Structure and photochemistry of a novel tetrazole-saccharyl conjugate isolated in solid argon

Ismael, A.; Borba, Ana; Duarte, Luís F.; Giuliano, B. M.; Gómez‐Zavaglia, Andrea; Cristiano, Maria Lurdes Santos

doi:10.1016/j.molstruc.2012.04.081

Cited by 9 publications

(12 citation statements)

References 45 publications

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“…From previous studies on pseudosaccharins, three isomers were reported for 2-allyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (ABIOD) [4], five isomers for allyl ether 3-(allyloxy)-1,2-benzisothiazole1,1-dioxide (ABID) [13] and six isomers for tetrazole-saccharyl [14]. The isomers for each pseudosaccharyl molecule were obtained through the rotation of two dihedral angles as will be explained in the next subsections.…”

Section: Resultsmentioning

confidence: 99%

“…In previous studies [4,13,14], the importance of isomerization in these systems has been demonstrated. As the R group can be very flexible, it gives rise to several possible isomers.…”

Section: Density Functional Calculations -Recent Progresses Of Theorymentioning

confidence: 93%

“…Tautomers are called as 1H tautomer and 2H tautomer, the first one is obtained when H is bonded to atom number 5 (Figure 2(c)) and the second one is obtained when H is bonded to the nitrogen atom beside to atom number 5 (Figure 2(d)) [14]. Relative energies were obtained for the same levels of theory as previous subsections.…”

Section: Density Functional Calculations -Recent Progresses Of Theorymentioning

confidence: 95%

“…Relaxation of molecular structures, vibrational frequencies, rotational constants and excited states were obtained through B3LYP [17,18], M06-2X [19] and PBE [20] exchange-correlation (XC) functionals, along with 6-311++G(3df,3pd), 6-31++G(3df,3pd), 6-311+G(d,p) and 6-31+G(d,p) [21,22] basis. The choice of the methodology was made taking as a starting point the level of theory used in previous studies [4,13,14]. Additionally, the other functionals and BSs were used in order to be able to compare the results and analyze the importance of the methodology.…”

Section: Theoretical Backgroundmentioning

confidence: 99%

“…were named according to the letters G = gauge ≈ 60°, Sk = Skew ≈ 120°, G′ = gauge′ ≈ −60°, Sk′ = Skew′ ≈ −120°, the angle formed by the atoms numbered as 1, 2, 3 and 4 was used to assign the first letter, while the angle formed by the atoms numbered as 2, 3, 4 and 5 were taken as reference for the second letter [14].…”

Section: Density Functional Calculations -Recent Progresses Of Theorymentioning

confidence: 99%

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DFT Calculations and Statistical Mechanics Applied to Isomerization of Pseudosaccharins

Cisneros-García¹,

Velázquez²,

Tenorio³

et al. 2018

Density Functional Calculations - Recent Progresses of Theory and Application

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In the present work, molar fractions were obtained as a function of temperature with different levels of theory for the most representative isomers of three systems belonging to the family of pseudosaccharins. The choice of those three systems was due to the fact that it is known in the scientific literature that these systems present very small differences in their relative energies which make a complicated experimental characterization, in addition these compounds are of interest in the biological area. These systems represent challenges not only from an experimental point of view but also from a theoretical point of view. From the theoretical perspective, this study is also complicated since several possible isomers with very similar energies are presented. The diagrams of species distribution (molar fractions) provide information that cannot be accessed through the electronic structure calculations at T = 0. Here, this tool was useful to identify the most probable isomer from several quasi-degenerate isomers and to discern if thermal effects favor any of them, as well as to find trends despite the different results of each level of theory.Additionally, an analysis was performed on vibrational, rotational and electronic data in order to know the reason of the behavior of molar fractions as function of temperature.

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Section: Resultsmentioning

confidence: 99%

“…In previous studies [4,13,14], the importance of isomerization in these systems has been demonstrated. As the R group can be very flexible, it gives rise to several possible isomers.…”

Section: Density Functional Calculations -Recent Progresses Of Theorymentioning

confidence: 93%

Section: Density Functional Calculations -Recent Progresses Of Theorymentioning

confidence: 95%

Section: Theoretical Backgroundmentioning

confidence: 99%

Section: Density Functional Calculations -Recent Progresses Of Theorymentioning

confidence: 99%

See 3 more Smart Citations

DFT Calculations and Statistical Mechanics Applied to Isomerization of Pseudosaccharins

Cisneros-García¹,

Velázquez²,

Tenorio³

et al. 2018

Density Functional Calculations - Recent Progresses of Theory and Application

View full text Add to dashboard Cite

show abstract

1,2‐Benzisothiazole 1,1‐Dioxide (Saccharinate)‐Based Compounds Synthesis, Reactivity and Applications

Frija

Fernandes

Guerreiro

et al. 2022

More Synthetic Approaches to Nonaromatic Nitrogen Heterocycles

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Synthesis, Structure, and Cytotoxicity of a New Sulphanyl‐Bridged Thiadiazolyl‐Saccharinate Conjugate: The Relevance of S⋅⋅⋅N Interaction

Cabral

Brás

Henriques

et al. 2018

Chemistry A European J

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Reports showing that the copper concentration is considerably higher in neoplasms than in normal tissues prompted the need to develop selective copper chelators. We disclosed recently that some N-linked tetrazole-saccharinates bind selectively to copper, forming complexes that are highly cytotoxic towards cancer cells. Because tetrazole-saccharinates are photolabile, due to the photoreactivity of tetrazoles, we proposed thiadiazolyl-saccharinates as an alternative. Herein we describe the synthesis, structure, and monomeric photochemistry of a sulphanyl-bridged thiadiazolyl-saccharinate, 3-[(5-methyl-1,3,4-thiadiazol-2-yl)sulphanyl]-1,2-benzothiazole 1,1-dioxide (MTSB). The monomeric structure, charge density analysis, and characteristic infrared spectrum of MTSB were investigated theoretically, using quantum chemical calculations, and also experimentally, using matrix-isolation infrared spectroscopy. The crystal structure was investigated by combining X-ray crystallography with infrared and Raman spectroscopies. Results show that the structure of isolated MTSB is similar to that found in the crystal, with an S⋅⋅⋅N interaction clearly contributing to the structure of the molecule and of the crystal. Matrix irradiation revealed a high photostability of MTSB, compared to parent tetrazole-saccharinates and to the 5-methyl-1,3,4-thiadiazole building block, emphasizing the photostabilizing effect of the saccharyl system. Finally, in vitro toxicity assays of MTSB showed a copper concentration-dependent toxicity against cancer cells, without affecting normal cells. In particular, MTSB was most effective towards the hepatic (HepG2), neuroblastoma (SH-SY5), and lymphoma cell lines (U937). Thus, MTSB represents a promising lead for cancer chemotherapy based on chelating agents.

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Structure and photochemistry of a novel tetrazole-saccharyl conjugate isolated in solid argon

Cited by 9 publications

References 45 publications

DFT Calculations and Statistical Mechanics Applied to Isomerization of Pseudosaccharins

DFT Calculations and Statistical Mechanics Applied to Isomerization of Pseudosaccharins

1,2‐Benzisothiazole 1,1‐Dioxide (Saccharinate)‐Based Compounds Synthesis, Reactivity and Applications

Synthesis, Structure, and Cytotoxicity of a New Sulphanyl‐Bridged Thiadiazolyl‐Saccharinate Conjugate: The Relevance of S⋅⋅⋅N Interaction

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