Electronic spectra of salts of dithiocarbamic acids

1979 ◽  
Vol 44 (8) ◽  
pp. 2487-2493 ◽  
Author(s):  
Drahomír Oktavec ◽  
Jozef Štefanec ◽  
Bohumil Síleš ◽  
Václav Konečný ◽  
Ján Garaj

The report gives synthesis and UV spectra of a series of alkali and ammonium salts of the dithiocarbamic acids derived from dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, diisopropyl-, diisobutyl-, methylisopropylamine, piperidine, morpholine, piperazine and pyrrolidine. The absorption bands due to transitions localized in the groups CSS (λmax ~ 260 nm) and NCS (λmax ~ 280 nm) show a red shift with increasing length of the alkyl chain. Increasing polarity of solvent causes, with some of the compounds, a small red shift of λmax of the band due to CSS group, but it causes a considerable blue shift of λmax of the band due to NCS group in all the studied compounds. The absorption band near 207 nm is ascribed to the carbon disulphide produced by decomposition of the dithiocarbamates.

1980 ◽  
Vol 45 (3) ◽  
pp. 791-799 ◽  
Author(s):  
Drahomír Oktavec ◽  
Bohumil Síleš ◽  
Jozef Štefanec ◽  
Elena Korgová ◽  
Ján Garaj

The synthesis and electronic spectra of the chelates of nickel(II) dithiocarbamates with ligands derived from dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, diisopropyl-, methylisopropylamine, piperidine, morpholine and piperazine are discussed. The absorption bands in the chelate spectra around 220 and 245 nm are assigned to absorption localized primarily in the S-C=S and N-C=S ligand groups. The analytically most important band with λmax around 330 nm assigned to M-L charge transfer is affected by alkyl substituents on the nitrogen atom and by the solvent polarity. The lengthening of the alkyl chain causes the increase in the intensity of the band and red-shift of its λmax; the increase of the polarity of the solvent leads to an increase in the band intensity and a blue shift.


1982 ◽  
Vol 47 (11) ◽  
pp. 2867-2875 ◽  
Author(s):  
Drahomír Oktavec ◽  
Jozef Štefanec ◽  
Bohumil Síleš ◽  
Ernest Beinrohr ◽  
Václav Konečný ◽  
...  

This work deals with the synthesis of dithiocarbamate chelates of Cu(II) and Zn(II) with ligands derived from dimethyl-, diethyl-, dipropyl-, dibutyl- and methylisopropylamine, piperidine and morpholine and the electronic spectra of these substances in the UV and visible regions. The absorption spectra of the cupric (and zinc(II)) chelates contain a single analytically important band around 270 (260) nm, assigned to the π-π* transition within the ligand, that is affected by the substituent on the nitrogen atom and the solvent polarity. Lengthening of the alkyl chain leads to increased intensity of the bands and a red shift of their λmax; increased solvent polarity leads to increased intensity of the bands and a blue shift.


Author(s):  
Xiaoyu Yuan ◽  
Shengke Yang ◽  
Jie Fang ◽  
Xueli Wang ◽  
Haizhen Ma ◽  
...  

In this study, the interaction between the humus and two antibiotics was studied by UV-Vis spectroscopy to describe the interaction mechanism and the effects of different environmental factors on the mechanism. Results showed that humic acid (HA) containing more aromatic groups was easily associated with antibiotics. In the HA-OTC, with the increase of the concentration of OTC, there were obvious absorption peaks in the 230–260 nm and 330–360 nm range, and the absorption band of the HA ultraviolet spectrum underwent a slight blue shift and the absorption intensity increased, demonstrating that a new ground state complex was generated. In the HA-SD, with the increase of SD concentration, an aromatic structure absorption peak appeared in the 190–220 nm range, and the peak value increased and the absorption band underwent a red shift, and the aromatization of HA decreased, which enhanced the interaction between the antibiotics and HA. With the increase of pH, the absorption band of HA, HA-OTC and HA-SD ultraviolet spectrum suffered a blue shift, the degree of polymerization of HA molecules decreased, and the number of adsorption binding sites increased, which resulted in the interaction of HA with antibiotics being enhanced. The absorption band of HA, HA-OTC and HA-SD displayed a red shift with the increase of ionic strength, which indicated that the repulsion within HA particles was weakened, and the molecular polymerization was strengthened and therefore, the interaction between antibiotics and HA was inhibited. The UV characteristics of the HA, HA-OTC and HA-SD systems were insensitive to the temperature. This study lays the foundation for better studying the effect of humus on the distribution of antibiotic residues in the environment.


2018 ◽  
pp. 57-62
Author(s):  
V. M. Odyntsova

The development of pharmaceutical chemistry confronts molecular spectroscopy the problem of calculating the electronic states, assumptions and explanations of the various properties of complex organic compounds. In recent years, following the basic optical characteristics of the electronic absorption spectra: the wave number of maximum absorption – νmax (in cm-1), the half-width of the absorption bands of – ∆ν1/2 (cm-1), the integral intensity of the absorption band (in l/mol·cm2), the oscillator strength of the electronic transition – f, the matrix element of the transition of electrons – Mik. began widely used. These constants allow you to determine the chromophores in the investigated substances, to establish the probability and the resolution of the electrons’ transition. Our goal was the calculation and study of the basic optical characteristics of the electronic absorption spectra of 5-(adamantane-1-yl)-4R-1,2,4-triazole-3-thione, namely 5-(adamantane-1-yl)-4-methyl-1,2,4-triazole-3-thione and 5-(adamantane-1-yl)-4-phenyl-1,2,4-triazole-3-thione derivatives. When deciding about the purity of the compounds we used melting point, thin layer chromatography and the results of elemental analysis. UV spectra of the investigated compounds was measured with a spectrophotometer Specord 200-222U214 (Germany). Elemental analyzer GmbH (Germany) was used for carrying out the elemental analysis. It is determined that the values of the half-width Δν½ and integrated intensity of the absorption bands (A), the oscillator strength (f) and matrix element of the transition (Mik) can be used as an important constants of 5-(adamantane-1-yl)-4R-1,2,4-triazole-3-thione derivatives for their identification and establishing a deep connection between spectra and structure of the molecule. For the studied compounds is the most characteristic absorption band in the medium wave spectrum with high values of A and f, which indicate about the permitted and probable transitions of electrons which give rise to the observed maxima. Based on the study of the basic optical characteristics of the electronic absorption spectra of 5-(adamantane-1-yl)-4R-1,2,4-triazole-3-thione derivatives is found that chromatofor in the studied molecules is the structure of 1,2,4-triazole and substituents (adamantane, methyl and phenyl radicals). A distinctive feature, namely 5-(adamantane-1-yl)-4-phenyl-1,2,4-triazole-3-thione 5-(adamantane-1-yl)-4-methyl-1,2,4-triazole-3-tion are the values A, f, Mik, which can be used to identify the investigated compounds.


In a previous paper, which gave an account of work on the infra-red absorption spectrum of nitrogen tetroxide there was necessarily included a preliminary survey of the spectrum of the dioxide, but no detailed description was given of the absorption bands, nor was any attempt made to deduce the structure of this molecule. Since that paper was communicated several other investigators have published accounts of work on the infra-red and electronic spectra of these two molecules and conflicting views have been expressed regarding the structure of the dioxide molecule. Bailey and Cassie ( loc. cit. ) have favoured a liner symmetrical structure resembling that of carbon dioxide or carbon disulphide, while Harris, Benedict and King and also Schaffert ( loc. cit. ) have contended that the form of the molecule is triangular with the nitrogen atom at the apex of an isosceles triangle. None of these workers report having examined any of the infra-red bands under high dispersion, although the contours of two of the strongest of the dioxide bands were reported by Bailey and Cassie. Yet a detailed knowledge of any possible fine structure in the strongest bands and of the contours of at least some of the weaker bands is of supreme importance in deciding the structure of the molecule. The purpose of the present paper is to give an account of the examination of the infra-red spectrum of the dioxide under high dispersion and from a critical discussion of the present date to show that all the evidence is in favour of this molecule having a triangular form. Experimental . For details of the experimental procedure the reader is referred to the earlier paper on nitrogen tetroxide and Table I contains a list of the observed bands as there given. Since the examination of the absorption beyond 1450 cm. -1 was done using a cell with rock-salt windows, it was not possible at that time to decide whether the absorption near 1350 cm. -1 was a true absorption band of NO 2 or whether it was due to the sodium nitrite which formed on the windows of the cell. The work of Schaffert ( loc. cit. ) in which a cell with very thin mica windows was used proves beyond doubt that there is an absorption band of NO 2 at 1373 cm. -1 . Again our observations were confined to wave-lengths less than 14 μ so we did not observe the absorption, which has also been confirmed by Schaffert ( loc. cit. ), reported by Bailey and Cassie ( loc. cit. ) at 15⋅6 μ (641 cm. -1 ).


2018 ◽  
Author(s):  
Adrian Cernescu ◽  
Michał Szuwarzyński ◽  
Urszula Kwolek ◽  
Karol Wolski ◽  
Paweł Wydro ◽  
...  

<div><div>Scattering-mode Scanning Near-Field Optical Microscopy (sSNOM) allows one to obtain absorption spectra in the mid-IR region for samples as small as 20 nm in size. This configuration has made it possible to measure FTIR spectra of the protein complement of membranes. (Amenabar 2013) We now show that mid-IR sSNOM has the sensitivity required to measure spectra of phospholipids in individual bilayers in the spectral range 800 cm<sup>-1</sup>–1400 cm<sup>-1</sup>. We have observed the main absorption bands of the dipalmitoylphosphatidylcholine headgroups in this spectral region above noise level. We have also mapped the phosphate absorption band at 1070 cm<sup>-1</sup> simultaneously with the AFM topography. We have shown that we could achieve sufficient contrast to discriminate between single and multiple phospholipid bilayers and other structures, such as liposomes. This work opens the way to further research that uses nano-IR spectroscopy to describe the biochemistry of cell membranes and model systems.</div></div><div></div>


2001 ◽  
Vol 56 (9-10) ◽  
pp. 878-885 ◽  
Author(s):  
Anna Krasowska ◽  
Maria Stasiuk ◽  
Malgorzata Oswiecimska ◽  
Arkadiusz Kozubek ◽  
Malgorzata Bien ◽  
...  

AbstractThree new groups of phenolic antioxidants, quaternary ammonium salts with a phenol ring and alkyl chains of different length (pyrrolidine ethyl esters of 3,5-di-t-butyl-4-hydroxydihydrocinnamic acid n-alkoxymethylchlorides (PYE-n) or n-alkylbromides (PYA-n) and 2-dimethylaminoethyl ester n-alkylbromides (PPA-n), were synthesized. Some of them were previously found to efficiently protect yeast cells against oxidants and to inhibit the production of thiobarbituric acid-reactive substances in whole yeast cells and in isolated membrane lipids. The new antioxidants (at 1-100 μm) abolished or diminished peroxidation of oliwe oil emulsions caused by the OH•-producing Fe2+ and RO• and ROO•-producing tertbutylhydroperoxide (TBHP) and the azo compounds 2,2′-azobis-(amidinopropane)dihydronitrile (AAPH) and 1,1′-azobis-(1-cyclohexanecarbonitrile) (ACHN): all present at 10 mᴍ . The efficiency of individual both antioxidants was examined in relation to the type of lipid peroxidation inducer, the site of antioxidant incorporation into the emulsion lipid phase, the length of the alkyl chain, and the maximum concentration of effective antioxidant monomers given by its critical micelle concentration. PYA-n class compounds were highly efficient against all peroxidation inducers and their efficiency did not depend on the position of their molecules in the lipid phase and/or on the aliphatic chain length. In contrast, the efficiency of PYE-n and PPA-n class compounds depended both on the type of oxidant and on the length of their aliphatic chain. Their potency against Fe2+ and ACHN increased with increasing alkyl chain length whereas with AAPH it dropped with increasing alkyl chain length. A similar pattern was found with the action of PYE-n against TBHP whereas in the PPA-n group an extending alkyl chain reduced the anti-TBHP efficiency. These relationships may not be entirely straightforward and other factors (chemical nature of each compound, its possible interaction with fluorescent probes used for diagnostics, etc.) may play a considerable and not yet quite clear role. PPA-n class antioxidants have the lowest critical micelle concentration, which may limit their efficiency. Nevertheless, these phenolic antioxidants can be conveniently employed as highly efficient inhibitors of lipid peroxidation.


1883 ◽  
Vol 36 (228-231) ◽  
pp. 285-286

After the reading of the note on chlorophyll at the meeting of the society on December 13th, I was reminded by Professor Stokes that e and others had succeeded in separating the complex to which the erm chlorophyll had previously been applied into two substances, or ather groups of substances, one characterised by its green colour and ed fluorescence, the other showing a more distinctly yellow colour without fluorescence, and he suggested to me that it would be advisable to ascertain whether the property of yielding glucose by decomposition with acids might not belong to one of these substances or groups of substances only. Professor Stokes at the same time kindly communicated to me the details of the process whereby he succeeded n effecting the separation referred to, a process depending on the action of carbon disulphide in' removing some of the bodies contained n an alcoholic solution of crude chlorophyll in preference to others. The process employed for the same purpose by Mr. Sorby is essentially the same. Before applying disulphide of carbon to an alcoholic extract of green leaves according to the process of Professor Stokes, it was necessary first to remove the ready-formed glucose, tannin, and other matters soluble in water, which almost always exist in such extracts, and which would by their presence have rendered the result of the experiment quite uncertain. This was done in the way I have already described. An ethereal solution of chlorophyll prepared by my method was evaporated, and the residue having been dissolved in alcohol, the solution was mixed with a quantity of carbon disulphide larger than the alcohol would dissolve, and the mixture well shaken. The carbon disulphide acquired a dark green colour, while the supernatant alcoholic liquid, containing principally the xanthophyll of Professor Stokes and Mr. Sorby, was yellow with a tinge of green. The two liquids having been separated, the lower dark green one was washed several times with alcohol to remove any of the xanthophyll that might still be present, and having then been mixed with a large quantity of alcohol, a current of air was passed through it to remove the excess of carbon disulphide as directed by Professor Stokes. In this way I obtained two liquids, one intensely green, the other deep yellow with only a tinge of green. The two liquids were found to contain substances essentially different so far as regards their products of decomposition with acids. The yellow liquid having been mixed with dilute sulphuric acid was evaporated in the waterbath, water being added during evaporation, until the liquid had lost nearly all its colour. A quantity of yellow fatty matter separated during evaporation, and this having been filtered off the liquid was found to contain an abundance of glucose. The yellow fatty matter insoluble in water, dissolved easily in alcohol, but the yellow solutio showed none of the characteristic absorption bands of “acid chloro phyll.” The dark green liquid, treated in exactly the same way yielded a dark green product insoluble in water. The filtrate Iron this gave a slight reaction with Fehling’s solution, but so trifling comparatively that I am inclined to attribute it to the presence o some substance not completely removed from the disulphide of carboi solution by washing with alcohol. The dark green product of tin action of acid insoluble in water was soluble, though with difficultyin boiling alcohol, the solution being dull green and showing the absorption bands due to “acid chlorophyll.” If, therefore, chloro phyll be defined as the constituent of the green parts of plants, which gives a spectrum showing the well-known bands at the red end, and yields by decomposition with acids the product or products going by the name of “acid chlorophyll,” of which Fremy’s phyllocyanin is the most important and most characteristic, then chlorophyll is not a glucoside. The glucoside which accompanies it and resembles it as regards solubility in various menstrua may have to be sought among the group of bodies to which the generic name of xanthophyll has been applied.


1987 ◽  
Vol 65 (9) ◽  
pp. 2013-2018 ◽  
Author(s):  
R. Manoharan ◽  
Sneh K. Dogra

The red shift observed in the absorption spectrum of 2,7-diaminofluorene (DAF) in ether and acetonitrile is either due to the proton-donating capacity of the solute or due to its dispersive interactions with the solvent and a blue shift in methanol and water is due to the proton-accepting nature of DAF. DAF acts as a proton donor in S1 state in all solvents. The red shift in the fluorescence spectrum of the monocation of DAF relative to that of DAF is not because of the —NH2 group becoming more basic but because of the large solvent relaxating in aqueous medium. On the other hand, the monocation of DAF in cyclohexane follows the normal blue shift in the fluorescence spectrum. pKa values for the various prototropic reactions in S0 and S1 states are determined and discussed.


Sign in / Sign up

Export Citation Format

Share Document