Fluoride-promoted oxidation of Fischer alkoxy carbene complexes: stoichiometric and catalytic conditions

The utility of fluoride anion as promoter of the oxidation of Fischer carbene complexes is presented. Two different and complementary methods that allow the fast and convenient preparation of carbene-derived esters in good yields have been developed using stoichiometric or catalytic quantities of fluoride ion.     

Cycloaddition reactions of alkoxy alkynyl Fischer carbene complexes with o-quinodimethanes (oQDMs)

[reaction: see text] The reaction of o-quinodimethanes (oQDMs) with alkoxy alkynyl Fischer carbene complexes is highly dependent on the carbene complex. Thus, for arylalkynyl carbene complexes, the initial [4 + 2]-cycloadduct evolves opening a new entry to the benzo[b]fluorene skeleton, which is present in many natural products. However, for alkenylalkynyl carbene complexes, the reaction takes place through the double bond, instead of the triple bond, in an unprecedented fashion, leading to new functionalized alkynyl carbene complexes.     

In situ generation of gold nanoparticles on a protein surface: Fischer carbene complex as reducing agent

Suitably designed, hydrophilic Fischer carbene complexes reduce HAuCl4 to produce stable gold nanoparticles localized on proteins in aqueous buffer solution.     

Oxidative demetalation of Fischer alkoxy carbene complexes with stoichiometric pyridine N-oxide and NaBH4-promoted demetalation of Fischer iminocarbene complexes with sulfur and selenium

Oxidation of Fischer alkoxy carbene complexes were systematically investigated with stoichiometric pyridine N-oxide (PNO) under mild conditions, forming ester products in good to excellent yields from the corresponding monocarbene complexes. Fischer alkoxy biscarbene complexes efficiently underwent stepwise oxidative demetalation under controlled conditions, resulting in ester-monocarbene and diester products, respectively. This oxidation protocol has demonstrated a generally efficient method to oxidize Fischer alkoxy carbene complexes under mild conditions, providing a new route to novel monocarbene complexes from Fischer biscarbene complexes. In the presence of NaBH₄, reactions of Fischer iminocarbene complexes with elemental sulfur or selenium in ethanol at ambient temperature regioselectively afforded thione or selone complexes by insertion of a sulfur or selenium atom into the MC bonds in Fischer carbene complexes, and metal-free selone was also obtained. The molecular structures of the iminocarbene complexes and selone derivatives were confirmed by X-ray crystallographic study. The NaBH₄-promoted demetalation protocol suggests a potential new route to demetalate Fischer aminocarbene complexes.     

Synthesis of nitrogen-containing compounds using chromium Fischer carbene complexes

Synthetic utility of the Fischer-type carbene complexes of chromium for the preparation of nitrogen-containing compounds is demonstrated. Alkoxy carbene complexes reacted with imines to give (optically active) 3-pyrrolines and beta-methoxy allylic amine derivatives in good yields. The amino carbene complexes reacted with alpha,beta-unsaturated aldehydes to give substituted pyrroles in good yields.     

Covalent immobilization of lysozyme on stainless steel. Interface spectroscopic characterization and measurement of enzymatic activity

A new strategy aiming at the protection of metallic surfaces against the growth of biofilms is presented here. This work reports the grafting of primary amines by aminosilanization of oxidized stainless steel followed by chemical coupling of the glycosidase lysozyme from hen egg white using glutaraldehyde as homobifunctional cross-linking agent. Controlled characterization of a stainless steel surface by X-ray photoelectron spectroscopy and Fourier transform infrared reflection-absorption spectroscopy at each step enabled the mode of binding, coverage, and orientation of the grafted molecules to be addressed. As a result, the stainless steel samples covered with a covalently immobilized layer of lysozyme showed some lytic activity on a suspension of bacteria Micrococcus lysodeikticus.     

Synthesis of monodisperse chromium nanoparticles from the thermolysis of a Fischer carbene complex

We successfully synthesized monodisperse chromium nanoparticles from the thermolysis of a Fischer carbene complex.     

One-pot synthesis of furo[2,3-h]quinoline and furo[2,3-h]isoquinoline derivatives using Fischer carbene complex

A new route for the synthesis of furo[2,3-h]quinoline and furo[2,3-h]isoquinoline derivatives have been explored through the coupling of carbene complexes with pyridine-bridged enynes. This reaction process, involving the annulation of both furan and benzene ring on to a pre-existing pyridine ring is highly efficient in the presence of triphenylphosphine as ligand additive.     

Competitive pathways in the reaction of lithium oxy-ortho-quinodimethanes and Fischer alkoxy alkynyl carbene complexes: synthesis of highly functionalised seven-membered benzocarbocycles

Up to four different outcomes have been found for the reaction between 1‐oxy‐ortho‐quinodimethanes (oQDMs) and alkoxy alkynyl Fischer carbene complexes (FCCs). The product formed depends on the structure of both reagents and on the reaction solvent. The pathways can be topologically classified as a [4C+2C], a [3(2C+O)+3C], and two different [4C+3C] processes and, in all these sequences, 1‐oxy‐oQDMs behave as enolates or as vinylogous enolates. The reaction of Choy and Yang’s unsubstituted oQDM 1 with tungsten alkynyl FCCs is solvent controlled; thus, selective formation of benzocycloheptenones can be achieved in THF, whereas exclusive synthesis of benzocycloheptene ketals is reached in diethyl ether. On the other hand, THF is the solvent of choice to form benzocycloheptene ketals when an alkyl or aryl group is placed at position 1 of the oQDM in its reaction with tungsten carbene complexes; however, a pyranylidene carbene complex is formed when a chromium carbene complex is used. Alternatively, the presence of bulky alkoxy groups in the FCC component favours a Diels–Alder aromatisation sequence, which leads to 1‐naphthyl FCCs. Furthermore, the isolation and the characterisation of several deuterated compounds by labelling experiments have provided some insight into the reaction pathways, and mechanisms consistent with those findings have been established and several reaction intermediates have been identified.     

Covalent immobilization of carbohydrates on sol-gel-coated microplates

Carbohydrate microarrays have attracted increasing attention in recent years because of their ability to monitor biologically important protein-carbohydrate interactions in a high-throughput manner. Here we have developed an effective approach to immobilizing intact carbohydrates directly on polystyrene microtiter plates coated with amine-functionalized sol-gel monolayers. Lectin binding was monitored by fluorescence spectroscopy using these covalent arrays of carbohydrates that contained six mono- and di-saccharides on the microplates. In addition, binding affinities of lectin to carbohydrates were also quantitatively analyzed by determining IC(50) values of lectin-specific antibody with these arrays. Our results indicate that microplate-based carbohydrate arrays can be efficiently fabricated by covalent immobilization of intact carbohydrates on sol-gel-coated microplates. The microplate-based carbohydrate arrays can be applied for screening of protein-carbohydrate interactions in a high-throughput manner.     

Synthesis of chromium N-heterocyclic carbene complexes using chromium Fischer carbenes as a source of chromium carbonyls

Chromium Fischer carbene complexes, [Cr{OMe(R)}(CO)₅] have been utilized as a source of chromium carbonyls in the synthesis of chromium NHC complexes. Using the synthetic method, chromium complexes of various NHC ligands were isolated in reasonable yields. Moreover, the method can be employed for the synthesis of molybdenum and tungsten NHC compounds.     

Covalent immobilization of heparin on a collagen film

Four procedures for the covalent immobilization of heparin (Hp) on a collagen film (CF) have been investigated. In three of them (methods (I–A, B, C), the CF was first treated with epichlorohydrin and ammonia and the Hp was added with the aid of CMBC (method I–A), by reductive amination in the presence of NaCH CN (method I–B), and with the aid of CMEC after succinylation (method I–C). In the fourth procedure (method II), the CF was activated by treatment with alkali and the Hp was added with the aid of CMEC. It was shown that the maximum amount of Hp was immobilized by method II.     

Covalent immobilization of heparin on a collagen film

Four procedures for the covalent immobilization of heparin (Hp) on a collagen film (CF) have been investigated. In three of them (methods (I–A, B, C), the CF was first treated with epichlorohydrin and ammonia and the Hp was added with the aid of CMBC (method I–A), by reductive amination in the presence of NaCH CN (method I–B), and with the aid of CMEC after succinylation (method I–C). In the fourth procedure (method II), the CF was activated by treatment with alkali and the Hp was added with the aid of CMEC. It was shown that the maximum amount of Hp was immobilized by method II.M. V. Lomonosov Moscow State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 700–704, September–October, 1987.     

Self-assembly of trehalose molecules on a lysozyme surface: the broken glass hypothesis

To help understand how sugar interactions with proteins stabilise biomolecular structures, we compare the three main hypotheses for the phenomenon with the results of long molecular dynamics simulations on lysozyme in aqueous trehalose solution (0.75 M). We show that the water replacement and water entrapment hypotheses need not be mutually exclusive, because the trehalose molecules assemble in distinctive clusters on the surface of the protein. The flexibility of the protein backbone is reduced under the sugar patches supporting earlier findings that link reduced flexibility of the protein with its higher stability. The results explain the apparent contradiction between different experimental and theoretical results for trehalose effects on proteins.     

Covalent immobilization of liposomes on plasma functionalized metallic surfaces

A method was developed to functionalize biomedical metals with liposomes. The novelty of the method includes the plasma-functionalization of the metal surface with proper chemical groups to be used as anchor sites for the covalent immobilization of the liposomes. Stainless steel (SS-316) disks were processed in radiofrequency glow discharges fed with vapors of acrylic acid to coat them with thin adherent films characterized by surface carboxylic groups, where liposomes were covalently bound through the formation of amide bonds. For this, liposomes decorated with polyethylene glycol molecules bearing terminal amine-groups were prepared. After ensuring that the liposomes remain intact, under the conditions applying for immobilization; different attachment conditions were evaluated (incubation time, concentration of liposome dispersion) for optimization of the technique. Immobilization of calcein-entrapping liposomes was evaluated by monitoring the percent of calcein attached on the surfaces. Best results were obtained when liposome dispersions with 5mg/ml (liposomal lipid) concentration were incubated on each disk for 24h at 37°C. The method is proposed for developing drug-eluting biomedical materials or devices by using liposomes that have appropriate membrane compositions and are loaded with drugs or other bioactive agents.     

An XPS study on the covalent immobilization of adhesion peptides on a glass surface

Covalent attachment of adhesive peptides to biomaterials surfaces can result in the formation of a bioactive and biomimetic surface. We have demonstrated that titanium surfaces grafted with adhesion peptides, reproducing sequences of fibronectin and vitronectin, can increase osteoblast adhesion compared to non-treated surfaces.We now extend our investigation to peptide immobilization on glass for studying human osteoblast adhesion and spreading. Silanization was used to anchor adhesion peptides to the glass surface through a selective or a non-selective immobilization. Investigated samples were analysed by XPS spectroscopy. Comparison between the results obtained using two different peptides and applying selective and non-selective immobilization will be discussed.