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Trichocyanines: a Red-Hair-Inspired Modular Platform for Dye-Based One-Time-Pad Molecular Cryptography.

Leone L, Pezzella A, Crescenzi O, Napolitano A, Barone V, d'Ischia M - ChemistryOpen (2015)

Bottom Line: These novel acidichromic cyanine-type dyes inspired by red hair pigments were synthesized and characterized with the aid of density functional theory (DFT) calculations.This versatile dye platform can generate an expandable palette of colors and appears to be specifically suited to implement an unprecedented single-use asymmetric molecular cryptography system.With this system, we intend to pioneer the translation of digital public-key cryptography into a chemical-coding one-time-pad-like system.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemical Sciences, University of Naples Federico II Via Cintia 4, 80126, Naples, Italy.

ABSTRACT
Current molecular cryptography (MoCryp) systems are almost exclusively based on DNA chemistry and reports of cryptography technologies based on other less complex chemical systems are lacking. We describe herein, as proof of concept, the prototype of the first asymmetric MoCryp system, based on an 8-compound set of a novel bioinspired class of cyanine-type dyes called trichocyanines. These novel acidichromic cyanine-type dyes inspired by red hair pigments were synthesized and characterized with the aid of density functional theory (DFT) calculations. Trichocyanines consist of a modular scaffold easily accessible via an expedient condensation of 3-phenyl- or 3-methyl-2H-1,4-benzothiazines with N-dimethyl- or o-methoxyhydroxy-substituted benzaldehyde or cinnamaldehyde derivatives. The eight representative members synthesized herein can be classified as belonging to two three-state systems tunable through four different control points. This versatile dye platform can generate an expandable palette of colors and appears to be specifically suited to implement an unprecedented single-use asymmetric molecular cryptography system. With this system, we intend to pioneer the translation of digital public-key cryptography into a chemical-coding one-time-pad-like system.

No MeSH data available.


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Color changes and charge states of trichocyanines 1–4 under different pH conditions.
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fig04: Color changes and charge states of trichocyanines 1–4 under different pH conditions.

Mentions: With all compounds, a significant bathochromic shift (>100 nm) was observed upon protonation, which modified and intensified the visible color remarkably. Whereas the dimethylamino-substituted derivatives display a marked ipsochromic shift accompanied by discoloration at pH<3, suggesting a doubly cationic state resulting from protonation of the dimethylamino group, the hydroxy derivatives display an opposite bathochromic shift upon increasing pH from 7 to 11, which can be accounted for by the onset of a deprotonated anion state. A list of the spectrophotometrically measured pKa values for all compounds is given in Table S2 in the Supporting Information. Based on this, it was verified that an addition sequence of ammonia–acetic acid–hydrochloric acid to compounds 1–4 implements two different series of three-state systems in the pH range of 0–11, corresponding to a (+2)–(+1)–(0) charge pattern for 1–2 (featuring the dimethylamino group—N-series) and to (+1)–(0)–(−1) for 3–4 (bearing the 3-OMe-4-OH substitution pattern—O series) (Figure 4).


Trichocyanines: a Red-Hair-Inspired Modular Platform for Dye-Based One-Time-Pad Molecular Cryptography.

Leone L, Pezzella A, Crescenzi O, Napolitano A, Barone V, d'Ischia M - ChemistryOpen (2015)

Color changes and charge states of trichocyanines 1–4 under different pH conditions.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4522187&req=5

fig04: Color changes and charge states of trichocyanines 1–4 under different pH conditions.
Mentions: With all compounds, a significant bathochromic shift (>100 nm) was observed upon protonation, which modified and intensified the visible color remarkably. Whereas the dimethylamino-substituted derivatives display a marked ipsochromic shift accompanied by discoloration at pH<3, suggesting a doubly cationic state resulting from protonation of the dimethylamino group, the hydroxy derivatives display an opposite bathochromic shift upon increasing pH from 7 to 11, which can be accounted for by the onset of a deprotonated anion state. A list of the spectrophotometrically measured pKa values for all compounds is given in Table S2 in the Supporting Information. Based on this, it was verified that an addition sequence of ammonia–acetic acid–hydrochloric acid to compounds 1–4 implements two different series of three-state systems in the pH range of 0–11, corresponding to a (+2)–(+1)–(0) charge pattern for 1–2 (featuring the dimethylamino group—N-series) and to (+1)–(0)–(−1) for 3–4 (bearing the 3-OMe-4-OH substitution pattern—O series) (Figure 4).

Bottom Line: These novel acidichromic cyanine-type dyes inspired by red hair pigments were synthesized and characterized with the aid of density functional theory (DFT) calculations.This versatile dye platform can generate an expandable palette of colors and appears to be specifically suited to implement an unprecedented single-use asymmetric molecular cryptography system.With this system, we intend to pioneer the translation of digital public-key cryptography into a chemical-coding one-time-pad-like system.

View Article: PubMed Central - PubMed

Affiliation: Department of Chemical Sciences, University of Naples Federico II Via Cintia 4, 80126, Naples, Italy.

ABSTRACT
Current molecular cryptography (MoCryp) systems are almost exclusively based on DNA chemistry and reports of cryptography technologies based on other less complex chemical systems are lacking. We describe herein, as proof of concept, the prototype of the first asymmetric MoCryp system, based on an 8-compound set of a novel bioinspired class of cyanine-type dyes called trichocyanines. These novel acidichromic cyanine-type dyes inspired by red hair pigments were synthesized and characterized with the aid of density functional theory (DFT) calculations. Trichocyanines consist of a modular scaffold easily accessible via an expedient condensation of 3-phenyl- or 3-methyl-2H-1,4-benzothiazines with N-dimethyl- or o-methoxyhydroxy-substituted benzaldehyde or cinnamaldehyde derivatives. The eight representative members synthesized herein can be classified as belonging to two three-state systems tunable through four different control points. This versatile dye platform can generate an expandable palette of colors and appears to be specifically suited to implement an unprecedented single-use asymmetric molecular cryptography system. With this system, we intend to pioneer the translation of digital public-key cryptography into a chemical-coding one-time-pad-like system.

No MeSH data available.


Related in: MedlinePlus