Multivariate linear regression with missing values

This contribution presents and discusses an efficient algorithm for multivariate linear regression analysis of data sets with missing values. The algorithm is based on the insight that multivariate linear regression can be formulated as a set of individual univariate linear regressions. All available information is used and the calculations are explicit. The only restriction is that the independent variable matrix has to be non-singular. There is no need for imputation of interpolated or otherwise guessed values which require subsequent iterative refinement.     

Two-dimensional self-assembly of linear molecular rods at the liquid/solid interface

We report on the synthesis and scanning tunneling microscopy (STM) studies of a series of linear molecular rods (1-5) comprising different numbers and/or spatial arrangements of perfluorinated benzene and benzene subunits interlinked with diacetylenes in the para position and decorated with or without terminal dodecyl chains. The molecules organize themselves into well-ordered 2D crystal structures at the liquid/solid interface through intermolecular and molecule-substrate interactions. Whereas the molecules substituted by dodecyl chains form the lamellar structures with alternating rigid core rows and alkyl chain rows, the unsubstituted ones change the orientation of the rigid backbones with respect to the lamellar axis. The molecular arrangement is not influenced by fluoro substituents on any phenyl ring of the backbone, which suggests that the interactions between the π-conjugated backbones are dominated by close packing rather than by the dipole moments of the rods or fluorine-based intermolecular interactions.     

Amide,urea and thiourea‐containing triphenylene derivatives: influence of H‐bonding on mesomorphic properties

The synthesis and thermotropic properties are reported for a series of hexaalkoxytriphenylenes that contain an amide, urea or thiourea group in one of their alkoxy tails. The intermolecular hydrogen bonding abilities of these molecules have a disturbing influence on the formation and stability of the columnar liquid crystalline phases. The stronger the hydrogen bonding the more the liquid crystallinity is suppressed, probably due to disturbance of the π–π stacking of the triphenylene discs. As a direct result, urea‐ and amide‐containing triphenylene derivatives are not liquid crystalline, but several thiourea derivatives show hexagonal columnar mesophases.     

Molecular recognition: comparative study of a tunable host-guest system by using a fluorescent model system and collision-induced dissociation mass spectrometry on dendrimers

Host-guest interactions between the periphery of adamantylurea-functionalized dendrimers (host) and ureido acetic acid derivatives (guest) were shown to be specific, strong and spatially well-defined. The binding becomes stronger when using phosphonic or sulfonic acid derivatives. In the present work we have quantified the binding constants for the host-guest interactions between two different host motifs and six different guest molecules. The host molecules, which resemble the periphery of a poly(propylene imine) dendrimer, have been fitted with an anthracene-based fluorescent probe. The two host motifs differ in terms of the length of the spacer between a tertiary amine and two ureido functionalities. The guest molecules all contain an acidic moiety (either a carboxylic acid, a phosphonic acid, or a sulfonic acid) and three of them also contain an ureido moiety capable of forming multiple hydrogen bonds to the hosts. The binding constants for all 12 host-guest complexes have been determined by using fluorescence titrations by monitoring the increase in fluorescence of the host upon protonation by the addition of the guest. The binding constants could be tuned by changing the design of the acidic part of the guest. The formation of hydrogen bonds gives, in all cases, higher association constants, demonstrating that the host is more than a proton sensor. The host with the longer spacer (propyl) shows higher association constants than the host with the shorter spacer (ethyl). The gain in association constants are higher when the urea function is added to the guests for the host with the longer spacer, indicating a better fit. Collision-induced dissociation mass spectrometry (CID-MS) is used to study the stability of the six motifs using the corresponding third generation dendrimer. A similar trend is found when the six different guests are compared.     

Metal speciation dynamics in colloidal ligand dispersions

In this work we propose a dynamic metal speciation theory for colloidal systems in which the complexing ligands are localized on the surface of the particles; i.e., there is spatial heterogeneity of binding sites within the sample volume. The differences between the complex formation and dissociation rate constants of complexes in colloidal dispersions and those in homogeneous solutions originate from the differences in kinetic and mass transport conditions. In colloidal systems, when the effective rate of dissociation of the surface complexes becomes fully diffusion controlled, its value is defined via the geometrical parameters of the particle. We assess the extent to which the conventional approach of assuming a homogeneously smeared-out ligand distribution overestimates the lability of surface complexes in colloidal ligand dispersions. The validity of the theory is illustrated by application to binding of lead and cadmium by carboxyl modified latex particles: our approach correctly predicts the formation/dissociation rate constants, which differ by several orders of magnitude from their homogeneous solution counterparts.     

Study of Hg22+ and complexes of NpO2+ and UO22+ in solution. examples of cation-cation interactions

Density functional theory (BPW91/TZ2P) is used to explore the nature of cation-cation interactions (CCIs) that exist between two actinyl cations in solution. Solvation, which is modeled using COSMO, favors the complexes (ONpO-ONpO)2+ and (ONpO-OUO)3+ over separated NpO2+(aq) and UO2(2+)(aq) cations because of the quadratic dependence of solvation on charge. For (OUO-OUO)4+, solvation effects, even though very large, are unable to overcome intrinsic electrostatic repulsion between the units. The actinyl-actinyl complexes are T-shaped, with the oxygen of one unit coordinated to the actinide metal of the other unit. The association free energies of (ONpO-ONpO)2+ and (ONpO-OUO)3+ are calculated as -42.1 and -29.2 kcal/mol. Explicit consideration of the first solvation shell at the B3LYP/LANL2DZ level suggests that the free energies of binding may be overestimated. The Hg2(2+) dication, though not considered a "traditional" CCI, is very similar to the actinyl-actinyl interaction. The binding free energy of Hg2(2+) in solution is calculated as -16.0 kcal/mol.     

Arsinothioyl-sugars produced by in vitro incubation of seaweed extract with liver cytosol analysed by HPLC coupled simultaneously to ES-MS and ICP-MS

It has been shown, that in vitro incubation of Laminaria digitata extract (containing mainly As-sugar 1 (glycerol-arsenoribose) and As-sugar 3 (sulfonate-arsenoribose)) with liver cytosol, produced the same two arsenicals, as when L. digitata extract was treated with H(2)S. By parallel use of HPLC-ICP-MS and HPLC-ES-MS the compounds displayed mainly m/z 345 and m/z 409. A pure As-sugar 1 standard was obtained, and a standard of arsinothioyl-sugar 1 (m/z 345) was produced, by purging a solution of As-sugar 1 with gaseous H(2)S. The identity of arsinothioyl-sugar 1 was characterised by ES-MS, 1D and 2D NMR. Arsinothioyl-sugar 1 showed the same chromatographic behaviour and MS characteristics as one of the two arsenic-containing compounds (m/z 345) produced by incubation of L. digitata extracts with liver cytosol, and as the product of the incubation of As-sugar 1 with liver cytosol (HPLC-ICP-MS, HPLC-ES-MS). Assuming that As-sugar 3 reacts in a similar way to As-sugar 1 with H(2)S, it is most likely that the second unknown (m/z 409) is arsinothioyl-sugar 3. The degradation of As-sugar 1 in acidic solution (100 mM HCl) was followed by (1)H-NMR, and the relative slow degradation (t(1/2)= 17 h) suggests that arsenosugars are taken up from the stomach in their original chemical form, hence the study of arsenosugar incubation in tissue is highly relevant. The arsinothioyls are a new group of organoarsenicals, which have only recently been identified in nature. Here, arsinothioyl sugars are detected for the first time. The in vitro formation of arsinothioyl-sugars in liver cytosol suggests that arsinothioyls may be of large biochemical and toxicological importance.     

Hydrogen bonds of RNA are stronger than those of DNA, but NMR monitors only presence of methyl substituent in uracil/thymine

Recently, Vakonakis and LiWang (J. Am. Chem. Soc. 2004, 126, 5688) reported experimental evidence for stronger hydrogen bonds in RNA A:U than in DNA A:T base pairs, which was based on differences in NMR shielding for adenine C2. We have analyzed the proposed correlation between NMR shielding and hydrogen-bond strength using density functional theory. Although we agree with the conclusion that A:U is more strongly bound, we find no correlation between the hydrogen-bond strength and the NMR shielding of C2. Our study shows that NMR merely probes the presence/absence of the methyl group in thymine/uracil, without any relation to the strength of the hydrogen bonds involved. In other words, one cannot infer the Watson-Crick hydrogen-bond strength from the NMR shielding constant of adenine C2.     

Chemical and thermal stability of alkanethiol and sulfur passivated InP(100)

InP(100) surfaces treated with Na2Sx9H20 and CnH(2n+1)SH are examined by contact angle measurement, X-ray photoelectron spectroscopy, and atomic force microscopy to determine the chemical and thermal behavior of these passivated surfaces. The surfaces coated by octadecanethiol (n = 18) self-assembled monolayers (SAMs) are found to be more stable toward oxidation than the S-passivated surface. The chemical stability of octadecanethiol SAMs in various environments is examined. The thiol monolayer is found to be stable in 0.1 M HCl but degrades in 0.1 M NaOH, boiling chloroform, and water. The behavior of these surfaces at elevated temperatures under a vacuum is also investigated. The octadecanethiol-coated InP(100) is stable up to 473 K, above which the films begin to degrade. Unlike other substrates on which the entire molecule including the sulfur headgroup desorbs together, on InP, the sulfur headgroup remains on the surface even after annealing to 673 K. These observations suggest that the desorption occurs by S-C bond cleavage as well as In-S bond cleavage. The sulfur of S-passivated InP is found to be more thermally stable than that of the octadecanethiol monolayer, perhaps due to their different bonding geometries and hence energies.