Search results for "Conjugation"
showing 10 items of 121 documents
Straightforward synthesis of bioconjugatable azo dyes. Part 2: Black Hole Quencher-2 (BHQ-2) and BlackBerry Quencher 650 (BBQ-650) scaffolds
2014
Abstract A further extension of the efficient synthetic methodology described in Part 1, to the aromatic bis-diazo scaffold of Black Hole Quencher-2 dye is presented. Bioconjugatable derivatives bearing either azido, terminal alkyne, or maleimide reactive group were easily obtained as well as the free-phenol form of BlackBerry® Quencher 650 (BBQ-650®) initially developed by Berry & Associates, Inc. Company. The efficient conjugation ability of azido- and maleimide-quenchers was demonstrated through the facile preparation of the first water-soluble and formylated BHQ-2 dyes and a FRET-based probe suitable for the in vitro/in cellulo detection of a cancer-associated protease namely urokinase-…
Amino-functional polyethers: versatile, stimuli-responsive polymers
2020
Due to the increasing demand for “smart” materials and systems e.g. for actuators, microvalves, but also for drug delivery, electrooptical devices and many other applications, multi-stimuli responsive materials such as amino-functional polymers are attracting increasing attention in recent years. The hydrophilic character and excellent biocompatibility of the polyether backbone, in combination with multi-stimuli responsive amine moieties, offer intriguing opportunities for a wide range of applications, such as bioconjugation, stimuli-responsive drug delivery and surface modification. Furthermore, the controlled introduction of amino-functionalities at the polyether backbone via copolymeriza…
Straightforward synthesis of bioconjugatable azo dyes. Part 1: Black Hole Quencher-1 (BHQ-1) scaffold
2014
Abstract Azo dyes are currently used to quench the fluorescence of energy donors in bioassays through Forster resonance energy transfer (FRET) phenomenon. Common examples of such dark quenchers are DABCYL and the three members of Black Hole Quencher® (BHQ) family. Yet, only carboxylic acid and phosphoramidite derivatives of such azo dyes are presently commercially available. This Letter presents a straightforward synthesis method to novel bioconjugatable quenchers derived from BHQ-1 scaffold and equipped with a reactive group being either azido, terminal alkyne, or maleimide. The potential utility of the ‘clickable’ azido and thiol-reactive derivatives was notably demonstrated through the p…
Cylindrical Brush Polymers with Polysarcosine Side Chains: A Novel Biocompatible Carrier for Biomedical Applications
2015
Cylindrical brush polymers constitute promising polymeric drug delivery systems (nanoDDS). Because of the densely grafted side chains such structures may intrinsically exhibit little protein adsorption (“stealth” effect) while providing a large number of functional groups accessible for bioconjugation reactions. Polysarcosine (PSar) is a highly water-soluble, nonionic and nonimmunogenic polypeptoid based on the endogenous amino acid sarcosine (N-methyl glycine). Here we report on the synthesis, characterization and biocompatibility of cylindrical brush polymers with either polysarcosine side chains or poly-l-lysine-b-polysarcosine side chains. The latter leads to block copolypept(o)id based…
Effective conjugation in conjugated polymers with strongly twisted backbones: A case study on fluorinated MEHPPV
2016
Conjugated polymers with strongly twisted backbones, such as MEHPPV with fluorinated vinylene units (F-MEHPPV), demand a redefinition of the all-important ‘effective conjugation length’ ECL, which we extract here by a facile graphical method. In MEHPPV (being essentially planar), the ECL coincides with the ‘maximum conducive chain length’ MCC and extends over about n ≈ 9 repetition units (RU). In F-MEHPPV, the MCC is similarly long with n ≈ 8, but the ECL localizes on just one RU. The strong twist in F-MEHPPV persists in the excited state, broadening the emission spectrum and quenching the fluorescence with reduced radiative and enhanced non-radiative rates.
Loss of Hyperconjugative Effects Drives Hydride Transfer during Dihydrofolate Reductase Catalysis
2019
Hydride transfer is widespread in nature and has an essential role in applied research. However, the mechanisms of how this transformation occurs in living organisms remain a matter of vigorous debate. Here, we examined dihydrofolate reductase (DHFR), an enzyme that catalyzes hydride from C4′ of NADPH to C6 of 7,8-dihydrofolate (H2F). Despite many investigations of the mechanism of this reaction, the contribution of polarization of the π-bond of H2F in driving hydride transfer remains unclear. H2F was stereospecifically labeled with deuterium β to the reacting center, and β-deuterium kinetic isotope effects were measured. Our experimental results combined with analysis derived from QM/MM si…
Probing the Folding of Peptide–Polymer Conjugates Using the π-Dimerization of Viologen End-Groups
2020
The synthesis of a foldable viologen-functionalized peptide–polymer conjugate is presented. The ABA-type triblock conjugate with a PEG polymer was capped with a FHFHF pentapeptide sequence and further modified with a viologen building block at both chain ends. The pH-responsive peptide domains fold into an intermediate structure inducing close proximity of the viologen units, which upon a reduction step form π-dimers of the radical cation. Overall the intramolecular folding and intermolecular self-assembly process leads to the formation of supramolecular nanorods. Mixing of viologen-peptide–polymer conjugates with unfunctionalized conjugates leads to crosslinking of the nanorods and hydroge…
Efficient Synthesis of 1,4,7-Triazacyclononane and 1,4,7-Triazacyclononane-Based Bifunctional Chelators for Bioconjugation (Eur. J. Org. Chem. 35/201…
2014
Efficient Synthesis of 1,4,7-Triazacyclononane and 1,4,7-Triazacyclononane-Based Bifunctional Chelators for Bioconjugation
2014
The reaction of diethylenetriamine with chloroacetaldehyde yielded a bicyclic aminal intermediate for the synthesis of 1,4,7-triazacyclononane (TACN), a macrocyclic polyamine the derivatives of which find applications as catalysts, bleaching agents, and chelators for medical imaging. This new synthetic protocol outperforms the synthetic methods described so far because it does not involve any cyclization step. Moreover, this aminal intermediate allowed access to a new family of TACN derivatives functionalized on the carbon skeleton, for example, C-aminomethyl-TACN. This novel compound is a precursor of valuable bifunctional chelating agents for nuclear medicine, in particular, for the prepa…