Search results for "Diimide"

The quantitative determination of metabolites of 6-mercaptopurine in biological materials. VII. Chemical synthesis by phosphorylation of 6-thioguanos…

1990

Abstract A fast and reliable two-step method has been established for the chemical synthesis of 6-thioguanosine 5′-monophosphate, 6-thioguanosine 5′-diphosphate and 6-thioguanosine 5′-triphosphate starting from the ribonucleoside. In the first step, 6-thioguanosine dissolved in triethyl phosphate, at high yield reacts with phosphorus oxide trichloride to 6-thioguanosine 5′-monophosphate which is purified by anion-exchange chromatography on DEAE-Sephadex using a step gradient of hydrochloric acid. In the second step, 6-thioguanosine 5′-monophosphate dissolved in water, reacts with phosphoric acid in the presence of pyridine/dicyclohexyl carbodiimide and is converted to 6-thioguanosine 5′-dip…

Amine functionalized ZrO2 nanoparticles as biocompatible and luminescent probes for ligand specific cellular imaging

2015

Surface functionalized ZrO2 nanoparticles show strong photoluminescence and are a versatile tool for cellular targeting due to their chemical functionality. They are highly photostable, biocompatible and amenable to coupling with bioligands (e.g. secondary goat anti-rabbit antibody (GAR) and tri-phenyl phosphine (TPP)) via carbodiimide chemistry. Antibody (GAR) functionalized ZrO2 nanoparticles were used to image the nuclear protein Sirt6, whereas triphenyl phosphonium ion (TPP) functionalized ZrO2 nanoparticles specifically targeted the mitochondria. The versatility and easiness of the ZrO2 surface modification opens up new possibilities for designing non-toxic water dispersible and photos…

Effects of metal–ligand coordination on the self-assembly behaviour of a crown ether functionalised perylenetetracarboxylic diimide

2012

A novel perylenetetracarboxylic diimide (PDI) derivative, N,N′-di(4′-benzo-15-crown-5-ether)-1,7-di(4-tert-butyl-phenoxy)perylene-3,4;9,10-tetracarboxylic diimide (CRPDI), has been synthesised and characterised. Dimerisation of CRPDI is induced by the presence of K+ in CHCl3 or spontaneously occurs in methanol, as revealed by absorption and emission spectroscopy. In particular, the formation of co-facial dimer in the presence of K+ proceeds in a three-stage process, as indicated by absorption spectroscopy. The belt- and rope-like nanostructures of CRPDI fabricated from methanol and CHCl3 solution in the presence of K+ are obtained by scanning electron microscopy. Furthermore, the conductivi…

Synthesis of peptides with α,β‐dehydroamino acids, V. coupling experiments with C‐terminal dehydrophenylalanine and dehydroalanine residues

1986

N-Protected model dipeptides of C-terminal (Z)-ΔPhe and ΔAla couple with glycine esters after activation with either diphenyl phosphorazidate (DPPA), N-cyclohexyl-N′-[2-(N-methylmorpholinio)ethyl]carbodiimide p-toluenesulfonate (WSC), N,N′-dicyclohexylcarbodiimide + 1-hydroxybenzotriazole (DCC + HOBt), or the mixed anhydride (MA) with isobutyl chlorocarbonate to give in good or mostly moderate yields the (Z)-ΔPhe-containing tripeptides 1 – 9 and ΔAla-containing tripeptides 11 – 19, respectively. In the MA and DPPA methods, further acylation products 20a – d are formed to a great extent, expecially during the ΔAla peptide syntheses. (E)-TFA-Gly-ΔPhe and Gly-OtBu, irrespective of the activati…

Synthesis of 1,3,5-Trisubstituted Hydantoins by Regiospecific Domino Condensation/Aza-Michael/O→N Acyl Migration of Carbodiimides with Activated α,β-…

2005

[reaction: see text] Carbodiimides and suitably activated alpha,beta-unsaturated carboxylic acids react effectively to afford a vast array of 1,3,5-trisubstituted hydantoins by means of a regiospecific domino condensation/aza-Michael/N--O acyl migration. The reaction works well in very mild conditions (20 degrees C, dichloromethane) with fumaric acid derivatives bearing an electron-withdrawing group in the beta position. Good results have been obtained also with less activated substrates bearing only one electron-withdrawing group in the beta position, using more polar solvents (acetonitrile, DMF), and in the presence of a base (2,4,6-trimethylpyridine). Reactions with asymmetric carbodiimi…

Synthetic Antitumor Vaccines Through Coupling of Mucin Glycopeptide Antigens to Proteins

2017

The requirements for coupling reactions of carbohydrate molecules very much depend upon the biological recognition processes that should be investigated and upon the target structures of the desired carbohydrate ligand. If the carbohydrate conjugate itself is the recognized ligand, as for example, the binding site of a P-selectin ligand comprising sialyl-LewisX and a specific peptide sequence, the natural glycoside bond must be installed. A stereoselective and regioselective block glycosylation between a sialyl-LewisX trichloroacetimidate and a partially deprotected Thomsen–Friedenreich antigen derivative was developed to achieve this aim. In contrast, the coupling reactions by which glycop…

Der Phenylacetyl-(PhAc-)Rest als enzymatisch ablösbare Schutzgruppe für Peptide und Kohlenhydrate: Selektive Schutzgruppenabspaltungen mit Penicillin…

1988

N-Phenylacetyl-(PhAc-)-aminosauren werden mit Aminosauremethyl-, -benzyl-, -allyl- und -tert-butylestern mit Hilfe des modifizierten Carbodiimidverfahrens oder unter Verwendung von EEDQ in guten Ausbeuten zu vollgeschutzten Dipeptiden verknupft. Der PhAc-Rest ist bei den Abspaltungen der C-terminalen Schutzgruppen stabil, kann jedoch aus den Peptiden unter nahezu neutralen Bedingungen selektiv mit Penicillin-Acylase (EC 3.5.1.11) abgelost werden. Das Enzym hydrolysiert den PhAc-Rest auch aus der 2-Position von acetylgeschutzter Glucose, der 3-Position von Di-O-isopropylidenglucose und der primaren OH-Gruppe von Di-O-isopropyliden-L-sorbose. Bei den enzymatischen Abspaltungsreaktionen bleibe…

1978

Synthesis and characterization of polymeric derivatives of the folic acid antagonist, Methotrexate, N-[4-(N-methyl-2,4-diamino-6-pteridinylmethylamino)benzoyl] glutamic acid (1a), a widely used antitumor agent, are described. Derivatives of poly(L-lysine), poly(iminoethylene), poly(vinyl alcohol), and carboxymethylcellulose with various contents (3–15 mole-%) of substituted repeating units were prepared by polymer-analogous amidation and transesterification of the dimethyl ester of 1a and with N-[2-(N-methylmorpholinio)ethyl]carbodiimide p-toluenesulfonate as coupling reagent. By nucleophilic addition reactions of the pteridinyl amino groups under mild conditions, 1a was bound without cross…

Umwandlung von 2-Bromäthoxycarbonyl-Schutzgruppen in 2-Phosphonioäthoxycarbonyl-Schutzgruppen für Aminosäuren1)

1976

Die Bromide 2 von 2-Phosphonioathoxycarbonylaminosauren (Peoc-Aminosauren) werden durch Umsetzung von 2-Bromathoxycarbonylaminosauren (Beoc-Aminosauren) mit tertiaren Phosphinen erhalten. Hierbei entstehen durch Reaktion mit Methyl(diphenyl)phosphin die mit der modifizierten Peoc-Gruppe geschutzten Verbindungen 2e - h in besonders guten Ausbeuten. Diese eignen sich zur Peptidsynthese nach dem Carbodiimid-Verfahren und sind besser in Wasser loslich als die entsprechenden Triphenylphosphonium-Derivate. Die Abspaltung der Me(Ph2)Peoc-Gruppe gelingt mit 0.01 N NaOH in Methanol/Wasser. Modification of 2-Brornoethoxycarbonyl Protective Groups to 2-Phosphonioethoxycarbonyl Protective Functions of …

Untersuchungen zu einem modell der herstellung von oligopeptiden mittels einer synthetischen matrizenreaktion

1970

Aktivierte Ester von Carbobenzoxyaminosauren mit drei phenolischen Zweikernverbindungen wurden dargestellt. Die anhydridmethode unter Verwendung von Chlorameisensaureathylester stellte sich dabei als gunstiger heraus als die Carbodiimidmethode unter Verwendung von Dicyclohexylcarbodiimid. Dies mag durch sterische Grunde bedingt sein. Uber gemischte Anhydride gelang auch die Verlangerung von Aminosaureestern zu Dipeptidestern. Die Ester von phenolischen Mehrkernverbindungen mit Aminosauren oder Peptiden konnen zur Darstellung von Oligopeptiden benutzt werden. Diese Reaktionsfolge, die als Modell einer Matrizenreaktion betrachtet werden kann, wurde an ihrem einfachsten Beispiel untersucht. Ac…