Search results for "MOLECULE"

POSS nanostructures in catalysis

2020

Polyhedral oligomeric silsesquioxanes (POSS) are organic-inorganic hybrid molecules piquing the interest of researchers thanks to their synergistic features. The great versatility of POSS nanostructures arises from the easy tunability of peripheral organic moieties combined with the high thermal and chemical stability of the inner inorganic core. In this review, we highlight the use of POSS nanostructures as molecular precursors for the synthesis of homogeneous and heterogeneous catalysts able to promote many processes including alkene epoxidation, C-C bond formation, CO2 conversion, "click reactions", hydrogenation, and ethylene polymerisation, among others. In this scenario, POSS units fo…

Diamondoids: functionalization and subsequent applications of perfectly defined molecular cage hydrocarbons

2014

The term “diamondoid” describes cage hydrocarbon molecules that are superimposable on the diamond lattice. Diamondoids that are formally built by face-fusing of adamantane units, namely diamantane, triamantane, tetramantane, etc., have fascinated chemists since the beginning of the last century. The functionalization of these perfectly defined (C,H)-molecules is described here. Thus, diamondoid halides and diamondoid alcohols are first rank precursors for amino and phosphine-substituted diamondoids that have proved to be highly useful in therapeutic applications and metal catalysis, respectively. The extent of functionalization and polyfunctionalization achieved for adamantane and diamantan…

Tetrazine Click Chemistry for the Modification of 1-Hydroxy-1,1-methylenebisphosphonic Acids: Towards Bio-orthogonal Functionalization of Gold Nanopa…

2016

Inverse electron demand Diels-Alder (iEDDA) was evaluated for the functionalization of gold nanoparticles. The reaction was first modelled with the free coating molecule 1-hydroxy-1,1-methylenebisphosphonate bearing an alkene functionality (HMBPene). A model tetrazine 3,6-dipyridin-2-yl-1,2,4,5-tetrazine (pyTz) was used, kinetic of the reaction was calculated and coupling products were analysed by NMR and HRMS. The reaction was then transposed at the nanoparticle surface. Gold nanoparticles bearing an alkene functionality were obtained using a one-pot methodology with HMBPene and the tetrazine click chemistry was evaluated at their surface using pyTz. The successful coupling was assessed by…

DNA Sensors for the Detection of Biomolecules and Biochemical Conditions

2017

Composite clay sorbents for immobilisation of biomolecules and cells

2015

Precision Anisotropic Brush Polymers by Sequence Controlled Chemistry

2020

The programming of nanomaterials at molecular length-scales to control architecture and function represents a pinnacle in soft materials synthesis. Although elusive in synthetic materials, Nature has evolutionarily refined macromolecular synthesis with perfect atomic resolution across three-dimensional space that serves specific functions. We show that biomolecules, specifically proteins, provide an intrinsic macromolecular backbone for the construction of anisotropic brush polymers with monodisperse lengths via grafting-from strategy. Using human serum albumin as a model, its sequence was exploited to chemically transform a single cysteine, such that the expression of said functionality is…

Multilayered Modelling of the Metallation of Biological Targets

2021

The unique property of metals – the remarkable ability to modulate the electronic structure of both metal center and bound ligands – is the reason for their omnipresence in enzymes and in metal-coordinating biological factors. Modern metallodrug chemistry began with the serendipitous unveiling of the antitumour properties of cisplatin, followed by an avalanche of synthesized novel metallodrugs. The metallation of biological targets has then become a new paradigm in the field of bioinorganic chemistry, and a plethora of computational approaches have been developed and utilized to ease the detailed comprehension of its mechnisms with a focus on medical applications. Studies of the electronic …

Hemicellulose hydrolysis catalysed by solid acids

2013

Depolymerising hemicellulose into platform sugar molecules is a key step in developing the concept of an integrated biorefinery. This reaction is traditionally catalysed by either enzymes or homogeneous mineral acids. We compared various solid catalysts for hemicellulose hydrolysis, running reactions in water, under neutral pH and relatively mild temperature and pressure (120°C and 10 bar) conditions. Sulphonated resins are highly active, but they leach out sulphonic groups. Sulphonated silicas are less active, but more stable. They have weakly and strongly bound sites and the strongly bound ones do not leach. Zeolites are moderately active and stable. Among them, H-ferrierite especially, d…

Clickable poly-L-lysine for the formation of biorecognition surfaces

2019

Biomolecules are immobilized onto surfaces employing the fast and stable adsorption of poly-l-lysine (PLL) polymers and the versatile copper-free click chemistry reactions. This method provides the combined advantages of versatile surface adsorption with density control using polyelectrolytes and of the covalent and orthogonal immobilization of biomolecules with higher reaction rates and improved yields of click chemistry. Using DNA attachment as a proof of concept, control over the DNA probe density and applicability in electrochemical detection are presented.

Theory of nucleation and crystal growth of polymers in concentrated solutions

1974

ABSTRACT The process of crystallization in concentrated solutions depends strongly on the rate of crystallization and the rate of long range diffusion of the polymer chains. If the crystallization proceeds slowly compared to diffusion, this type of crystal nucleus will be formed for which the free energy of nucleation is smallest. By taking into account entropy effects which are characteristic for chain molecules one can show that the crystal with smallest free energy of nucleation is a crystal with almost regular chain folds on the surfaces. The influence of supercooling, concentration and molecular weight on the thickness and growth rate of such crystals is discussed. If the crystallizati…