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

A new set of covalent atomic radii has been deduced from crystallographic data for most of the elements with atomic numbers up to 96. The proposed radii show a well behaved periodic dependence that allows us to interpolate a few radii for elements for which structural data is lacking, notably the noble gases. The proposed set of radii therefore fills most of the gaps and solves some inconsistencies in currently used covalent radii. The transition metal and lanthanide contractions as well as the differences in covalent atomic radii between low spin and high spin configurations in transition metals are illustrated by the proposed radii set.

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Covalent radii revisited

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

The Halogen Bond

Halogen Bonding in Supramolecular Chemistry.

Kraitchman has shown that a single isotopic substitution on an atom is sufficient to determine directly the coordinates of that atom with respect to the principal axes of the original molecule. Kraitchman's formulas represent exact solutions of the equations for the equilibrium moments of inertia. However, the effects of the zero‐point vibrations are such that the coordinates obtained by substitution from the ground state moments of inertia I0 are systematically less than r0. These coordinates have here been called r (substitution) or rs, and it is found that rs≃(r0+re)/2, and Is= ∑ imirsi2≃(I0+Ie)/2.In the usual method of solution, the coordinate of one atom is determined from the equation for I0, and therefore the difference I0—Is must be made up by this one coordinate. This introduces a large error in the structures normally determined from ground state constants, and results in variations of 0.01 A in structures determined from different sets of isotopic species. If instead, we obtain the structure on...

A new criterion for the determination of molecular structures from ground state rotational constants

Microwave spectra of the complexes KrAuF and KrAgBr have been measured for the first time using a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by laser ablation of the metal from its solid and allowing the resulting plasma to react with an appropriate precursor (Kr, plus SF6 or Br2) contained in the backing gas of the jet (usually Ar). Rotational constants; geometries; centrifugal distortion constants; vibration frequencies; and 197Au, 79Br, and 81Br nuclear quadrupole coupling constants have all been evaluated. The complexes are unusually rigid and have short Kr−Au and Kr−Ag bonds. The 197Au nuclear quadrupole coupling constant differs radically from its value in an AuF monomer. In addition 83Kr hyperfine structure has been measured for KrAuF and the previously reported complex KrAgF. The geometry of the latter has been reevaluated. Large values for the 83Kr nuclear quadrupole coupling constants have been found for both complexes. Both the 197Au and 83Kr hyperfine...

Microwave spectra and structures of KrAuF, KrAgF, and KrAgBr; 83Kr nuclear quadrupole coupling and the nature of noble gas-noble metal halide bonding.

[Cu.(H2O)n]2+ Clusters: The First Evidence of Aqueous Cu(II) in the Gas Phase

An experimental study of the stability and coordination of oxygen- and nitrogen-containing ligands in association with Mg2+ in the gas phase has been undertaken. The ligands chosen exhibit a wide range of physical properties in terms of their ionization energies, dipole moments, and polarizabilities, and a simple electrostatic model reveals a semiquantitative trend between these properties and the ability of each ligand to stabilize Mg2+. The model clearly demonstrates why water is extremely effective at stabilizing Mg2+, and in this respect, CO2 also proves to be a good ligand. Evidence of a discrete first solvation shell is apparent only for those ligands which do not display hydrogen bonding. For water, methanol, and ethanol, hydrogen bonding leads to extended solvation units for which the boundaries are less obvious. However, for more complex alcohols, steric interactions appear to negate the influence of hydrogen bonding. Discrete solvation shells are observed for most aprotic ligands, and the optimu...

A Gas-Phase Study of the Coordination of Mg2+ with Oxygen- and Nitrogen-Containing Ligands

Studies of gas phase M+(L)n cluster ions (where M is a metal atom and L is a ligand molecule) assist our understanding of solvation and chemical processes that involve metal ions. The recent development of pulsed, tuneable OPO (optical parametric oscillator) sources capable of generating infrared light at frequencies between 1000 and 4000 cm−1 has allowed the vibrational spectra of many species to be assigned for the first time. This perspective reviews infrared spectroscopy of metal-containing cluster ions to date and discusses future opportunities.

Frontiers in the infrared spectroscopy of gas phase metal ion complexes

A technique has been developed that provides a solution to the very considerable technical problem of preparing gas-phase complexes from transition metals in their higher oxidation states, i.e., Cu(II), Cr(III), Fe(II), etc. Charge transfer prevents complexes, such as [Cu·(H2O)n]2+, from being prepared via nucleation about an ion core, and yet these ions are pivotal to an understanding of transition metal chemistry. Discussed here are new results from a technique that appears capable of producing complexes from a wide variety of metals and ligands. Data are presented for copper(II) in association with 20 different ligands, including water, ammonia, pyridine, tetrahydrofuran, and benzene. For each [Cu·Ln]2+ system, two important quantities are identified:  (i) the minimum number of ligands required to form a stable unit and (ii) the value of n for which the intensity distribution reaches a maximum. The data show considerable variation as a function of the composition and size of solvent molecule, with evid...

Nicholas R. Walker

Papers

Microwave spectra and structures of KrAuF, KrAgF, and KrAgBr; 83Kr nuclear quadrupole coupling and the nature of noble gas-noble metal halide bonding.

[Cu.(H2O)n]2+ Clusters: The First Evidence of Aqueous Cu(II) in the Gas Phase

A Gas-Phase Study of the Coordination of Mg2+ with Oxygen- and Nitrogen-Containing Ligands

Frontiers in the infrared spectroscopy of gas phase metal ion complexes

Coordination and Chemistry of Stable Cu(II) Complexes in the Gas Phase