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The concept of secondary bond covers a wide range of non-covalent interactions involving an acceptor (or electrophilic) molecule and an electron donor (or nucleophilic) one. It involves triel, tetrel, pnictogen, chalcogen, halogen, and aerogen bonds as well as hydrogen bonds. Such interactions yield complexes in which the internuclear distance of the electrophilic and nucleophilic centers is intermediate between the sums of the covalent and van der Waals radii of these atoms. These complexes can be considered as precursors of hypothetical nucleophilic substitution or addition reactions. As a consequence of the least motion principle, in the complex, the arrangement of the ligands around the electrophilic center should look like that of the hypothetical transition state or addition product. In a same fashion, the geometry around the nucleophilic center is determined by the location of the lone pair or of the bond involved in the interaction. In this picture of secondary bonding, the structure of the valence shell of the electrophilic atoms determines the geometry of the complex rather than the group to which belongs the elemental atom. The reorganization of the complexes in terms of the arrangement of the bonding and non-bonding electronic domains around the electrophilic center enables to rationalize the geometries in a systematic fashion. A set of VSEPR inspired rules enabling the building up of secondary bonded isomers are proposed and checked by quantum chemical calculations performed on representative test systems of the AX 4-n E n type. Graphical Abstract An example of secondary interaction: FClO[Formula: see text].

Delocalization of the electron density in the proton donor fragment has been studied for 21 complexes, A-HB (A = F, Cl; B = Ne, Ar, CO 2 , N 2 , FH, ClH, H 2 O, PH 3 , NH 3 , Cl - , F - , covering the whole range of hydrogen bond strength. The proton donor and proton acceptor fragments are defined by a minimum variance principle achieved by the ELF partition. It is shown that the variance of the proton donor population as well as the charge transfer between the fragments calculated from the ELF partition is always smaller than that evaluated within the QTAIM framework. For both partition schemes, the variance and the charge transfer are correlated with the hydrogen bond strength. It is shown that the variance varies as the square root of the value of the ELF at the hydrogen bond interaction point (i.e. the saddle point at the boundary of the proton donor and proton acceptor moieties)η vv' providing a numerical proof of the conjecture that the ELF partition satisfies a minimum variance condition and an explanation of the success of the core valence bifurcation index as an indicator of the hydrogen bond strength. The ELF technique has been then applied to the study of hydrogen bonded crystals for which the variance of the fragment population has been estimated from η vv' . The systems investigated are KHF 2 , KDP and ice VIII. The results are consistent with very strong hydrogen bonds in the two former crystals and medium-weak bonding in ice. In ice VIII the variance, and therefore the hydrogen bond strength, increases with pressure yielding a phase transition toward ice X in which the hydrogen bond is characterized as very strong. Our study emphasizes the importance of the partition scheme which defines the proton donor fragment and the role of electron density delocalization between the fragments which is, according to us, often improperly termed as covalence.

Polarized IR and Raman spectra of single crystal were measured at room and at low temperature. The polarized IR spectra were measured by transmission and specular reflection method. The IR-microscope was used for vibrational measurement of small monocrystals. Assignment of the bands is proposed on the basis of oriented gas model approximation. The polarized vibrational spectra are discussed in relation to the crystal structure and possible proton conductivity and phase transition.

Complete (full) set of the polarised IR and Raman spectra for the gamma-glycine single crystal at room temperature are presented. The polarised IR spectra were measured by the specular reflection method and the spectra of the imaginary parts of the refractive indices were computed by Kramers-Kronig transformation. The polarised properties of the bands are discussed with respect to the normal coordinate analysis (literature data) and diffraction crystal data (oriented gas model approximation). A very good agreement between the polarised properties of the bands and simple models of vibrations are observed for the stretching vibrations of the CH2 and COO- group. It is not the case for most of the deformation vibrations of the carboxylic group and of the skeleton. The polarization properties of the stretching vibrations of the NH3+ group are determined by their hydrogen bondings.

Human serum albumin (HSA) binding with endogenous metabolites and drugs is substantially decreased in chronic renal and liver diseases. To test the hypothesis that the decreased binding ability is caused by conformational changes of the protein, we analyzed infrared and Raman spectra of HSA isolated from healthy donors and patients with chronic uremia and liver cirrhosis. Uremia did not affect the secondary structure of HSA but modified the environment of its Asp/Glu residues. Liver cirrhosis increased the amount of extended and beta-structures, modified the environment of Asp/Glu and Tyr side chains, and changed the configuration of disulfide bridges in albumin molecules. The conformational changes of "cirrhotic" albumin were not caused by reversibly bound ligands and resembled a partial unfolding of the protein induced by adsorption on the charcoal surface. The dramatic structural alterations of HSA in liver cirrhosis may be caused by its oxidative modification and might underlie the decreased binding ability and changed body distribution of albumin.

The effects of two food-related chemicals (sodium saccharin and linoleic acid) on the levels of Her2/neu and p53 mRNA in a non-cancerous human breast epithelial cell line (HBL-100) were tested in comparison with the effects of the known tumor promoter phorbol 12-myristate 13-acetate (TPA). Treatments were made both with and without prior treatment with two well-known tumor initiators, N-nitroso-N-methylurea (NMU) or 7,12-dimethylbenz[a]anthracene (DMBA). The effects in general were small, the greatest being increases of 46-67% in Her2/neu mRNA levels in response to treatments with TPA or sodium saccharin following NMU treatments. These results demonstrate that sodium saccharin following NMU treatments might be involved in transcriptional regulation of Her2/neu in HBL-100 cells and suggest that its effects may not be limited to urinary bladder.

Adult female B6C3F1 mice received distilled water only or water containing 1.0, 10, or 100 ppb of aldicarb daily for 34 days. The target concentration of aldicarb present in the 100 ppb dosing solution was analytically verified. To further develop an immune profile of this compound, following aldicarb exposure, the ability of splenic natural killer cells and specifically sensitized cytotoxic T-lymphocytes to lyse YAC-1 lymphoma and P815 tumor cells, respectively, was evaluated. To supplement the functional assays, the impact of aldicarb exposure on the percentages and absolute numbers of total T-cells, T-suppressor, T-helper, and B-cells was evaluated. The absence of statistically significant effects on any of these parameters supports earlier reports that aldicarb does not result in adverse effects on the immune system of mice.

The basic components of a data- and methodbase system useful for both individual diagnosis and (group-study) research in neuropsychology are described. Such a system enables one to organize, access and evaluate large data-sets of behavioural, neuroradiological and neurological information. The most important component of the system, the data- and methodbase management system, is described in some detail. It operates on databases comprised of Aachen Aphasia Test examinations and standardized CT evaluations as well as on methodbases containing various sets of analysis routines for the psychometric evaluation of (individual) aphasia test results and the evaluation and (graphical) presentation of standardized (individual) CT lesions. Although exemplified for AAT scores the techniques and principles employed are applicable to data- and methodbase systems in general.

The in vivo pulmonary immune response of rats to local stimulation with antigen was assessed by measuring antigen-specific antibody and antibody-secreting cells utilizing enzyme-immunoassay technology. Sprague-Dawley rats were immunized subcutaneously with ovalbumin (OA) emulsified in Freund's incomplete adjuvant, challenged with OA intratracheally on Day 19 and sacrificed 1, 2, 3, or 4 days later. Specific antibody-secreting cells in the lung-associated lymph nodes were enumerated with the ELISA-SPOT assay and antibody concentration in the pulmonary lavage fluids and sera was assessed with the ELISA. The greatest response for each parameter was on Day 2. Cellular infiltration of the lung was minimal. Cellular infiltrates consisted mainly of polymorphonuclear leukocytes and were most numerous in the lavage fluid on Days 1 and 2 and in the lung parenchyma on Day 2 after challenge. Local production versus serum transudation of antibody was evaluated by comparing the levels of OA-specific antibody to albumin in the lavage fluid and serum. The data showed that antibody in the lungs was primarily produced locally.