Sample records for diazotization

  1. 40 CFR 721.10034 - Substituted pyridine coupled with diazotized substituted nitrobenzonitrile, diazotized...


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted pyridine coupled with... Specific Chemical Substances § 721.10034 Substituted pyridine coupled with diazotized substituted... as substituted pyridine coupled with diazotized substituted nitrobenzonitrile, diazotized...

  2. Photosensitive diazotized poly(ethylene glycol) covalent capillary coatings for analysis of proteins by capillary electrophoresis.

    Yu, Bing; Chen, Xin; Cong, Hailin; Shu, Xi; Peng, Qiaohong


    A new method for the fabrication of covalently cross-linked capillary coatings of poly(ethylene glycol) (PEG) is described using diazotized PEG (diazo-PEG) as a new photosensitive coating agent. The film of diazo-PEG depends on ionic bonding and was first prepared on the inner surface of capillary by self-assembly, and ionic bonding was converted into covalent bonding after reaction of ultraviolet light with diazo groups through unique photochemical reaction. The covalently bonded coating impedance adsorption of protein on the central surface of capillary and hence the four proteins ribonuclease A, cytochrome c, bovine serum albumin, and lysosome can be baseline separated by using capillary electrophoresis (CE). The covalently cross-linked diazo-PEG capillary column coatings not only improved the CE separation performance for proteins compared to non-covalently cross-linked coatings or bare capillary but also showed a remarkable chemical solidity and repeatability. Because photosensitive diazo-PEG took the place of the highly noxious and silane moisture-sensitive coating reagents in the fabrication of covalent coating, this technique shows the advantage of being environment-friendly and having a high efficiency for CE to make the covalently bonded capillaries.

  3. Determination of para-arsanilic acid with improved diazotization reaction using differential pulse cathodic stripping voltammetry in aqueous system.

    Misni, Marpongahtun; Sathishkumar, Palanivel; Ahamad, Rahmalan; MohdYusoff, Abdull Rahim


    Para-arsanilic acid (p-ASA) has been widely used in the poultry industry to promote growth and prevent dysentery. It is excreted unchanged in the manure and released into non-target sites causing organoarsenic pollution risk to the environment and living system. Therefore, simple and effective analytical strategies are demanded for determining the samples that contain p-ASA. However, direct determination of both p-ASA and ortho-arsanilic acid (o-ASA) using differential pulse cathodic stripping voltammetry (DPCSV) gives the similar voltammograms that directly hamper the analysis used by the DPCSV technique. In this study, a method to determine and differentiate p-ASA from o-ASA via diazotization and coupling reaction of the amine groups followed by the direct DPCSV determination of diazo compounds is presented. The diazotization reaction carried out at pH 1.5 and 0 ± 1°C for 10 min showed two reduction peaks in DPCSV at-70 mV and -440 mV vs. Ag/AgCl (KCl 3 M). However, when the diazotization reaction was performed at pH 12.5 and 0 ± 1°C for 40 min, a coloured azo compound was produced and the DPCSV showed only one reduction peak that appeared at -600 mV vs. Ag/AgCl (3 M of KCl). The results of this study show that only p-ASA compound gave a reduction peak, whereas o-ASA compound did not give any peak. The detection limit of p-ASA was found to be 4 × 10(-8 )M. As a result, the proposed electro-analytical technique might be a good candidate to determine and differentiate the p-ASA present in the poultry and environmental samples.

  4. Histochemical evaluation of catechins in PEG stressed transgenic tea plants using catechin-specific-diazotized sulfanilamide reagent.

    Bhattacharya, A; Sharma, M; Gulati, A; Joshi, R; Chanda, S K; Ahuja, P S


    We investigated the applicability of catechin-specific-reagent (CSR) for histochemical evaluation of catechins. The diazotized arylamine moiety in CSR reacts specifically with the A-ring of catechins to yield a golden yellow complex. This makes it highly specific for spectrophotometric quantification of catechins. Therefore, microtome cut sections of untransformed and osmotin-expressing transgenic leaves and stem of tea were stained with CSR. We found catechins in the form of golden yellow globules. The catechin globules increased in the structurally intact and highly turgid cells of osmotin expressing transgenic tea plants after stress treatment with 20% PEG; by contrast, the cells in non-transgenic plants accumulated fewer catechin globules. Spectrophotometric quantification of catechins also confirmed higher levels in transgenics compared to untransformed plants. We found elevated accumulation of catechins in stress tolerant cells of tea leaves.

  5. Batch and Continuous-Flow One-Pot Processes using Amine Diazotization to Produce Silylated Diazo Reagents.

    Audubert, Clément; Gamboa Marin, Oscar Javier; Lebel, Hélène


    A novel synthesis of trimethylsilyldiazomethane (TMSCHN2 ) by diazotization of trimethylsilylmethylamine (TMSCH2 NH2 ) is reported using batch and continuous flow synthesis. The latter affords a daily production of 275 g (2.4 mol) of TMSCHN2 . Other silylated methylamines were also successfully reacted under the developed reaction conditions to furnish various silicon-bearing diazomethane reagents. The applicability of the process is highlighted by disclosure of batch and continuous flow one-pot esterification and 1,3-dipolar cycloaddition processes. Furthermore, the high-yielding esterification of carboxylic acids with silylated and substituted methylamines in continuous flow is disclosed. Finally, work-up and purification procedures are reported for the preparation of a 2-MeTHF solution of TMSCHN2 , which can be used in rhodium-catalyzed methylenation and homologation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Diazotization of kynurenine by acidified nitrite secreted from indoleamine 2,3-dioxygenase-expressing myeloid dendritic cells.

    Hara, Toshiaki; Yamakura, Fumiyuki; Takikawa, Osamu; Hiramatsu, Rie; Kawabe, Tsutomu; Isobe, Ken-Ichi; Nagase, Fumihiko


    Indoleamine 2,3-dioxygenase (IDO)-initiated tryptophan metabolism along the kynurenine (Kyn) pathway regulates T-cell responses in some dendritic cells (DC) such as plasmacytoid DC. A Kyn assay using HPLC showed that samples were frequently deproteinized with trichloroacetic acid (TCA). In the present study, bone marrow-derived myeloid DC (BMDC) were differentiated from mouse bone marrow cells with GM-CSF. CpG oligodeoxynucleotides (CpG) induced the expression of IDO protein with NO production in BMDC cultured for 24 h. The concentrations of Kyn in the culture supernatants were not increased by stimulation with CpG but rather decreased by based on the Kyn assay after deproteinization with TCA. The level of Kyn exogenously added into the cell-free culture supernatant of BMDC stimulated with CpG was severely decreased by deproteinization with TCA but not methanol, and the decrease was prevented when BMDC was stimulated with CpG in the presence of a NOS inhibitor. Under acidic conditions, Kyn reacted with nitrite produced by BMDC, and generated a new compound that was not detected by Ehrlich reagent reacting with the aromatic amino residue of Kyn. An analysis by mass spectrometry showed the new compound to be a diazotization form of Kyn. In conclusion, the deproteinization of samples by acidic treatment should be avoided for the Kyn assay when NO is produced.

  7. Synthesis of Disperse Dyes from Pyridone and Resorcinol Coupled to Diazotized 2-Amino-4-chloro-5-formylthiazole and Application to Polyester

    Yusuf Y. Lams


    Full Text Available The aim of this study was to synthesize disperse dyes in the derivative of 2-amino-4-chloro-5-formylthiazole by conventional diazotization and couplings with pyridone and resorcinol. The dyes were characterized by visible absorption spectroscopy, IR spectral studies, and 1H and 13C NMR. The pyridone and resorcinol substituted dyes exhausted well with good depth on 100% polyester fabrics with a shade of brown and purple colours, respectively. The heteroatom and the intrinsic conjugation in the thiazole structure results in high bathochromic shifts and lead to brightness of shades. The dyed fabrics showed very good to excellent wash fastness and moderate to good light and perspiration fastness properties.

  8. Reliable SERS detection of nitrite based on pH and laser irradiance-dependent diazotization through a convenient sampling micro-chamber.

    Gao, Mengyue; Fang, Wei; Ren, Jiaqiang; Shen, Aiguo; Hu, Jiming


    Nitrites (NO2(-) ions) in food and drink play an important role in human health but require complicated operations before detection. Herein, we present a rationally designed SERS-enabled micro-chamber that comprised a drawn glass capillary with a tiny orifice (∼50 μm) at the distal tip, wherein the gold nanoparticles (Au NPs) are compactly coated on the inner wall surface. In this chamber, nitrites specifically trigger a pH and laser irradiance-dependent diazotization starting from p-aminothiophenol (PATP) absorbed onto the surface of Au NPs to form p,p'-dimercaptoazobenzene (DMAB) molecules, in which the presence of NO2(-) ions above 30.7 μM (1.38 ppm) in the siphoned liquid sample can be identified relying on SERS peak (1141 cm(-1)) intensity of the emerging azo moiety. Except for pH conditions, laser irradiance is more important but easily neglected in previous studies, which is capable of preventing generation of errors when the detection sensitivity was pursued through increasing the laser power. In this case, several real samples (rather than simple water samples), including honey, pickled vegetable and fermented bean curd, had been successfully detected accurately through such a convenient sampling micro-chamber. The SERS-enabled device could potentially be facilely incorporated with portable Raman instruments for a special application of food inspection in rapid and field analysis of NO2(-) ions.

  9. Diazotization of the amino acid [closo-1-CB9H8-1-COOH-6-NH3] and reactivity of the [closo-1-CB9H8-1-COO-6-N2]- anion.

    Ringstrand, Bryan; Kaszynski, Piotr; Young, Victor G


    A comparative study of the reactivity of dinitrogen acids [closo-1-CB(9)H(8)-1-COOH-10-N(2)] (3[10]) and [closo-1-CB(9)H(8)-1-COOH-6-N(2)] (3[6]) was conducted by diazotization of a mixture of amino acids [closo-1-CB(9)H(8)-1-COOH-6-NH(3)] (1[6]) and [closo-1-CB(9)H(8)-1-COOH-10-NH(3)] (1[10]) with NO(+)BF(4)(-) in the presence of a heterocyclic base (pyridine, 4-methoxypyridine, 2-picoline, or quinoline). The 10-amino acid 1[10] formed an isolable stable 10-dinitrogen acid 3[10], while the 6-dinitrogen carboxylate 3[6](-) reacted in situ, giving products of N-substitution at the B6 position with the heterocyclic solvent (4[6]). The molecular and crystal structures for pyridinium acid 4[6]a were determined by X-ray crystallography. The electronic structures and reactivity of the 6-dinitrogen derivatives of the {1-CB(9)} cluster were assessed computationally at the B3LYP/6-31G(d,p) and MP2/6-31G(d,p) levels of theory and compared to those of the 10-dinitrogen, 2-dinitrogen, and 1-dinitrogen analogues.

  10. Elucidation of the Mechanism of Redox Grafting of Diazotated Anthraquinone

    Chernyy, Sergey; Bousquet, Antoine; Torbensen, Kristian;


    Redox grafting of aryldiazonium salts containing redox units may be used to form exceptionally thick covalently attached conductingfilms, even in the micrometers range, in a controlled manner on glassy carbon and gold substrates. With the objective to investigate the mechanism of this process in ...

  11. 40 CFR 721.10045 - Diazotized substituted heteromonocycle coupled with naphthalene sulfonic acid derivative, nickel...


    ... coupled with naphthalene sulfonic acid derivative, nickel complex, alkaline salt (generic). 721.10045... derivative, nickel complex, alkaline salt (generic). (a) Chemical substance and significant new uses subject... heteromonocycle coupled with naphthalene sulfonic acid derivative, nickel complex, alkaline salt (PMN P-02-737)...


    M. V. C. B. Cortes


    Full Text Available Abstract The main goal of this research was the synthesis of enantiopure R(--3-aminoisobutyric acid from dihydrothymine with good yield, high stereospecificity and relative simplicity. Seventy two percent yield of the product was obtained in three steps. Step one consisted of dihydrothymine racemization. Step two was a dihydropyrimidinase reaction involving the Pseudomonas aeruginosa 10145 bacterial strain as the biocatalyst. Step three was performed with a diazotization reaction. The bacteria's enzymes determined the stereochemistry of the process since the diazotization reaction did not interfere at this point. The results of this work provide an interesting method for the production of commercial β-amino acids from other substituteddihydrothymines.

  13. Synthesis, biological activity and dyeing performance of some novel azo disperse dyes incorporating pyrazolo[1,5-a]pyrimidines for dyeing of polyester fabrics

    Sayed, Ahmed Z.; Aboul-Fetouh, Mahmoud S.; Nassar, Hesham S.


    Several novel pyrazolopyrimidine azo compounds were achieved from diazotization of 4-aminoacetanilide and coupling with malononitrile and then refluxed with hydrazine hydrate to furnish 3,5-diamino-4-(4-acetamidophenylazo)-1H-pyrazole. The later compound was diazotized and coupled with substituted α-cyanocinnamate, α-cyanocinnamonitrile, 2-cyano-3-ethoxyacrylic acid ethyl ester, chalcones and ethylacetoacetate to produce novel dyestuffs. Structures of the dyes were fully characterized by using FT-IR, 1H NMR, mass spectroscopy and elemental analysis. The dyes were applied to polyester fiber, affording satisfactory results and showed biological activity towards various microorganisms.

  14. Synthesis of radioiodinated cis- and trans- 1,2-diphenyl-3,3-dichloro-cyclopropanes: potential radiopharmaceuticals for estrogen dependent

    Basmadjian, G.P.; Gilliland, D.L.; Magarian, R.A.; Ice, R.D. (Oklahoma Univ., Oklahoma City (USA). Health Sciences Center); Marchand, A.P. (Oklahoma Univ., Norman (USA). Dept. of Chemistry)

    Two non-steroidal compounds labelled with radioiodine, for breast cancer screening, have been developed. They are cis-trans-cyclopropyl analogs of cis- and trans-stilbene. Radioiodination with /sup 125/I or /sup 131/I was carried out by 1) exchange labelling 2) melt labelling 3) diazotization and 4) thallium iodination 5) triazine hydrolysis. The last two methods were the most efficient.

  15. Determination of Distribution Coefficient of Nitrous Acid and Evaluation of Influential Factors

    ZHU; Li-yang; CHEN; Yan-xin; TANG; Hong-bin; HE; Hui


    Nitrous acid is inevitably present in Purex process,thus,it is desired to build a HNO2 distribution model which could be incorporated into Purex computer simulation code.In this work base titration and diazotization-coupling reaction was used to determine the concentration of HNO3 and HNO2 in both

  16. A novel synthetic route for 2-[2-(2,2,2-trifluoroethoxy)phenoxy] ethanamine

    Xiao Chuan Luo; Guo Hua Chen; Hui Bin Zhang; Wen Long Huang


    2-[2-(2,2,2-Trifluoroethoxy)phenoxy]ethanamine is the key intermediate of Silodosin, the α1-adrenoceptor antagonist for thetreatment of benign prostatic hyperplasia. In order to obtain this intermediate, we developed a novel synthetic route by utilizing 2-nitrochlorobenzene as the starting material via O-alkylation, reduction, diazotization, acidolysis, etherification, condensation andhydrazinolysis. The highlight of this method lies on its convenience and economy in accessing this intermediate.

  17. Synthesis and Evaluation of Changes Induced by Solvent and Substituent in Electronic Absorption Spectra of New Azo Disperse Dyes Containig Barbiturate Ring


    Six azo disperse dyes were prepared by diazotizing 4-amino hippuric acid and coupled with barbituric acid and 2-thiobarbituric acid. Then, the products were reacted with aromatic aldehyde, sodium acetate, and acetic anhydride, and oxazolone derivatives were formed. Characterization of the dyes was carried out by using UV-Vis, FT-IR, 1H NMR and 13C NMR, and mass spectroscopic techniques. The solvatochromic behavior of azo disperse dyes was evaluated in various solvents. The effects of substitu...

  18. The chemistry of 1,1-dithiolates


    A series of thieno[3,2-e]-3,4-dihydro-1,2,3-triazin-4-ones (V) and thieno[3,4-e]-3,4-dihydro-1,2,3-triazin-4-ones (VI) were prepared by diazotation of 3-aminothiophene-2-carboxamides (III) and 4-amino-thiophene-3-carboxamides (IV), respectively, both obtained by cyclization of 2-cyanoethylene-1,1...

  19. Efficient Route to Deuterated Aromatics by the Deamination of Anilines.

    Burglova, Kristyna; Okorochenkov, Sergei; Hlavac, Jan


    One-step replacement of NH2 groups in ring-substituted anilines by deuterium is reported. Approaches comprising both solid-phase and solution-phase syntheses can be used on a large variety of substrates. The method uses diazotization in a mixture of water and either dichloromethane or chloroform, which serve as a source of hydrogen. This protocol can be used as a general method for fast and easy incorporation of deuterium into an aromatic system using deuterated chloroform.

  20. The chemistry of 1,1-dithiolates


    A series of thieno[3,2-e]-3,4-dihydro-1,2,3-triazin-4-ones (V) and thieno[3,4-e]-3,4-dihydro-1,2,3-triazin-4-ones (VI) were prepared by diazotation of 3-aminothiophene-2-carboxamides (III) and 4-amino-thiophene-3-carboxamides (IV), respectively, both obtained by cyclization of 2-cyanoethylene-1,1...

  1. Design and Synthesis of Novel 5-Sulfoxide-substituted Pyrazolo[5,1-d] [1,2,3,5]tetrazin-4(3H)ones


    A series of novel 5-sulfoxide-substituted pyrazolo[5,1-d][1,2,3,5]tetrazin-4(3H)ones 4a-j were designed and efficiently synthesized via a diazotization of 5-amine-3-methylsulfinyl1H-pyrazole, followed by cycloaddition with aryl isocyanate. A possible reaction mechanism is outlined and discussed. These new compounds exhibit some biological activity as preliminary bioassay indicated. Their structures were confirmed with1 H NMR, IR and elemental analysis.

  2. Microwave-Assisted Synthesis of 3,5-Dibenzyl-4-amino-1,2,4-triazole and its Diazo Ligand, Metal Complexes Along with Anticancer Activity

    Anjali Jha


    Full Text Available Synthesis of 3,5-dibenzyl-4-amino-1,2,4-triazole was accomplished via a conventional method as well as microwave irradiation method, followed by diazotization and coupling with 2,4-pentanedione. The dinucleating ligand was isolated and complexed with Ni(II, Cu(II and Ru(III chlorides. These complexes were screened on Jurkat, Raji & PBMC cell lines for anticancer activity. Ruthenium complexes showed potential anticancer activities.

  3. Microwave-Assisted Synthesis of 3,5-Dibenzyl-4-amino-1,2,4-triazole and its Diazo Ligand, Metal Complexes Along with Anticancer Activity

    Anjali Jha; Murthy, Y. L. N.; Durga, G.; Sundari, T. T.


    Synthesis of 3,5-dibenzyl-4-amino-1,2,4-triazole was accomplished via a conventional method as well as microwave irradiation method, followed by diazotization and coupling with 2,4-pentanedione. The dinucleating ligand was isolated and complexed with Ni(II), Cu(II) and Ru(III) chlorides. These complexes were screened on Jurkat, Raji & PBMC cell lines for anticancer activity. Ruthenium complexes showed potential anticancer activities.

  4. Facile and Sensitive Spectrophotometric Technique for the Determination of Carbofuran in its Formulations, Water and Grain Samples with Substituted Anilines

    V. Harikishna


    Full Text Available Methods are described for the determination of carbofuran in its formulations, in water and grain samples by the diazotization coupling spectrophotometric technique, using substituted anilines such as 4-bromoaniline, 4-methylaniline and 4-aminobenzaldehyde as the coupling agents. The orange red colour formed with 4-bromoaniline shows maximum absorption at 478 nm, yellow colour obtained with 4-methylaniline have maximum absorption at 465 nm whereas a red colour derivative formed with 4-aminobenzaldehyde shows λmax at 472 nm. The methods could be successfully applied for the determination of carbofuran in its formulations, water and grain samples.

  5. Synthesis of (p-Formylphenyl)azo Calix[4]arenes

    BAI,Zhu(柏祝); YU,Lei(俞磊); LU,Guo-Yuan(陆国元); GUO,Xun(郭勋)


    Five novel azo calix[4]arenes were reported.The p-aminobenzaldehyde was diazotized with sodium nitrite in aqueous hydrochloride solution.Mono-,bis-,tris- and tetrakis(p-formylphenyl)azo calix[4]arenes (including proximal and distal isomers) were obtained respectively by diazo-coupling in different molar ratio to calix[4]arene (1) under pH=7.5-8.5 at 0-5℃.All (p-formylphenyl)azo calix[4]arenes were characterized by 1H NMR,13C NMR,IR,MS (ESIMS) spectroscopies and elemental analysis.

  6. [Color reactions for identification of sodium cromoglycate].

    Görlitzer, K; Badia, G; Jones, P G


    Chromone-2-carboxylic acid (3) reacts with aminopyrazolone (2) in methanolic hydrochloric acid to yield the orange-red polymethine dye 4. Treating dimethyl cromoglicate (6) with compound 2 and perchloric acid leads to the tetraperchlorate 7 of the red azamerocyanine 8. The phenol 9, obtained from alkaline hydrolysis of sodium cromoglicate (1a), couples with diazotized sulfanilic acid to form the red azo dye 10. The chromone 6 condenses with 1,3-dimethylbarbituric acid (DMBA) in acetic anhydride/acetic acid to the red oxonole 12. Cromoglicinic acid (1b) reacts under these conditions to yield the yellow polymethine dye 14, whose structure is elucidated by X-ray analysis.

  7. Synthesis and Evaluation of Changes Induced by Solvent and Substituent in Electronic Absorption Spectra of New Azo Disperse Dyes Containig Barbiturate Ring

    Hooshang Hamidian


    Full Text Available Six azo disperse dyes were prepared by diazotizing 4-amino hippuric acid and coupled with barbituric acid and 2-thiobarbituric acid. Then, the products were reacted with aromatic aldehyde, sodium acetate, and acetic anhydride, and oxazolone derivatives were formed. Characterization of the dyes was carried out by using UV-Vis, FT-IR, 1H NMR and 13C NMR, and mass spectroscopic techniques. The solvatochromic behavior of azo disperse dyes was evaluated in various solvents. The effects of substituents of aromatic aldehyde, barbiturate, and thiobarbiturate ring on the color of dyes were investigated.




    Full Text Available The aim of the present work was to synthesize certain coumarinyl pyrazoline-5-one derivatives and to elucidate the potential role of these compounds as antimicrobial, antioxidant and anti-tubercular agents. The coumarinyl pyrazoline-5-one derivatives were prepared by condensing the unsaturated ester of diazotized Anilines with 6-bromo substituted Coumarin-3- acid hydrazides. All the synthesized compounds showed promising anti-tubercular activity against Mycobacterium tuberculosis and some of them showed significant in vitro antioxidant activity and antimicrobial activity.

  9. Cellulose sulphuric acid as a biodegradable catalyst for conversion of aryl amines into azides at room temperature under mild conditions

    Firouzeh Nesmati; Ali Elhampour


    This article describes simple and efficient method for the diazotization and azidation of different aromatic amines over cellulose sulphuric acid, sodium nitrite and sodium azide under mild conditions at room temperature. Various aryl amines possessing electron-withdrawing groups or electron-donating groups have been converted into the corresponding aryl azides with 71-99% yields. The use of mild reaction conditions, avoids the use of harmful acids and toxic solvents and short reaction times are advantages of this methodology. The selected catalyst is found to be highly efficient and recyclable.

  10. Synthesis with Nitriles: Synthesis of Some New Mercaptopyridazine, Mercaptopyridazino[1,6-a]quinazoline and Thiophene Derivatives

    Mariam A. Al-Sheikh


    Full Text Available 2-(1-(4-Bromophenyl-2-thiocyanatoethylidenemalononitrile (3 undergoes azo coupling with diazotized aromatic amines to afford arylhydrazone derivatives, which are readily cyclized to afford the corresponding 3(2H-pyridazinimine derivatives upon reflux in aqueous NaOH. Under similar condition an o-cyanoarylhydrazone derivative was cyclized into 6H-pyridazino[1,6-a]quinazolin-6-imine, which in turn was easily transformed into 6H-pyridazino[1,6-a]quinazolin-6-one on reflux in ethanolic/HCl. Compound 3 afforded substituted 5-acetylthiophene derivatives upon reflux in AcOH/HCl mixtures.

  11. Synthesis and Application of Azo Disperse Reactive Dyes derived from p-Aminobenzaldehyde

    Iyabo Fasansi


    Full Text Available Disperse reactive dyes were synthesized by diazotizing p-aminobenzaldehyde and coupling with different substituted pyridones and 2-naphthol. The dyeing performance of the dyes was assessed on polyester, nylon, cotton and wool fabrics. The dyes obtained gave various shades of yellow with good depth, brightness and leveling properties on the fabrics. The dyed fabric showed fairly good to very good light fastness and very good to excellent fastness to washing, hot pressing and rubbing. The dyebath exhaustion on the polyester, nylon, wool and cotton fabrics was found to be very good and fixation on wool was better than on cotton fabric.

  12. Synthesis, characterization and application of new azo dyes derived from uracil for polyester fibre dyeing

    Yazdanbakhsh, Mohamad-reza; Abbasnia, Masoumeh; Sheykhan, Mehdi; Ma'mani, Leila


    Some novel uracil derived azo compounds were synthesized by diazotization of substituted aromatic amines, amidine- and guanidine-like amines such as 2-aminopyridine and 2-aminopyrimidine, ortho-hydroxy aniline and ortho-hydroxy naphthyl amines and coupling reaction with 6-amino-1,3-dimethyluracil. Structures of the dyes were fully characterized by spectroscopic techniques (UV, 1H NMR, 13C NMR, CHN and IR). The dyes were applied to polyester, affording orange-yellow shades and the wash fastness of the dyeings was excellent.

  13. Synthesis, spectral features and biological activity of some novel hetarylazo dyes derived from 8-chloro-4-hydroxyl-2-quinolone

    Yahyazadeh, Asieh; Yousefi, Hessamoddin


    In this study, 8-chloro-4-hydroxyl-2-quinolone was synthesized from cyclocondensation of corresponding dianilide and subsequently used as a potent coupling component with some diazotized heterocyclic amines. These compounds were characterized by UV-vis, FT-IR, 1H NMR spectroscopic techniques and elemental analysis. Absorption spectra of these dyes were measured in six polar solvents and discussed with respect to the nature of solvents and substituted groups. The effects of acid, base, temperature and concentration on the visible absorption spectra of the dyes were reported. In addition, the antimicrobial activity of the dyes was explored in detail.

  14. Studies on Synthesis and Dyeing Preformance of Acid Dyes Based on 4,7-Dihydroxy-3,8-di-α-naphthylazo-1,10-phenanthroline-2,9-Dione

    B. V. Patel


    Full Text Available Some new azo acid dyes were prepared by coupling various diazotized acid components such as anthranilic acid, sulphanilic acid, laurentacid, peri acid, tobias acid, H-acid, J-acid, gamma acid, sulphotobias acid,4-aminotoluiene-3-sulphonic acid, 5-sulpho- anthranilic acid, 2-naphthylamine-3,6,8-trisulphonic acid, bronner acid, metanilic acid and cleve acid with 4,7-dihydroxy-3,8-di-α-naphthylazo-1,10-phenanthroline-2,9-dione. The dyes were characterized by elemental, IR and TLC analyses. Their dyeing performance as acid dyes has been assessed on viscose rayon, wool and cotton fibres.

  15. Immobilization of denatured DNA to macroporous supports: II. Steric and kinetic parameters of heterogeneous hybridization reactions.

    Bünemann, H


    The accessibility of immobilized DNA has been shown to depend more crucially on the method of immobilization than on the type of support used for fixation. When sonicated denatured DNA is coupled via diazotization or via cyanogen bromide reaction to solid Sephadex G-25 and Cellex 410 or to macroporous Sephacryl S-500 and Sepharose C1-6B its accessibility varies from 100 to 24 percent. Generally the loss of accessibility is linked to a depression of the melting temperature of DNA helices forme...

  16. Heteroarylazo derivatives of cyclohexane-1,3-dione and their metal complexes

    Ummathur Muhammed Basheer


    Full Text Available The coupling of diazotized 2-aminothiazole and 2-aminobenzo-thiazole with cyclohexane-1,3-dione yielded a new type of tridentate ligand systems (HL. Analytical, IR, 1H NMR, 13C NMR and mass spectral data indicate the existence of the compounds in the intramolecularly hydrogen bonded azo-enol tautomeric form. Monobasic tridentate coordination of the compounds in their [CuL(OAc] and [ML2] complexes [M = Ni(II and Zn(II] has been established on the basis of analytical and spectral data. The Zn(II chelates are diamagnetic while Cu(II and Ni(II complexes showed normal paramagnetic moment.

  17. Synthesis, characterization, and fluorescence study of phthalhydrazidylazo derivative of an unsaturated diketone and its metal complexes

    PALLIKKAVIL, Radhika; UMMATHUR, Muhammed Basheer; KRISHNANKUTTY, Krishnannair


    The coupling of diazotized luminol with the unsaturated diketone 1,7-diphenylhepta-4,6-diene-1,3-dione yielded a new type of tridentate ligand (H2L). Analytical, IR, 1H NMR, and mass spectral data indicate the existence of the compound in the intramolecularly hydrogen-bonded keto-hydrazone tautomeric form. Dibasic tridentate coordination of the compound in its [ML(H2O)] complexes [M = Cu(II), Ni(II) and Zn(II)] was established on the basis of analytical and spectral data. The Ni(II) an...

  18. Synthesis of Certain 3-Aminopyrazolo[5,4-b]pyridine and 3,4-Substituted Pyrido[2',3': 3,4]pyrazolo[5,1-c][1,2,4]triazine Derivatives

    EL-LOUH Ali Khader Khalil; ABUNADA Nada Mohamed; EL-SHOUBAKI Mohamed


    2-Thioxo-1,2-dihydropyridine derivatives 2a,2b were reacted with methyl iodide to give 2-methylthiopyridines 3a,3b,which were reacted with hydrazine hydrate to produce 3-aminopyrazolo[5,4-b]pyridines 4a,4b.Compounds 4a,4b were diazotized to afford the corresponding diazonium salts 5a,5b,which were reacted with some active methylene compounds 6a-6h to give the corresponding pyrido[2',3': 3,4]pyrazole[5,1-c] [ 1,2,4]triazines 7-14.

  19. A dual-responsive fluorescence method for the detection of clenbuterol based on BSA-protected gold nanoclusters.

    Cao, Xueling; Li, Hongwei; Lian, Lili; Xu, Na; Lou, Dawei; Wu, Yuqing


    The illegal feeding of clenbuterol (CLB) to domestic animals and the potential harm of it to human health lead an urgent requirement for the efficient detection of CLB, especially in the edible meat. In this paper we reported a new fluorescence method for the detection of trace amount of CLB by using the BSA-protected gold nanoclusters (AuNCs@BSA). Under the excitation of either 280 or 500 nm the emission of AuNCs@BSA was quenched obviously by diazotized CLB, supplying a dual-responsive fluorescence method to detect CLB in aqueous solution. In addition, the linear response of the fluorescence intensity of AuNCs@BSA to diazotized CLB allowed the quantitative detection of CLB in a range of 4.0 nM-300 μM upon excitation at two wavelength, and the limit of detection for CLB was 3.0 nM upon 280 nm excitation and 1.6 nM upon 500 nm excitation, respectively. In addition, the dual-responsive mechanism of AuNCs@BSA to CLB was investigated in detail by using several CLB analogues and reference compounds. Particularly, the proposed method was successfully applied to detect CLB in pork mince and the results were validated well by HPLC, illustrating it could be used as a reliable, rapid, and cost-effective technique for the determination of CLB residues in real samples.

  20. Synthesis and investigation of antimicrobial activity and spectrophotometric and dyeing properties of some novel azo disperse dyes based on naphthalimides.

    Shaki, Hanieh; Gharanjig, Kamaladin; Khosravi, Alireza


    A series of novel disperse dyes containing azo group were synthesized through a diazotization and coupling process. The 4-amino-N-2-aminomethylpyridine-1,8-naphthalimide was diazotized by nitrosylsulphuric acid and coupled with various aromatic amines such as N,N-diethylaniline, N,N-dihydroxyethylaniline, 8-hydroxyquinoline, and 2-methylindole. Chemical structures of the synthesized dyes were characterized by Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), proton nuclear magnetic resonance ((1) H NMR), carbon nuclear magnetic resonance ((13) C NMR), elemental analysis, and ultraviolet-visible (UV-visible) spectroscopy. The spectrophotometric data of all dyes were evaluated in various solvents with different polarity. Eventually, the dyes were applied on polyamide fabrics in order to investigate their dyeing properties. The fastness properties of the dyed fabrics such as wash, light, and rubbing fastness degrees were measured by standard methods. Moreover, the color gamut of the synthesized dyes was measured on polyamide fabrics. Results indicated that some of the synthesized dyes were able to dye polyamide fabrics with deep shades. They had very good wash and rubbing fastness degrees and moderate-to-good light fastness on polyamide fabrics. The antibacterial and antifungal activities of the synthesized dyes were evaluated in soluble state and on the dyed fabrics. The results indicated that dye 2 containing N,N-dihydroxyethylaniline as coupler had the highest activity against all the bacteria and fungi used.

  1. One-pot Synthesis of 2-Nitro-4,5-dicyano-1H-imidazole

    XU Cheng; BIFu-qiang; FAN Xue-zhong; LI Ji-zhen; WANG Bo-zhou; GE Zhong-xue; LIU Qing; ZHANG Guo-fang


    In the last few decades,nitroimidazoles have been investigated mostly due to their properties as antibiotics,radiosensitizers and anti-protozoans[1 -3].Recently these nitroimidazoles,such as 2,4-dinitroimidazole,1-methyl-2,4,5-trinitroimidazole and their energetic salts, have attracted renewed attention for their favorable explosive performance as well as improved safety characteristics[4,5].Because of the activity of cyano group,2-nitro-4,5-dicyano-1 H-imidazole (NDCI) could be used as an intermediate in the synthesis of novel energetic materials containing nitroimidazole moiety.NDCI has been synthesized by the procedure given by Yixin Lu and coworkers[6],where the diazotization reaction and the Sandmeyer reaction were separately achieved.NDCI was obtained by adding a solution of sodium nitrite to 2-diazo4,5-dicyanoimidazole which was generated by diazotization of 2-amino-4,5-dicyano-1H-imidazole ( ADCI ) with sodium nitrite in water-hydrochloric acid and collected by filtration.Dry 2-diazo-4,5-dicyanoimidazole was so sensitive to shock that its separation may cause explosion[7].

  2. A novel electrochemiluminescence sensor for the detection of nitroaniline based on the nitrogen-doped graphene quantum dots.

    Chen, Shufan; Chen, Xueqian; Xia, Tingting; Ma, Qiang


    Nitrogen-doped graphene quantum dots (N-GQDs), as a new class of carbon nanomaterials, have potential application in sensor, fuel cells, optoelectronics field due to their stable photoluminescence (PL) and electrocatalytic activity. Herein, a facile novel electrochemiluminescence (ECL) signal-on method for nitroaniline (NA) sensing based on N-GQDs and chitosan was developed. Chitosan displays high water permeability, hydrophilic property and good adhesion to load the N-GQDs to the glassy carbon electrode (GCE) surface. N-GQDs have shown as highly active reagent and catalyst for rapid diazotization reaction of anilines. When NA was added to the electrolyte solution consisting of mineral acid and sodium nitrite, N-GQDs/chitosan modified electrode exhibited obvious enhancement of ECL intensity, which was ascribed to the occurrence of diazotization reaction of NA. Therefore, NA can be detected with high selectivity based on the N-GQDs/chitosan ECL system. To the best of our knowledge, it is the first report about the NA detection based on the catalysis and ECL capabilities of N-GQDs. There was a wide linear ECL intensity response ranging from 0.01 to 1μmolL(-1) NA. The practicability of the ECL sensing platform in real water samples has shown the satisfactory results. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Spectrophotometric and high performance liquid chromatographic methods for sensitive determination of bisphenol A.

    Zhuang, Yafeng; Zhou, Meng; Gu, Jia; Li, Xiangmei


    A new spectrophotometric method for the determination of trace amounts of bisphenol A based on a diazotization-coupling reaction was developed. In acidic solution, clenbuterol was first diazotized with sodium nitrite, then coupled with bisphenol A to from an azo-compound [I] in NH3-NH4Cl buffer, which shows a maximum absorption at 410 nm. The effects of the amount of sodium nitrite, diazo reaction time, the amount of clenbuterol, coupling reaction time and coupling reaction temperature have been examined. Under the optional conditions, the determination of the linear range of bisphenol A is 0.24-8.4 μg/mL, correlation coefficient is 0.9905 and detection limit of this method is 0.15 μg/mL. The spectrophotometric method is simple, rapid, high sensitivity with better accuracy. High performance liquid chromatography (HPLC) technique combined with this new spectrophotometric method has been also developed for the measurement of bisphenol A. The analysis was achieved on a C18 column using water and methanol as a mobile phase and the detection was done spectrophotometrically at 410 nm. These reported methods were applied to the determination of bisphenol A in hot water in contact with commercially available table-water bottle samples.

  4. Synthesis of Pinoxaden%除草剂唑啉草酯的合成研究



    以2,6-二乙基-4-甲基苯胺为原料,经重氮化、偶联、醇解、酯胺解,最后与特戊酰氯酯化,制备得到唑啉草酯。产品质量分数大于97%,收率为26.6%(以2,6-二乙基-4-甲基苯胺计)。%Using 2,6-diethyl-4-methylaniline as starting material, pinoxaden was synthesized by diazotization, coupling, alcoholysis, ammonolysis and esterification. The purity of pinoxaden was more than 97%, and the total yield was 26.6%.

  5. Highly Dispersed Palladium Nanoparticles on Functional MWNT Surfaces for Methanol Oxidation in Alkaline Solutions

    WANG zhe; ZHU Zan-Zan; LI You-Xiang; LI Hu-Lin


    Palladium nanoparticles were crystallized on 4-aminobenzoic acid monolayer-grafted multi-walled carbon nanotubes (MWNT) by diazotization. The structure and nature of the resulting Pd/MWNT composite were characterized by transmission electron microscopy and X-ray diffraction, the results show that the chemically synthesized Pd nanoparticles were homogeneously dispersed and well-separated from one another on the modified MWNT surfaces. Cyclic voltammogram showed that the Pd-MWNT composite materials performed higher electrocatalytic activity and better long-term stability toward methanol oxidation in alkaline solution than Pd-C. The results imply that the Pd-MWNT composite materials as a promising support material improve the excellent electrocatalytic activity for methanol oxidation greatly. So the Pd/MWNT composites have a good application potential to fuel cells.

  6. Production of Leather Brown RH%皮革棕RH生产合成



    The production process of leather brown RH was given. Diazotization and coupling reaction composition, pH value, time, temperature, reaction end point were stated in detail. And the performance index of products in leather application was pointed out.%主要论述了皮革棕RH产品,车间的生产工艺操作流程,对重氮化、偶合各反应组成,pH值、时间、温度、反应终点作了进一步的详细说明,最后论述了产品在皮革上的应用性能指标。

  7. Synthesis and dyeing properties of some new monoazo disperse dyes derived from 2-amino-4-(2′,4′-dichlorophenyl-1,3 thiazole

    Divyesh R. Patel


    Full Text Available Ten new monoazo disperse dyes (4a–j have been synthesized by coupling of diazotized 2-amino-4-(2′,4′-dichlorophenyl-1,3 thiazole (2 with various N-alkyl derivatives of substituted aniline (3a–j and their dyeing performance on polyester fiber has been assessed. These dyes are characterized by elemental analysis, UV–vis spectra, IR and NMR spectroscopy. The absorption maxima (λmax were recorded in DMF and were found to be in the range of 530–600 nm. The dyed polyester fabric showed fair to very good light fastness and very good to excellent washing and rubbing fastness properties with superior depth and levelness.

  8. Synthesis and evaluation of changes induced by solvent and substituent in electronic absorption spectra of some azo disperse dyes.

    Mohammadi, Asadollah; Yazdanbakhsh, Mohammad Reza; Farahnak, Lahya


    Five azo disperse dyes were prepared by diazotizing 4'-aminoacetophenone and p-anisidine and coupling with varies N-alkylated aromatic amines. Characterization of the dyes was carried out by using UV-vis, FTIR and 1H NMR spectroscopic techniques. The electronic absorption spectra of dyes are determined at room temperature in fifteen solvents with different polarities. The solvent dependent maximum absorption band shifts, were investigated using dielectric constant (ɛ), refractive index (n) and Kamlet-Taft polarity parameters (hydrogen bond donating ability (α), hydrogen bond accepting ability (β) and dipolarity/polarizability polarity scale (π*)). Acceptable agreement was found between the maximum absorption band of dyes and solvent polarity parameters especially with π*. The effect of substituents of coupler and/or diazo component on the color of dyes was investigated. The effects of acid and base on the visible absorption maxima of the dyes are also reported.

  9. Brief synthesis of 1H-indazole-3-carbaldehyde%1H-吲唑-3-甲醛的简便合成

    朱五福; 王海燕; 曹云云; 白玫; 宫平


    1H-Indazole-3-carbaldehyde was obtained by the ring opening of indole in acid condition, and the followed di-azotization with.sodium nitrite,then cyclization,with the yield 36% . This method has the advantage of low cost,simple operation, short reaction time and it is. Also suitable for industrial production.%以吲哚为原料,酸性条件下与亚硝酸钠发生重氮化反应,重氮盐环合得到标题化合物,收率36%,该方法原料易得、操作简单、反应时间短,适合工业化生产.

  10. Synthesis and characterization of polyurethane-grafted single-walled carbon nanotubes via click chemistry.

    Rana, Sravendra; Cho, Jae Whan; Kumar, Indresh


    Polyurethane (PU)-grafted carbon nanotubes were synthesized by the coupling of alkyne moiety decorated single walled carbon nanotube (SWCNT) with azide moiety containing PU using Cu(I) catalyzed Huisgen [3 + 2] cycloaddition click chemistry. The azide moiety containing poly(s-caprolactone)diol was synthesized by ring-opening polymerization and further used for PU synthesis. Alkyne-functionalizion of SWCNT was completed by the reaction of p-aminophenyl propargyl ether with SWCNT using a solvent free diazotization procedure. Nuclear magnetic resonance, Fourier transform infrared, and Raman spectroscopic measurements confirmed the functionalization of SWCNT. Scanning electron microscopy and transmission electron microscopy images showed an excellent dispersion of SWCNTs, and specially debundling of SWCNTs could be observed due to polymer assisted dispersion. A quantitative grafting was successfully achieved even at high content of functional groups.

  11. Advances in the chemistry of monocyclic amino- and nitrofuroxans

    Makhova, N. N.; Kulikov, A. S.


    The review summarizes data on the development of methods of synthesis and reactivity of monocyclic amino- and nitrofuroxans published in the last 20-25 years. The details of the synthesis of aminofuroxans based on the Schmidt and Curtius rearrangements involving acetyl- and azidocarbonylfuroxans, respectively, are discussed. Specific features of the transformations of functional substituents in aminofuroxans are described. In consideration of the reactivity of aminofuroxans, the attention is focused on the oxidation, diazotization and the Mannich reaction. Methods of synthesis of nitrofuroxans based on the oxidation of nitroglyoximes and the nitrosation of unsaturated compounds and dipotassium salts of 2-substituted 2-hydroxyimino-1,1-dinitroethanes are covered. The reactivity of nitrofuroxans comprises the nucleophilic substitution, reduction and thermal furoxan ring opening to form nitrile oxides. The bibliography includes 111 references.

  12. Simple and sensitive spectrophotometric methods for the analysis of mesalamine in bulk and tablet dosage forms

    Bala Sekaran Chandra


    Full Text Available Three simple, sensitive, economical and reproducible spectrophotometric methods (A, B and C are described for determination of mesalamine in pure drug as well as in tablet dosage forms. Method A is based on the reduction of tungstate and/or molybdate in Folin Ciocalteu's reagent; method B describes the reaction between the diazotized drug and α-naphthol and method C is based on the reaction of the drug with vanillin, in acidic medium. Under optimum conditions, mesalamine could be quantified in the concentration ranges, 1-30, 1-15 and 2-30 µg mL-1 by method A, B and C, respectively. All the methods have been applied to the determination of mesalamine in tablet dosage forms. Results of analysis are validated statistically.

  13. Study of Novel Oligomeric Azo Dyes

    Patel J. R.


    Full Text Available Diazotization of p-anisidine and coupling with 3-amino-phenol-Formaldehyde (APF resin give oligomaric azo dye TAPF, based on 3-amino-phenol-Formaldehyde (APF polymer. The TAPF was then treated with 5-chloro methyl-8-quinolinol hydrochloride in the presence of a THF in alkaline medium (pH 9-10 at room temperature for 7 hrs. The resultant oligomaric ligand designated as azo polyphenol-formaldehyde-5-chloromethyl-8-quinolinol (AAPFQ was characterized by elemental analysis, IR spectral studies, and thermogravimetry. The polymeric metal chelates of AAPFQ with Cu2+, Zn2+, Mn2+, Ni2+, Fe3+ and Co2+ metal ions were prepared and characterised by metal:ligand ratio, IR and reflectance studies, magnetic properties and thermogravimetry. The AAPFQ sample was also screened for its chelating and ion-exchanging properties. Batch equilibration method has been adopted for evolution of ion-exchange properties.

  14. Spectroscopic studies on two mono nuclear iron (III) complexes derived from a schiff base and an azodye

    Mini, S., E-mail:; Sadasivan, V., E-mail: [University College, M G Road, Palayam, Thiruvananthapuram 695 034 Kerala (India); Meena, S. S., E-mail:; Bhatt, Pramod, E-mail: [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)


    Two new mono nuclear Fe(III) complexes of an azodye (ANSN) and a Schiff base (FAHP) are reported. The azodye is prepared by coupling diazotized 1-amino-2-naphthol-4-sulphonicacid with 2-naphthol and the Schiff base is prepared by condensing 2-amino-3-hydroxy pyridine with furfural. The complexes were synthesized by the reaction of FeCl{sub 3}Ðœ‡2H{sub 2}O with respective ligands. They were characterized on the basis of elemental analysis and spectral studies like IR, NMR, Electronic and M.ssbauer. Magnetic susceptibility and Molar conductance of complexes at room temperature were studied. Based on the spectroscopic evidences and other analytical data the complexes are formulated as[Fe(ANSN)Cl(H{sub 2}O){sub 2}] and [Fe(FAHP)Cl{sub 2}(H{sub 2}O){sub 2}].

  15. Optical sensing elements for nitrogen dioxide (NO.sub.2) gas detection, a sol-gel method for making the sensing elements and fiber optic sensors incorporating nitrogen dioxide gas optical sensing elements

    Mechery, Shelly John; Singh, Jagdish P.


    A sensing element, a method of making a sensing element, and a fiber optic sensor incorporating the sensing element are described. The sensor can be used for the quantitative detection of NO.sub.2 in a mixture of gases. The sensing element can be made by incorporating a diazotizing reagent which reacts with nitrous ions to produce a diazo compound and a coupling reagent which couples with the diazo compound to produce an azo dye into a sol and allowing the sol to form an optically transparent gel. The sensing element changes color in the presence of NO.sub.2 gas. The temporal response of the absorption spectrum at various NO.sub.2 concentrations has also been recorded and analyzed. Sensors having different design configurations are described. The sensing element can detect NO.sub.2 gas at levels of parts per billion.

  16. Synthesis, spectral features and biological activity of some novel hetarylazo dyes derived from 6-amino-1,3-dimethyluracil

    Yousefi, Hessamoddin; Yahyazadeh, Asieh; Yazdanbakhsh, Mohammad Reza; Rassa, Mehdi; Moradi-e-Rufchahi, Enayat O.'llah


    A series of hetarylazoaminouracil dyes were prepared by coupling of 6-amino-1,3-dimethyluracil with eight diazotized heterocyclic amines in nitrosyl sulphuric acid. The prepared azo dyes were characterized by UV-Vis, FT-IR, 13C NMR, 1H NMR spectroscopic techniques and elemental analysis. The solvatochromism of dyes was evaluated with respect to wavelength of maximum absorption (λmax) in seven solvents with different polarities: acetic acid, methanol, water, chloroform, acetonitrile, dimethyl sulfoxide and dimethyl formamide. The effects of acid, base and concentration of the dye on the visible absorption spectra were also reported. In addition, the antimicrobial activity of the synthesized dyes was evaluated on Escherichia coli, Bacillus subtilis, Micrococcus leuteus and Pseudomonas aeruginosa.

  17. Synthesis of Calix[4]resorcinarene Based Dyes and its Application in Dyeing of Fibres

    Vinod K. Jain


    Full Text Available Four new ʻupper rimʼ azocalix[4]resorcinarene have been synthesized by coupling calix[4]resorcinarene with different diazotized aromatic compounds of sulphanilic acid, anthranilic acid, o-aminophenol and p-aminobenzoic acid. The prepared compounds were characterized based on m.p., elemental analysis, FT-IR, 1H-NMR. These dyes have been used for the dyeing of textile fibres like cotton and wool. Their fastness properties such as fastness to sunlight, water, washings, and perspiration have also been studied. The synthesized dyes have been employed for computerized colour strength determination through colour matching with known standards. Their L, A*, B* values as well as the colour difference values such as ∆L, ∆A*, ∆B*, ∆C and ∆H have also been reported.

  18. Use of polyurethane foam and 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline for determination of nitrite by diffuse reflectance spectroscopy and colorimetry.

    Apyari, V V; Dmitrienko, S G; Ostrovskaya, V M; Anaev, E K; Zolotov, Y A


    Polyurethane foam (PUF) has been suggested as a solid polymeric reagent for determination of nitrite. The determination is based on the diazotization of end toluidine groups of PUF with nitrite in acidic medium followed by coupling of polymeric diazonium cation with 3-hydroxy-7,8-benzo-1,2,3,4-tetrahydroquinoline. The intensely colored polymeric azodye formed in this reaction can be used as a convenient analytic form for the determination of nitrite by diffuse reflectance spectroscopy (c (min) = 0.7 ng mL(-1)). The possibility of using a desktop scanner, digital camera, and computer data processing for the numerical evaluation of the color intensity of the polymeric azodye has been investigated. A scanner and digital camera can be used for determination of nitrite with the same sensitivity and reproducibility as with diffuse reflectance spectroscopy. The approach developed was applied for determination of nitrite in river water and human exhaled breath condensate.

  19. Synthesis and Biological Evaluation of Novel 5,7-Dichloro-1,3-benzoxazole Derivatives

    N. D. Jayanna


    Full Text Available A new class of 5,7-dichloro-1,3-benzoxazole derivatives 4–11 were synthesized by fusing 5,7-dichloro-2-hydrazino-1,3-benzoxazole 3 nucleus with aliphatic acids, active methylene compounds, and with selected esters to form heterocyclic ring systems like 1,2,4-triazoles, pyrazoles, and triazine moieties. The compound 3 on diazotization reaction affords the tetrazole compound. The synthesized compounds were characterized by 1H NMR, IR, Mass, and 13C NMR spectral data and screened for cytotoxic, antimicrobial, antioxidant, and antilipase activities. The compounds 4, 5, and 8 have shown significant antimicrobial activities, whereas compounds 6 and 8 have been emerged as leading cytotoxic agents. The compounds 9, 10, and 11 were found to be strong enzyme inhibitors.

  20. Novel 2-phenyl-3-{4’-[N-(4”-aminophenylcarbamoyl]-phenyl}-quinazoline-4(3Hone-6-sulphonic acidbased mono azo reactive dyes



    Full Text Available A series of new heterocyclic mono azo reactive dyes 7a–m were prepared by diazotization of 2-phenyl-3-{4’-[N-(4”-aminophenylcarbamoyl]-phenyl}-quinazoline-4(3H-one-6-sulphonic acid (3 and coupling with various cyanurated coupling components 6a–m and their dyeing performance on silk, wool and cotton fibres was assessed. These dyes were found to give a variety of colour shades with very good depth and levelness on the fibres. All the compounds were identified by conventional method (IR and 1H-NMR and elemental analyses. The percentage dye bath exhaustion on different fibres was reasonably good and acceptable. The dyed fibre showed moderate to very good fastness to light, washing and rubbing.

  1. Studies on Properties of p—Nitrophenylazo Calix[4]arene Derivatives

    金传明; 归敏芝; 陆国元; 郭勋; 张宏; 游效曾


    The p-nitrophenylazo calix[4] arene derivatives la-ld with nonlinear optical(NLO)properties were prepared by the diazo-coupling reaction of calix[4]arene with p-nitrophenyl diazonium.The diazotization reaction of p-nltroaniline was caried out with isoamyl nitrite as a source of nitrous acid in EtONa/EtOH under refluxing conditon.X-Ray crystallographic analysis and 1H NMR sptectra reveal that they exist as cone conformation in crystal state or in soution.HRS measurements at 1064 nm in THF indicate that p-nitrophenylazo calix[4]arenes have higher hyperpolarizability βz values than the corresponding reference compound 4-(4-nitrophenylazo)-2,6-dimethyl-phenol,without red shift of the charge transfer band.The tetrakis p-nitropheylazo calix[4]arene(2)with longer alkyl chains can form monolayer aht the air/water interface.

  2. Mesomeric Effects of Graphene Modified with Diazonium Salts: Substituent Type and Position Influence its Properties.

    Bouša, Daniel; Jankovský, Ondřej; Sedmidubský, David; Luxa, Jan; Šturala, Jiří; Pumera, Martin; Sofer, Zdeněk


    In the last decade, graphene and graphene derivatives have become some of the most intensively studied materials. Tuning of the electronic and electrochemical properties of graphene is of paramount importance. In this study, six diazonium-modified graphenes containing different functional groups according to the diazonium salt precursor were investigated. These diazonium moieties have a strong mesomeric (resonance) effect and act as either electron-donating or -withdrawing species. Different graphene precursors, such as thermally and chemically reduced graphenes were studied. All the products were characterized in detail by elemental combustion analysis, FTIR spectroscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. Resistivity and zeta potential measurements were consistent with theoretical (DFT) calculations. The results show that chemical modification of graphene by diazotation strongly influences its properties, creating a huge application potential in microelectronics, energy storage and conversion devices, and electrocatalysis.

  3. The isolation of plasma membrane from protoplasts of soybean suspension cultures.

    Galbraith, D W; Northcote, D H


    A procedure for the isolation of plasma membranes from protoplasts of suspension-cultured soybean is described. Protoplasts were prepared by enzymic digestion of the cell wall and the plasma membrane was labelled with radioactive diazotized sulphanilic acid. The membrane systems from broken protoplasts were separated by continuous isopycnic sucrose gradient centrifugation. Radioactivity was localized in a band possessing a buoyant density of 1-14 g ml-1. The activities of NADPH- and NADH-cytochrome c reductase, fumarase, Mg2+-ATPase, IDPase and acid phosphodiesterase in the various regions of the density gradient were determined. A plasma membrane fraction was selected which was relatively uncontaminated with membranes derived from endoplasmic reticulum, tonoplasts and mitochondria. The results indicated that Mg2+-ATPase and possibly acid phosphodiesterase were associated with the plasma membrane.

  4. Synthesis and anti-depressant evaluation of novel pyrazolone derivatives

    Vijay Kumar Merugumolu


    Full Text Available Diazotization of substituted anilines with NaNO2 and concentrated hydrochloric acid at 0ºC gave the diazonium chlorides. Coupling of substituted aryl diazonium chlorides with ethyl acetoacetate in methanol gave ethyl-2-aryl-hydrazono-3-oxobutyrates (2a-h. Reaction of (2a-h with naphthoic carbohydrazide (3 gave the title compounds pyrazolone derivatives (4a-h. The newly synthesized compounds were screened for their in vivo anti-depressant activity by tail suspension test and forced swimming test. Some of the tested compounds 4f, 4g showed very good activity when compared to the standard drug imipramine. The newly synthesized compounds were characterized by physical parameters and the structures were elucidated by spectral data.

  5. Optimization of biobleaching of paper pulp in an expanded bed bioreactor with immobilized alkali stable xylanase by using response surface methodology.

    Senthilkumar, Sundar Rajan; Dempsey, Michael; Krishnan, Chandraraj; Gunasekaran, Paramasamy


    Purified alkali stable xylanase from Aspergillus fischeri was immobilized on polystyrene beads using diazotization method. An expanded bed bioreactor was developed with these immobilized beads to biobleach the paper pulp in continuous mode. Response surface methodology was applied to optimize the biobleaching conditions. Temperature (degrees C), flow rate of pulp (ml/min) and concentration of the pulp (%) were selected as variables in this study. Optimal conditions for biobleaching process were reaction temperature 60 degrees C, flow rate of 2 ml/min and 5% (w/v) of pulp. The kappa number reduced from 66 in the unbleached pulp to 20 (reduction of 87%). This system proves to be a better option for the conventional chlorine based pulp bleaching.

  6. Synthesis of azo pyridone dyes

    Mijin Dušan Ž.


    Full Text Available Over 50% of all colorants which are used nowdays are azo dyes and pigments, and among them arylazo pyridone dyes (and pigments have became of interest in last several decades due to the high molar extinction coefficient, and the medium to high light and wet fastness properties. They find application generally as disperse dyes. The importance of disperse dyes increased in the 1970s and 1980s due to the use of polyester and nylon as the main synthetic fibers. Also, disperse dyes were used rapidly since 1970 in inks for the heat-transfer printing of polyester. The main synthetic route for the preparation of azo dyes is coupling reaction between an aromatic diazo compound and a coupling component. Of all dyes manufactured, about 60% are produced by this reaction. Arylazo pyridone dyes can be prepared from pyridone moiety as a coupling component, where substituent can be on nitrogen, and diazonim salts which can be derived from different substituted anilines or other heterocyclic derivatives. In addition, arylazo dyes containing pyridone ring can be prepared from arylazo diketones or arylazo ketoesters (obtained by coupling β-diketones or β-ketoesters with diazonim salts by condensation with cyanoacetamide. Disazo dyes can be prepared by tetrazotizing a dianiline and coupling it with a pyridone or by diazotizing aniline and coupling it with a dipyridone. Trisazo dyes can be also prepared by diazotizing of aniline and coupling it with a tripyridone or by hexazotizing a trianiline and coupling it with a pyridone. The main goal of this paper is to give a brief review on the synthesis of arylazo pyridone dyes due to the lack of such reviews. In addition, some properties of arylazo pyridone dyes as light fastness and azo-hydrazon tautomerism are disccused.

  7. Synthesis of Ultraviolet Absorber UV-1130%紫外线吸收剂UV-1130的合成研究

    安平; 李阳; 陈立功


    以邻硝基苯胺、3-(3-叔丁基-4-羟基-苯基)-丙酸甲酯、PEG-300等为主要原料,经Michael加成、去烷基、重氮化、偶合、还原、酯化、酯交换等多步反应合成了UV-1130,目标产物总收率为70.7%(以邻硝基苯胺计)。经两步法合成了中间体3-(3-叔丁基-4-羟基-苯基)-丙酸甲酯,并且筛选出对甲苯磺酸作为相应的去烷基催化剂;确定了稀盐酸为重氮化反应的无机酸;还原反应中n(中间体3)∶n(保险粉)∶n(氢氧化钠)=1∶6∶10;酯交换反应催化剂为对甲苯磺酸。%A ultraviolet absorber, UV-1130, is prepared with o-nitroaniline, 3-(3-tert-butyl-4-hydroxy- phenyl)-propionic acid methyl ester and PEG-300 as main materials, and via Michael addition, dealkylation,diazotization, coupling, reduction, esterification and transesterification, the yield of product can be attained 70.7% based on o-nitroaniline. Intermediate 3-(3-tert-Butyl-4-hydroxy-phenyl)-propionic acid methyl ester is prepared by 2 steps, and screened out the corresponding dealkylation catalyst; the inorganic acid of diazotization is hydrochloric acid; in reduction n(intermediate 3):n(sodium hydrosulfite):n(sodium hydroxide)=1:6:10; the catalyst of transesterification is p-toluene sulfonic acid.

  8. Synthesis and structural identification of Pirfenidone%吡非尼酮的合成及结构确证



    Objective To synthesize Pirfenidone, a novel antifibrotic drug. Methods Pirfenidone was synthesized from 2-amino-5-methylpyridin,via diazotization,hydrolysis,N-phenylation. Results The structure of Pirfenidone was confirmed by ESI-MS,UV,IR, NMR,MS,DSC and TGA. The total yield was 49. 0% and the purity of Pirfenidone ≥99. 9%. Conclusions The method is a better process with simple procedure,good yield and high purity.%目的:合成抗纤维化药物吡非尼酮。方法以2-氨基-5-甲基吡啶为原料,经重氮化水解为5-甲基-2(1H)-吡啶酮,再经N-芳基化反应得到吡非尼酮。结果合成的吡非尼酮经高分辨质谱、紫外吸收光谱、红外吸收光谱、核磁共振谱、质谱和热分析确证结构,总收率为49.0%,纯度≥99.9%。结论该合成工艺操作简便,收率高,纯度高,是合成吡非尼酮的较好方法。

  9. Synthesis and characterization of covalently bound benzocaine graphite oxide derivative

    Kabbani, Ahmad; Kabbani, Mohamad; Safadi, Khadija


    Graphite oxide (GO) derived materials include chemically functionalize or reduced graphene oxide (exfoliated from GO) sheets, assembled paper-like forms , and graphene-based composites GO consists of intact graphitic regions interspersed with sp3-hybridized carbons containing hydroxyl and epoxide functional groups on the top and bottom surfaces of each sheet and sp2-hybridized carbons containing carboxyl and carbonyl groups mostly at the sheet edges. Hence, GO is hydrophilic and readily disperses in water to form stable colloidal suspensions Due to the attached oxygen functional groups, GO was used to prepare different derivatives which result in some physical and chemical properties that are dramatically different from their bulk counterparts .The present work discusses the covalent cross linking of graphite oxide to benzocaine or ethyl ester of para-aminobenzoic acid,structure I,used in many over-the-counter ointment drug.Synthesis is done via diazotization of the amino group.The product is characterized via IR,Raman, X-ray photoelectron spectroscopy as well as electron microscopy.

  10. Determination of Sudan I and a newly synthesized Sudan III positional isomer in the color additive D&C Red No. 17 using high-performance liquid chromatography.

    Weisz, Adrian; James, India C; Tae, Christian J; Ridge, Clark D; Ito, Yoichiro


    Specifications in the Code of Federal Regulations for the color additive D&C Red No. 17 (Colour Index 26100) limit the levels of two subsidiary colors, 1-(phenylazo)-2-naphthol (Sudan I) and 1-[[2-(phenylazo)phenyl]azo]-2-naphthalenol (Sudan III o-isomer), to 3% and 2%, respectively. The present work reports the development of a high-performance liquid chromatography (HPLC) method for the quantitative determination of these subsidiary colors. Since Sudan III o-isomer needed to be synthesized for use as a reference material, a two-step procedure was devised: (i) preparative-scale synthesis of the intermediate 2-aminoazobenzene (2AAB) and its purification by counter-current chromatography and (ii) diazotization of 2AAB and coupling with 2-naphthol. Characterization of the newly synthesized Sudan III o-isomer is also reported. Sudan I and Sudan III o-isomer were quantified by using five-point calibration curves with data points ranging from 0.108 to 3.240% and 0.077 to 2.227% by weight, respectively. The HPLC method is rapid (14 min for the total analysis cycle) and simple to implement. It was applied to the analysis of test portions from 25 batches of D&C Red No. 17 submitted to the U.S. Food and Drug Administration (USFDA) for certification, and it has recently been implemented by USFDA for routine batch certification of that color additive.

  11. Study on the Synthesis of Trifloxystrobin%肟菌酯合成新工艺

    柴兵; 闻冲; 陈晓东; 李宗成


    [目的]为避免使用剧毒品氰化钠,研究了一种有效制备肟菌酯的新方法.[方法]以邻甲基苯胺为原料,经过重氮化反应、甲基化反应、溴代反应,最后与间三氟甲基苯乙酮肟缩合得到目标产物肟菌酯.[结果]产品的含量大于97%(HPLC-外标法),总产率达31%.[结论]该法避免使用氰化钠,各步反应收率也较好,有进一步研究的价值.%[Aims] In order to avoid using high toxic reagent-sodium cyanide, a new efficient method was reported for preparing trifloxystrobin. [Methods] 2-Methyl aniline was used as starting material, followed by diazotization, methylation, bromination and condensation with 3'-(trifluoromethyl) acetophenone oxime, to get the target compound-trifloxystrobin. [Results] The purity of the product was over 97% (HPLC-External Standard Method), the overall yield was 31%. [Conclusions] This reported route can avoid the use of sodium cyanide with good yield of each step, which was worthy for further research.

  12. Synthesis and pharmacological studies of aminoxy containing 2,4,6-trisubstituted-s-triazine derivatives

    Jain Shilpi


    Full Text Available Arylamines on diazotization and further treatment with dicyandiamide yielded aryldicyandiamide (1a-d, which on addition with aminoxy compound (2 gave corresponding biguanides (3a-d. Cycloaddition of biguanide with ethylchloroacetate furnished 2,4,6-trisubstituted-s-triazines (4a-d. Subsequent treatment of these compounds with N-hydroxyphthalimide or N-hydroxysuccinimide in presence of triethylamine gave final compounds (5a-h. IR, 1 H NMR and mass spectra were used to confirm their structure. Compounds (5a-h were screened for antibacterial ( Escherichia coli, Proteus vulgaris, Klebsiella pneumoniae, Pseudomonas aureus and Staphylococcus aureus and antifungal ( Candida albicans and Aspergillus fumigatus activities. Antibacterial activity revealed that compounds 5a, 5b, 5c, 5g showed comparable activity against bacteria P. vulgaris, P. aureus, where rest of the compounds showed weak activity against all the pathogenic bacteria. The fungicidal data indicated that compound 5d possess high level activity and rest of the compounds showed comparable to the standard.

  13. A novel fiber optic spectrophotometric determination of nitrite using Safranin O and cloud point extraction.

    Filik, Hayati; Giray, Derya; Ceylan, Burak; Apak, Reşat


    A novel fiber optic spectrophotometric method for nitrite determination in different samples is suggested, based on the reaction of nitrite with Safranin O in acidic medium to form a diazo-safranin, which is subsequently coupled with pyrogallol in alkaline medium to form a highly stable, red azo dye, followed by cloud point extraction (CPE) using a mixed micelle of a nonionic surfactant, Triton X-114, with an anionic surfactant, sodium dodecyl sulphate (SDS). The reaction and extraction conditions (e.g., acidity for diazotization and alkalinity for pyrogallol coupling, and other reagent concentrations, time, and tolerance to other ions) were optimized. Linearity was obeyed in a concentration range up to 230 μg L(-1), and the detection limit of the method is 0.5 μg L(-1) of nitrite ion. The molar absorptivity for nitrite of the Safranin-diazonium salt (ɛ(610 nm) =4 × 10(3) L mol(-1)cm(-1)) existing in literature was greatly enhanced by pyrogallol coupling and CPE enrichment (ɛ(592 nm)=1.39 × 10(5) L mol(-1)cm(-1)). The method was applied to the determination of nitrite in tap water, lake water and milk samples with an optimal preconcentration factor of 20.

  14. Synthesis, structural elucidation, solvatochromism and spectroscopic properties of some azo dyes derived from 6-chloro-4-hydroxyquinoline-2(1H)-one

    Rufchahi, E. O. Moradi; Gilani, A. Ghanadzadeh; Taghvaei, V.; Karimi, R.; Ramezanzade, N.


    Malondianilide (I) derived from p-chloroaniline was cyclized to 6-chloro-4-hydroxyquinoline-2(1H)-one (II) in moderately good yield using polyphosphoric acid as catalyst. This compound was then coupled with some diazotized aromatic amines to give the corresponding azo disperse dyes 1-12. A systematic study of the effect of solvent, acid, base and pH upon the electronic absorption spectra of the dyes 1-12 was carried out. In DMSO, DMF, CH3CN, CHCl3, EtOH and acidic media (CH3COOH, acidified EtOH) these dyes that theoretically may be involved in azo-hydrazone tautomerism have been detected only as hydrazone tautomers T1 and T2. The acidic dissociation constants of the dyes were measured in 80 vol% ethanol-water solution at room temperature and ionic strength of 0.1. The results were correlated by the Hammett-type equation using the substituent constants σx.

  15. Ultrasound-assisted dispersive liquid-liquid microextraction of tetracycline drugs from egg supplements before flow injection analysis coupled to a liquid waveguide capillary cell.

    Rodríguez, Michael Pérez; Pezza, Helena Redigolo; Pezza, Leonardo


    A simple, rapid, and efficient ultrasound-assisted dispersive liquid-liquid microextraction (US-DLLME) method was developed for extraction of tetracycline residues from egg supplement samples, with subsequent determination by flow injection analysis (FIA) coupled to a liquid waveguide capillary cell (LWCC) and a controlled temperature heating bath. Tetracyclines react with diazotized p-sulfanilic acid, in a slightly alkaline medium, to form azo compounds that can be measured at 435 nm. The reaction sensitivity improved substantially (5.12-fold) using an in-line heating temperature of 45 °C. Multivariate methodology was used to optimize the factors affecting the extraction efficiency, considering the volumes of extraction and disperser solvents, sonication time, extraction time, and centrifugation time. Good linearity in the range 30-600 μg L(-1) was obtained for all the tetracyclines, with regression coefficients (r) higher than 0.9974. The limits of detection ranged from 6.4 to 11.1 μg L(-1), and the recoveries were in the range 85.7-96.4 %, with relative standard deviation lower than 9.8 %. Analyte recovery was improved by approximately 6 % when the microextraction was assisted by ultrasound. The results obtained with the proposed US-DLLME-FIA method were confirmed by a reference HPLC method and showed that the egg supplement samples analyzed were suitable for human consumption.

  16. Synthesis, spectra and electrochemistry of dinitro-bis-{2-(phenylazo)pyrimidine} ruthenium(II). Nitro-nitroso derivatives and reactivity of the electrophilic nitrosyl centre

    Prithwiraj Byabartta


    Silver-assisted aquation of blue cis-trans-cis-RuCl2(Raapm)2 (1a-1e) leads to the synthesis of solvento species, blue-violet cis-trans-cis-[Ru(OH2)2(Raapm)2](ClO4)2 [Raapm = -R-C6H4-N=N-C4H3-NN, (2a-2e), abbreviated as N,N'-chelator, where N(pyrimidine) and N(azo) represent N and N' respectively; R = H (a), -Me (b), -Cl (c), -Me (d), -Cl (e) that react with NO2 in warm EtOH to give violet dinitro complexes of the type, Ru(NO2)2(Raapm)2 (3a-3e). The nitrite complexes are useful synthons of electrophilic nitrosyls, and on triturating the dinitro compounds with conc. HClO4, nitro-nitrosyl derivatives are isolated. The solution structure and stereoretentive transformation in each step have been established from 1H NMR results. The compounds are redox active and display one metal-centred oxidation and successive ligand-based reductions. The (NO) >1900 cm-1 strongly suggests the presence of linear Ru-N-O bonding. The electrophilic behaviour of metal-bound nitrosyl has been proved in one case by reacting with a bicyclic ketone, camphor, containing an active methylene group and an arylhydrazone with an active methine group. Diazotization of primary aromatic amines with strongly electrophilic mononitrosyl complexes in acetonotrile and dichloromethane solutions has been thoroughly studied.

  17. Synthesis and antimicrobial evaluation of some novel thiazole, pyridone, pyrazole, chromene, hydrazone derivatives bearing a biologically active sulfonamide moiety.

    Darwish, Elham S; Fattah, Azza M Abdel; Attaby, Fawzy A; Al-Shayea, Oqba N


    This study aimed for the synthesis of new heterocyclic compounds incorporating sulfamoyl moiety suitable for use as antimicrobial agents via a versatile, readily accessible N-[4-(aminosulfonyl)phenyl]-2-cyanoacetamide (3). The 2-pyridone derivatives were obtained via reaction of cyanoacetamide with acetylacetone or arylidenes malononitrile. Cycloaddition reaction of cyanoacetamide with salicyaldehyde furnished chromene derivatives. Diazotization of 3 with the desired diazonium chloride gave the hydrazone derivatives 13a-e. Also, the reactivity of the hydrazone towards hydrazine hydrate to give Pyrazole derivatives was studied. In addition, treatment of 3 with elemental sulfur and phenyl isothiocyanate or malononitrile furnished thiazole and thiophene derivatives respectively. Reaction of 3 with phenyl isothiocyanate and KOH in DMF afforded the intermediate salt 17 which reacted in situ with 3-(2-bromoacetyl)-2H-chromen-2-one and methyl iodide afforded the thiazole and ketene N,S-acetal derivatives respectively. Finally, reaction of 3 with carbon disulfide and 1,3-dibromopropane afforded the N-[4-(aminosulfonyl) phenyl]-2-cyano-2-(1,3-dithian-2-ylidene)acetamide product 22. All newly synthesized compounds were elucidated by considering the data of both elemental and spectral analysis. The compounds were evaluated for both their in vitro antibacterial and antifungal activities and showed promising results.

  18. Validated spectophotometric methods for the assay of cinitapride hydrogen tartrate in pharmaceuticals

    Satyanarayana K.V.V.


    Full Text Available Three simple, selective and rapid spectrophotometric methods have been established for the determination of cinitapride hydrogen tartrate (CHT in pharmaceutical tablets. The proposed methods are based on the diazotization of CHT with sodium nitrite and hydrochloric acid, followed by coupling with resorcinol, 1-benzoylacetone and 8-hydroxyquinoline in alkaline medium for methods A, B and C respectively. The formed azo dyes are measured at 442, 465 and 552 nm for methods A, B and C respectively. The parameters that affect the reaction were carefully optimized. Under optimum conditions, Beer’s law is obeyed over the ranges 2.0-32.0, 1.0-24.0 and 1.0-20.0 μg. mL-1 for methods A, B, and C, respectively. The calculated molar absorptivity values are 1.2853 x104, 1.9624 x104 and 3.92 x104 for methods A, B and C, respectively. The results of the proposed procedures were validated statistically according to ICH guidelines. The proposed methods were successfully applied to the determination of CHT in Cintapro tablets without interference from common excipients encountered.

  19. Sterically encumbered 2,6-dibenzhydryl-4-methylphenyl derived ligand systems: synthesis and structures



    Bulky 2,6-dibenzhydryl-4-methylaniline, I undergoes diazotization upon treatment with H₂SO₄/NaNO₂, which upon further reaction with KI affords 1-iodo-2,6-dibenzhydryl-4-methylbenzene, 1. Reaction of I with one equivalent of acetylacetone in ethanol under reflux condition affords mono-Schiff base, 4-(2,6-dibenzhydryl-4-methylphenylamino)pent-3-ene-2-one, 2. Similarly, I reacts with half equivalent of 2-hydroxy-5-methylisophthalaldehyde or one-third equivalent of 2,4,6-trihydroxybenzene-1,3,5- tricarbaldehyde in ethanol under reflux condition to afford bis-Schiff base, 2,6-bis(((2,6-dibenzhydryl-4-methylphenyl)imino)methyl)-4-methylphenol, 3 and tris-Schiff base, 2,4,6-tris(((2,6-dibenzhydryl-4- methylphenyl)amino)methylene)cyclohexane-1,3,5-trione, 4, respectively. Further, I upon reaction with triflic acid affords (2,6-dibenzhydryl-4-methylphenyl)ammonium triflate, 5 whereas upon reaction with HBr and HCl affords co-crystals I·HBr, 6 and I·HCl, 7. All the new products were isolated in moderate to good yield and characterized by spectroscopic (IR,ESI-mass,NMR,UV-Vis) and microanalytical (CHN) techniques, in additionto a single crystal X-ray diffraction study for 1, 2 and 4-7.

  20. Iodine-123 labeled derivatives of methylphenidate: potential SPECT radiopharmaceuticals for brain dopamine transporters

    Pan, D.; Gatley, S.J.; Chen, R.; Ding, Y.-S. [Brookhaven National Lab., Upton, NY (United States)


    Since dl-threo-[{sup 11}C]methylphenidate (Ritalin) and especially the more active enantiomer, d-threo-[{sup 11}C]methylphenidate, have favorable properties for PET studies, we prepared two radioiodinated analogs of methylphenidate, p-[{sup 123}I]iodomethylphenidate and m-[{sup 123}I]iodo-p-hydroxymethylphenidate with a view to evaluating them as potential SPECT tracers. To prepare p-[{sup 123}I]iodomethylphenidate, the p-tributyltin derivative was prepared from the previously reported p-bromomethylphenidate and reacted under acidic conditions with I-123 iodide plus chloramine-T at room temperature for 90 seconds. The predomimant radioactive product was obtained in 85% radiochemical yield and > 10 Ci/{mu}mol specific radioactivity after HPLC purification. It had the same HPLC retention time as a spectroscopically characterized non-radioactive p-iodomethylphenidate standard prepared via nitration of methylphenidate and diazotization, after protection of the secondary amino group by benzoylation. A second radioiodinated methylphenidate derivative, m-[{sup 123}I]iodop-hydroxymethylphenidate was prepared in 80% radiochemical yield by direct iodination of the known p-hydroxymethylphenidate. In this case the non-radioactive standard was prepared by iodination of p-hydroxyritalinic acid using I{sub 2} and iodic acid, followed by esterification. (author).

  1. Liquid chromatography tandem mass spectrometry analysis of photodegradation of a diazo compound: a mechanistic study.

    Meetani, M A; Hisaindee, S M; Abdullah, F; Ashraf, S S; Rauf, M A


    The photolytic degradation of the diazo dye, Amido Black, using UV/H(2)O(2) has been carried out experimentally and parameters for most efficient dye degradation have been determined. The degradation of the dye was followed by UV-Vis spectroscopy, HPLC, and LC-MS and is proposed to be initiated by ()OH radicals formed by the photolysis of H(2)O(2). A detailed study was also carried out using LC-MS and LC-MS/MS to determine the degradation pathway of the dye as well as to identify some of the intermediate products formed. Our results suggest that Amido Black degradation occurs preferentially by ()OH radical attack at the more electron rich diazo functionality of the molecule. Furthermore, evidence is presented that subsequent steps in this diazo dye degradation pathway include radical denitration, radical desulfonation and radical diazotization. This report is one of the very few studies that have proposed possible mechanistic pathways for the degradation pathways of a diazo compound.

  2. Effect of chemical functionalization on the electrochemical properties of conducting polymers. Modification of polyaniline by diazonium ion coupling and subsequent reductive degradation

    Acevedo, Diego F.; Rivarola, Claudia R.; Miras, Maria C. [Departamento de Quimica, Universidad Nacional de Rio Cuarto, Ruta Nacional 8, Km 601, X5804ZAB, Rio Cuarto, Cordoba (Argentina); Barbero, Cesar A., E-mail: [Departamento de Quimica, Universidad Nacional de Rio Cuarto, Ruta Nacional 8, Km 601, X5804ZAB, Rio Cuarto, Cordoba (Argentina)


    The electrochemical properties of polyaniline (PANI) can be altered by coupling the polymer with aryldiazonium ions. The ions are synthesized by diazotization of aromatic primary amines (1-aminoanthraquinone, sulphadiazine and 4-cyanoaniline) bearing functional groups which are then linked to the polyaniline backbone. All materials produced are electroactive, suggesting that the reaction involves coupling of the diazonium ion with the aromatic rings and not nucleophilic substitution by the aminic nitrogen of PANI on the aryl cations. The electrochemical properties of the modified polymers are different to those of PANI, likely due to electronic and steric effects of the attached groups. Reductive degradation of the azo linkages, using dithionite ion, removes the attached moieties leaving primary amino groups attached to the polyaniline backbone. In that way, the effect of the attached groups on the electrochemical properties of PANI is eliminated. FTIR spectroscopy measurement of the different polymers supports the proposed mechanism. Using the method a polymer containing redox (anthraquinone) groups, which could be used for charge storage, is obtained. Additionally a material containing sulphadiazine moieties, which can be released in vivo by bacterial activity, is also produced. The molecule is a well-known sulfa drug with bacteriostatic activity. The reaction sequence seems to be of general application to modify polyanilines, by attaching functional groups, and then to produce a PANI backbone bearing primary amino groups. Evidence is presented on the kinetic control of attached group removal.

  3. Simple and sensitive method for the quantification of total bilirubin in human serum using 3-methyl-2-benzothiazolinone hydrazone hydrochloride as a chromogenic probe

    Nagaraja, Padmarajaiah; Avinash, Krishnegowda; Shivakumar, Anantharaman; Dinesh, Rangappa; Shrestha, Ashwinee Kumar


    We here describe a new spectrophotometric method for measuring total bilirubin in serum. The method is based on the cleavage of bilirubin giving formaldehyde which further reacts with diazotized 3-methyl-2-benzothiazolinone hydrazone hydrochloride giving blue colored solution with maximum absorbance at 630 nm. Sensitivity of the developed method was compared with Jendrassik-Grof assay procedure and its applicability has been tested with human serum samples. Good correlation was attained between both methods giving slope of 0.994, intercept 0.015, and R2 = 0.997. Beers law obeyed in the range of 0.068-17.2 μM with good linearity, absorbance y = 0.044 Cbil + 0.003. Relative standard deviation was 0.006872, within day precision ranged 0.3-1.2% and day-to-day precision ranged 1-6%. Recovery of the method varied from 97 to 102%. The proposed method has higher sensitivity with less interference. The obtained product was extracted and was spectrally characterized for structural confirmation with FT-IR, 1H NMR.

  4. Beta-D-glucosyl and alpha-D-galactosyl Yariv reagents: syntheses from p-nitrophenyl-D-glycosides by transfer reduction using ammonium formate.

    Basile, Dominick V; Ganjian, Iraj


    Yariv beta-D-glucosyl (4a) and Yariv alpha-d-galactosyl (4b) reagents are multivalent phenylglycosides. The beta-D-glucosyl reagent is considered diagnostic for arabinogalactan proteins (AGPs) to which it can reversibly bind, stain, and precipitate. The alpha-D-galactosyl reagent does not bind AGPs and is used as a control. In a new strategy, we accomplished the large scale synthesis of the Yariv reagents in one continuous step by a transfer reduction method and without a need for any specialized apparatus. As the starting material, p-nitrophenyl-D-glycosides (1) were reduced to p-aminophenyl-D-glycosides (2) using ammonium formate as the hydrogen donor. The excess formate was converted to formic acid and ammonia, which then were removed from the reaction by simple distillation. Without isolation, p-aminophenyl-D-glycosides were diazotized (3) and coupled to phloroglucinol to give the Yariv reagents in approximately 40% yield. AGPs are a major component of gum arabic, an emulsifying agent widely used in the food and pharmaceutical industries. Increasing interest in AGPs prompted the development of a relatively easy and inexpensive method for the synthesis of these reagents.

  5. 以芳香胺玻璃为载体的固定化的胆固醇脂酶和胆固醇氧化酶%Cholesterol Esterase and Cholesterol Oxidase Immobilized onto Arylamine Glass Beads

    VoMalik; S.Singh; 等


    Cholesterol esterase (Cease) from bovine pancreas and cholesterol oxidasc (COD) from Bravibacterium recombinant type have been innobilized individually and co-immobilized onto arylamine glass (pore diameter 55nm) through the process of diazotization. Cease and COD retained 92.65% and 85.54% of the initial activity with conjugation yields of 7.2 mg/g and 8.3mg/g support respectively when imnobilized individually on arylamine glass beads, but retained 89.58% of the initial activity with a conjugation yield of 2.9 mg/g support when co-immobilized on the same support. The effects of pH, temperature, time of incubation, substrate concentration, serum inorganic salts & metabolites, thermal stability, storage stability in cold and reusability on the immobilized enzymes were studied and compared with those of free enzymes. The analytic use of both individually immobilized and co-immobilized enzymes in discrete analysis of total and free cholesterol in serum is demonstrated.

  6. Facile heterocyclic synthesis and antimicrobial activity of polysubstituted and condensed pyrazolopyranopyrimidine and pyrazolopyranotriazine derivatives

    Hafez Hend N.


    Full Text Available Reaction of 6-amino-3-methyl-4-(substituted phenyl-1,4- dihydropyrano[2,3-c]pyrazole-5-carbonitrile (1 with triethylorthoformate followed by treatment with hydrazine hydrate, formic acid, acetic acid, phenylisocyanate, ammonium thiocyanate and formamide afforded the corresponding pyranopyrimidine derivatives 2-6. Cyclocondensation of 1 with cyclohexanone afforded pyrazolopyranoquinoline 7. One-pot process of diazotation and de-diazochlorination of 1 afforded pyrazolopyranotriazine derivative 8, which upon treatment with secondary amines afforded 9 and 10a- c. Condensation of 2 with aromatic aldehyde gave the corresponding Schiff bases 11a,b, the oxidative cyclization of the hydrazone with appropriate oxidant afforded 11-(4- fluorophenyl- 2-(4-substituted phenyl-10-methyl-8,11-dihydropyrazolo-[ 4’,3’:5,6]pyrano[3,2-e][1,2,4]triazolo[1,5-c]pyrimidines (12a,b. Structures of the synthesized compounds were confirmed by spectral data and elemental analysis. All synthesized compounds were evaluated for antibacterial and antifungal activities compared to norfloxacin and fluconazole as standard drugs. Compounds 9, 10c, 12a and 15 were found to be the most potent antibacterial agents, with activity equal to that of norfloxacin. On the other hand, compound 5 exhibited higher antifungal activity compared to fluconazole.

  7. Synthesis, spectroscopic characterization and thermal studies of some lanthanide(Ⅲ) nitrate complexes with a hydrazo derivative of 4-aminoantipyrine

    K. Mohanan; C.J. Athira; Y. Sindhu; M.S. Sujamol


    A heterocyclic ligand synthesized by the coupling of diazotized 4-aminoantipyrine with acetylacetone reacted with lanthanide(Ⅲ) nitrate to form complexes of the type [Ln(HAAP)2(NO3)3] where, Ln=La(Ⅲ), Ce(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), or Gd(Ⅲ) and HAAP=3-{[2-(N-1-pheny1-2,3-dimethylpyrazol-3-in-5-on-4-yl)]hydrazone}pent-2,3,4-trione. The ligand and metal complexes were characterized on the basis of elemental analysis, molar conductance, magnetic susceptibility measurements, UV-Visible, infrared, far infrared and proton NMR spectral data. The spectral data revealed that the ligand existed in the hydrazo form and coordinated to the metal ion without deproto-nation in a neutral tridentate manner, through carbonyl oxygen of pyrazolone ring, hydrazo nitrogen and carbonyl oxygen of the acetylace-tone moiety. The molar conductance values adequately supported their non-electrolytic nature. The ligand and the praseodymium(Ⅲ) com-plex were subjected to X-ray diffraction studies. Thermal decomposition behavior of the lanthanum(Ⅲ) complex was also examined.moiety.

  8. Multistep flow synthesis of 5-amino-2-aryl-2H-[1,2,3]-triazole-4-carbonitriles.

    Jacq, Jérôme; Pasau, Patrick


    1,2,3-Triazole has become one of the most important heterocycles in contemporary medicinal chemistry. The development of the copper-catalyzed Huisgen cycloaddition has allowed the efficient synthesis of 1-substituted 1,2,3-triazoles. However, only a few methods are available for the selective preparation of 2-substituted 1,2,3-triazole isomers. In this context, we decided to develop an efficient flow synthesis for the preparation of various 2-aryl-1,2,3-triazoles. Our strategy involves a three-step synthesis under continuous-flow conditions that starts from the diazotization of anilines and subsequent reaction with malononitrile, followed by nucleophilic addition of amines, and finally employs a catalytic copper(II) cyclization. Potential safety hazards associated with the formation of reactive diazonium species have been addressed by inline quenching. The use of flow equipment allows reliable scale up processes with precise control of the reaction conditions. Synthesis of 2-substituted 1,2,3-triazoles has been achieved in good yields with excellent selectivities, thus providing a wide range of 1,2,3-triazoles.

  9. Synthesis, cytotoxicity, antimicrobial and anti-biofilm activities of novel pyrazolo[3,4-b]pyridine and pyrimidine functionalized 1,2,3-triazole derivatives.

    Nagender, P; Malla Reddy, G; Naresh Kumar, R; Poornachandra, Y; Ganesh Kumar, C; Narsaiah, B


    A series of novel pyrazolo[3,4-b]pyridine and pyrimidine functionalized 1,2,3-triazole derivatives 8a-g and 9a-g were prepared starting from 6-trifluoromethylpyridine-2(1H)one 2 via selective O-alkylation, followed by cyclisation using hydrazine hydrate to obtain 6-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridin-3-amine 4. Compound 4 was diazotized followed by reaction with sodium azide, resulted in 3-azido-6-(trifluoromethyl)-1H-pyrazolo[3,4-b]pyridine 5. Compound 5 was further cyclized with N-/O-propargylated pyrimidine derivatives under Sharpless conditions and obtained compounds 6 and 7, respectively. Each set of compounds 6 and 7 were alkylated with different alkyl halides and obtained respective products 8 and 9. All the products were screened for cytotoxicity against four human cancer cell lines such as A549-Lung (CCL-185), MCF7-Breast (HTB-22), DU145-Prostate (HTB-81) and HeLa-Cervical (CCL-2), compounds 9d, 9e and 9f which showed promising activity have been identified. The products were also screened for antimicrobial, anti bio-film and MBC activities. Promising compounds in each case have been identified.

  10. Preparation and characterization of water-soluble carbon nanotube reinforced Nafion membranes and so-based ionic polymer metal composite actuators

    Ru, Jie; Wang, Yanjie; Chang, Longfei; Chen, Hualing; Li, Dichen


    In this paper, we developed a new kind of ionic polymer metal composite (IPMC) actuator by doping water-soluble sulfonated multi-walled carbon nanotube (sMWCNT) into Nafion matrix to overcome some major drawbacks of traditional IPMCs, such as relatively low bending deformation and carring capacity at low driving voltages. Firstly, sMWCNT was synthesized via diazotization coupling reaction, and then doped into Nafion matrix by casting method. Subsequently, the electrochemical and electromechanical properties of sMWCNT-reinforced Nafion membranes and the corresponding IPMCs were investigated. Finally, the effects of sMWCNT on the performances of IPMCs were evaluated and analyzed systematacially. The results showed that sMWCNT was homogeneously dispersed in Nafion matrix without any entangled structure or obvious agglomeration. The main factors for superior actuation performances, like water-uptake ratio, proton conductivity and elastic modulus, increased significantly. Compared to the pure Nafion IPMC and MWCNT/Nafion IPMC, much superior electrochemical and electromechanical performances were achieved in the sMWCNT/Nafion IPMC, which were attributed to the numerous insertion sites, high surface conductivity and excellent mechanical strength as well as the homogeneous dispersity of the incorporated sMWCNT. Herein, a trace amount of sMWCNT can improve the performances of IPMCs significantly for realistic applications.

  11. Increasing the Affinity Between Carbon-Coated LiFePO4/C Electrodes and Conventional Organic Electrolyte by Spontaneous Grafting of a Benzene-Trifluoromethylsulfonimide Moiety.

    Delaporte, Nicolas; Perea, Alexis; Lebègue, Estelle; Ladouceur, Sébastien; Zaghib, Karim; Bélanger, Daniel


    The grafting of benzene-trifluoromethylsulfonimide groups on LiFePO4/C was achieved by spontaneous reduction of in situ generated diazonium ions of the corresponding 4-amino-benzene-trifluoromethylsulfonimide. The diazotization of 4-amino-benzene-trifluoromethylsulfonimide was a slow process that required a high concentration of precursors to promote the spontaneous grafting reaction. Contact angle measurements showed a hydrophilic surface was produced after the reaction that is consistent with grafting of benzene-trifluoromethylsulfonimide groups. Elemental analysis data revealed a 2.1 wt % loading of grafted molecules on the LiFePO4/C powder. Chemical oxidation of the cathode material during the grafting reaction was detected by X-ray diffraction and quantified by inductively coupled plasma atomic emission spectrometry. Surface modification improves the wettability of the cathode material, and better discharge capacities were obtained for modified electrodes at high C-rate. In addition, electrochemical impedance spectroscopy showed the resistance of the modified cathode was lower than that of the bare LiFePO4/C film electrode. Moreover, the modified cathode displayed superior capacity retention after 200 cycles of charge/discharge at 1 C.

  12. Synthesis and dyeing properties of new disazo disperse dyes for polyester and nylon fabrics

    Tarulata B. Shah


    Full Text Available Diazotized aryl amines were coupled with two stenhouse salt namely, N-(5-phenylamino-penta-4-ol-2,4-diene-1-ylideneanilines hydrochloride [S1 (RH or S2 (ROH] to furnish two series of disazo disperse dyes (S1D1–10 and S2D1–10. The structure of all the dyes was established by estimating number of azo groups, elemental analysis and spectral studies (IR, 1H-NMR, UV/Visible. The structure–property relationship was discussed by using electronic absorption spectra of the dyes. These dyes were applied to polyester and nylon fabrics as disperse dyes by using temperature exhaust dyeing method. The relevant dyeing characteristics, such as dyeability on fabrics, wash-fastness and light-fastness were evaluated. Fabrics dyed with these dyes furnished generally deep and bright intense hues ranging from light yellow to orange to reddish brown. The color fastness of the dyed fabric was assessed by determining wash-fastness and light-fastness properties.

  13. Immobilization of denatured DNA to macroporous supports: II. Steric and kinetic parameters of heterogeneous hybridization reactions.

    Bünemann, H


    The accessibility of immobilized DNA has been shown to depend more crucially on the method of immobilization than on the type of support used for fixation. When sonicated denatured DNA is coupled via diazotization or via cyanogen bromide reaction to solid Sephadex G-25 and Cellex 410 or to macroporous Sephacryl S-500 and Sepharose C1-6B its accessibility varies from 100 to 24 percent. Generally the loss of accessibility is linked to a depression of the melting temperature of DNA helices formed on the support. This correlation shows a characteristic course for a particular coupling method. DNA coupled under denaturing conditions may become totally inaccessible when only 3 percent of its bases are involved in the covalent linkage. Kinetic experiments with sonicated E.coli DNA have shown that the rate constants for renaturation or hybridization reactions are very similar for DNA immobilized by different methods to solid or macroporous supports. Generally the second order rate constant for a heterogeneous reaction (between mobile and immobilized DNA) is about one order of magnitude smaller than that of the analogous homogeneous reaction (in solution).

  14. Synthesis and Antimicrobial Activity of Furochromone, Benzofuran and Furocoumarin Derivatives Bearing Sulfonyl Moiety

    Sadia A. Hessein


    Full Text Available New visnagin-9-sulfonamide derivatives 3 and 4a−c were synthesized through the reaction of visnagin-9-sulfonyl chloride 2 with amino compounds. Acetylation of compounds 4b and 4c gave the monoacetyl and diacetyl derivatives 5 and 6, respectively. Diazotization reaction of compound 4b afforded the corresponding benzotriazole derivative 8. Pyrazole and thiopyrimidine derivatives 9 and 10 were obtained via the opening of pyrone ring upon reaction of compound 3 with hydrazine hydrate and thiourea, respectively. In addition, hydrolysis of compound 3 with potassium hydroxide furnished the visnaginone derivative 11 which used as starting material for synthesize benzofuran derivatives 12−14 and bergaptene derivatives 15−17. The synthesized compounds were tested for antimicrobial activity. Furochromone derivatives 3, 4a−c, 5, 6 and 8 (visnagin-9-sulfonamide derivatives demonstrate moderate antibacterial and antifungal activities compared with the antibacterial and antifungal activites of the standard drugs. Benzofuran derivatives 11−14 (visnaginone derivatives showed the lowest antimicrobial activity among all the compounds investigated in this study. Furocoumarin derivatives 15a,b, 16 and 17 (furobenzopyransulfonamide [bergaptensulfonamides] are moderately active against all the tested strains. This work is licensed under a Creative Commons Attribution 4.0 International License.

  15. Catechol functionalized aminopropyl silica gel: synthesis, characterization and preconcentrative separation of uranium(VI) from thorium(IV)

    Metilda, P.; Mary Gladis, J.; Prasada Rao, T.P. [Regional Research Lab. (CSIR), Trivandrum (India)


    A novel solid phase extractant is prepared by chemically immobilizing catechol with diazotized aminopropyl silica gel. The resulting catechol functionalized silica gel (CASG) was characterized by FTIR, and microanalysis and was used for selective enrichment of uranium(VI) from other inorganic ions. The optimum pH range for maximum sorption of uranium(VI) and thorium(IV) was found to be in the range 3.5-6.0. The above actinides were eluted with 10 cm{sup 3} of 1.0 mol dm{sup -3} HCl and determined by using an Arsenazo III spectrophotometric procedure. The calibration graph was rectilinear over the uranium(VI) concentration in the range 2-100 {mu}g dm{sup -3} with a relative standard deviation of 2.15% (for 25 {mu}g of uranium(VI) present in 1.0 dm{sup 3} of sample). The validation of the developed preconcentration procedure was carried out by analyzing marine sediment (MESS-3, NRC, Canada) and soil (IAEA soil-7, Austria) reference materials. The developed preconcentration method enables a simple instruments like a spectrophotometer gave comparable values of uranium(VI) to that of standard inductively coupled plasma-mass spectrometric values during the analysis of real soil and sediment samples. (orig.)

  16. 4-羟基-5-乙氧基苯胺的合成%Synthesis of 5-Ethoxyl-4-hydroxylaniline

    李志华; 狄庆锋


    以苯胺为原料,经重氮化、偶合、还原得到4-羟基-5-乙氧基苯胺.合成中,通过保险粉还原偶氮化合物的方法在芳香环上引进氨基,不仅产物收率高(总收率86%,较文献提高了26.3%),而且还原产物容易分离,粗品纯度可达95%.本合成路线中间体均不经提纯,且氨基的引入中避免了贵金属的加氢还原,是一条适合大规模生产4-羟基-5-乙氧基苯胺的新合成工艺路线.%5-Ethoxyl-4-hydroxylaniline was prepared through diazotization of aniline,coupling with o-ethoxyl phenol and followed by the reduction of azo compounds with sodium hyposulfite in overall yield of 86% and 95% HPLC purity.The yield was increased by 26.3% compared with the literature.This synthesis avoids noble metal catalized hydrogenation and is suitable for mass production without purification of the intermediates.

  17. Halo- and azidodediazoniation of arenediazonium tetrafluoroborates with trimethylsilyl halides and trimethylsilyl azide and sandmeyer-type bromodediazoniation with Cu(I)Br in [BMIM][PF6] ionic liquid.

    Hubbard, Abigail; Okazaki, Takao; Laali, Kenneth K


    Reaction of [ArN(2)][BF(4)] salts immobilized in [BMIM][PF(6)] ionic liquid (IL) with TMSX (X = I, Br) and TMSN(3) represents an efficient method for the preparation of iodo-, bromo-, and azido-derivatives via dediazoniation. The reactions can also be effected starting with ArNH(2) by in situ diazotization with [NO][BF(4)] followed by reaction with TMSX or TMSN(3). Depending on the substituents on the benzenediazonium cation, competing fluorodediazoniation (ArF formation) and hydrodediazoniation (ArH formation) were observed. Dediazoniation with TMSN(3) and with TMSI generally gave the highest chemoselectivity toward ArN(3) and ArI formation. The IL was recycled and reused up to 5 times with no appreciable decrease in the conversions. Multinuclear NMR monitoring of the interaction of [ArN(2)][BF(4)]/TMSX, [BMIM][PF6]/TMSX, and [BMIM][PF(6)]/TMSX/[ArN(2)][BF(4)] indicated that TMSF is formed primarily via [ArN(2)][BF(4)]/TMSX, generating [ArN(2)][X] in situ, which gives ArX on dediazoniation. Competing formation of ArF in Sandmeyer-type bromodediazoniation of [ArN(2)][BF(4)] with Cu(I)Br immobilized in the IL points to significant involvement of heterolytic dediazoniation.

  18. Spectrophotometric determination of nitrite in soil and water using cefixime and central composite design

    Shariati-Rad, Masoud; Irandoust, Mohsen; Mohammadi, Shabnam


    The present paper seeks to develop a simple method for the spectrophotometric determination of nitrite in soil and water samples and also measure optimum reaction conditions along with other analytical parameters. The method is based on the diazotization-coupling reaction of nitrite with cefixime and 1-naphthylamine in an acidic solution (Griess reaction). The final product that is an azo dye has an orange color with maximum absorption at 360 nm which Beer's Law is obeyed over the concentration range 0.02-15.00 mg L-1 of nitrite. Optimal conditions of the variables affecting the reaction were obtained by central composite design (CCD). A detection limit of 4.3 × 10-3 mg L-1 was obtained for determination of nitrite by the proposed method. The proposed method was successfully applied to determine nitrite in soil and water samples. The molar absorptivity of the product of the reaction and RSD in determination of nitrite in real samples are 4.1 × 103 (L mol-1 cm-1) and lower than 10%, respectively.

  19. A simple and sensitive spectrophotometric method for the determination of trace amounts of nitrite in environmental and biological samples using 4-amino-5-hydroxynaphthalene-2,7-disulphonic acid monosodium salt

    Nagaraja, Padmarajaiah; Al-Tayar, Naef Ghllab S.; Shivakumar, Anantharaman; Shrestha, Ashwine K.; Gowda, Avinash K.


    A very simple, sensitive, fairly selective and rapid spectrophotometric method for the determination of trace amounts of nitrite has been described. This method is based on the diazotized intramolecular coupling of electrophilic diazonium cation with the phenolic group of 4-amino-5-hydroxynaphthalene-2,7-disulphonic acid monosodium salt (AHNDMS) in a phosphate buffer solution of pH 7.5. The cyclic product has a purple color with maximum absorbance at 560 nm and is stable for 6 h. Optimum reaction conditions and other important analytical parameters for the maximum color development were established. Beer's law was found to obey for nitrite in the concentration range of 0.1-1.6 μg ml -1 with molar absorptivity of 2.6 × 10 4 l mol -1 cm -1 and Sandell's sensitivity of 0.0075 μg ml -1. The effect of interfering ions on the determination is described. The recommended method was applied for the determination of nitrite in different water, soil and human saliva samples. The performance of the recommended method was evaluated in terms of Student's t-test and variance ratio F-test, which indicated the significance of proposed method over the reference method.

  20. 三氟甲基水杨酸及其中间体的合成方法%Methods for Synthesis of Trifluoromethylsalicylic Acid and its Intermediate

    钟远辉; 陈友宝; 钟光祥


    4-三氟甲基水杨酸、间三氟甲基苯酚是农药、医药等的关键原料和中间体。文章综述了4-三氟甲基水杨酸的合成方法;重点介绍了其合成原料-间三氟甲基苯酚的合成方法,包括重氮化水解法、羟基化法、三氟甲基化法、催化氢化法、过氧化氢氧化法等。%4-(Trifluoromethyl)salicylic acid and m-trifluoromethylphenol is critical intermediate and raw material in the field of pesticide, medicine and others. This article summarizes the methods for synthesis of 4-(trifluoromethyl)salicylic acid, also mainly introduces the synthetic methods of m-Trifluoromethylphenol, the synthetic material of 4-(trifluoromethyl)salicylic acid, including the diazotization and hydrolysis of trifluoromethylaniline, the hydroxylation, the trifluoromethylate, the catalytic hydrogenation, the oxidation of bezotrifluoride with hydrogen peroxide, and so on.

  1. Synthesis and spectroscopic characterization of some lanthanide(III nitrate complexes of ethyl 2-[2-(1-acetyl-2-oxopropylazo]-4,5-dimethyl-3-thiophenecarboxyate



    Full Text Available Ethyl 2-[2-(1-acetyl-2-oxopropylazo]-4,5-dimethyl-3-thiophenecarboxyate was synthesized by coupling diazotized ethyl 2-amino-4,5-dimethylthiophene-3-carboxylate with acetylacetone. Based on various spectral studies and elemental analysis, an intramolecularly hydrogen-bonded azo-enol structural form was assigned for the ligand. This ligand is versatile in forming a series of lanthanide(III complexes, viz., lanthanum(III, cerium(III, praseodymium(III, neodymium(III, samarium(III and gadolinium(III, which were characterized through various spectral studies, elemental analysis, magnetic susceptibility measurements, molar conductance and thermal analysis. The spectral data revealed that the ligand acted as a neutral tridentate, coordinating to the metal ion through one of the azo nitrogen atoms, the ester carbonyl and the enolic oxygen of the acetylacetone moiety, without deprotonation. Molar conductance values adequately supported their non-electrolytic nature. The ligand and lanthanum(III complex were subjected to X-ray diffraction studies. In addition, the lanthanum(III complex underwent a facile transesterification reaction on refluxing with methanol for a long period. The thermal behaviour of the lanthanum(III complex was also examined

  2. Simple and clean determination of tetracyclines by flow injection analysis

    Rodríguez, Michael Pérez; Pezza, Helena Redigolo; Pezza, Leonardo


    An environmentally reliable analytical methodology was developed for direct quantification of tetracycline (TC) and oxytetracycline (OTC) using continuous flow injection analysis with spectrophotometric detection. The method is based on the diazo coupling reaction between the tetracyclines and diazotized sulfanilic acid in a basic medium, resulting in the formation of an intense orange azo compound that presents maximum absorption at 434 nm. Experimental design was used to optimize the analytical conditions. The proposed technique was validated over the concentration range of 1 to 40 μg mL- 1, and was successfully applied to samples of commercial veterinary pharmaceuticals. The detection (LOD) and quantification (LOQ) limits were 0.40 and 1.35 μg mL- 1, respectively. The samples were also analyzed by an HPLC method, and the results showed agreement with the proposed technique. The new flow injection method can be immediately used for quality control purposes in the pharmaceutical industry, facilitating monitoring in real time during the production processes of tetracycline formulations for veterinary use.

  3. Direct functionalization of pristine single-walled carbon nanotubes by diazonium-based method with various five-membered S- or N- heteroaromatic amines

    Leinonen, Heli; Lajunen, Marja, E-mail: [University of Oulu, Department of Chemistry (Finland)


    Reactivity of five-membered, variously substituted, heteroaromatic diazonium salts was studied toward pristine single-walled carbon nanotubes (SWCNTs), prepared by high-pressure CO conversion (HiPCO) method. Average size range of individual HiPCO SWCNTs was 0.8-1.2 nm (diameter) and 100-1,000 nm (length). Functionalizations were performed by a one-pot diazotization-dediazotization method with methyl-2-aminothiophene-3-carboxylate, 2-aminothiophene-3-carbonitrile, 2-aminoimidazole sulfate, or 3-aminopyrazole in acetic acid using sodium nitrite at room temperature or by heating. According to Raman and Fourier transform infrared spectroscopy, all used heterocyclic diazonium salts formed a covalent bond with SWCNTs and yielded new kinds of five-membered heterocycle-functionalized SWCNTs. Methyl-2-thiophenyl-3-carboxylate-functionalized SWCNTs formed a highly soluble, stable dispersion in tetrahydrofuran (THF), 3-pyrazoyl-functionalized SWCNTs in ethanol, and 2-imidazoyl- or 2-thiophenyl-3-carbonitrile-functionalized SWCNTs in ethanol and THF. The thermogravimetric analysis as well as energy-filtered transmission electron microscopy imaging of the products confirmed the successful functionalization of SWCNTs.

  4. Development of excretion stimulating techniques for radioactive materials via complex formation

    Takaya, Haruo; Uchiumi, Akira; Takatsu, Akiko [National Inst. of Materials and Chemical Research, Tsukuba, Ibaraki (Japan)


    With an aim to establish an effective technique to eliminate RI metals incorporated into an organism through rapid excretion out of the body, development of complex forming agents which fill the following conditions was attempted; (1) it is able to form a stable complex with RI metal ion targetted, (2) the cell toxicity is low and (3) it has no effects on the physiologically essential metal ions. As such complex-foaming agents which allow to excrete Ni and Cd incorporated, several sugar-formazan derivatives were synthesized by introducing various functional groups into 4-0-{alpha}-D-glucopyranosyl {beta}-D-glucopyranose, a reducing disaccharide. First, maltose-phenylhydrazine was synthesized from phenylhydrazine and maltose, and its solution in ethylacetate-pyridine was added with diazotized o-aminophenol. Thus, maltose-formazan was obtained. Six kinds of formazan derivatives were able to foam the respective complexes with Co, Ni, Cu, Zn and Cd, but not with Mg, Ca, Fe, etc., suggesting that these derivatives are usable as an excreting agent for Ni and Cd. (M.N.)

  5. Synthesis and Antimicrobial Evaluation of Some Novel Thiazole, Pyridone, Pyrazole, Chromene, Hydrazone Derivatives Bearing a Biologically Active Sulfonamide Moiety

    Elham S. Darwish


    Full Text Available This study aimed for the synthesis of new heterocyclic compounds incorporating sulfamoyl moiety suitable for use as antimicrobial agents via a versatile, readily accessible N-[4-(aminosulfonylphenyl]-2-cyanoacetamide (3. The 2-pyridone derivatives were obtained via reaction of cyanoacetamide with acetylacetone or arylidenes malononitrile. Cycloaddition reaction of cyanoacetamide with salicyaldehyde furnished chromene derivatives. Diazotization of 3 with the desired diazonium chloride gave the hydrazone derivatives 13a–e. Also, the reactivity of the hydrazone towards hydrazine hydrate to give Pyrazole derivatives was studied. In addition, treatment of 3 with elemental sulfur and phenyl isothiocyanate or malononitrile furnished thiazole and thiophene derivatives respectively. Reaction of 3 with phenyl isothiocyanate and KOH in DMF afforded the intermediate salt 17 which reacted in situ with 3-(2-bromoacetyl-2H-chromen-2-one and methyl iodide afforded the thiazole and ketene N,S-acetal derivatives respectively. Finally, reaction of 3 with carbon disulfide and 1,3-dibromopropane afforded the N-[4-(aminosulfonyl phenyl]-2-cyano-2-(1,3-dithian-2-ylideneacetamide product 22. All newly synthesized compounds were elucidated by considering the data of both elemental and spectral analysis. The compounds were evaluated for both their in vitro antibacterial and antifungal activities and showed promising results.

  6. 1,2-Bis-(1-{l_brace}3-pyridyl-{r_brace}3-methyltriazen-3-yl)ethane: synthesis and x-ray crystal structure

    Vaughan, K.; Turner, E.; Jenkins, H. [Saint Mary' s Univ., Dept. of Chemistry, Halifax, Nova Scotia (Canada)]. E-mail:


    3-Aminopyridine is diazotized in the conventional manner and the diazonium salt coupled with N,N'-dimethylethylenediamine to afford the title compound (1), which is a potential antitumour agent. The compound has been characterized by spectroscopic methods. The {sup 1}H NMR spectrum shows evidence of rotational conformerism, from the observation of broadening of the N-methyl signals in the room-temperature spectrum. Low-temperature NMR spectra (down to 223 K) show the presence of three distinct rotamers. The crystal structure of 1,2-bis-(1-{l_brace}3-pyridyl-{r_brace}3-methyltriazen-3-yl)ethane (1) has been determined by single crystal X-ray diffraction analysis. The bis-triazene (1) exists as the 'staggered' conformation in the solid state, with an 'anti-anti' configuration around the N-N bond of the triazene units. The crystal structure of 1 is compared with the closely related bis-triazene 2 and also compared with the simple mono-triazene 3. Crystal data for 1, C{sub 14}H{sub 18}N{sub 8}: orthorhombic, space group Pbca, a=11.2550(8) ANGSTROM, b=8.8507(6) ANGSTROM, c=15.0069(10) ANGSTROM, {beta}=90{sup o} and V=1494.91(18) ANGSTROM{sup 3}, for Z=4. (author)

  7. Sequential injection kinetic spectrophotometric determination of quaternary mixtures of carbamate pesticides in water and fruit samples using artificial neural networks for multivariate calibration

    Chu, Ning; Fan, Shihua


    A new analytical method was developed for the simultaneous kinetic spectrophotometric determination of a quaternary carbamate pesticide mixture consisting of carbofuran, propoxur, metolcarb and fenobucarb using sequential injection analysis (SIA). The procedure was based upon the different kinetic properties between the analytes reacted with reagent in flow system in the non-stopped-flow mode, in which their hydrolysis products coupled with diazotized p-nitroaniline in an alkaline medium to form the corresponding colored complexes. The absorbance data from SIA peak time profile were recorded at 510 nm and resolved by the use of back-propagation-artificial neural network (BP-ANN) algorithms for multivariate quantitative analysis. The experimental variables and main network parameters were optimized and each of the pesticides could be determined in the concentration range of 0.5-10.0 μg mL -1, at a sampling frequency of 18 h -1. The proposed method was compared to other spectrophotometric methods for simultaneous determination of mixtures of carbamate pesticides, and it was proved to be adequately reliable and was successfully applied to the simultaneous determination of the four pesticide residues in water and fruit samples, obtaining the satisfactory results based on recovery studies (84.7-116.0%).

  8. An economical and safe procedure to synthesize 2-hydroxy-4-pentynoic acid: A precursor towards ‘clickable’ biodegradable polylactide

    Quanxuan Zhang


    Full Text Available 2-Hydroxy-4-pentynoic acid (1 is a key intermediate towards ‘clickable’ polylactide which allows for efficient introduction of a broad range of pendant functional groups onto polymers from a single monomer via convenient ‘click’ chemistry with organic azides. The incorporation of various pendant functional groups could effectively tailor the physicochemical properties of polylactide. The reported synthesis of 1 started from propargyl bromide and ethyl glyoxylate. However, both of starting materials are expensive and unstable; especially, propargyl bromide is shock-sensitive and subjected to thermal explosive decomposition, which makes the preparation of 1 impractical with high cost and high risk of explosion. Herein, we report a simple, economical and safe synthetic route to prepare 1 using cheap and commercially available diethyl 2-acetamidomalonate (4 and propargyl alcohol. The desired product 1 was obtained via alkylation of malonate 4 with propargyl tosylate followed by a one-pot four-step sequence of hydrolysis, decarboxylation, diazotization and hydroxylation of propargylic malonate 5 without work-up of any intermediate.

  9. I mproved Synthesis of 1 H, 4 H -3,6-dinitropyrazolo [ 4,3-C ] pyrazole%3,6-二硝基吡唑[4,3-c]并吡唑的合成工艺改进

    易文斌; 朱春琳; 王金星; 张怡; 蔡春


    1 H,4H-3,6-dinitropyrazolo [4,3-C] pyrazole (DNPP) was synthesized from acetylacetone via monocyclization,diazotization, bicyclization, nitration, oxidation, and decarboxylative nitration. The overall yield of DNPP was 11.3% and 4%higher than that reported before. The synthesis of 4-amino-3,5-dimethylpyrazole was carried out by one-pot method which shows a number of advantages in comparison with the procedure adapted in the literature, including eliminating the use of mixture acid and iron power, shorting the reaction time (from 72 h to 24 h), improving the yield (from 79.1% to 92.0% ), and simplifying the post-treatment. In addition, both nitration and decarboxylative nitration were studied.%3,6-二硝基吡唑[4,3-c]并吡唑(DNPP),是一种新型氮杂环含能材料.以乙酰丙酮为原料,经环化、重氮化、双环构建、硝化、氧化、脱羧硝化等反应合成了DNPP,得率为1 3.3%,比文献值提高了4%.考察了一锅法制备中间体4-氨基-3,5-二甲基吡唑的合成工艺、硝化工艺和脱羧硝化工艺.

  10. Synthesis, spectroscopic characterization, electrochemical behaviour and thermal decomposition studies of some transition metal complexes with an azo derivative

    Sujamol, M. S.; Athira, C. J.; Sindhu, Y.; Mohanan, K.


    Complexes of manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) with a novel heterocyclic azo derivative, formed by coupling diazotized 2-amino-3-carbethoxy-4,5-dimethylthiophene with acetylacetone were synthesized and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, UV-vis, IR, 1H NMR and EPR spectral data. Spectral studies revealed that the ligand existed in an internally hydrogen bonded azo-enol form rather than the keto-hydrazone form and coordinated to the metal ion in a tridentate fashion. Analytical data revealed that all the complexes exhibited 1:1 metal-ligand ratio. On the basis of electronic spectral data and magnetic susceptibility measurements, suitable geometry was proposed for each complex. The nickel(II) complex has undergone facile transesterification reaction when refluxed in methanol for a long period. The ligand and the copper(II) complex were subjected to X-ray diffraction study. The electrochemical behaviour of copper(II) complex was investigated by cyclic voltammetry. The thermal behaviour of the same complex was also examined by thermogravimetry.

  11. Determination of benzidine in the food colours tartrazine and sunset yellow FCF, by reduction and derivatization followed by high-performance liquid chromatography.

    Lancaster, F E; Lawrence, J F


    Free and bound benzidine, a non-sulphonated aromatic amine (NSAA), were determined in the food colours tartrazine and sunset yellow FCF. Bound amines were released by reducing with sodium dithionite, then total NSAAs were extracted into chloroform, transferred to aqueous acid solution and diazotized with sodium nitrite before coupling with 2-naphthol-3,6-disulphonic acid, disodium salt (R-salt). Coloured benzidine and aniline derivatives (BZDRS and ANRS) were analysed using reversed-phase ion pair high-performance liquid chromatography (HPLC) and an absorbance detector set at 548 nm. Levels of total benzidine were similar to those reported in studies conducted in the USA, and ranged from < 5 to 270 ng/g. Total aniline was also determined (0.2-188 micrograms/g). Recoveries of benzidine with this method were found to be lower than expected (average ca 46%), but were reproducible. Detection limits were 15-20 ng BZDRS/g (3-4 ng benzidine/g). Mass spectrometry (LC-MS) was evaluated for identifying and determining purity of the standards, but difficulties were encountered when the methodology was applied to commercial samples.

  12. L-lysine pro-prodrug containing trans-ferulic acid for 5-amino salicylic acid colon delivery: synthesis, characterization and in vitro antioxidant activity evaluation.

    Cassano, Roberta; Trombino, Sonia; Cilea, Alessia; Ferrarelli, Teresa; Muzzalupo, Rita; Picci, Nevio


    In the present work, we report the synthesis of a new 5-amino salicylic acid (5-ASA) pro-prodrug, useful in Crohn disease treatment, and the evaluation of its antioxidant activity. Using as pharmacological carrier L-lysine amino acid and taking advantage of its intrinsic chemical reactivity, due to the presence of two amino groups, placed on the chiral center and in epsilon-position, we inserted trans-ferulic acid in epsilon-position, through amidation reaction, esterified with methanol the carboxylic group and, finally, submitted the free amino group to diazotation with 5-ASA, principal drug for inflammatory bowel diseases (IBD) care. All intermediates of synthesis and the final product (derivative A) were characterized with usual spectroscopic techniques, as FT-IR, GC/MS and (1)H-MNR. Finally, the derivative A antioxidant activity in inhibiting the lipid peroxidation, in rat-liver microsomal membranes, induced in vitro by two different sources of free radicals, 2,2'-azobis (2-amidinopropane) (AAPH) and tert-butyl hydroperoxide (tert-BOOH), was evaluated. Our pro-prodrug could be successfully applied in pharmaceutical field both as prodrug of 5-ASA than as carrier of trans-ferulic acid.

  13. The syntheses of radiolabelled Org 5222 and its main metabolite Org 30526

    Vader, Jan; Kaspersen, Frans; Sperling, Eric; Schlachter, Irene; Terpstra, Annie; Hilberink, Peter; Wagenaars, Gerard (N.V. Organon, Oss (Netherlands). Scientific Development Group)


    The syntheses of trans-5-chloro-2,3,3a-12b-tetrahydro-2-methyl-1H-dibenz[2,3:6,7] oxepino[4 ,5-c]pyrrole (Org 5222), a potential antipsychotic compound, labelled with [sup 3]H, [sup 14]C and [sup 36]Cl and trans-5-chloro-2,3,3a,12b-tetrahydro-1H-dibenz[2,3:6,7]-oxepino[4, 5-c] pyrrole (Org 30526) labelled with [sup 3]H are described. [sup 3]H-labelled Org 5222 of low specific activity was prepared by a base catalyzed exchange with tritiated water of an amide precursor, [sup 3]H-labelled Org 5222 with a high specific activity by a catalytic reductive dehalogenation. [sup 3]H-labelled Org 30526 was prepared both by demethylation of [sup 3]H-Org 5222 and by catalytic reductive iodination of 11-iodo-Org 30526. [sup 14]C-labelled Org 5222 was synthesized in 6 steps using [sup 14]C-sarcosine as starting material. [sup 36]Cl-labelled Org 5222 was prepared by diazotation reaction in the presence of H[sup 36]Cl. (author).

  14. Azocalix[4]pyrrole Amberlite XAD-2: new polymeric chelating resins for the extraction, preconcentration and sequential separation of Cu(II), Zn(II) and Cd(II) in natural water samples.

    Jain, Vinod K; Mandalia, Hiren C; Gupte, Hrishikesh S; Vyas, Disha J


    Two novel azocalix[4]pyrrole Amberlite XAD-2 polymeric chelating resins were synthesized by covalently linking diazotized Amberlite XAD-2 with calix[4]pyrrole macrocycles. The chelating resins were used for extraction, preconcentration and sequential separation of metal ions such as Cu(II), Zn(II) and Cd(II) by column chromatography prior to their determination by UV/vis spectrophotometry or flame atomic absorption spectrophotometry (FAAS) or inductively coupled plasma atomic emission spectroscopy (ICP-AES). Various parameters such as effect of pH on absorption, concentration of eluting agents, flow rate, total sorption capacity, exchange kinetics, preconcentration factor, distribution coefficient, breakthrough capacity and resin stability, were optimized for effective separation and preconcentration. The resin showed good ability for the separation of metal ions from binary and ternary mixture on the basis of pH of absorption and concentration of eluting agents. The newly synthesized resins showed good potential for trace enrichment of Cu(II), Zn(II) and Cd(II) metal ions, especially for Cu(II), as compared to the earlier reported resins. The synthesized resins were recycled at least 8-10 times without much affecting column sorption capacity. The presented method was successfully applied for determination of Cu(II), Zn(II) and Cd(II) in natural and ground water samples.

  15. Synthesis and Crystal Structure of 5-Diazo-4-ethoxycarbonyl-3-methylthio Pyrazol

    邹小毛; 胡方中; 杨华铮


    The crystal of the title compound, 5-diazo-4-ethoxycarbonyl-3-methylthio pyrazole, has been prepared and determined by X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 29.174(8), b = 4.7592(12), c = 15.956(4) A, β =117.632(4)°, C7H8N4O2S, Mr = 212.23, V = 1962.7(9) A3, Z = 8, Dx = 1.436 g/cm3, S = 1.000,μ(MoKα) = 0.31 mm-1, T = 298(2) K, F(000) = 880, R = 0.0658 and wR = 0.1741 for 1091independent reflections with I ≥ 2σ(I). The crystal of the title compound is formed with π-πinteractions through electrostatic attractions. Moreover, no HSO4- exists in the crystal structure.Therefore, only diazo pyrazole was obtained rather than either diazonium salt of the corresponding pyrazole or diazoaminopyrazole when 5-amino-4-ethoxycarbonyl-3-methylthio pyrazole was diazotized with sodium nitrite, catalyzed by sulfuric acid at 0 ℃.

  16. Synthesis of an oxytetracyline-tolidin-BSA immunogen and antibodies production of anti-oxytetracyline developed for oxytetracyline residue detection with enzyme-linked immunosorbent assays technique

    Widiastuti R


    Full Text Available An oxytetracycline-tolidin-bovine serum albumin (OTC-tolidin-BSA-conjugate was synthezed as immunogen for producing specific antibodies in immunized rabbits that would be used as reagent for development of OTC residue detection with enzym-linked immunoassays technique. The immunogen was prepared through diazotization tolidin and subsequently reacted with OTC. The red purple immunogen of OTC-tolidin-BSA absorbed at wave lengths of 277 nm and 488 nm under UV screening absorbances and confirmation with the high performance liquid chromatography (HPLC showed the absence of peak at retention time of 3.46 minutes. Characaterized result with SDS-PAGE showed the molecular weight of the OTC-tolidin-BSA at 69.79 kDA. Subsequently, the immunogen was immunized into New Zealand rabbits in order to produce the polyclonal antibodies. The antibodies were purified using a protein A sepharose column. The OD optimum responses of 0.92 to 1.20 were obtained from the second fractionation at dilution of 1/1000 by titrating the antibodies and OTC-tolidin-BSA coating antigen at concentration of 10 µg/mL on several bleeding times.

  17. Microwave Assisted Condensation Reactions of 2-Aryl Hydrazonopropanals with Nucleophilic Reagents and Dimethyl Acetylenedicarboxylate

    Rita M. Borik


    Full Text Available The reaction of methyl ketones 1a-g with dimethylformamide dimethylacetal (DMFDMA afforded the enaminones 2a-g, which were coupled with diazotized aromatic amines 3a,b to give the corresponding aryl hydrazones 6a-h. Condensation of compounds 6a-h with some aromatic heterocyclic amines afforded iminoarylhydrazones 9a-m. Enaminoazo compounds 12a,b could be obtained from condensation of 6c with secondary amines. The reaction of 6e,h with benzotriazolylacetone yielded 14a,b. Also, the reaction of 6a,b,d-f,h with glycine and hippuric acid in acetic anhydride afforded pyridazinone derivatives 17a-f. Synthesis of pyridazine carboxylic acid derivatives 22a,b from the reaction of 6b,e with dimethyl acetylenedicarboxylate (DMAD in the presence of triphenylphosphine at room temperature is also reported. Most of these reactions were conducted under irradiation in a microwave oven in the absence of solvent in an attempt to improve the product yields and to reduce the reaction times.

  18. Scanning near-field optical microscopy on rough surfaces: applications in chemistry, biology, and medicine


    Full Text Available Shear-force apertureless scanning near-field optical microscopy (SNOM with very sharp uncoated tapered waveguides relies on the unexpected enhancement of reflection in the shear-force gap. It is the technique for obtaining chemical (materials contrast in the optical image of “real world” surfaces that are rough and very rough without topographical artifacts, and it is by far less complicated than other SNOM techniques that can only be used for very flat surfaces. The experimental use of the new photophysical effect is described. The applications of the new technique are manifold. Important mechanistic questions in solid-state chemistry (oxidation, diazotization, photodimerization, surface hydration, hydrolysis are answered with respect to simultaneous AFM (atomic force microscopy and detailed crystal packing. Prehistoric petrified bacteria and concomitant pyrite inclusions are also investigated with local RAMAN SNOM. Polymer beads and unstained biological objects (rabbit heart, shrimp eye allow for nanoscopic analysis of cell organelles. Similarly, human teeth and a cancerous tissue are analyzed. Bladder cancer tissue is clearly differentiated from healthy tissue without staining and this opens a new highly promising diagnostic tool for precancer diagnosis. Industrial applications are demonstrated at the corrosion behavior of dental alloys (withdrawal of a widely used alloy, harmless substitutes, improvement of paper glazing, behavior of blood bags upon storage, quality assessment of metal particle preparations for surface enhanced RAMAN spectroscopy, and determination of diffusion coefficient and light fastness in textile fiber dyeing. The latter applications include fluorescence SNOM. Local fluorescence SNOM is also used in the study of partly aggregating dye nanoparticles within resin/varnish preparations. Unexpected new insights are obtained in all of the various fields that cannot be obtained by other techniques.

  19. Synthesis and structural characterization of new oxovanadium(IV) complexes derived from azo-5-pyrazolone with prospective medical importance

    Bagdatli, Emine; Altuntas, Eylem; Sayin, Ulku


    Four novel o-hydroxy substituted aryl-(msbnd H, sbnd Cl, sbnd Br, sbnd CH3) azo-5-pyrazolone compounds (2a-d, respectively) were synthesized as azo-group containing ligands by diazotization of aryl amines then coupled with 1-(4-chlorophenyl)-3-isopropyl-1H-pyrazol-5(4H)-one (1) and the structures were confirmed by FTIR, UV-Visible, GC-MS or ESI-LCMS and NMR spectroscopic techniques. As a result, the first synthesis of azo-5-pyrazolone based oxovanadium(IV) complexes (3a-d) was achieved by interaction of 2a-d with half equivalent of vanadyl sulphate pentahydrate in a methanolic medium with moderate to high yields (67, 74, 60, 71 for 3a-d, respectively). The resulting complexes were characterized using FTIR, UV-Visible, ESI-LCMS and EPR spectroscopic techniques as well as with thermogravimetric (TG/DTG) analysis. They have the composition [VO(L)2]·H2O; (3a-c) or [VO(L)2]·CH3OH; (3d) where LH is an azo-5-pyrazolone compound as the ligand (2a-d). The electronic spectra of the complexes are typical of oxovanadium(IV) complexes showing a low intensity band near 500 nm. Spectroscopic results have shown that azo-5-pyrazolone compounds have acted bidendate and the coordination sites are hydroxyl-substituent on the -azo phenyl-aromatic ring and the pyrazolone carbonyl-moiety. The thermal data confirm that the complexes have methanol (3a-c) or water (3d) molecule outside the coordination sphere and the complexes show similar thermogravimetric decomposition fragments which are consistent with the proposed structures. A distorted octahedral geometry has been proposed for these complexes mainly with EPR and the other spectral techniques.

  20. 3,4-双(3′-硝基苯-1′-基)氧化呋咱的两种合成方法%Two Synthetic Methods of 3,4-Bis(3′-nitrophenyl-1′-yl)furoxan

    杨建明; 薛云娜; 李春迎; 葛忠学; 吕剑


    3, 4-Bis ( 3'-nitrophenyl-l'-yl) furoxan was synthesized by two methods ( oxidative dehydrogenation reaction and dimerization reaction of nitrile oxide). The target compound was characterized by IR.NMR,elemental analysis and DSC. The target compound was obtained with yield of 32. 4% by the oxidative dehydrogenation reaction which involved nitration oi benzil,hydroamine addition,and oxidative cyclization, and the target compound was obtained with yield of 21.0% by the dimerization reaction of nitrile oxide which involved hydroamine addition of benzonitrile, diazotization, intermolecular cyclization and nitration of 3,4-bisphenyl furoxan. DSC curve shows that the exothermic peak of the opening-ring for 3 ,4-bis(3'-nitrophenyl-1'-yl)furoxan is 280.7 ℃ with releasing heat of 1142 J · g~(-1).%分别采用邻二肟氧化脱氢和氧化腈二聚反应两种方法合成了3,4-双(3′-硝基苯-1′-基)氧化呋咱,并利用红外光谱、核磁共振、元素分析、DSC等对其进行了表征.邻二肟氧化脱氢法经苯偶酰硝化反应、羟胺加成、邻二肟氧化关环反应得到目标化合物,总收率为32.4%;氧化腈二聚法经苯甲腈加成、重氮化、氧化腈二聚反应、硝化反应得到了目标产物,总收率为21.0%.DSC结果表明氧化呋咱环开裂放热峰值为280.7 ℃,放热量为1142 J·g~(-1).

  1. Interaction between lidocaine hydrochloride (with and without adrenaline) and various irrigants: A nuclear magnetic resonance analysis

    Vidhya, Nirmal; Karthikeyan, Balasubramanian Saravana; Velmurugan, Natanasabapathy; Abarajithan, Mohan; Nithyanandan, Sivasankaran


    Background: Interaction between local anesthetic solution, lidocaine hydrochloride (with and without adrenaline), and root canal irrigants such as sodium hypochlorite (NaOCl), ethylene diamine tetra-acetic acid (EDTA), and chlorhexidine (CHX) has not been studied earlier. Hence, the purpose of this in vitro study was to evaluate the chemical interaction between 2% lidocaine hydrochloride (with and without adrenaline) and commonly used root canal irrigants, NaOCl, EDTA, and CHX. Materials and Methods: Samples were divided into eight experimental groups: Group I-Lidocaine hydrochloride (with adrenaline)/3% NaOCl, Group II-Lidocaine hydrochloride (with adrenaline)/17% EDTA, Group III- Lidocaine hydrochloride (with adrenaline)/2% CHX, Group IV-Lidocaine hydrochloride (without adrenaline)/3% NaOCl, Group V-Lidocaine hydrochloride (without adrenaline)/17% EDTA, Group VI-Lidocaine hydrochloride (without adrenaline)/2% CHX, and two control groups: Group VII-Lidocaine hydrochloride (with adrenaline)/deionized water and Group VIII-Lidocaine hydrochloride (without adrenaline)/deionized water. The respective solutions of various groups were mixed in equal proportions (1 ml each) and observed for precipitate formation. Chemical composition of the formed precipitate was then analysed by nuclear magnetic resonance spectroscopy (NMR) and confirmed with diazotation test. Results: In groups I and IV, a white precipitate was observed in all the samples on mixing the respective solutions, which showed a color change to reddish brown after 15 minutes. This precipitate was then analysed by NMR spectroscopy and was observed to be 2,6-xylidine, a reported toxic compound. The experimental groups II, III, V, and VI and control groups VII and VIII showed no precipitate formation in any of the respective samples, until 2 hours. Conclusion: Interaction between lidocaine hydrochloride (with and without adrenaline) and NaOCl showed precipitate formation containing 2,6-xylidine, a toxic compound

  2. Isolation of two biologically active cell surface proteins from Brucella abortus by chromatofocusing

    Tabatabai, L.B.; Deyoe, B.L.


    Brucella abortus contains a group of immunogenic cell surface proteins which have potential value as a vaccine or as a diagnostic reagent for the prevention and diagnosis of bovine brucellosis. Under nondenaturing conditions, these proteins range in molecular weight from 10,000-124,000, as determined by high performance liquid chromatography (HPLC) on TSK 3000sw. By analytical isoelectrofocusing, 6 major protein bands could be distinguished with pI's ranging from 4.0 to 6.0 and 3 additional major proteins with pI's of 7.5, 9.5, and 10. By chromatofocusing on Polybuffer Exchanger 94 with a pH gradient from 6-4, two of the six proteins from pI 4-6 were separated, a pI 4.9 and a pI 4.7 protein; a third fraction contained the high pI proteins. The former two proteins were homogeneous by analytical isoelectrofocusing, and a molecular weight of 54,000 daltons was found for both protein species by HPLC on TSK 3000sw. The pI 4-6 and not the pI 9.5 and 10 proteins, could be radiolabeled when intact cells were radioiodinated with diazotized (/sup 125/I)-iodosulfanilic acid. Biological activity of the proteins as assessed in lemmings indicated that immunization with the pI 4.7 and 4.9 proteins afforded better protection against experimental brucellosis than immunization with the high pI proteins. These results support our view that a single surface protein may be sufficient for the prevention of experimental brucellosis.

  3. Self-assembled multilayer films of sulfonated graphene and polystyrene-based diazonium salt as photo-cross-linkable supercapacitor electrodes.

    Xiong, Zhiyuan; Gu, Tonghan; Wang, Xiaogong


    Photo-cross-linkable multilayer films composed of sulfonated reduced graphene oxide (SRGO) and polystyrene-based diazonium salt (PSDAS) were fabricated by electrostatic layer-by-layer (LbL) self-assembly. Polystyrene with narrow molecular weight distribution was synthesized by atom transfer radical polymerization (ATRP), and cationic PSDAS was prepared through nitration, reduction, and diazotization reactions. Negatively charged SRGO nanosheets were prepared through prereduced by NaBH4, modified by diazonium salt of sulfanilic acid, and then further reduced by hydrazine. The multilayer films were obtained by alternately dipping substrates in the PSDAS solution and SRGO dispersion in acidic conditions. The cross-linking between the components occurred during the multilayer formation process and was further achieved by the UV light irradiation after the film preparation. The assembling process and surface morphology of LbL multilayer films were monitored by UV-vis spectroscopy, atomic force microscopy (AFM), and scanning electron microscopy (SEM). The cross-linking between SRGO and PSDAS was verified by attenuated total reflectance FTIR (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and contact angle measurement. The graphene nanosheets were found to be homogeneously distributed in the cross-linked network of the films. The large accessible surface area of graphene nanosheets and the cross-linking structure afforded the LbL films with high specific capacitance and excellent cyclic stability when used as supercapacitor electrodes. At a sweeping rate of 10 mV/s, the film with nine bilayers exhibited a specific capacitance of 150.4 F/g with ideal rectangular cyclic voltammogram. Large capacitance retention of 97% was observed after 10 000 charge-discharge cycles under the scanning rate of 1000 mV/s. This new approach for preparing graphene-containing multilayer films can be used to develop supercapacitor electrodes and other functional devices.

  4. XPS and NRA investigations during the fabrication of gold nanostructured functionalized screen-printed sensors for the detection of metallic pollutants

    Jasmin, Jean-Philippe; Miserque, Frédéric; Dumas, Eddy; Vickridge, Ian; Ganem, Jean-Jacques; Cannizzo, Caroline; Chaussé, Annie


    An all covalent nanostructured lead sensor was built by the successive grafting of gold nanoparticles and carboxylic ligands at the surface of self-adhesive carbon screen-printed electrodes (SPEs). Surface analysis techniques were used in each step in order to investigate the structuration of this sensor. The self-adhesive surfaces were made from the electrochemical grafting of p-phenylenediamine at the surface of the SPEs via diazonium salts chemistry. The quantity of grafted aniline functions, estimated by Nuclear Reaction Analysis (NRA) performed with p-phenylenediamine labelled with 15N isotope, is in agreement with an almost complete coverage of the electrode surface. The subsequent diazotization of the aniline functions at the surface of the SPEs was performed; X-ray Photoelectron Spectroscopy (XPS) allowed us to consider a quantitative conversion of the aniline functions into diazonium moieties. The spontaneous grafting of gold nanoparticles on the as-obtained reactive surfaces ensures the nanostructuration of the material, and XPS studies showed that the covalent bonding of the gold nanoparticles at the surface of the SPEs induces a change both in the Au-4f (gold nanoparticles) and Cl-2p (carbon ink) core level signals. These unusual observations are explained by an interaction between the carbon ink constituting the substrate and the gold nanoparticles. Heavy and toxic metals are considered of major environmental concern because of their non-biodegradability. In a final step, the grafting of the carboxylic ligands at the surface of the SPEs and an accumulation step in the presence of lead(II) cations allowed us to evidence the interest of nanostructured materials as metallic pollutants sensors.

  5. 一种新型Hsp90抑制剂的合成及其抑制活性%Synthesis of Novel Hsp90 Inhibotor and Its Inhibition

    张晓颖; 张杰; 李伟; 王小龙


    对氨基苯甲酸经重氮化后再与2-氯乙酰乙酸乙醅反应制得(Z)4-[2-(1-氯-2-乙氧基-2-羰亚甲基)肼基]苯甲酸(1);1与二甲基环己二酮成环后再与对羟基环己胺完成酰胺化反应合成了一种新型Hs90抑制剂——N-(4-羟基环己基)-4-[1-(6,6-二甲基-4-氧-3-乙酰氧基-4,5,6,7-四氢吲唑)]苯甲酰胺(3),其结构经1 H NMR表征.荧光偏振法研究结果表明3对Hsp90α具有明显的抑制活性.%(Z)-4-[2-(l-chloro-2-ethoxy-2-oxoethylidene)hydrazinyl]benzoic acid(l) was prepared from p-aminobenzoic acid by diazotization, then reacted with ethyl 2-chloro-acetoacetate. A novel Hsp90 inhibotor, ethyl l-{4-[ (4-hydroxycyclohexyl)carbamoyl]phenyl} -6,6-dimethyl-4-oxo-4,5,6, 7-tetrahydro-lH-indazole-3-carboxylate(3), was synthesized by cyclization between 1 and 5,5-dime-thyl-cyclohexane-1,3-dione, then amidation with p-hydroxyl-cyclohexylamine. The structure was characterized by ' H NMR. The result from fluorescence polarization showed that 3 exhibited good inhibition against Hsp90a.

  6. Synthesis and Ultraviolet Spectrum Analysis of Five Azophenols Compounds%五种偶氮苯酚的合成和紫外光谱分析

    吴平; 任国庆; 鲍长坤; 陈颖; 夏文明


    以苯胺、水杨醛、水杨酸、对羟基苯甲醛、对羟基苯甲酸、对甲苯酚等为原料通过重氮偶合反应制得5种相应的偶氮苯酚化合物,粗产品以乙醇和水为溶剂重结晶纯化。通过紫外光谱对产物进行表征,考查了5种化合物中不同取代基种类及其位置对紫外吸收光谱的影响,随着甲基、醛基、羧基三种取代基的电负性的逐渐增大,不管酚羟基在偶氮键的邻位还是对位,最大吸收波长都逐渐发生红移。%The aniline, salicylic aldehyde, salicylic acid, hydroxy benzaldehyde, hydroxybenzoic acid and p-cresol were used as raw material occurring diazotization reaction to obtain five azophenols compounds, then crude products were purified by ethanol and water as recrystallization solvent. The products were characterized by UV spectra, and the effect on the UV absorption spectra of different substituents in the five compounds was investigated. Along with the increasing of electronegativity of the substituents ( methyl, aldehyde and carboxyl group) , regardless of phenolic hydroxyl in the ortho or para position of azo bond, the maximum absorption wavelength were gradually red shifted.

  7. 甲(月朁)型铁络合染料的合成研究%Study on the synthesis of iron complex formazan dyes

    夏姚姚; 贾建洪; 高建荣; 陶晓敏


    Two formazan iron complex dyes were obtained through nitrogen coupling reaction of the diazonium salt with substituted hydrazone,the diazo salt of 2-aminophenol and iron ion.The intermediate, 4-sulfophenylhydrazine-benzaldehydedrazone, was synthesized from 4-aminobenzenesulfonic acid through diazotization,reduction and condensation with substituted aldehyde.The process for preparation of the key intermediate substituted hydrazone was studied and the optimal process parameters were selected as follows: reduction temperature was 40 ℃, n (sodium bisulfite )∶ n (phenylhydrazine)=2.25∶ 1, to restore the pH value was 6, the yield was 89.6 %.It was also found that the electron-donating groups on the central carbon atom of formazan iron complex dyes would bring red-shift.The products of the structure were confirmed by 1HNMR,MS and UV.%以对氨基苯磺酸为原料,经过重氮化、还原与取代醛缩合,合成对氨基苯磺酸基苯腙.该中间产物与2-氨基酚的重氮盐反应,合成甲(月朁)化合物,再经二价铁离子络合,得两个甲(月朁)型铁络合染料.对关键中间体取代苯腙的合成工艺进行了考察,得到了较优工艺参数:还原温度40℃,n(亚硫酸氢钠):n(苯肼)=2.25:1,还原pH=6,收率89.6%.甲(月朁)型铁络合染料中心碳原子上接供电子基团将产生红移现象.产品经1HNMR,MS,UV表征确定了结构.

  8. Electron miscroscopy and histochemical studies on four Egyptian helminthes eggs of medical importance.

    Mahmoud, Lily H; el-Alfy, Nadia M


    By SEM the Fasciola gigantica egg is ovoid with a small knob like operculum, while the egg of Heterophyes heterophytes is broad oval with the operculum more tapering. The egg shell of fertilized Ascaris lumbricoides has interconnected ridges and peak-like projections, while the egg of Enterobius vermicularis is flattened with a thicker margin at the curved side. By TEM, Fasciola egg shell consists of fine reticulum fibrils of three layers. The outer lipoprotein of perivitelline membrane beneath which 2 membranes separated by inclusions, middle of protein globules and inner lipoprotein layer with minute electron-dense granules of melanin or polymer origin, in some parts of the shell giving the egg its brown coloration. The Heterophyes egg shell is more or less similar to that of Fasciola but lacking the minute electron-dense granules. The egg shell of Ascaris has outer ulterine layer with three consecutive layers, basal lipoprotein layer and the inner lipid or ascaroside layer which is the most resistant layer. The Enterobius egg shell consists of five layers, external uterine, internal uterine, vitelline, chitinous and lipid layer. Histochemically, Fasciola egg shell consists of nine amino-acids, and that of Heterophyes consists of ten amino acids. In Ascaris, the lipid layer characteristically consists 25% protein and 75% lipid. The histochemical examination of Enterobius as a detailed example, showed different degrees of reactions with mercuric bromophenol blue, diazotization coupling, Sakaguchi reaction, Sudan black and Mallory's triple stain. Temperature showed marked effect on eggs survival. Eggs of Fasciola and Heterophyes withstand more low temperatures but those of Ascaris and Enterobius withstand more high ones. There are marked correlations between the egg shell constitution, histochemical compositions on one hand and water permeability and egg dryness on the other hand. The results were photographed and discussed.

  9. 吡啶联三唑类衍生物的合成及杀虫活性%Synthesis and insecticidal activity of a series of novel substituted pyridine linked triazole derivatives

    许天明; 姬文娟; 蔡飞; 邢家华; 孔小林


    l-(2-chloropyridin-3-yl)-5-methyl-lH-l ,2,3-triazole-4-carbonyl chloride (5) was synthesized using 2-chloropyridine as raw materials by diazotization, azide substitution, cyclization, and acyl chlorination. Then 13 novel title compounds were synthesized by acylation of (5) with substituted anilines. The structures of the compounds were confirmed by LC-MS and 'H NMR. The bioassay showed that all the compounds exhibit some insecticidal activity at concentration of 500 mg/L, among them,the mortality ratio of some compounds against Mythimna separate were 100%. While among the compounds , except the mortality ratio of ZJ-7 compounds against Mythimna separate were 100% at concentration of 100 mg/L, the mortality ratio of of the most compounds decreased significantly at concentration of 100 mg/L,some compounds even have no insecticidal activity .%以3-氨基-2-氯吡啶(1)为起始原料,经重氮化、叠氮化、环合和酰氯化反应,生成1-(2-氯吡啶-3-基)-5-甲基-1H-1,2,3-三唑4-甲酰氯(5),(5)与取代苯胺反应,制得13个未见文献报道的吡啶联三唑类化合物,其结构通过1H NMR和LC-MS表征.初步生物活性测定结果表明:在500 mg/L质量浓度下,所有目标化合物对粘虫Mythimna separate均有一定的杀虫活性,部分化合物致死率达100%;但在100 mg/L下,除化合物ZJ-7的致死率仍达100%外,其余化合物的活性明显降低,甚至无活性.

  10. Preparation and performance of two new chelants for recycling Co(Ⅱ) from spent Li-ion batteries%用于回收废旧锂离子电池中Co(Ⅱ)的2种新型螯合剂的制备及其性能

    湛雪辉; 周随安; 曹芬; 李侠; 李飞


    以对甲基苯硫酚为原料,通过硝化、还原、重氮化等一系列反应合成4-甲基-2-羟基硫酚(A).考察重氮化过程中NaNO2的用量、硫酸浓度、反应温度以及水解时硫酸浓度对产率的影响.在最佳影响因素下得到最高产率71.2%.通过氯磺化、还原以及最佳反应条件合成含有邻羟基苯硫酚的螯合树脂(B).使用傅里叶红外光谱表征4-甲基-2-羟基硫酚与螯合树脂.在废旧锂离子电池浸出液中进行分批实验考察4-甲基-2-羟基硫酚与螯合树脂的性能,并且使用HCI溶液提取所螯合的Co2+.研究结果表明:螯合树脂显示良好的可循环性.%4-methyl-2-hydroxythiophenol(A) was synthesized by nitration, reduction and diazotization of p-thiophenol. The influence of dosage of NaNO2, concentration of sulfuric acid, temperature and concentration of H2SO4 in hydrolysis reaction on the yield of 4-methyl-2-hydroxythiophenol was studied. A high yield (71.2%) was achieved under the optimal reaction conditions. And a new chelating resin (B) containing o-hydroxythiophenol was synthesized through chlorosulfonation, reduction and the optimal reactions above. The FT-IR was used to identify the formation of 4-methyl-2-hydroxythiophenol and chelating resin. The adsorption performance of 4-methyl-2-hydroxythiophenol and chelating resin was processed in batch solution which was generated by leaching from LiCoO2, and finally Co2+ was eluted from chelant with HC1 solution. Chelating resin displays good recyclability.

  11. 常见腌制食品中亚硝酸盐含量的测定%Determination of Nitrite Content in Common Preserved Foods

    彭晓娅; 董祥


    采用可见分光光度法,利用亚硝酸根可与中性红试剂、8-羟基喹啉发生重氮反应,然后在氨性溶液中又会生成偶氮染料,反应体系在λ=560nm处有最大吸收峰,测得亚硝酸根的标准吸收曲线方程为A=0.26232C-0.00169,相关系数R=0.99873。此方法测定腌制食品中亚硝酸盐含量均没有超过国家食品中亚硝酸盐含量规定标准(≤20mg/kg),但散装产品较正规包装产品的亚硝酸根含量高,消费者应尽量以新鲜蔬菜为主食,少吃腌菜,特别是散装类型的,注重健康饮食。%By using visible spectrophotometry, the nature could occur diazotization reaction with reagent neutral red, 8-hydroxyquinoline, and then the azo dyes were formed in the ammonia solution. The reaction system had the maximum absorption peak at the wavelength of λ=560 nm, the standard nitrite absorption curve equation wasA=0.262 32C-0.001 69, the correlation coeffcientR was 0.998 73. Using this method to determine the content of nitrite in pickled foods did not exceed the range of Chinese National Food Standard, but the bulk product is higher than the regular packing product's nitrite content. Consumers should try to eat fresh vegetables as the staple food, less sour pickles, especially bulk types, focus on healthy eating.

  12. 4-苄氧基-1H-吲唑的合成新方法%A New Synthesis Route of 4-(Benzyloxy)-lH-Indazole

    田丹; 朱金丽; 张素梅; 项蕊; 汤艳峰


    4-(benzyloxy)-lH-indazole (VI) is synthesized via five-step reaction: hydrogenation, acetylation, nucle- ophilic substitution, diazotization and aminolysis by using the 2-methyl-3-nitrophenol( I ) as starting materials. And the total yield is 76.3%. The structure of the aim compound is characterized by FrIR,1H NMR and ESI-MS. In this paper, the synthesis procedure of 1-(4-(benzyloxy)-lH-indazol-l-yl)ethanone (V) is investigated in detail. The re- sults show that the yield is 87.1% when the molar ratio of isoamyl nitrite to N- (3- (benzyloxy)-2- methylphenyl)acetamide( IV ) is 1.6:1, the reaction temperature is 90 ~C, and the reaction time is 16 h. This synthesis route is easy to handle and has high yield.%以2-甲基-3-硝基苯酚(I)为原料,先后经过加氢还原、乙酰化、亲核取代、关环及胺解反应,合成了4-苄氧基-1H-吲唑(VI),总的收率为76.3%,所得目标化合物采用FTIR、1HNMR及ESI-MS进行结构表征.研究了4-苄氧基-1-乙酰基-吲唑(V)的合成工艺,结果表明,当亚硝酸异戊酯与N-(3-苄氧基-2-甲基苯基)乙酰胺(Ⅳ)的体积比为1.6:1,反应温度为90℃,反应时间为16h时,收率可达87.1%.该合成方法具有操作简单、收率高的优势.

  13. High-performance liquid chromatography of the renal blood flow marker p-aminohippuric acid (PAH) and its metabolite N-acetyl PAH improves PAH clearance measurements.

    Decosterd, L A; Karagiannis, A; Roulet, J M; Bélaz, N; Appenzeller, M; Buclin, T; Vogel, P; Biollaz, J


    PAH (N-(4-aminobenzoyl)glycin) clearance measurements have been used for 50 years in clinical research for the determination of renal plasma flow. The quantitation of PAH in plasma or urine is generally performed by colorimetric method after diazotation reaction but the measurements must be corrected for the unspecific residual response observed in blank plasma. We have developed a HPLC method to specifically determine PAH and its metabolite NAc-PAH using a gradient elution ion-pair reversed-phase chromatography with UV detection at 273 and 265 nm, respectively. The separations were performed at room temperature on a ChromCart (125 mmx4 mm I.D.) Nucleosil 100-5 microm C18AB cartridge column, using a gradient elution of MeOH-buffer pH 3.9 1:99-->15:85 over 15 min. The pH 3.9 buffered aqueous solution consisted in a mixture of 375 ml sodium citrate-citric acid solution (21.01 g citric acid and 8.0 g NaOH per liter), added up with 2.7 ml H3PO4 85%, 1.0 g of sodium heptanesulfonate and completed ad 1000 ml with ultrapure water. The N-acetyltransferase activity does not seem to notably affect PAH clearances, although NAc-PAH represents 10.2+/-2.7% of PAH excreted unchanged in 12 healthy subjects. The performance of the HPLC and the colorimetric method have been compared using urine and plasma samples collected from healthy volunteers. Good correlations (r=0.94 and 0.97, for plasma and urine, respectively) are found between the results obtained with both techniques. However, the colorimetric method gives higher concentrations of PAH in urine and lower concentrations in plasma than those determined by HPLC. Hence, both renal (ClR) and systemic (Cls) clearances are systematically higher (35.1 and 17.8%, respectively) with the colorimetric method. The fraction of PAH excreted by the kidney ClR/ClS calculated from HPLC data (n=143) is, as expected, always 1). In conclusion, HPLC not only enables the simultaneous quantitation of PAH and NAc-PAH, but may also provide more

  14. 分光光度法测定果蔬中残杀威残留量%Spectrophotometric Determination of Residual Amount of Propoxur in Fruit and Vegetable

    李满秀; 刘佳; 王翠


    在碱性条件下残杀威水解生成酚盐,在盐酸介质中对氨基苯磺酸与亚硝酸根发生重氮化反应,上述所得酚盐和重氮化产物在氨性溶液中偶联生成偶氮染料,此偶联产物的最大吸收波长为427nm,据此提出了分光光度法测定果蔬中残杀威含量的方法。残杀威的质量浓度在0.17-2.04mg·L^-1范围内与其吸光度呈线性关系,检出限(3s/k)为0.03mg·L^-1。方法用于测定果蔬中残杀威的含量,相对标准偏差(n=5)在0.3%-0.79/6之间,加标平均回收率为96%。%In an ammoniaeal solution, azo dye was formed between phenate (produced by hydrolysis of propoxur in an alkaline medium) and diazo compound (produced by diazotization between sulfanilic acid and nitrite), with its absorption max. at the wavelength of 427 nrn, Based on these facts, a spectrophotometric method for determination of propoxur in fruit and vegetable was proposed. Linear relationship between the values of absorbance and mass concentration of propoxur was obtained in the range of 0. 17-2. 04 mg · L-1 , with detection limit (3s/k) of 0. 03 mg · L^-1. The present method was used in the analysis of samples of fruit and vegetable, giving values of RSD's (n=5) in the range of 0. 30%-0. 7%. Test for recovery was performed by standard addition method, result of average recovery obtained was 96 %.

  15. 3,4-二(3',5'-二硝基苯-1'-基)氧化呋咱的合成及热分解机理%Synthesis and Thermal Decomposition Mechanism of 3,4-Bis( 3',5 ′-dinitrobenzene-1 ′-yl) furoxan

    李亚南; 张志忠; 周彦水; 王伯周; 葛忠学


    3,4-Bis(3',5'-dinitrobenzene-1 '-yl) furoxan was synthesized via five-step reactions of oximation ,diazotization, denitrification,cyclization and nitration using benzonitrile as starting materials. The reaction conditions were optimized,and the cyclization could be performed at 2 ~ 10 ℃ within 3 h and Na2CO3 in excess of 20% with a yield of about 64.7%. The product's structure was characterized by IR,NMR,MS and elemental analysis. In addition,the mechanism of the key reaction-cyclization was suggested. The vicarious nucleophilic substitution of hydrogen(VNS) reaction of the target compound was explored,and it could not go under the conditions applied by the authors. Furthermore,the thermal decomposition of this furoxan was studied with differential scanning calorimetry ( DSC), IR, and thermogravimetry/mass spectrum( TG/MS) ,and the related mechanism was proposed and analysed in detail. The initial step of decomposition is dissociation of N-O bond with coordination oxygen in furoxan ring.%以苯甲腈为原料,经肟化、重氮化、脱氮、环化及硝化五步反应合成了3,4-二(3',5'-二硝基苯-1'-基)氧化呋咱;利用红外光谱、核磁共振、质谱、元素分析等手段鉴定了化合物的结构;探索了此化合物的氢的亲核取代(VNS)反应;探讨了关键反应-氧化呋咱成环反应机理;优化了肟化、氧化呋咱成环及硝化的反应条件;利用差示扫描量热(DSC)等多种热分析手段研究了目标化合物的热分解机理.结果表明,氧化呋咱成环反应的最佳条件:Na2CO3为理论量的1.20倍,反应温度2~1 0℃,反应时间3 h,收率64.7%;目标化合物的热分解首先发生在氧化呋咱环含配位氧的N-O键.

  16. Design, synthesis and antifungal activity of 2-aryl-2, 3-dihydro-4H-1,3-benzothiazin-4-one derivatives%2-芳基-2,3-二氢-4H-1,3-苯并噻嗪-4-酮类化合物的设计、合成及抗真菌活性

    耿红健; 高宁; 李裕鑫; 张卫军; 苏昕; 郭春


    目的 设计并合成2-芳基-2,3-二氢4H-1,3-苯并噻嗪-4-酮类化合物,测定体外抗真菌活性、建立初步构效关系.方法 以邻氨基苯甲酸为起始原料,经过重氮化及硫代反应制得二硫代水杨酸,再经过氯代、氨解、缩合等步骤制得目标化合物.采用2倍浓度稀释法,选用8种临床上常见的致病真菌为测试菌株,以氟康唑和伊曲康唑为阳性对照药,测试了目标化合物的体外抗真菌活性.结果与结论 设计并合成了24个2-芳基-2,3-二氢-4H-1,3-苯并噻嗪-4-酮类化合物,目标化合物的结构经1H-NMR、MS确证;活性测试结果表明,目标化合物对测试真菌表现出不同程度的体外抑菌活性,所有化合物对红色毛藓菌和根霉菌的活性均好于阳性对照药.%Objective To study the design, synthesis and antifungal activity of 2-aryl-2,3-dihydro-4-H-l ,3-benzothiazin-4-one derivatives and establish their preliminary SAR. Methods The target compounds were synthesized from anthranilic acid through diazotization, thionation reaction followed by chloronation, am-monolysis and condensation. The antifungal assay against eight isolates of fungi was carried out in vitro by two-fold dilution method,took fluoconazole and itroconazole as the control drugs. Results and Conclusions Twenty-four compounds were synthesized and characterized by 'H-NMR,ES-MS. Preliminary pharmacological results showed that all compounds displayed antifungal activities against the tested fungi in different levels , and exhibited better activity than that of control drugs against T. rubrum and Rhizopu

  17. Establishment and Application of ELISA Method for Detection of Clenbuterol Hydrochloride in Animal Foods%动物性食品中盐酸克伦特罗ELISA检测方法的建立及应用

    周群标; 桑亚新; 王丽; 李星; 王向红


    Objective:An indirect enzyme-linked immunosorbent assay (ELJSA) was developed to detect Clenbuterol hydrochloride in animal foods in order to ensure food safety. Methed: Hapten clenbuterol was conjugated with Bovine Sera Albumin (BSA) and Ovalbumin(OVA) by diazotization to produce immunogen BSA-CL and OVA-CL used for immunizing rabbit. The rabbit antiserum was purified with ammonium sulfate fractionation to prepare polyclonal antibody a-gainst clenbuterol hydrochloride. An indirect enzyme-linked immunosorbent assay (ELJSA) was developed to detect and quantitate clenbuterol hydrochloride. Results: The optimum concentration of envelope antigen is 10 u,g/mL, optimum dilution rate of antibody is 1:1000, visual detection limit of the assay is 0.05 ng/mL, and the ICX was 2.18 ng/mL, the average recovery rate was 90.78%. Conclusion: The method established is sensitive and the procedure of sample pretreat-ment is simple and quick. It was proved to widely use to detect the CL residues in animal foods online.%目的:建立动物性食品中盐酸克伦特罗残留快速检测技术,确保食品安全.方法:以盐酸克伦特罗重氮化后分别连接到牛血清蛋白(BSA)和卵清蛋白(OVA)上制得免疫原BSA-CL和包被抗原OVA-CL.通过免疫得到多抗血清,经硫酸铵沉淀,Sephrose 4B-proteinA对抗体进行纯化,在此基础上建立间接竞争ELISA方法.结果表明:包被抗原的最适质量浓度为10 μg/mL,抗体的最佳稀释度为1∶1000;该方法的IC50为2.18 ng/mL,最低检测限达0.05 ng/mL,与沙丁胺醇和妥洛特罗的交叉反应率分别为8.28%和7.75%,平均加标回收率为90.78%.结论:该法灵敏度高,样品前处理简便、快速,适用于动物源性食品中盐酸克伦特罗残留的大批量现场检测.

  18. 动物性食品中氨苯砜dcELISA的检测%Development of a direct competitive enzyme-linked immunosorbent assay for detection of dapsone in animal foods

    郑小娇; 张晶; 张亚卓; 史晨杉; 王向红


    A direct competitive enzyme-linked immunosorbent assay (ELISA) was developed to detect Dapsone in animal foods.Hapten dapsone was conjugated with Bovine Sera Albumin (BSA) by diazotization to produce immunogen BSA-DDS used for immunizing rabbit.The rabbit antiserum was purified with ProteinA-Sephros 4B to prepare polyclonal antibody against dapsone.A direct enzyme-linked immunosorbent assay (ELISA) was developed to detect and quantitate dapsone.The bewt synthesis of BSA-DDS and the conjugated-ratio was 1 ∶ 10.The IC50 was 4.78 ng/mL,visual detection limit was 0.03 ng/mL,and recoveries of dapsone in spiked samples ranged from 75.45% ~ 91.75%.The artificial antigens can be used for preparing specificity anti-dapsone antibody.The method is sensitive and the procedure of sample pretreatment is simple and quick.It is suitable to use in the detection of DDS residues in animal foods on site.%建立了动物性食品中氨苯砜残留快速检测技术.将氨苯砜重氮化后连接到牛血清蛋白(BSA)上制得免疫原BSA-DDS,免疫新西兰大耳白兔获得多克隆抗体,经ProteinA-Sephros 4B对抗体进行纯化,在此基础上建立直接竞争ELISA方法.结果显示:该方法可制备目标抗原BSA-DDS和抗体,氨苯砜与载体蛋白偶联比可达到1:10;建立的直接竞争ELISA方法的IC50为4.78 ng/mL,最低检测限达0.03 ng/mL,加标回收率为75.45% ~91.75%.

  19. 5-氨基邻甲苯酚的合成工艺研究%Study on the Synthesis Process of 5-Amino O-methylphenol

    叶思景; 王街雄; 熊俊超; 程华


    The papaer introduced the synthesis of 5-amino o-methylphenol process route,and improved the synthesis process with o-toluidine as the basic raw material for the synthesis of large red base G,diazotization,hydrolysis,preparation of the final reduction in raw material selection,process parameter design,energy consumption.In the it made significant improvements and achieved great results,the main choice of o-toluidine as raw material,the use of orthogonal reaction conditions were optimized to obtain the appropriate reaction time,reaction temperature and the molar ratio and more good yield.Through analysis and comparison,the more advanced technology in the country,with material accessible,process stability,high yield,reasonable and reliable technology,the higher purity in target product and so on.%文章介绍了合成5-氨基邻甲苯酚工艺路线,并改进了以邻甲苯胺为合成基本原料进行合成大红色基G、重氮化、水解,最后还原的制备工艺,在原料选择、工艺参数设计、能耗方面做出了重大改进,并且取得了很大的效果,主要选择邻甲苯胺作原料,利用正交法优化了反应条件,得到了合适的反应时间、反应温度和投料比及较理想的产率。通过分析比较,该工艺在国内比较先进,具有原料易得、工艺稳定、收率高、技术合理可靠、目标产物纯度高等优点。

  20. N6-烷基-2-烷氧基腺苷化合物的合成及抗血小板凝集活性%Synthesis of 2-Alkoxy-N6-alkyl Adenosine Compounds and Their Anti-platelet Aggregation Activity

    吴兆军; 李顺来; 丁忠仁; 杜洪光


    Guanosine (1) as the starting material was protected by acetic anhydride to get 2',3',5'-tri-O-acetyl-guanosine (2), then chlorinated with phosphorus oxychloride to obtain 2-amino-6-chloro-9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)purine (3). Compound 3 was diazotized and hydrolyzed, subsequently reacted with several alkyl halides respectively to afford 2-alkoxy-6-chloro-9-(2',3',5'-tri-O-acetyl-β-D-ribofuranosyl)purine (4a~4c). 2-Alkoxy-N6-alkyl adenosine compounds 5a~5c were acquired by aminolysis and deprotection reaction of compounds 4a~4c. All compounds 5a~5c have not been reported so far. The structures of compounds 5a~5c were identified by 1H NMR, 13C NMR, IR and HRMS techniques. What is more, the anti-platelet aggregation rates for the final compounds were measured. At a concentration of 100 μmol/L, the test results of the biological activity of anti-platelet aggregation showed that N6-(4-methylbenzyl)-2-benzyloxy adenosine (5c3) and N6-(2-phenethyl)-2-benzyloxy adenosine (5c4) have a relatively low aggregation rate and have a certain anti-platelet aggregation activity.%以鸟瞟呤核苷(1)为原料,经羟基保护得到2’,3’,5’-三-O-乙酰基鸟嘌呤核苷(2),2与三氯氧磷反应得到2-氨基-6-氯-9-(2’,3’,5’-三-O-乙酰基-β-D-呋喃核糖)嘌呤(3),3经重氮化、水解和O-烷基化得到2-烷氧基-6-氯-9-(2’,3’,5’-三-O-乙酰基-β-D-呋喃核糖)嘌呤(4a~4c),4a~4c经胺解和水解脱保护反应得到12个未见报道的N6-烷基-2-烷氧基腺苷化合物5a~5c.化合物的结构经1HNMR,13C NMR,IR和HRMS等得到表征,同时对合成的N6-烷基-2-烷氧基腺苷化合物进行了抗血小板凝集活性测试.结果表明,在测试浓度为100 μmol/L时,N6-(4-甲基苄基)-2-苄氧基腺苷(5c3)和N6-(2-苯乙基)-2-苄氧基腺苷(5c4)具有相对较低的聚集率,具有一定的抗血小板凝集活性.

  1. Research progress of rosin based nitrogen heterocyclic derivatives%松香基含氮杂环衍生物的研究进展

    李娟; 李保同; 徐永霞; 刘泽学; 段久芳; 韩春蕊; 查显俊


    Rosin can be endowed with the special biological and optical activities by adding heterocyclic ring. Rosin based nitrogen heterocyclic derivatives introducing nitrogen heterocyclic ring in rosin is an important part of rosin derivatives. The progress of rosin based nitrogen heterocyclic derivatives,such as imidazoline,thiadizole,oxadiazoles,furazan,quinoline,indole,and acridine,are systematically summarized according to the modification of carboxyl,phenanthrene ring and composite. Classification is based on themodification of 18 carbonyl acylating,18 alkyl carbon atoms cyclization, 18 alkyl connected to the nitrogen atom cyclization,11,12 carbon ring formation,12,13 carbon ring formation,13,14 carbon ring formation and comprehensive cyclization according to the reaction of reduction,amination,acyl,condensation,closed loop on carboxyl and oxidation,electrophilic substitution reaction (bromine,selective nitration),diazotization,condensation and closed loop on phenanthrene ring. Not only the application of biological activity,corrosion activity,properties of fluorescence and surface activity are summarized in detail,but also the synthesis and development trends of rosin based nitrogen heterocyclic derivatives are reviewed and forecasted respectively. What is more,the development prospect of this compounds in functional areas,such as organic metal catalytic materials and dye-sensitized solar cells,is pointed out.%在松香中引入杂环,可赋予松香特殊的生物和光学等活性,而松香基含氮杂环衍生物则是在松香中引入含氮的杂环,是松香基衍生物的重要组成部分。本文以羧基改性、菲环改性和综合改性为主线,根据羧基上的还原、胺化、酰基化、缩合、闭环等反应和菲环上的氧化、亲电取代反应(溴代、选择性硝化)、重氮化、缩合和闭环等反应类型,由18位羰基酰化改性、18位烷基碳原子成环改性、18位烷基相连氮原子成环改性、11,12

  2. Phage as a Genetically Modifiable Supramacromolecule in Chemistry, Materials and Medicine.

    Cao, Binrui; Yang, Mingying; Mao, Chuanbin


    Filamentous bacteriophage (phage) is a genetically modifiable supramacromolecule. It can be pictured as a semiflexible nanofiber (∼900 nm long and ∼8 nm wide) made of a DNA core and a protein shell with the former genetically encoding the latter. Although phage bioengineering and phage display techniques were developed before the 1990s, these techniques have not been widely used for chemistry, materials, and biomedical research from the perspective of supramolecular chemistry until recently. Powered by our expertise in displaying a foreign peptide on its surface through engineering phage DNA, we have employed phage to identify target-specific peptides, construct novel organic-inorganic nanohybrids, develop biomaterials for disease treatment, and generate bioanalytical methods for disease diagnosis. Compared with conventional biomimetic chemistry, phage-based supramolecular chemistry represents a new frontier in chemistry, materials science, and medicine. In this Account, we introduce our recent successful efforts in phage-based supramolecular chemistry, by integrating the unique nanofiber-like phage structure and powerful peptide display techniques into the fields of chemistry, materials science, and medicine: (1) successfully synthesized and assembled silica, hydroxyapatite, and gold nanoparticles using phage templates to form novel functional materials; (2) chemically introduced azo units onto the phage to form photoresponsive functional azo-phage nanofibers via a diazotization reaction between aromatic amino groups and the tyrosine residues genetically displayed on phage surfaces; (3) assembled phage into 2D films for studying the effects of both biochemical (the peptide sequences displayed on the phages) and biophysical (the topographies of the phage films) cues on the proliferation and differentiation of mesenchymal stem cells (MSCs) and induced pluripotent stem cells (iPSCs) and identified peptides and topographies that can induce their osteogenic

  3. Adsorption Effect of AmberliteXAD-4 Resin Based Calix[4]arene on Bilirubin in Aqueous Medium%杯【4】芳烃修饰Amberlite XAD-4树脂对水介质中胆红素的吸附性能

    熊振湖; 朱乐; 王月


    通过偶氮化反应将杯【4】芳烃接枝到AmberliteXAD-4树脂上,采用FTIR、SEM等方法,表征了杯【4】芳烃修饰AmbertiteXAD-4树脂的结构.吸附实验表明,杯【4】芳烃修饰AmberliteXAD-4树脂对胆红素的吸附容量远远大于单纯AmberliteXAD-4树脂.在温度为25℃,胆红素浓度为20mg/L、吸附时间为2h的条件下,胆红素的平衡去除率在90%以上;而相同条件下的单纯AmberliteXAD-4树脂对胆红素的去除率仅为32.8%.水溶液中修饰树脂达到吸附平衡的时间为2h左右,而且温度越高达到平衡吸附的时间越短.在近中性(pH=5~7)条件下修饰树脂对胆红素的吸附容量达到最大值,为2.1medg,但随pH的降低或增大吸附容量均迅速降低.%The calix[4]arene is connected to Amberlite XAD-4 resin covalently through a diazotization reaction. The structure of Amberlite XAD-4 resin based on calix[4]arene is characterized using FT-IR, SEM. The sorption results show that Amberlite XAD-4 resin based on calix[4]arene has much better removal to the bilirubin in aqueous solutions than Amberlite XAD-4 resin which are presence alone in aqueous solutions. The removal rate of bilirubin is over 90% at equilibrium, at the conditions of 25℃, the concentration of bilirubin is 20 mg/L and the adsorption time is 2 h. At the same conditions, the removal of bilirubin from Amberlite XAD-4 resin is 2.8% alone. The equilibrium time is 2h and decreases with an increase in temperature. When the aqueous solution stays near the neutral (pH = 5 - 7), the adsorption capacity of Amberlite XAD-4 resin modified with calix[4]arene to the bilirubin reaches maximum value, which is 2.1 mg/g but the value decreases rapidly when the pH increases or decreases

  4. Removal of diclofenac on calyx [4] arene based Amberlite XAD-4 resin from aqueous solutions.%杯[4]芳烃修饰Amberlite XAD-4树脂去除水中双氯芬酸

    王月; 熊振湖; 周建国


    The calyx [4] arene was synthesized and connected to Amberlite XAD-4 resin covalently through a diazotization bound. The structure of Amberlite XAD-4 resin base on calyx [4] arene was characterized using FT-IR, SEM and TG/DTA. The sorption results showed that Amberlite XAD-4 resin base on calyx [4] arene had much better removal to the diclofenac in aqueous solutions than Amberlite XAD-4 resin and calyx [4] arene which were presence alone in aqueous solutions. The removal rate of diclofenac increased rapidly with the calyx [4] arene modified Amberlite XAD-4 resin dosage. In the condition of DCF concentration was 20mg/L, when the Amberlite XAD-4 resin base on calyx [4] arene dosage came up to 80mg/L, the removal rate of diclofenac was 92.8% and reached equilibrium, the corresponding amount adsorbed was 34.02mg/g. Kinetic analyses were conducted using pseudo first-order and second-order models. The linear correlation coefficients and standard deviations of Langmuir and Freundlich isotherms were determined, and the results revealed that Langmuir and Freundlich isotherm were fitted the experimental data well. The thermodynamic parameters calculated indicated, AH and AG were negative, which predicated adsorption process of diclofenac on f Amberlite XAD-4 resin base on calyx [4] arene resin was exothermic and spontaneous.%通过偶氮化反应将合成的去叔丁基杯[4]芳烃连接到Amberlite XAD-4树脂上,并且采用FTIR、SEM和TG/DTA法表征了杯[4]芳烃修饰Amberlite XAD-4树脂的结构.结果表明,水溶液中杯[4]芳烃修饰Amberlite XAD-4树脂对双氯芬酸的去除率远大于单独AmberliteXAD-4树脂和杯[4]芳烃.双氯芬酸的浓度为20mg/L时,随着杯[4]芳烃修饰AmberliteXAD-4树脂投加量的增加,双氯芬酸的去除率增加很快.当吸附剂量增加到80mg/L时,双氯芬酸的去除率为92.8%,并且达到吸附平衡,吸附的双氯芬酸量为34.02mg/g.Langmuir和Freundlich等温线与实验数据均有很好的拟合度.

  5. 《化学通报》网络版(Chemistry Online)2001年4月论文摘要


    B在155℃分解,生成2,6-二氯氟苯(C),产率91.5%;C在无水Na2SO4作用下与HNO3/H2SO4在15℃反应90min,得到2,6-二氯-3-硝基氟苯(D),产率95.1%;D在18-冠-6的催化下与氟化钾在150℃反应12h,重复套用母液,得到2,3,4-三氟硝基苯(E),平均产率62.0%。标题化合物E的总收率达到47.9%,纯度为99.0%。   2,3,4-Trifluoronitrobenzene was synthesized from 2,6\\|dichloroaniline (A) through four steps:(1)diazotization with NaNO2/HCl,HBF4 to give 2,6\\|dichlorophenyl\\|diazonium borofluoride complex (B);(2)decomposition of B at 155℃ to form 2,6\\|dichloro\\|fluorobenzene (C);(3)nitration in the presence of anhydrous Na2SO4 with the formation of 2,6\\|dichloro\\|3\\|nitro fluorobenzene (D);(4) fluorization by reaction with KF in the presence of 18\\|crown\\|6 at 150℃ to give the titled product.The overall yield from A reaches 47.9% with 99.0% purity. [W01039] 甲状腺激素及其脱碘酶 Thyroxine and Deiodinase 廉革伟 丁 兰 赵大庆 倪嘉缵** (中国科学院长春应用化学研究所稀土化学与物理开放实验室 长春 130022)   本文对甲状腺素、脱碘酶及其模拟研究进行了综述。评述了本领域中存在的问题,并就脱碘酶、其催化机制及其模拟研究的方向提出了作者的看法。   Thyroxine,deiodinase and its mimics are reviewed in this paper,the problems in this field are discussed and the trends of the studies in the field proposed. [W01040] 生物膜传质研究进展* Progress in the Mass Transfer through Biofilms 曹宏斌 钟方丽 李鑫钢** (天津大学化工学院化学工程研究所 天津 300072)   基质向生物膜传递的速率直接影响到生物膜在许多领域的应用效率。近年来,研究人员对它进行了广泛的研究。本文重点介绍近年来国内外有关生物膜结构和生物膜内、外传质的研究成果。   Mass transport rates beside