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Combination of orthogonal supramolecular interactions in polymeric architectures.

Supramolecular polymers represent a highly interesting approach towards new "smart materials". A recent strategy includes the combination of different "orthogonal" non-covalent binding sites within one polymer system. Different functionalities can be introduced in a highly defined way by controlled self-assembly processes. This feature article presents highlights in the supramolecular polymer chemistry of multiple hydrogen-bonding, metal complexation (especially of bi- and terpyridines) and host-guest interactions as well as recent advances in combining these interactions in novel polymers.

Journal Article↗

Alkoxo-bridged copperII complexes as nodes in designing solid-state architectures. The interplay of coordinative and d10-d10 metal-metal interactions in sustaining supramolecular solid-state architectures.

Four novel polymeric coordination networks have been obtained through self-assembly processes involving alkoxo-bridged copperII species as nodes, and anionic cyano-complexes as linkers: infinity2[{Cu2(pa)2}{M(CN)2}2](M=Ag, 1; Au, 2), (infinity)3[{Cu4(mea)4}{Au(CN)2}4.H2O]3, and (infinity)3[{Cu2(pa)2}{Ni(CN)4}](pa = deprotonated propanolamine; mea = deprotonated monoethanolamine). The supramolecular architectures of compounds 1, and 2 are sustained by argentophilic or strong aurophilic interactions. The solid-state architectures of 1 and 2, which are isomorphous, consist of infinite layers, constructed from binuclear alkoxo-bridged nodes and [M(CN)2]- spacers. The layers are stacked in an offset parallel mode, and are further interconnected through Ag...Ag or Au...Au contacts (1: Ag...Ag 3.015 A; 2: Au....Au 3.069 A). Compound 3 consists of unique fourfold interpenetrating diamondoid nets. The diamondoid topology is built of heterocubane {Cu4O4} nodes, which are connected by [Au(CN)2]- rods. The Cu-O distances within the {Cu4O4} node vary between 1.927(2) and 2.679(1) A, showing unsymmetric bridging of the copper atoms. Aurophilic interactions are established between the bridging and terminal [Au(CN)2]- metalloligands, and connect the interpenetrating nets, resulting in infinite chains of gold atoms (the Au...Au distances vary between 3.253 and 3.305 [Angstrom]). Compound 4 exhibits a 3-D network constructed from {Cu2(pa)2]2+ nodes connected by square-planar [Ni(CN)4]2- ions. Compounds 1, 2 and 4 are weakly paramagnetic. The cryomagnetic investigation of reveals a gradual increase, followed by a decrease of the chiMT product, as the temperature is lowered. A superposition of ferro- (J1=+20.8 cm(-1)) and antiferromagnetic (J2=-6.4) interactions within the tetranuclear node was found. Antiferromagnetic interactions are established between the tetranuclear nodes (theta=-2.99 K).

Journal Article↗

Structural and zeolitic features of a series of heterometallic supramolecular porous architectures based on tetrahedral {M(C2O4)4}4- primary building units.

The utilization of tetrahedral pre-formed coordination compounds {M(C2O4)4}4- (M = Zr(IV), U(IV); C2O4(2-) = oxalate) permitted the efficient construction of rare examples of heteronuclear supramolecular nano-porous architectures. A series of metal-organic coordination frameworks prepared by association of these building units with either Mn2+, Cd2+, or Mg2+ have been structurally characterized and are described. Their 3-D chemical scaffold is based on the primary tetrahedral building unit but their pore sizes and topologies could be varied through the M2+ metal ion involved in the assembling process, and the anionic tetrahedral moiety. These structures display channels with apertures up to 12 Angstrom x 8 Angstrom which are emptied of solvates at mild temperatures without affecting the chemical scaffold, the integrity of which is maintained up to 250-300 degrees C. A certain degree of flexibility of the coordination polymers upon guest release is suggested by the temperature dependence of the powder X-ray patterns and N2 sorption experiments, but reversible and selective sorption of small molecules has been observed substantiating that these open-frameworks behave like sponges.

Cadmium↗

Self-assembled monolayers of alkanethiols on Au(111): surface structures, defects and dynamics.

The surface structures, defects and dynamics of self-assembled monolayers (SAMs) on Au(111) are reviewed. In the case of the well-known c(4 x 2) and radical 3 x radical 3 R30 degrees surface structures, the present discussion is centered on the determination of the adsorption sites. A more complex scenario emerges for the striped phases, where a variety of surface structures that depends on surface coverage are described. Recently reported surface structures at non-saturation coverage show the richness of the self-assembly process. The study of surface dynamics sheds light on the relative stability of some of these surface structures. Typical defects at the alkanethiol monolayer are shown and discussed in relation to SAMs applications.

Gold↗

Supramolecular architectures assembled by the interaction of purine nucleobases with metal-oxalato frameworks. Non-covalent stabilization of the 7H-adenine tautomer in the solid-state.

The synthesis, crystal structure and variable-temperature magnetic measurements of the compounds [Mn(mu-ox)(H2O)(7H-pur-kappaN9)]n (1), {[Mn(mu-ox)(H2O)2].(7H-ade).(H2O)}n (2) and {[Cu(mu-ox)(H2O)(7H-ade-kappaN9)][Cu(mu-ox)(mu-H2O)(7H-ade-kappaN9)]. approximately 10/3H2O}n (3), (where ox: oxalato dianion, pur: purine, and ade: adenine) are reported. Compounds 1and 2 contain one-dimensional chains in which manganese(II) atoms are bridged by bis-bidentate oxalato ligands. The distorted octahedral geometry around each metal centre is completed in compound 1 by one water molecule and the imidazole N9 donor site of the purine ligand, which is a rare example of direct binding between the Mn(II) ion and the N donor site of an isolated nucleobase. Unlike 1, the adenine moiety in compound 2 is not bonded to manganese atoms and the metal coordination polyhedron is filled by two water molecules in a cis-arrangement. Its crystal building is constructed from pi-stacked layers of Watson-Crick hydrogen-bonded adenine...(H2O2)...adenine aggregates and zig-zag Mn(II)-oxalato chains held together by means of a strong network of hydrogen bonding interactions. The nucleobase exists in the lattice as the 7H-adenine tautomer which represents an unprecedented solid-state characterization of this minor tautomer as free molecule (without metal coordination) stabilized through non-covalent interactions. Compound consists of two slightly different [Cu(ox)(H2O)(7H-ade-kappaN9)] units in which the nucleobase coordinates through the imidazole N9 atom. The planar complex entities are parallel stacked and joined by means of long Cu-O bonds involving oxygen atoms from the oxalato and the aqua ligands, giving one-dimensional chains with a [4 + 1] square-planar pyramidal and a [4 + 2] octahedral coordination around the metal centre, respectively. Self-assembled process of compound 3 is further driven by an in-plane network of hydrogen bonding interactions to generate a porous 3D structure containing parallel channels filled by guest water molecules. Variable-temperature magnetic susceptibility measurements of all the complexes show the occurrence of antiferromagnetic interactions between the paramagnetic centres. DFT calculations have been performed to check the influence of packing in the stability of the 7H-amino tautomer of 2 and in the complex geometry of 3.

Adenine↗

Adsorption kinetics of L-glutathione on gold and structural changes during self-assembly: an in situ ATR-IR and QCM study.

The adsorption of L-glutathione (gamma-Glu-Cys-Gly) from ethanol on gold surfaces was studied in situ by both attenuated total reflection infrared (ATR-IR) spectroscopy and using a quartz crystal microbalance (QCM). The molecule is firmly anchored to the gold surface through the thiol group. Different IR signals of adsorbed L-glutathione, notably the amide I and nu(-COOH), show significantly different behavior with time, which reveals that their increase is not related to adsorption (mass uptake) alone. This indicates that structural transformations take place during the formation of the self-assembled monolayer (SAM). In particular, the intensity of the acid signal increases quickly only within the first couple of minutes. The complexity of the self-assembling process is confirmed by QCM measurements, which show fast mass uptake within about 100 s followed by a considerably slower regime. The structural change superimposed on the mass uptake is, based on the in situ time-resolved ATR-IR measurements, assigned to the interaction of the acid group of the Gly moiety with the surface. The latter group is protonated in ethanol but deprotonates upon interaction with the gold surface. The protonation-deprotonation equilibrium is sensitive to external stimuli, such as the presence of dissolved L-glutathione molecules. The interaction of the acid group with the surface and concomitant deprotonation proceeds via two distinguishable steps, the first being a reorientation of the molecule, followed by the deprotonation.

Adsorption↗

Surface self-assembly of the cyanuric acid-melamine hydrogen bonded network.

A hydrogen-bonded bimolecular network formed between cyanuric acid (CA) and melamine (M), CA x M, has been prepared by a surface-based self-assembly process; the monolayer CA x M network is prepared under ultra-high vacuum conditions either by sequential deposition of CA followed by M, or through simultaneous deposition of the component molecular species.

Journal Article↗

Cooperative binding and self-assembling behavior of cationic low molecular-weight dendrons with RNA molecules.

Tri(ethylene glycol) derived, low molecular-weight dendrons with various amine end groups were synthesized and characterized for their properties of binding and self-assembling with RNA using the Candida ribozyme as a model RNA molecule. These dendritic compounds form stable complexes and well-defined nanoscale particles with RNA molecules via electrostatic interactions and self-assembly process, while leaving the other terminal of the tri(ethylene glycol) chain accessible for targeting. This suggests that dendrimers of this type hold great promise for specific RNA targeting and RNA delivery.

Candida↗

Supramolecular 'flat' Mn9 grid complexes--towards functional molecular platforms.

Flat, quantum dot like arrays of closely spaced, electron rich metal centres are seen as attractive subunits for device capability at the molecular level. Mn(II)9 grids, formed by self-assembly processes using 'tritopic' pyridine-2,6-dihydrazone ligands, provide easy and pre-programmable routes to such systems, and have been shown to exhibit a number of potentially useful physical properties, which could be utilized to generate bi-stable molecular based states. Their ability to form surface monolayers, which can be mapped by STM techniques, bodes well for their possible integration into nanometer scale electronic components of the future. This report highlights some new Mn(II)9 grids, with functionalized ligand sites, that may provide suitable anchor points to surfaces and also be potential donor sites capable of further grid elaboration. Structures, magnetic properties, electrochemical properties, surface studies on HOPG (highly ordered pyrolytic graphite), including the imaging of individual metal ion sites in the grid using CITS (current imaging tunneling spectroscopy) are discussed, in addition to an analysis of the photophysics of a stable mixed oxidation state [Mn(III)4Mn(II)5] grid. The grid physical properties as a whole are assessed in the light of reasonable approaches to the use of such molecules as nanometer scale devices.

Journal Article↗

Collagen reorganization in leech wound healing.

BACKGROUND INFORMATION: Leeches respond to surgical lesions with the same sequence of events as that described for wound healing in vertebrates, where collagen is important for the development of tensions in healing wounds, functioning as an extracellular scaffold for accurate regeneration of the structures disrupted by surgical or traumatic actions. RESULTS: In surgically lesioned leeches, newly synthesized collagen is arranged in hierarchical structures. Fibrils can be packed and shaped to form cords or tubular structures, thus acting as an extracellular scaffold that directs and organizes the outgrowth of new vessels and the migration of immune cells towards lesioned tissues. In these animals, the general architecture of collagen fibrils, generated during tissue regeneration, shows similarities to both the structural pattern of collagen bundles and assembly processes observed in several vertebrate systems (fish scales, amphibian skin and human cornea). CONCLUSIONS: The production of extracellular matrix during wound healing in leeches is a surprising example of conservation of an extremely close relationship between the structure and function of molecular structures. It could be hypothesized that collagen structures, characterized not only by a striking structural complexity, but also by multifunctional purposes, are anatomical systems highly conserved throughout evolution.

Animals↗

Polyester synthases: natural catalysts for plastics.

Polyhydroxyalkanoates (PHAs) are biopolyesters composed of hydroxy fatty acids, which represent a complex class of storage polyesters. They are synthesized by a wide range of different Gram-positive and Gram-negative bacteria, as well as by some Archaea, and are deposited as insoluble cytoplasmic inclusions. Polyester synthases are the key enzymes of polyester biosynthesis and catalyse the conversion of (R)-hydroxyacyl-CoA thioesters to polyesters with the concomitant release of CoA. These soluble enzymes turn into amphipathic enzymes upon covalent catalysis of polyester-chain formation. A self-assembly process is initiated resulting in the formation of insoluble cytoplasmic inclusions with a phospholipid monolayer and covalently attached polyester synthases at the surface. Surface-attached polyester synthases show a marked increase in enzyme activity. These polyester synthases have only recently been biochemically characterized. An overview of these recent findings is provided. At present, 59 polyester synthase structural genes from 45 different bacteria have been cloned and the nucleotide sequences have been obtained. The multiple alignment of the primary structures of these polyester synthases show an overall identity of 8-96% with only eight strictly conserved amino acid residues. Polyester synthases can been assigned to four classes based on their substrate specificity and subunit composition. The current knowledge on the organization of the polyester synthase genes, and other genes encoding proteins related to PHA metabolism, is compiled. In addition, the primary structures of the 59 PHA synthases are aligned and analysed with respect to highly conserved amino acids, and biochemical features of polyester synthases are described. The proposed catalytic mechanism based on similarities to alpha/beta-hydrolases and mutational analysis is discussed. Different threading algorithms suggest that polyester synthases belong to the alpha/beta-hydrolase superfamily, with a conserved cysteine residue as catalytic nucleophile. This review provides a survey of the known biochemical features of these unique enzymes and their proposed catalytic mechanism.

Acyltransferases↗

Actin filaments play a permissive role in the inhibition of store-operated Ca2+ entry by extracellular ATP in rat brown adipocytes.

Stimulation of P2 receptors with micromolar concentration of ATP evokes a transient increase in [Ca2+]i (intracellular free Ca2+ concentration), primarily due to release of Ca2+ from intracellular stores; such stimulation also triggers almost complete suppression of thapsigargin-evoked sustained [Ca2+]i increase mediated through a store-operated Ca2+ entry pathway in rat brown adipocytes. We investigated the role of cytoskeletal actin in the inhibitory effect of the extracellular ATP on store-operated Ca2+ entry, using fura 2 fluorescence for continuous measurement of [Ca2+]i, and using Alexa fluor 488-phalloidin staining of actin. Disassembly of actin networks by cytochalasin D (1 microM) or latrunculin A (3 microM) prevented the inhibitory effect of ATP (10 microM) on the thapsigargin (100 nM)-evoked store-operated Ca2+ entry, without changing the effect of ATP in increasing [Ca2+]i. In normal cells, bath application of ATP induced a transient [Ca2+]i increase, consisting of a rapid increase (the rising phase) and the subsequent decrease (the declining phase) to a lower steady level despite the continued presence of the agonist. Disruption of actin assemblies did not significantly affect the rising phase, but prevented the declining phase. Cells incubated with 10 microM ATP for 4 min demonstrated marked accumulations of actin filaments at the cell periphery, showing protrusions at the cell surface; this actin-assembly process is mediated through P2 receptors. In cells treated with cytochalasin D or latrunculin A, extracellular ATP did not induce actin redistribution. These results suggest that the actin reorganization plays a role in ATP-induced inhibition of store-operated Ca2+ entry in rat brown adipocytes.

Actin Cytoskeleton↗

Tissue-specific cytochrome c oxidase assembly defects due to mutations in SCO2 and SURF1.

The biogenesis of eukaryotic COX (cytochrome c oxidase) requires several accessory proteins in addition to structural subunits and prosthetic groups. We have analysed the assembly state of COX and SCO2 protein levels in various tissues of six patients with mutations in SCO2 and SURF1. SCO2 is a copper-binding protein presumably involved in formation of the Cu(A) centre of the COX2 subunit. The function of SURF1 is unknown. Immunoblot analysis of native gels demonstrated that COX holoenzyme is reduced to 10-20% in skeletal muscle and brain of SCO2 and SURF1 patients and to 10-30% in heart of SCO2 patients, whereas liver of SCO2 patients' contained normal holoenzyme levels. The steady-state levels of mutant SCO2 protein ranged from 0 to 20% in different SCO2 patient tissues. In addition, eight distinct COX subcomplexes and unassembled subunits were found, some of them identical with known assembly intermediates of the human enzyme. Heart, brain and skeletal muscle of SCO2 patients contained accumulated levels of the COX1.COX4.COX5A subcomplex, three COX1-containing subcomplexes, a COX4.COX5A subcomplex and two subcomplexes composed of only COX4 or COX5A. The accumulation of COX1.COX4.COX5A subcomplex, along with the virtual absence of free COX2, suggests that the lack of the Cu(A) centre may result in decreased stability of COX2. The appearance of COX4.COX5A subcomplex indicates that association of these nucleus-encoded subunits probably precedes their addition to COX1 during the assembly process. Finally, the consequences of SCO2 and SURF1 mutations suggest the existence of tissue-specific functional differences of these proteins that may serve different tissue-specific requirements for the regulation of COX biogenesis.

Brain↗

Fibrin assembly after fibrinopeptide A release in model systems and human plasma studied with magnetic birefringence.

Magnetically induced birefringence was used to monitor fibrin polymerization after the release of the small negatively charged A fibrinopeptides from human fibrinogen by the action of the snake-venom-derived enzymes reptilase and ancrod. A range of conditions was investigated. Fibrin polymerization in solutions of purified fibrinogen shows a distinct break near the gelation point. On addition of Ca2+ or albumin the lag period is shortened, fibre thickness is increased and the break in assembly almost vanishes, probably because both of these additives promote lateral aggregation. There are minor differences in the kinetics, depending on the venom enzyme used. The kinetics of fibrin assembly in model systems containing either Ca2+ or albumin and in human plasma with a largely dormant coagulation cascade are very similar. Therefore in the latter condition there is no significant alteration in the assembly process due to interaction between fibrin or the venom enzymes and any of the plasma proteins. When the cascade is activated, the polymerization progress curves have a character that resembles a combination of the reactions observed when the venom enzymes and endogenously generated thrombin separately induce coagulation, except for a region near gelation where, paradoxically, polymerization appears to be slower on activation. The low-angle neutron-diffraction patterns from oriented gels made with thrombin or reptilase are identical. Therefore at low resolution the packing of the monomers within fibres is the same when fibrinopeptide A only or both fibrinopeptides A and B are removed.

Ancrod↗

Discovery that the assembly of the dipyrromethane cofactor of porphobilinogen deaminase holoenzyme proceeds initially by the reaction of preuroporphyrinogen with the apoenzyme.

The assembly process of the dipyrromethane cofactor of Escherichia coli porphobilinogen deaminase holoenzyme is initiated by the reaction of the porphobilinogen deaminase apoenzyme with preuroporphyrinogen. The resulting enzyme-bound tetrapyrrole (bilane) is equivalent to the holoenzyme intermediate complex ES2 and yields the dipyrromethane cofactor by reactions of the normal catalytic cycle. These observations indicate that preuroporphyrinogen, rather than porphobilinogen, is the preferred precursor for the dipyrromethane cofactor and explain the existence of the D84A and D84N deaminase mutants as catalytically inactive ES2 complexes.

Apoenzymes↗