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Host Molecules (host + molecule)
Selected AbstractsMagnetic susceptibility: Further insights into macroscopic and microscopic fields and the sphere of LorentzCONCEPTS IN MAGNETIC RESONANCE, Issue 1 2003C.J. Durrant Abstract To make certain quantitative interpretations of spectra from NMR experiments carried out on heterogeneous samples, such as cells and tissues, we must be able to estimate the magnetic and electric fields experienced by the resonant nuclei of atoms in the sample. Here, we analyze the relationships between these fields and the fields obtained by solving the Maxwell equations that describe the bulk properties of the materials present. This analysis separates the contribution to these fields of the molecule in which the atom in question is bonded, the "host" fields, from the contribution of all the other molecules in the system, the "external" fields. We discuss the circumstances under which the latter can be found by determining the macroscopic fields in the sample and then removing the averaged contribution of the host molecule. We demonstrate that the results produced by the, so-called, "sphere of Lorentz" construction are of general validity in both static and time-varying cases. This analytic construct, however, is not "mystical" and its justification rests not on any sphericity in the system but on the local uniformity and isotropy, i.e., spherical symmetry, of the medium when averaged over random microscopic configurations. This local averaging is precisely that which defines the equations that describe the macroscopic fields. Hence, the external microscopic fields, in a suitably averaged sense, can be estimated from the macroscopic fields. We then discuss the calculation of the external fields and that of the resonant nucleus in NMR experiments. © 2003 Wiley Periodicals, Inc. Concepts Magn Reson Part A 18A: 72,95, 2003 [source] A C2 -Chiral Bis(amidinium) Catalyst for a Diels,Alder Reaction Constituting the Key Step of the Quinkert,Dane Estrone SynthesisEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 9 2003Svetlana B. Tsogoeva Abstract A novel C2 -chiral bis(amidinium) salt 12 has been synthesised from 5-(tert -butyl)isophthalic acid. The hydrogen-bond-mediated association of dienophiles 3a and 3b with the chiral host molecule 12 accelerates the Diels,Alder reactions with diene 2 by more than three orders of magnitude. In addition, enantioselective formation of the desired adducts is observed under catalysis with 12. Good ratios of 4a(b) + ent - 4a(b)/5a(b) + ent - 5a(b) from 1:10 to 1:22 were found in all reactions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Thiourea Based Tweezer Anion Receptors for Selective Sensing of Fluoride IonsCHINESE JOURNAL OF CHEMISTRY, Issue 5 2007You-Ming Zhang Abstract Three 3,3,-di(4-substituted-phenyl)-1,1,-isophthaloylbis(thiourea) compounds were designed as novel neutral anion receptors, and synthesized by simple steps in good yields. The single crystal structure of receptor 1 shows that a solvent molecule was captured by the host molecule through intermolecular hydrogen bonding. Moreover, it was self-assembled as a supramolecular system for the presence of abundant inter- and intramolecular hydrogen bonding and ,-, interactions between phenyl groups. Their application as anion receptors has been examined by UV-Vis and 1H NMR spectroscopy, showing that they had a higher selectivity for fluoride than other halides. The host and guest formed a 1:1 stoichiometry complex through hydrogen bonding interactions in the first step, then following a process of deprotonation in presence of an excess of F, in the solvent of DMF. [source] Analysis of the Voltammetric Response of Electroactive Guests in the Presence of Non-Electroactive Hosts at Moderate ConcentrationsELECTROANALYSIS, Issue 18 2004Sandra Mendoza Abstract In this work, we present a method to analyze the voltammetric response of reversible redox systems involving molecules that, bearing m non-interactive electroactive sites, can undergo fast complexation equilibria with host molecules present at concentrations of the same order of magnitude as those of the electroactive guest. The approach focuses on systems for which the relative values of the binding constants for the oxidized and reduced forms of the guest result in the displacement of the voltammetric response of the electroactive molecule as the concentration of the host is increased in the electrolytic solution. This behavior is commonly known as "one wave shift behavior". Based on a series of assumptions, the method allows calculation of all the thermodynamic parameters that describe the electrochemical and complexation equilibria of a given host-guest system. The main strength of the suggested method, however, relies on the fact that it only requires cyclic voltammetry data and that it can be used for systems in which large concentrations of the host can not be employed either due to important changes of the ionic strength or to solubility problems. Although the accuracy of the obtained information is limited by the quality of the data provided by the technique, and by the assumptions employed, it certainly represents an excellent starting point for subsequent refinement either using digital simulations or an independent experimental technique. [source] Dicopper(II) Complexes with the Enantiomers of a Bidentate Chiral Reduced Schiff Base: Inclusion of Chlorinated Solvents and Chiral Recognition of1,2-Dichloroethane Rotamers in the Crystal LatticeEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2006Vamsee Krishna Muppidi Abstract Bisphenoxo-bridged dicopper(II) complexes [Cu2Ln2Cl2] {1 (n = 1) and 2 (n = 2)} with the N,O-donor reduced Schiff bases N -(2-hydroxybenzyl)-(R)-,-methylbenzylamine (HL1) and N -(2-hydroxybenzyl)-(S)-,-methylbenzylamine (HL2) have been synthesised and characterised. In both 1 and 2, the bidentate chiral ligands coordinate the metal centres through the secondary amine N atom and the bridging phenolate O atom. The chloride ion occupies the fourth coordination site and completes a slightly distorted square-planar NO2Cl environment around each copper(II) centre. Magnetic susceptibility measurements in the solid state suggest a strong antiferromagnetic interaction between the metal centres in both complexes. Both 1 and 2 readily form 1:1 host-guest compounds with chlorinated solvents such as CH2Cl2, CHCl3 and Cl(CH2)2Cl. All the host-guest compounds crystallise in noncentrosymmetric space groups. 1·CH2Cl2 and 2·CH2Cl2 crystallise in the P21 space group while 1·CHCl3, 2·CHCl3, 1·Cl(CH2)2Cl and 2·Cl(CH2)2Cl crystallise in the P212121 space group. In these inclusion crystals, the C,H···Cl interactions between the guest and the host molecules are primarily responsible for enclatheration of the chloroalkane molecules. In the case of CH2Cl2, one of its Cl atoms acts as the acceptor. On the other hand, for CHCl3 and Cl(CH2)2Cl, the metal coordinated Cl atom of the host complex acts as the acceptor. The structures of 1·(P)-Cl(CH2)2Cl and 2·(M)-Cl(CH2)2Cl provide rare examples for chiral recognition of the right handed (P) and the left handed (M) gauche forms of Cl(CH2)2Cl in molecular assemblies. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Mimicry in plant-parasitic fungiFEMS MICROBIOLOGY LETTERS, Issue 2 2006Henry K. Ngugi Abstract Mimicry is the close resemblance of one living organism (the mimic) to another (the model), leading to misidentification by a third organism (the operator). Similar to other organism groups, certain species of plant-parasitic fungi are known to engage in mimetic relationships, thereby increasing their fitness. In some cases, fungal infection can lead to the formation of flower mimics (pseudoflowers) that attract insect pollinators via visual and/or olfactory cues; these insects then either transmit fungal gametes to accomplish outcrossing (e.g. in some heterothallic rust fungi belonging to the genera Puccinia and Uromyces) or vector infectious spores to healthy plants, thereby spreading disease (e.g. in the anther smut fungus Microbotryum violaceum and the mummy berry pathogen Monilinia vaccinii-corymbosi). In what is termed aggressive mimicry, some specialized plant-parasitic fungi are able to mimic host structures or host molecules to gain access to resources. An example is M. vaccinii-corymbosi, whose conidia and germ tubes, respectively, mimic host pollen grains and pollen tubes anatomically and physiologically, allowing the pathogen to gain entry into the host's ovary via stigma and style. We review these and other examples of mimicry by plant-parasitic fungi and some of the mechanisms, signals, and evolutionary implications. [source] Host collagen signal induces antigen I/II adhesin and invasin gene expression in oral Streptococcus gordoniiMOLECULAR MICROBIOLOGY, Issue 2 2003Catherine Heddle Summary Microbial interactions with host molecules, and programmed responses to host environmental stimuli, are critical for colonization and initiation of pathogenesis. Bacteria of the genus Streptococcus are primary colonizers of the human mouth. They express multiple cell-surface adhesins that bind salivary components and other oral bacteria and enable the development of polymicrobial biofilms associated with tooth decay and periodontal disease. However, the mechanisms by which streptococci invade dentine to infect the tooth pulp and periapical tissues are poorly understood. Here we show that production of the antigen I/II (AgI/II) family polypeptide adhesin and invasin SspA in Streptococcus gordonii is specifically upregulated in response to a collagen type I signal, minimally the tri-peptide Gly-Pro-Xaa (where Xaa is hydroxyproline or alanine). Increased AgI/II polypeptide expression promotes bacterial adhesion and extended growth of streptococcal cell chains along collagen type I fibrils that are characteristically found within dentinal tubules. These observations define a new model of host matrix signal-induced tissue penetration by bacteria and open the way for novel therapy opportunities for oral invasive diseases. [source] 25-Allyloxy-5,11,17,23-tetra- tert -butyl-26,27,28-trihydroxycalix[4]arene chloroform disolvateACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2010Tobias Gruber In the title solvated calixarene, C47H60O4·2CHCl3, the host chalice displays an almost undistorted cone conformation, stabilized by three strong O,H...O hydrogen bonds at the calixarene's lower rim. One chloroform solvent molecule is fixed in the calixarene cavity by C,H..., interactions, while the second is accommodated in a clathrate-like mode in elliptical packing voids. These voids are spanned by six host molecules connected via C,H..., contacts and van der Waals interactions. Within the crystal structure, one tert -butyl group of the calixarene host is disordered over two orientations, with occupancies of 0.884,(4) and 0.116,(4). Furthermore, both solvent molecules show disorder, with occupancies of 0.857,(2) and 0.143,(2) for the cavitate-type, and 0.9359,(17) and 0.0641,(17) for the clathrate-type chloroform solvent molecules. [source] Channel-forming solvates of 6-chloro-2,5-dihydroxypyridine and its solvent-free tautomer 6-chloro-5-hydroxy-2-pyridoneACTA CRYSTALLOGRAPHICA SECTION C, Issue 10 2009Sean R. Parkin On crystallization from CHCl3, CCl4, CH2ClCH2Cl and CHCl2CHCl2, 6-chloro-5-hydroxy-2-pyridone, C5H4ClNO2, (I), undergoes a tautomeric rearrangement to 6-chloro-2,5-dihydroxypyridine, (II). The resulting crystals, viz. 6-chloro-2,5-dihydroxypyridine chloroform 0.125-solvate, C5H4ClNO2·0.125CHCl3, (IIa), 6-chloro-2,5-dihydroxypyridine carbon tetrachloride 0.125-solvate, C5H4ClNO2.·0.125CCl4, (IIb), 6-chloro-2,5-dihydroxypyridine 1,2-dichloroethane solvate, C5H4ClNO2·C2H4Cl2, (IIc), and 6-chloro-2,5-dihydroxypyridine 1,1,2,2-tetrachloroethane solvate, C5H4ClNO2·C2H2Cl4, (IId), have I41/a symmetry, and incorporate extensively disordered solvent in channels that run the length of the c axis. Upon gentle heating to 378,K in vacuo, these crystals sublime to form solvent-free crystals with P21/n symmetry that are exclusively the pyridone tautomer, (I). In these sublimed pyridone crystals, inversion-related molecules form R22(8) dimers via pairs of N,H...O hydrogen bonds. The dimers are linked by O,H...O hydrogen bonds into R46(28) motifs, which join to form pleated sheets that stack along the a axis. In the channel-containing pyridine solvate crystals, viz. (IIa),(IId), two independent host molecules form an R22(8) dimer via a pair of O,H...N hydrogen bonds. One molecule is further linked by O,H...O hydrogen bonds to two 41 screw-related equivalents to form a helical motif parallel to the c axis. The other independent molecule is O,H...O hydrogen bonded to two related equivalents to form tetrameric R44(28) rings. The dimers are ,,, stacked with inversion-related dimers, which in turn stack the R44(28) rings along c to form continuous solvent-accessible channels. CHCl3, CCl4, CH2ClCH2Cl and CHCl2CHCl2 solvent molecules are able to occupy these channels but are disordered by virtue of the site symmetry within the channels. [source] Structural effects on the solid-state photodimerization of 2-pyridone derivatives in inclusion compoundsACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2009Marina Telzhensky The structures of six crystalline inclusion compounds between various host molecules and three guest molecules based on the 2-pyridone skeleton are described. The six compounds are 1,1,-biphenyl-2,2,-dicarboxylic acid,2-pyridone (1/2), C14H10O4·2C5H5NO, (I,a), 1,1,-biphenyl-2,2,-dicarboxylic acid,4-methyl-2-pyridone (1/2), C14H10O4·2C6H7NO, (I,c), 1,1,-biphenyl-2,2,-dicarboxylic acid,6-methyl-2-pyridone (1/2), C14H10O4·2C6H7NO, (I,d), 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol,1-methyl-2-pyridone (1/2), C30H22O2·2C6H7NO, (II,b), 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol,4-methy-2-pyridone (1/2), C30H22O2·2C6H7NO, (II,c), and 4,4,,4,,-(ethane-1,1,1-triyl)triphenol,6-methyl-2-pyridone,water (1/3/1), C20H18O3·3C6H7NO·H2O, (III,d). In two of the compounds, (I,a) and (I,d), the host molecules lie about crystallographic twofold axes. In two other compounds, (II,b) and (II,c), the host molecules lie across inversion centers. In all cases, the guest molecules are hydrogen bonded to the host molecules through O,H...O=C hydrogen bonds [the range of O...O distances is 2.543,(2),2.843,(2),Å. The pyridone moieties form dimers through N,H...O=C hydrogen bonds in five of the compounds [the range of N...O distances is 2.763,(2),2.968,(2),Å]. In four compounds, (I,a), (I,c), (I,d) and (II,c), the molecules are arranged in extended zigzag chains formed via host,guest hydrogen bonding. In five of the compounds, the guest molecules are arranged in parallel pairs on top of each other, related by inversion centers. However, none of these compounds underwent photodimerization in the solid state upon irradiation. In one of the crystalline compounds, (III,d), the guest molecules are arranged in stacks with one disordered molecule. The unsuccessful dimerization is attributed to the large interatomic distances between the potentially reactive atoms [the range of distances is 4.027,(4),4.865,(4),Å] and to the bad overlap, expressed by the lateral shift between the orbitals of these atoms [the range of the shifts from perfect overlap is 1.727,(4),3.324,(4),Å]. The bad overlap and large distances between potentially photoreactive atoms are attributed to the hydrogen-bonding schemes, because the interactions involved in hydrogen bonding are stronger than those in ,,, interactions. [source] Methylazacalixpyridines: Remarkable Bridging Nitrogen-Tuned Conformations and Cavities with Unique Recognition PropertiesCHEMISTRY - A EUROPEAN JOURNAL, Issue 36 2006Han-Yuan Gong Abstract Methylazacalix[n]pyridines (n = 4, 8) and methylazacalix[m]arene[n]pyridines (m = n = 2, 4) have been synthesized by a convenient fragment coupling approach starting from 2,6-dibromopyridine, 2,6-diaminopyridine, and benzene-1,3-diamine. Thanks to the intrinsic electronic nature of nitrogen, which can adopt mainly sp2 hybridization, allowing it variously to conjugate, partially conjugate, or not conjugate with the adjacent one or two pyridine rings, the resulting nitrogen-bridged calixpyridine derivatives act as a unique class of macrocyclic host molecules with intriguing conformational structures offering fine-tunable cavities and versatile recognition properties. Whilst in solution it is fluxional, in the solid state methylazacalix[4]pyridine adopts a 1,3-alternate conformation with a C2v symmetry in which every two bridging nitrogen atoms conjugate with one pyridine ring. After protonation, the methylazacalix[4]pyridinium species has a different conjugation system of its four bridging nitrogen atoms, yielding the similar twisted 1,3-alternate conformations with an approximate S4 symmetry. The cavity of each protonated methylazacalix[4]pyridine, however, varies finely to accommodate guest species of different size and geometry, such as planar DMF or HO2CCO2, ion, a twisted HO2CCO2, ion, and a tetrahedral ClO4, ion. As giant macrocyclic hosts, both methylazacalix[8]pyridine and methylazacalix[4]arene[4]pyridine interact efficiently with fullerenes C60 and C70 through van der Waals forces. Their ease of preparation, versatile conformational structures, and recognition properties make these multinitrogen-containing calixarenes or cyclophanes unique and powerful macrocyclic hosts in supramolecular chemistry. [source] Complexes of Diquat with Dibenzo-24-Crown-8CHINESE JOURNAL OF CHEMISTRY, Issue 9 2009Shijun Li Abstract The complexation between dibenzo-24-crown-8 (1) and diquat (2) was investigated in detail by NMR, MS and X-ray analysis. It was found that dibenzo-24-crown-8 and diquat formed a 1:1 complex 1·2 in acetone with Ka=2.0×102 L·mol,1, but, as shown by X-ray analysis, a crystalline 2:1 host:guest inclusion complex 12·2 was isolated, in which a single molecule of diquat is enclosed in the concave cavity provided by two dibenzo-24-crown-8 host molecules. Both results are different from the previously assumed stoichiometry of the complexation between dibenzo-24-crown-8 and diquat. This result enriches the range of host-guest complexes based on dibenzo-24- crown-8 and provides new opportunities for developing more complicated structures and chemosensors for diquat. [source] | |||||||||||||