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PubMed1994

Solid-state properties and crystal structure of gliclazide.

The solid-state characterization of gliclazide, for which no analytical standard was previously available, has been completed by extensive structural and physical analytical examination. The crystal and molecular structure for gliclazide was determined by single-crystal X-ray diffraction. Gliclazide crystallizes in the monoclinic space group P2(1)/n, with the unit cell dimensions a = 10.828(2) A, b = 14.342(19) A, c = 11.005(6) A, and with beta = 106.97(2) degrees, V = 1635(12) A3, and Z = 4. The gliclazide molecule is articulated in an open extended conformation about the sulphonylurea nucleus. Two gliclazide molecules form a complex with one calcium atom to facilitate the transport of calcium ions across the pancreatic beta cells necessary for the stimulation of insulin secretion. The only conformation that allows for the close apposition of the tolyl groups, and therefore the formation of the gliclazide:calcium complex, is the extended conformer.

Calorimetry, Differential Scanning↗

PubMed2004

Molecular architecture of photosynthetic membranes in Rhodobacter sphaeroides: the role of PufX.

The effects of the PufX polypeptide on membrane architecture were investigated by comparing the composition and structures of photosynthetic membranes from PufX+ and PufX- strains of Rhodobacter sphaeroides. We show that this single polypeptide profoundly affects membrane morphology, leading to highly elongated cells containing extended tubular membranes. Purified tubular membranes contain helical arrays composed solely of dimeric RC-LH1-PufX (RC, reaction centre; LH, light harvesting) complexes with apparently open LH1 rings. PufX- cells contain crystalline membranes with a pseudo-hexagonal packing of monomeric core complexes. Analysis of purified complexes by electron microscopy and atomic force microscopy shows that LH1 and PufX form a continuous ring of protein around each RC. A model of the tubular membrane is presented with PufX located adjacent to the stained region created by a vacant LH1beta. This arrangement, coupled with a flexible ring, would give the RC QB site transient access to the interstices in the lattice, which might be of functional importance. We discuss the implications of our data for the export of quinol from the RC, for eventual reduction of the cytochrome bc1 complex.

Bacterial Proteins↗

PubMed1992

Calculation of the free energy of association for protein complexes.

We have developed a method for calculating the association energy of quaternary complexes starting from their atomic coordinates. The association energy is described as the sum of two solvation terms and an energy term to account for the loss of translational and rotational entropy. The calculated solvation energy, using atomic solvation parameters and the solvent accessible surface areas, has a correlation of 96% with experimentally determined values. We have applied this methodology to examine intermediates in viral assembly and to assess the contribution isomerization makes to the association energy of molecular complexes. In addition, we have shown that the calculated association can be used as a predictive tool for analyzing modeled molecular complexes.

Capsid↗

PubMed2004

Removal of trivalent and hexavalent chromium with aminated polyacrylonitrile fibers: performance and mechanisms.

Aminated polyacrylonitrile fibers (APANFs) were prepared and used as an adsorbent in a series of batch adsorption experiments for the removal of Cr(III) and Cr(VI) species from aqueous solutions of different pH values. The results show that significant amounts of Cr(III) or Cr(VI) species can be adsorbed by the APANFs, although the adsorption performances was greatly dependent upon the solution pH values. In general, the amounts of adsorption for Cr(III) species increased whereas that for Cr(VI) decreased with the increase of the solution pH values, which suggests that different adsorption mechanisms dominated the removal of Cr(III) or Cr(VI) species on the APANFs. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy revealed that the adsorption of Cr(III) species on the APANFs was largely attributed to the formation of surface complexes between the nitrogen atoms on the APANFs and the Cr(III) species adsorbed, but the adsorption of Cr(VI) species on the APANFs was more likely effected through the formation of hydrogen bonds at high solution pH values or through both electrostatic attraction and surface complexation at low solution pH values. It was found that the Cr(VI)-adsorbed APANFs can be effectively regenerated in a basic solution and be reused almost without any loss of the adsorption capacity, while the Cr(III)-adsorbed APANFs needed to be regenerated in an acidic solution and the regeneration appeared to be less effective.

Acrylic Resins↗

PubMed1996

A New Donor Atom System [(SNN)(S)] for the Synthesis of Neutral Oxotechnetium(V) Mixed-Ligand Complexes.

A new approach to the "3 + 1" mixed ligand oxotechnetium complexes of the general formula TcOL1L2, with ligands (L1H(2)) containing the SNN donor set and various monodentate thiols as coligands (L2H) is reported. The ligands L1H(2) (1-3, general formula R(1)CH(2)CH(2)NHCH(2)C(R(2))(2)SH where R(1) = N(CH(3))(2) and R(2) = H in 1, R(1) = pyrrolidin-1-yl and R(2) = H in 2, and R(1) = piperidin-1-yl and R(2) = CH(3) in 3) act as tridentate SNN chelates to the TcO(3+) core, leaving open one coordination site cis to the oxo group. In the presence of a monodentate thiol (L2H) and using (99)Tc(V)-gluconate as precursor, the vacancy is filled by the thiol which acts as the coligand. With this approach four neutral oxotechnetium complexes (4-7, general formula TcO[R(1)CH(2)CH(2)NCH(2)C(R(2))(2)S][SR] where RSH = p-methoxybenzenethiol, or p-methylbenzenethiol or benzyl mercaptan) were prepared in high yield by reacting L1H(2) and L2H with Tc(V)-gluconate in a ratio 1:1:1. The complexes were characterized by elemental analysis and spectroscopic methods. Complete assignments of (1)H and (13)C NMR resonances were made for all complexes. X-ray crystallographic studies of 5 (R(1) = pyrrolidin-1-yl, R(2) = H, RSH = p-methylbenzenethiol) and 7 (R(1) = piperidin-1-yl, R(2) = CH(3), RSH = benzyl mercaptan) showed that the complexes crystallize in the monoclinic space group P2(1)/n (a = 10.223(1) Å, b = 9.283(1) Å, c = 18.337(2) Å, beta = 97.262(2) degrees, V = 1726.3(4) Å(3), Z = 4; a = 11.876(2) Å, b = 10.470(2) Å, c = 17.098(3) Å, beta = 105.990(4) degrees, V = 2043.8(6) Å(3), Z = 4, for 5 and 7, respectively). Complexes5 and 7 have distorted square pyramidal coordination geometry with the oxo ligand in the axial position. The steric requirements of the oxo group cause the Tc atom to be displaced 0.68 Å out of the mean equatorial plane of the NNSS donor atoms in both complexes.

Journal Article↗

PubMed2004

Sulfur bridging interactions of cis-planar NiII-S2N2 coordination units with nickel(II), copper(I,II), zinc(II), and mercury(II): a library of bridging modes, including NiII(micro2-SR)2MI,II rhombs.

Sulfur bridging interactions between three cis-planar NiII-S2N2 complexes and NiII, CuI,II, ZnII, and HgII reactants were investigated by synthesis and X-ray crystal structures of some 24 complexes. This work was stimulated by recent crystallographic structures of the A-cluster of carbon monoxide dehydrogenase/acetylcoenzyme A synthase. This bridged biological assembly has the minimal formulation [Fe4S4]-(micro2-SCys)-[M((micro2-SCys)2Gly)Ni] with M = NiII, CuI, and ZnII at sites distal and proximal, respectively, to the iron-sulfur cluster. Bridges supported by representations of the distal nickel site were sought by reactions of the complexes [NiII(LH-S2N2)]2- and [NiII(LR-S2N2)], with 5-5-5 chelate ring patterns. Reaction products implicate the bridges Ni-(micro2-S)1,2-M in a variety of molecular structures, some with previously unknown connectivities of bridge atoms. The most frequently encountered bridge units are the nonplanar rhombs Ni(2-S)2M involving both sulfur atoms of a given complex. Those with M = NiII are biologically relevant inasmuch as the catalytic metal at the proximal site is nickel. The complex [Ni(L-655)]2-, containing the 6-5-5 ring pattern and coordination sphere of the distal nickel site, was prepared and structurally characterized. It was shown to sustain Ni2(micro2-S)2 rhombic interactions in the form of trinuclear [[Ni(L-655)]2Ni]2- and [[Ni(L-655)]Ni(R2PCH2CH2PR2)] (R = Et, Ph) in which the second NiII simulates the proximal site. Bridging interactions of NiII-S2N2 complexes are summarized, and geometrical features of Ni2(2-S)2 rhombs in these complexes, as dependent on ring patterns, are considered (LH-S2N2 = N,N'-ethylenebis(2-mercaptoisobutyramide)(4-); LR-S2N2 = trans-rac-N,N'-bis(2-mercapto-2-methylprop-1-yl)-1,2-cyclohexanediamine(2-); L-655 = N-(2-mercaptopropyl)-N'-(2'-mercaptoethyl)glycinamide(4-)).

Bridged-Ring Compounds↗

PubMed2005

Synthesis and crystal structure of unprecedented oxo/hydroxo-bridged polynuclear gallium(III) aqua complexes.

Two new polynuclear oxo/hydroxo-bridged polynuclear gallium(III) aqua complexes are obtained upon treatment of Ga(3+)(aq) with pyridine: the supramolecular compound of macrocyclic cavitand cucurbit[6]uril with gallium complex containing 32 metal atoms [Ga(32)(mu(4)-O)(12)(mu(3)-O)(8)(mu(2)-O)(7)(mu(2)-OH)(39)(H(2)O)(20)](PyH subsetC(36)H(36)N(24)O(12))(3)(NO(3))(6).53H(2)O (1) and the tridecanuclear complex [Ga(13)(mu(3)-OH)(6)(mu(2)-OH)(18)(H(2)O)(24)](NO(3))(15).12H(2)O (2). It follows that two modes of nucleation exist when Ga(3+)(aq) is hydrolyzed: one around the tetrahedral GaO(4) units (complex 1) and the other around the octahedral GaO(6) units (complex 2). This is the first time that polynuclear oxo/hydroxo-bridged aqua complexes of Ga(III) have been isolated without the use of other ligands to control or block olygomerization.

Journal Article↗

PubMed2005

Coordination networks with flexible ligands based on silver(I) salts: complexes of 1,3-bis(phenylthio)propane with silver(I) salts of PF6-, CF3COO-, CF3CF2COO-, CF3CF2)CF2COO-, p-TsO-, and CF3SO3-.

The synthesis and characterization of nine coordination networks based on 1,3-bis(phenylthio)propane, L(3), and silver(I) salts of PF(6)(-) (1), CF(3)COO(-) (2), CF(3)CF(2)COO(-) (3), CF(3)CF(2)CF(2)COO(-) (4), p-TsO(-) (5, 6), and CF(3)SO(3)(-) (7-9) are reported. Only 1 and other "isostructural" complexes with weakly coordinating anions such as ClO(4)(-) and SbF(6)(-) are of the host-guest type. In all the other complexes, the anions and the acetone molecules, when present, are coordinated to the metal. Most of the complexes studied here form a 2D-coordination network. Only 4 and 5 adopt a polymer-like chain structure. The packing of the chains of 4 is pseudohexagonal compact, while that of 5 is of the centered type. In complex 1, the silver atom is tetrahedrally coordinated to the sulfur atoms of four different ligands. The PF(6)(-) anions and acetone molecules, sandwiched between silver-ligand cationic sheets, are held through van der Waals interactions. In each of the three perfluorocarboxylates (2-4), two silver atoms are joined by the anions in a diatomic bridging mode. The Ag...Ag distances are sufficiently short to indicate weak metal...metal interactions. The dimeric units in 2 and 3 are interconnected through the ligands, thereby generating a 2D-network of neutral sheets, while, in 4, the dimeric units are bound to four ligands and a 1D-coordination polymer is generated. In the case of the sulfonate anions (p-TsO(-) and CF(3)SO(3)(-)), the crystallization solvent influences the structure adopted. Thus, in 5, 7, and 9 obtained from petroleum ether, or other nonpolar solvents, two silver atoms are bound in a double-bridge fashion, while a monobridge mode is noted for 6 and 8, both recrystallized from diethyl ether. In 8, both bridging types are observed. The thermogravimetric investigation, in the room temperature-450 degrees C interval, of complexes 1, 3, and 7, which incorporate acetone molecules in their crystal structures, reveals a two-step weight loss for 1 (the acetone molecules are lost first followed by the ligands, leaving behind the silver salt), while complexes 3 and 7 decompose in a single step to metallic silver.

Journal Article↗

PubMed1984

Chelation of cadmium.

The toxicity of cadmium is determined by chelation reactions: in vivo, Cd2+ exists exclusively in coordination complexes with biological ligands, or with administered chelating agents. The Cd2+ ion has some soft character, but it is not a typical soft ion. It has a high degree of polarizability, and its complexes with soft ligands have predominantly covalent bond characteristics. Cd2+ forms the most stable complexes with soft donor atoms (S much greater than N greater than 0). The coordination stereochemistry of Cd2+ is unusually varied, including coordination numbers from 2 to 8. Even though the Cd2+ ion is a d10 ion, disturbed coordination geometries are often seen. Generally, the stability of complexes increases with the number of coordination groups contributed by the ligand; consequently, complexes of Cd2+ with polydentate ligands containing SH groups are very stable. Cd2+ in metallothionein (MT) is coordinated with 4 thiolate groups, and the log stability constant is estimated to 25.5. Complexes between Cd2+ and low molecular weight monodentate or bidentate ligands, e.g., free amino acids (LMW-Cd), seem to exist very briefly, and Cd2+ is rapidly bound to high molecular weight proteins, mainly serum albumin. These complexes (HMW-Cd) are rapidly scavenged from blood, mainly by the liver, and Cd2+ is redistributed to MT. After about 1 day the Cd-MT complex (MT-Cd) almost exclusively accounts for the total retained dose of Cd2+, independent of the route of exposure. MT-Cd is slowly transferred to and accumulated in kidney cortex. The acute toxicity and interorgan distribution of parenterally administered Cd2+ are strongly influenced by preceding MT induction, or decreased capacity for MT synthesis; however, the gastrointestinal (GI) uptake of Cd2+ seems unaffected by preceding MT induction resulting in considerable capacity for Cd2+ chelation in intestinal mucosa, and this finding indicates that endogenous MT is not involved in Cd2+ absorption. The toxicity of parenterally administered Cd2+ is strongly enhanced when administered as complexes with NTA or STPP , but it is much decreased when administered as a complex with EDTA. In chronic oral exposure the toxicity and GI uptake of Cd2+ is not changed when Cd2+ is administered as a complex with the detergent formula chelating agents NTA, EDTA and STPP . The uptake of Cd2+ from ligated intestine in vivo was not affected by administration of Cd2+ as complexes with CYS or GSH, but significantly reduced by complexation with EDTA or BAL. The acute toxicity of orally administered Cd2+ is reduced when Cd2+ is administered as a complex with EDTA.(ABSTRACT TRUNCATED AT 400 WORDS)

Animals↗

PubMed2003

Clamp-loader-helicase interaction in Bacillus. Leucine 381 is critical for pentamerization and helicase binding of the Bacillus tau protein.

Recently, we revealed the architecture of the clamp-loader-helicase (tau-DnaB) complex in Bacillus by atomic force microscopy imaging and constructed a structural model, whereby a pentameric clamp-loader interacts with the hexameric helicase. Crucial to this model is the assumption that the clamp-loader forms a pentamer in the absence of other components of the clamp-loader complex such as deltadelta'. Here, we show that the Bacillus subtilis tau protein, even in the absence of deltadelta', interacts as a pentamer with the hexameric DnaB and that the L381 of tau is critical for the integrity of the tau oligomer and interaction with DnaB. The effects of the L381A mutation were confirmed by gel filtration, ultracentrifugation, circular dichroism, cross-linking studies, and genetic replacement of the dnaX gene with a mutant L381A dnaX gene in vivo. The L381A protein is able to support growth in vivo only when expressed in high quantities. Finally, despite the fact that a mutation at P465 has been reported to result in a thermosensitive gene in vivo, a P465L mutant protein interacts with DnaB in vitro suggesting that this defect is not a result of a defective tau-DnaB interaction.

Amino Acid Sequence↗

PubMedDate not supplied

Contribution of peptide backbone atoms to binding of an antigenic peptide to class I major histocompatibility complex molecule.

Antigenic peptides are thought to bind to class I major histocompatibility complex (MHC) molecules through three modes of interaction: van der Waals interaction and, to a lesser extent, hydrogen bonding of anchor side chain atoms to residues comprising the binding pockets of the MHC molecule; hydrogen bonding of N- and C-termini to residues at the ends of the binding groove; and hydrogen bonding of peptide backbone atoms to residues lining the binding groove. To dissect the relative contribution of each of these interactions to class I MHC-peptide stability, a retro inverso (RI) analog of VSV-8. an H-2Kb restricted cytotoxic T lymphocyte (CTL) epitope and terminally modified variants of both VSV-8 and RI VSV-8 were synthesized and their ability to target H-2Kb bearing cells for CTL mediated lysis was compared. None of RI VSV-8 analogs elicited lysis of target cells by CTL specific for VSV-8 nor did they appear to compete with the native peptide for binding to H-2Kb. In contrast, terminally modified VSV-8 peptides elicited target lysis. These findings suggest that side chain topochemistry of the peptide is insufficient for stable peptide binding to H-2Kb; rather, hydrogen bonding of the peptide backbone atoms to H-2Kb side chain atoms appears to play a major role in the stability of the complex. Computer modeling confirmed that none of the RI analogs participate in the extensive hydrogen bonding network between the peptide backbone and the MHC molecule seen in the native structure.

Animals↗

PubMed1999

Iron Chemistry of a Pentadentate Ligand That Generates a Metastable Fe(III)-OOH Intermediate.

In an effort to gain more insight into the factors controlling the formation of low-spin non-heme Fe(III)-peroxo intermediates in oxidation catalysis, such as activated bleomycin, we have synthesized a series of iron complexes based on the pentadentate ligand N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-(bis-2-pyridylmethyl)amine). The following complexes have been prepared: [(N4Py)Fe(II)(CH(3)CN)](ClO(4))(2) (1), [(N4Py)Fe(II)Cl](ClO(4)) (2), [(N4Py)Fe(III)OMe](ClO(4))(2) (3), and [(N4Py)(2)Fe(2)O](ClO(4))(4) (4). Complexes 1 and 2 have low- and high-spin Fe(II) centers, respectively, whereas 3 is an Fe(III) complex that undergoes a temperature-dependent spin transition. The iron centers in the oxo-bridged dimer 4 are antiferromagnetically coupled (J = -104 cm(-)(1)). Comparison of the crystal structures of 1, 3, and 4 shows that the ligand is well suited to accommodate both Fe(II) and Fe(III) in either spin state. For the high-spin Fe(III) complexes 3 and 4 the iron atoms are positioned somewhat outside of the cavity formed by the ligand, while in the case of the low-spin Fe(II) complex 1 the iron atom is retained in the middle of the cavity with approximately equal bond lengths to all nitrogen atoms from the ligand. On the basis of UV/vis and EPR observations, it is shown that 1, 3, and 4 all react with H(2)O(2) to generate the purple low-spin [(N4Py)Fe(III)OOH](2+) intermediate (6). In the case of 1, titration experiments with H(2)O(2) monitored by UV/vis and (1)H NMR reveal the formation of [(N4Py)Fe(III)OH](2+) (5) and the oxo-bridged diiron(III) dimer (4) prior to the generation of the Fe(III)-OOH species (6). Raman spectra of 6 show distinctive Raman features, particularly a nu(O-O) at 790 cm(-)(1) that is the lowest observed for any iron-peroxo species. This observation may rationalize the reactivity of low-spin Fe(III)-OOH species such as "activated bleomycin".

Journal Article↗

PubMed2004

Matrix reactivity of Al and Ga atoms (M) in the presence of silane: generation and characterization of the eta2-coordinated complex M.SiH4, the insertion product HMSiH3, and the MI species MSiH3 in a solid argon matrix.

Matrix isolation experiments give evidence for the formation of the loosely bonded metal-silane complex M.SiH(4) by the spontaneous reaction of Al or Ga atoms (M) with silane in a solid Ar matrix at 12 K; however, Ga(2) appears to insert spontaneously into an Si--H bond to form HGaGaSiH(3), probably with the structure HGa(micro-SiH(3))Ga. In M.SiH(4) the metal atom is eta(2)-coordinated by the silane, resulting in a species with C(2v) symmetry. The complex has a distinctive photochemistry: it can be converted on photolysis at lambda approximately 410 or approximately 254 nm to its tautomer, HMSiH(3), which also has a doublet ground electronic state and from which it can be regenerated with lambda approximately 580 nm radiation. Broadband UV-visible photolysis (lambda=200-800 nm) results in decomposition of HMSiH(3), the univalent species MSiH(3) being the only detectable product. The experimental data collected for several silane isotopomers (SiH(4), SiD(4), and SiD(3)H) and different reagent concentrations, together with the results of sophisticated quantum chemical calculations, are used to explore in detail the properties of the detected species and the reaction pathways compassing their formation.

Journal Article↗

PubMed2003

Mitochondrial ATP synthasome. Cristae-enriched membranes and a multiwell detergent screening assay yield dispersed single complexes containing the ATP synthase and carriers for Pi and ADP/ATP.

The terminal step of ATP synthesis in intact mitochondria is catalyzed by the ATP synthase (F(0)F(1)) that works in close synchrony with the P(i) and ADP/ATP carriers. Each carrier consists of only a single polypeptide chain in dimeric form, while the ATP synthase is highly complex consisting in animals of 17 known subunit types and more than 30 total subunits. Although structures at high resolution have been obtained for the water-soluble F(1) part of the ATP synthase consisting of only five subunit types, such structures have not been obtained for either the complete ATP synthase or the P(i) and ADP/ATP carriers. Here, we report that all three proteins are localized in highly purified cristae-like vesicles obtained by extensive subfractionation of the mitochondrial inner membrane. Moreover, using a multiwell detergent screening assay, 4 nonionic detergents out of 80 tested were found to disperse these cristae-like vesicles into single soluble complexes or "ATP synthasomes" that contain the ATP synthase in association with the P(i) and ADP/ATP carriers. These studies offer new mechanistic insights into the terminal steps of oxidative phosphorylation in mitochondria and set the stage for future structural efforts designed to visualize in atomic detail the entire complex involved. They also provide evidence that the cristae are a subcompartment of the inner membrane.

Animals↗

PubMed2006

Binding of gold clusters with DNA base pairs: a density functional study of neutral and anionic GC-Aun and AT-Aun (n = 4, 8) complexes.

Binding of clusters of gold atoms (Au) with the guanine-cytosine (GC) and adenine-thymine (AT) Watson-Crick DNA base pairs was studied using the density functional theory (DFT). Geometries of the neutral GC-Au(n) and AT-Au(n) and the corresponding anionic (GC-Au(n))(-1) and (AT-Au(n))(-1) (n = 4, 8) complexes were fully optimized in different electronic states, that is, singlet and triplet states for the neutral complexes and doublet and quartet states for the anionic complexes, using the B3LYP density functional method. The 6-31+G basis set was used for all atoms except gold. For gold atoms, the Los Alamos effective core potential (ECP) basis set LanL2DZ was employed. Vibrational frequency calculations were performed to ensure that the optimized structures corresponded to potential energy surface minima. The gold clusters around the neutral GC and AT base pairs have a T-shaped structure, which satisfactorily resemble those observed experimentally and in other theoretical studies. However, in anionic GC and AT base pairs, the gold clusters have extended zigzag and T-shaped structures. We found that guanine and adenine have high affinity for Au clusters, with their N3 and N7 sites being preferentially involved in binding with the same. The calculated adiabatic electron affinities (AEAs) of the GC-Au(n)complexes (n = 4, 8) were found to be much larger than those of the isolated base pairs.

Adenine↗

PubMed2004

Inclusion complexes of V-amylose with undecanoic acid and dodecanol at atomic resolution: X-ray structures with cycloamylose containing 26 D-glucoses (cyclohexaicosaose) as host.

Crystal structures are reported of cycloamylose containing 26 D-glucose residues (CA26, cyclohexaicosaose, C156H260O130) in complexes with undecanoic acid (CA26 x 2C10H21COOH x 34.95 H2O, orthorhombic P2(1)2(1)2(1), one CA26 and two bound undecanoic acids F1 and F2 in the asymmetric unit, resolution 0.95 angstroms) and with dodecanol ((CA26)(0.5) x C12H25OH x 32.0H2O, monoclinic C2, half a CA26 binding one dodecanol, A, in the asymmetric unit, resolution 1.0 angstroms). The macrocycle of CA26 is folded like the figure '8' into two 10 D-glucoses long left-handed V-amylose helices forming approximately 5A wide V-channels that are occupied by undecanoic acid (F1, F2) or dodecanol (A) as guest molecules. The functional head groups of the guests near the O(6) ends of the V-channels are hydrogen bonded with d-glucose O(6)n-H; the aliphatic termini beyond C(9) protrude from the O(2), O(3) ends. Parts of the aliphatic chains enclosed in the V-channels are all-trans except for one torsion angle each (approximately 130 degrees ) in undecanoic acid molecules F1 and F2. There are several (guest)C-H...O hydrogen bonds to O(4) and O(6) of CA26 in both complexes, and H...H van der Waals interactions with d-glucose C(3)-H and C(5)-H dominate. C(5)-H determine the position of the aliphatic chains of undecanoic acid F1 and of dodecanol A in contrast to F2 where both C(3)-H and C(5)-H contribute equally, probably because the V-channel is narrower than in F1 and in dodecanol. Complexes of polymeric V-amylose with fatty acids and alcohols studied by X-ray fiber diffraction could not provide the here described high resolution.

Amylose↗

PubMed2000

Ternary Gd(III)L-HSA adducts: evidence for the replacement of inner-sphere water molecules by coordinating groups of the protein. Implications for the design of contrast agents for MRI.

Two novel gadolinium(III) chelates based on the structure of the heptadentate macrocyclic 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) ligand have been synthesized and their relaxometric and luminescent properties thoroughly investigated. They contain two water molecules in the inner coordination sphere in fast exchange with the bulk solvent and bear either a p-bromobenzyl or a p-phosphonatomethylbenzanilido substituent for promoting further interaction with macromolecular substrates. Upon interaction with human serum albumin the expected relaxation enhancement is not observed owing to displacement of the two inner-sphere water molecules of the complexes by a donor atom (likely from a carboxylate group) on the protein and possibly the phosphate anion of the buffered solution, respectively. We modeled the observed behavior by measuring the decrease of the relaxation rate of the water protons upon addition of malonate anion to aqueous solutions of the complexes. Conversely, no change in the hydratation state of the Gd(III) center for both complexes has been observed when the substrate for the formation of the macromolecular adduct is represented by poly-beta-cyclodextrin.

Contrast Media↗

PubMed2004

Hydrogen-bond mediation of supramolecular aggregation in neutral bis-(C6F5)Pt complexes with aromatic H-bond donating ligands. A synthetic and structural study.

Six pentafluorophenylplatinum(II) complexes containing proton acceptor atoms (F) and pyridine-like aromatic ligands able to act as proton donors have been synthesized and characterized, with emphasis on the factors that mediate their supramolecular aggregation in the solid state--hydrogen bonds and pi-pi interactions. The crystal structure analyses of the mononuclear complexes cis-[Pt(C6F5)2(napy)](1), cis-[Pt(C6F5)2(CH2napy)](3), cis-[Pt(C6F5)2(2-ammpy)](5), and cis-[Pt(C6F5)2(2-bipym)](6) reveal the influence of D-HPt and D-HF (D=C, N) hydrogen bonding on the organization of molecules into stacks, which can be further interconnected to generate channels. The prevalence of hydrogen bonding over pi-pi interactions between aromatic rings in establishing the nature of the observed supramolecular aggregation is demonstrated.

Journal Article↗