This takes advantage of the presence of carboxylate co2 groups in silk and wool. Synthesis and optical properties of pentamethine cyanine dyes. Synthesis of nearinfrared heptamethine cyanine dyes by jamie l. Phthalocyanine h2pc is a large, aromatic, macrocyclic, organic compound with the formula c 8 h 4 n 2 4 h 2 and is of theoretical or specialized interest. Synthesis of a novel heptamethinecyanine dye for use in near.
Five of them 1ad and 1f emit red and nearinfrared fluorescence at 600800 nm. Cyanine is the nonsystematic name of a synthetic dye family belonging to polymethine group. International journal of organic chemistry, 8, 282297. Synthesis of pentamethine cyanine dyes 34 and 35 containing a cyclopentene ring in the pentmethine chain was accomplished by condensing 2methylcylcopentane1,3diones 30, 31 with quaternary salts of 2methylbenzothiazolium 32, 33 at 210c in the presence of triethylamine equation 9. Practical syntheses of lysineselective, succinimidyl ester derivatives.
The synthesis results in two variants of the probes consisting of either one or two oligonucleotide residues bearing a quencher at the 3 end attached to the dye, with the first variant being predominant. A dye which in the past have shown promising dnabinding and fluorescent is a cyanine dye called boxto. The good fluorescence characteristics can be used to improve the detection sensitivity, which reduces background interference from intracellular environment or tissues. Pdf four tetramethylindodicarbocyaninederived carboxylicacids have been prepared using a modified onepot procedure for the dye. The synthesis results in two variants of the probes. Novel nearinfrared cyanine dyes for fluorescence imaging. Compared with wellknown symmetric cyanine dye 6c, the asymmetric dyes 5a and 5b contain only one active group on their molecules, and should benefit from quantitative protein labeling. Facile synthesis of thiolreactive cy3 and cy5 derivatives. The cyanine dyes cy3 and cy5 have proven valuable in numerous applications involving conjugation with proteins. The carbon chain contributes to the overall shape of the molecule being linear.
We were surprised to observe that commercialavailable cyanine. A series of mesochlorine substituted heptamethine cyanine dyes and related heptamethine cyanine dyes unsubstituted on the vinyl chain were synthesized by condensation of 2,3,3trimethyl indolenium salts with reactive intermediates, 2chloroformyl3hydroxymethylenecyclohexene or n5phenylamino2,4phentadienylidene aniline monohydroc hloride. The word cyanin is from the english word cyan, which conventionally means a shade of bluegreen close to aqua and is derived from the greek. H 2 pc has a twodimensional geometry and a ring system consisting of 18. The nir cyanine dye of interest, heptamethine cyanine dye nir1. The synthesis of a geometrically constrained and near. Different methods in the synthesis of monobiheterocyclic six mem bered cyanine dyes. A cyanine dye molecule consists of 2 nitrogencontaining heterocycles connected by an elongated, unsaturated carbon chain. Phthalocyanine h 2 pc is a large, aromatic, macrocyclic, organic compound with the formula c 8 h 4 n 2 4 h 2 and is of theoretical or specialized interest. The electronic visible adsorption spectra of all the synthesized cyanine dyes were investigated in 95% ethanol solution. Microwave synthesis of cyanine dyes january 2010 the journal of microwave power and electromagnetic energy.
In this project a chemical analog to the already existing boxto has been synthesized via synthesis of a benzothiazolium salt and a quinolinium salt followed by a condensation of these into the final dye. It is composed of four isoindole units linked by nitrogen atoms. Novel nearinfrared cyanine dyes for fluorescence imaging in biological systems by nilmi t. Cyanine dye dutp analogs for enzymatic labeling of dna. Compared with wellknown symmetric cyanine dye 6c, the asymmetric dyes 5a and 5b contain only one active group on their molecules, and should benefit from quantitative protein labeling and purifying. Synthesis of taqman probes using bisphosphoramidite of. Dyes for dye sensitized solar cells synthesis and computational study corneliu i. A novel nearinfraredabsorbing heptamethinecyanine dye kfh3 that contains four nbutyl groups was synthesized for use in highly efficient dyesensitized solar cells with porous zinc oxide zno prepared at low temperature, and resulted in remarkable performance characteristics, such as a conversion effi. The synthesis of unsymmetrical carbocyanine dyes is excellent for modifying a dyes absorption wavelength, preparing it for conjugation, or altering the dyes polarity or solubility. In an accompanying paper, we present a study of the dissociation of these dyes from dna under conditions typical for biotechnical application 35. Maleimide groups react with sulfhydryls under neutral ph conditions to form a thioether linkage figure. Cyanine dyes are an interesting class of near infrared nir dyes that have captured the interest of the scientific community. The journal of physical chemistry c 2017, 121 28, 1504915062. They are efficient substrates for dna polymerases and can be incorporated into dna probes by standard nick translation, random priming and polymerase chain reactions.
Synthesis and photophysical properties of novel highly stable. The alkylated amide 2 was then converted to the thioketone 3 under reflux with phosphorous pentasulfide in pyridine. Benzc,dindoliumcontaining monomethine cyanine dyes. A method of the synthesis of taqman probes with the use of bisphosphoramidite of cyanine dye cy3 was proposed. Synthesis, spectral properties, and use in the preparation of internally quenched fluorescent probes. Pdf synthesis and optical properties of cyanine dyes with. The synthesis of an azo dye requires two organic compounds a diazonium salt and a coupling component. Microwave synthesis of near infrared heptamethine cyanine dye. Synthesis and applications of benzothiazole containing.
Reagents for the labeling of biomolecules maksim v. The scope of the previously reported catchandrelease method using. The asymmetric redshifted monomethine cyanine dyes were synthesized as shown in scheme 1. The photophysical behavior of the cyanines was investigated using. The cyanine dyes such as pyrvinium pamoate 1, stilbazium iodide 2, bidimazium iodide 3, and dithiazanine iodide 4 possess a pseudo amidinium system characterised by a quaternary nitrogen and a tertiary nitrogen joined together by a chain of several conjugated carbon atoms. Optimal labeling conditions have been identified which yield probes with 2040. The scope of the previously reported catchandrelease method using sulfonyl chloride resin1 has now been extended to include pentamethine and watersoluble cyanine dyes. Fluorogenic peptide nucleic acids pnas functionalized with indoline derivatives are used to specifically sense g. Synthesis of new symmetrical mono, tri, and pentamethine cyanine dyes with two nammonioalkyl substituents was developed. The synthesis began with the alkylation of benzc,dindol21hone 1 by reflux with iodobutane in acetonitrile. The photophysical behavior of the cyanines was investigated using uvvis and steadystate fluorescence in solution, as well as their association with bovine serum albumin bsa in phosphate buffer solution pbs. Cyanine dyes featuring alkyl carboxylic acids have been previously explored extensively for both dyesensitized solar cells and conjugation of other groups onto the dye. The first bridged cyanine dye synthesis was published in 1933 where.
Heterocyclic polymethine dyes synthesis, properties and. Processes are described for synthesizing suitable heterocyclic and indole derivatives as precursors for the aforementioned cyanine dyes. Synthesis, spectroscopic characterizations, and ionspecific cooperative adsorption at the surface of tio2 anatase nanoparticles. A novel nearinfraredabsorbing heptamethinecyanine dye kfh3 that contains four nbutyl groups was synthesized for use in highly efficient dyesensitized solar cells with porous zinc. Synthesis and photophysical properties of novel highly. They are not the dyes that are directly seen in the photo, but the unseen dyes which are. Synthesis of heptamethine cyanine dyes ubc open collections. Solidphase methods for the synthesis of cyanine dyes the.
New cyanines were prepared by an efficient and practical route with satisfactory overall yield from lowcost starting materials. We report here a series of studies that explore solidphase methodologies for the synthesis of various cyanine dyes. Nov 01, 2003 herein we present the synthesis and dna. A new method for the synthesis of heptamethine cyanine. Solidphase methods for the synthesis of cyanine dyes. Herein we report the synthesis of seven monomethine cyanine dyes that have been successfully prepared with various heterocyclic moieties such as quinoline, benzoxazole, benzothiazole, dimethyl indole, and benzeindole adjoining benzc,dindol1ium, which was found to directly influence their optical and energy profiles. Kvach institute of physical organic chemistry, surganova, minsk 220072, belarus, fax. In dye chemistry, as is well known, many roads lead to the same goal. Henary abstract carbocyanine dyes are organic compounds. Cyanine dye cy3, possesses many excellent characteristics, such as good chemical stability, good fluorescence absorbance, and a high molar absorption coefficient 12. In this paper, we describe the synthesis and the photophysical properties of two novel nearinfrared nir cyanine dyes nir5. Us6437141b2 cyanine dyes and synthesis methods thereof. Pdf six cyanine dyes with aromatic azonia skeleton 1a. The presence of the pyridine ring in the pentamethine chain makes the dye more rigid and the cationic charge makes it water soluble.
If dmfdg is used during synthesis, deprotect in ammonium. Cyanine dye should be dissolved in organic solvent first, and added to a solution of biomolecule protein, peptide, aminolabeled dna in appropriate aqueous buffer. The most commonly used nearinfrared cyanine dyes contain an aryl ether that is not fully stable towards nucleophiles. However, cationic dyes can be used to dye protein fibres and, in fact, the first synthetic dye mauveine was a basic dye that was used for dyeing silk. In an accompanying paper, we present a study of the dissociation. We also report a new and chemically distinct synthetic strategy, employing the stepwise attack of. The word cyanin is from the english word cyan, which conventionally means a shade of blue. The dye is useful in labeling a variety of target molecules. Synthesis and optical properties of cyanine dyes with an. This short chapter provides a background to the subsequent. The synthesis of four cyanine phosphoramidites and activated esters cy3, cy3. The synthesis of cyanine dye 22 was carried out by condensation reaction between compound 21 and 2,3dimethyl benzothiazole tetrafluoroborate in the presence of.
Cyanine 3 and cyanine 5 supports are also offered to allow simpler production of 3 cyanine dyelabelled oligonucleotides. Jan 01, 2016 synthesis of the chlorocyclohexenylcy7bisnorbornenylbromide 7 synthesis and characterization of heptamine cyanine dyes are well described by the li group 28. Replacement of the aryl ether by a more stable carboncarbon bond can improve the stability. Synthesis of a new betanaphthothiazole monomethine cyanine. Reversible synthesis and characterization of dynamic imino analogues of trimethine and pentamethine cyanine dyes kamel meguellati, martin spichty, and sylvain ladame isis universite. Cyanine dyes are known best for their application in color photography. Six cyanine dyes with an aromatic azonia skeleton 1af were obtained by the reaction of chlorinated heptamethylene cyanine and 2aminopyridine derivatives. The synthesis of cyanine dye 22 was carried out by condensation reaction between compound 21 and 2,3dimethyl benzothiazole tetrafluoroborate in the presence of sterically hindered hunig base. Synthesis and optical properties of pentamethine cyanine. Cyanine dye is the nonsystematic name of a family of fluorescent dyes with excellent photophysical properties such as high fluorescence quantum yield, emission at long wave. Synthesis of a novel heptamethinecyanine dye for use in. Reversible synthesis and characterization of dynamic imino. In the last step of the synthesis, conditions for the removal of the phthalimide protecting group in cyanine dyes using hydrazine monohydrate and an ethanol solution of menh 2 were selected.
Reversible synthesis and characterization of dynamic imino analogues of trimethine and pentamethine cyanine dyes kamel meguellati, martin spichty, and sylvain ladame isis. All results demonstrated that asymmetric dye 5a possesses better photostability, which can be a good fluorescent labeling reagent for protein. Cyanine dyes that have a thiolreactive group are typically maleimide derivatives. Synthesis of a new beta naphthothiazole monomethine cyanine dye for the detection of dna in aqueous solution. A cyanine dye having the formula wherein r 1 r 8 are each independently selected from a group consisting of hydrogen, c 1 c 6 alkyl group, and c 0 c 4 alkyl group having a hydrophilic. Cyanine dye is the nonsystematic name of a family of fluorescent dyes with excellent photophysical properties such as high fluorescence quantum yield, emission at long wave lengths and high photostability.
Bibliography includes bibliographical references and index. Synthesis and characterization of heptamethine cyanine dyes. They are efficient substrates for dna polymerases and can be incorporated into. Deprotection of oligos containing cyanine dyes may be carried out with ammonium hydroxide at room temperature, regardless of the base protecting groups on the monomers used. Cyanine dye based compounds for tumor imaging with and without photodynamic therapy. Cyanine dyes are amongst the earliest quaternary ammonium salts, which were evaluated against helminths. Synthesis of novel fluorescent benzothiazole cyanine dyes as.
Cyanine dye dutp analogs for enzymatic labeling of dna probes. Fernando under the direction of professor lucjan strekowski. Synthesis of different classes of fivesix membered. Synthesis of nearinfrared heptamethine cyanine dyes. A series of mesochlorine substituted heptamethinecyanine dyes and related heptamethine cyanine dyes unsubstituted on the vinyl chain were synthesized by condensation of 2,3,3. Synthesis of merocyanine dyes all the approaches to the synthesis of merocyanines relied on the socalled cyanine condensation. Pdf photoexcitation processes in oligomethine cyanine. The synthesis began with the alkylation of benzc,dindol21hone 1 by reflux with.
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