronic Structure Calculations: Dinitrogen Reduction in Nitrogenase and Synthetic Model Systems (Felix Tuczek). Hydrogenases: Theoretical Investigations Towards Bioinspired H 2 Production and Activation (Maurizio Bruschi, Giuseppe Zampella, Claudio Grego, Luca Bertini, Piercarlo Fantucci and Luca De Gioia). Computational Studies: Cisplatin (Yogita Mantri and Mu-Hyun Baik). Computational Methods: Modeling of Reactivity in Zn-Containing Enzymes (Jon I. Mujika, Adrian J. Mulholland and Jeremy N. Harvey). Combined Density Functional Theory (DFT) and Electrostatics Study of the Proton Pumping Mechanism in Cytochrome c Oxidase (Jason Quenneville, Dragan M. Popovi&c and Alexei A. Stuchebrukhov). Computational Studies: Proton/Water Coupling to Metal in Biological Reaction Mechanisms (Y. Bu and R. I. Cukier). Computational Studies: Chemical Evolution of Metal Sites (Kasper P. Jensen). Part 3: Case Studies - Inorganic. Electronic Structure Calculations: Transition Metal-NO Complexes (Abhik Ghosh, Jeanet Conradie and Kathrin H. Hopmann). Structural Origins of Noninnocent Coordination Chemistry (Robert K. Szilagyi). Electronic Structure of Metal-Metal Bonds (John E. McGrady). Computational Methods: Transition Metal Clusters (Regis Gautier, Jean-Francois Halet and Jean-Yves Saillard). Computational Methods: Heteropolyoxoanions (Josep M. Poblet and Xavier Lopez). Electronic Structure Calculations: Metal Carbonyls (Chantal Daniel). Potential Energy Surfaces for Metal-Assisted Chemical Reactions (Tiziana Marino, Maria del Carmen Michelini, Nino Russo, Emilia Sicilia and Marirosa Toscano). Computational Methods: Lanthanides and Actinides (M. Dolg and X. Cao). Spin-Orbit Coupling: Effects in Heavy Element Chemistry (Nikolas Kaltsoyannis). Noble Gas Compounds: Reliable Computational Methods (David A. Dixon). Computational Studies: Boranes (Oottikkal Shameema and Eluvathingal D. Jemmis). Multiple Aromaticity, Multiple Antiaromaticity, and Conflicting Aromaticity in Inorganic Systems (Dmitry Yu. Zubarev and Aledander I. Boldyrev). Theoretical Aspects of Main Group Multiple Bonded Systems (Ioan Silaghi-Dumitrescu, Petronela Petrar, Gabriela Nemes and R. Bruce King). Index.

Computational inorganic and bioinorganic chemistry

We report the preparation and new insight into photophysical properties of luminescent hydroxypyridonate complexes [M(III)L](-) (M = Eu or Sm) of the versatile 3,4,3-LI(1,2-HOPO) ligand (L) We report the crystal structure of this ligand with Eu(III) as well as insights into the coordination behavior and geometry in solution by using magnetic circular dichroism In addition TD-DFT calculations were used to examine the excited states of the two different chromophores present in the 3,4,3-LI(1,2-HOPO) ligand We find that the Eu(III) and Sm(III) complexes of this ligand undergo a transformation after in situ preparation to yield complexes with higher quantum yield (QY) over time It is proposed that the lower QY in the in situ complexes is not only due to water quenching but could also be due to a lower degree of f-orbital overlap (in a kinetic isomer) as indicated by magnetic circular dichroism measurements

/pdf/new-insights-into-structure-and-luminescence-of-eu-iii-and-3mrq9sixvw.pdf

New insights into structure and luminescence of Eu(III) and Sm(III) complexes of the 3,4,3-LI(1,2-HOPO) ligand.

Comparison of FeIV=O heme and non-heme species: electronic structures, bonding, and reactivities.

A superstructured tetraphenylporphyrin with a covalently attached proximal imidazole axial base and three distal imidazole pickets has been developed as a model for the active site of terminal oxidases such as cytochrome c oxidase. The oxygen adduct of the Fe-only heme (at low temperature) has a diamagnetic NMR and is EPR silent, which taken together with a resonance Raman oxygen isotope sensitive band (νFe−O) at 575/554 cm-1 (16O2/18O2) indicates formation of a six-coordinate heme−superoxide complex. Unexpectedly, the Fe/Cu complex, where the copper is in a trisimidazole environment ∼5 A above the heme plane, displays similar characteristics:  a diamagnetic NMR, EPR silence, and νFe−O at 570/544 cm-1. This indicates the dioxygen adduct of this Fe/Cu system is also a superoxide. This contrasts with previously characterized partially reduced dioxygen intermediates of binuclear heme/copper complexes that form Fe/Cu μ-peroxo complexes.

Edward I. Solomon

Papers

Spectroscopic and chemical studies of the ascorbate oxidase trinuclear copper active site: comparison to laccase

Computational inorganic and bioinorganic chemistry

New insights into structure and luminescence of Eu(III) and Sm(III) complexes of the 3,4,3-LI(1,2-HOPO) ligand.

Comparison of FeIV=O heme and non-heme species: electronic structures, bonding, and reactivities.

Spectroscopic evidence for a heme-superoxide/Cu(I) intermediate in a functional model of cytochrome c oxidase.