Metal Ion Complexation: A Route to 2 D Templates?

The two-dimensional ordering of a number of 2,2'-bipyridine derivatives at the liquid/solid interface has been investigated by scanning tunneling microscopy. By appropriate functionalization of the bipyridine units, their intermolecular distance can be tuned, which has proved to be crucial for complexation with metal ions. The in situ addition of metal salts (Pd(2+), Cu(2+)), leading to the formation of metal-bipyridine complexes, has a dramatic influence on the two-dimensional ordering of the molecules and suggests that these complexes could be used as templates.     

Bonding in [CuNRR’]<Subscript>4</Subscript> type clusters

Many polynuclear Cu(I) compounds have been synthesized, but the problem whether there is direct or no direct Cu-Cu bonding in these compounds is not clear. The electronic structure of [CuNRR’]₄ type clusters was investigated by using density functional methods. The results of geometrical optimization are in good agreement with experiment, and the localization of MO’s shows that there are four Cu-Cu σ bonds to form the square Cu₄ ring in addition to the four bridging Cu-N-Cu bonds. A concept of the covalence of molecular fragments is proposed to describe the bonding in these clusters.     

Random coil phosphorus chemical shift of deoxyribonucleic acids

Random coil phosphorus chemical shift has been studied using 16 17-nucleotide DNA sequences. Due to the presence of residual base stacking in these sequences, the temperature and sequence effects were investigated at 50 and 55 degrees C. The phosphorus chemical shifts of random coil DNA sequences have been found to be independent of temperature. Sequence effect analysis shows that the phosphorus chemical shift of a nucleotide in a random coil DNA sequence depends on both its 5'- and 3'-nearest neighbors. A trimer model has been used to establish the random coil 31P chemical shift prediction protocol which shows an accuracy of 0.02 ppm.     

Simultaneous determination of <Emphasis Type="SmallCaps">L</Emphasis>-arginine and its mono- and dimethylated metabolites in human plasma by high-performance liquid chromatography–mass spectrometry

A simple, fast, sensitive, and reproducible isocratic liquid chromatography–mass spectrometry (LC-MS) method coupled with an atmospheric pressure chemical ionization (APCI) interface for simultaneous separation and determination of L-arginine (ARG) and its methylated metabolites, N-monomethyl-L-arginine (MMA), N^G,N^G-dimethylarginine (asymmetric dimethyl arginine, ADMA), and N^G,N^G-dimethylarginine (symmetric dimethyl arginine, SDMA), in human plasma is presented. Sample pretreatment is not required other than deproteinization with 5-sulfosalicylic acid (5-SSA). Satisfactory chromatographic separation was achieved on a 2.0×150-mm Shimadzu VP-ODS column by using a mobile phase consisting of water/acetonitrile (90/10, v/v) containing 0.5% trifluoroacetic acid (TFA). Positive selective ion monitoring (SIM) mode was chosen for quantification of each analyte. The positively protonated molecular ions [M+H]⁺ of ARG, MMA, ADMA, and SDMA were monitored at m/z 175, 189, 203, and 203, respectively. L-Homoarginine was used as the internal standard (IS) for the assay. The limits of quantification (LOQs) were found to be 1.0 mol L^–1 for ARG, and 0.2 mol L^–1 for MMA, ADMA, and SDMA. The inter-assay precision and accuracy were in the range of 1.8–4.9% and –3.0–5.0%, respectively. The intra-assay precision and accuracy were in the order of 1.7–4.6 and –2.6–4.0%, respectively. The recoveries were between 90.0 and 106.6%. The levels of ARG, MMA, ADMA, and SDMA in human plasma were also determined using the developed method.     

Mechanochemical preparation of hydrogen-bonded adducts between the diamine 1,4-diazabicyclo[2.2.2]octane and dicarboxylic acids of variable chain length: an X-ray diffraction and solid-state NMR study

Mechanical mixing of solid dicarboxylic acids of variable chain length HOOC(CH(2))(n)COOH (n = 1-7) with solid 1,4-diazabicyclo[2.2.2]octane generates the corresponding salts or co-crystals of the formula [N(CH(2)CH(2))(3)N]-H-[OOC(CH(2))(n)COOH] (n=1-7). Preparation of the same systems from solution has been instrumental for a full characterization of the mechanochemical products by means of single-crystal and powder-diffraction X-ray analyses, as well as by solid-state NMR. The acid-base adducts, whether involving proton transfer from the COOH group to the N-acceptor, that is having ((-))O...H-N((+)) interactions, or the formation of neutral O-H...N hydrogen bonds, show a melting point alternation phenomenon analogous to that shown by the neutral carboxylic acids. The carbon chemical shift tensors of the COOH group obtained from the sideband intensity of low speed spinning NMR spectra provide a reliable criterion for assigning the protonation state of the adducts.     

Are the Elements Elementary? Nineteenth-Century Chemical and Spectroscopical Answers

We analyze the role and influence of a tradition of research linked to the concept of primary matter in nineteenth-century studies on the nature of the elements.The suggestion of William Prout (1785-1850) in 1816 that the atomic weights of pure chemical elements are whole numbers and multiples of the atomic weight of hydrogen, taken as unity, was met with serious confutations,which in turn prompted several attempts to save Prouts hypothesis.We discuss these attempts in detail and the objections raised against them, for instance by Dmitry Ivanovich Mendeleev (1834-1907). We pay particular attention to the use of spectroscopy as a method for proving the existence of elementary forms of matter inside atoms. Leaders in this field of research were two English scientists, the astrophysicist Norman Lockyer (1836-1920) and the chemist William Crookes (1832- 1919). Both of their approaches involved the idea of primary matter. However, while Crookess approach proved to be incorrect, Lockyers ideas survived for several years and supported the discovery of the electron by J.J.Thomson (1856-1940).