Structure of genipin in solution: a combined experimental and theoretical study

Tommaso, Stefania Di; David, Priscilla; Picolet, Karine; Gabant, Marion; David, Hervé; Morancais, J. L.; Gomar, Jérôme; Leroy, Frédéric; Adamo, Carlo

doi:10.1039/c3ra42147c

Cited by 15 publications

(25 citation statements)

References 35 publications

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“…In the second step, another amine group from the biopolymer (in blue) will attack the methoxycarbonyl group to produce a secondary amide-type linkage, with the concomitant release of methanol, to produce the crosslinked compound 20. As commented in the section before, according to Di Tomasso et al [68,69] probably the first step would alternatively proceed via a previous opening of the hemiacetal 1 to the dialdehyde 4, which will be attacked by the amino group in red of the biopolymer to furnish 20.…”

Section: Reactivity Of Genipin As Cross-linker Agentmentioning

confidence: 98%

“…In spite of the high industrial applicability of genipin and the great number of processes in which it has been used, a full characterization of its structure has not been available until recently [68,69]. In fact, the structure of genipin in solid state was described by Trevor et al (2008), assigning the absolute configuration of the three sterocentres of the molecule as 1S, 4aR, 7aR [70].…”

Section: Chemisty Of Genipinmentioning

confidence: 99%

“…In fact, the structure of genipin in solid state was described by Trevor et al (2008), assigning the absolute configuration of the three sterocentres of the molecule as 1S, 4aR, 7aR [70]. Di Tommaso et al (2013) reported a detailed study (using 1H-NMR and corroborated by computational chemistry) of the structure of genipin in solution at different pH values [68]. These authors described that at highly alkaline pH values (around 13) genipin is not stable and undergoes self-polymerization; while in slightly alkaline medium (pH = 8) 1H-NMR signals indicate the existence of a single compound in which both rings are fused following a cis stereochemistry.…”

Section: Chemisty Of Genipinmentioning

confidence: 99%

“…Nevertheless, if the contribution of one (six-members ring TS 1-2 (H 2 O)) or two (eight-members ring TS 1-2 (H 2 O) 2 ) is considered, as shown in Figure 4, the activation energy drops to about 29 and 17 kcal mol −1 , respectively, due to the decrease of the ring strain. In addition, the process becomes less endothermic (5.6 kcal mol −1 ) when two molecules of water are added [68].…”

Section: Chemisty Of Genipinmentioning

confidence: 99%

“…Similarly, the conversion of 2 into 4 via transition state TS 2-4 ( Figure 3) was also modelled [68], reporting an activation enthalpy of 60 kcal mol −1 (no water involved) which is reduced to 22.3 kcal mol −1 when two water molecules are involved. On the other hand, the endothermicity of the reaction increased from −4 (no water) up to −2 kcal mol −1 (2 explicit water molecules).…”

Section: Chemisty Of Genipinmentioning

confidence: 99%

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Genipin as An Emergent Tool in the Design of Biocatalysts: Mechanism of Reaction and Applications

et al. 2019

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Genipin is a reagent isolated from the Gardenia jasminoides fruit extract, and whose low toxicity and good crosslinking properties have converted it into a reactive whose popularity is increasing by the day. These properties have made it widely used in many medical applications, mainly in the production of chitosan materials (crosslinked by this reactive), biological scaffolds for tissue engineering, and nanoparticles of chitosan and nanogels of proteins for controlled drug delivery, the genipin crosslinking being a key point to strengthen the stability of these materials. This review is focused on the mechanism of reaction of this reagent and its use in the design of biocatalysts, where genipin plays a double role, as a support activating agent and as inter- or intramolecular crosslinker. Its low toxicity makes this compound an ideal alterative to glutaraldehyde in these processes. Moreover, in some cases the features of the biocatalysts prepared using genipin surpassed those of the biocatalysts prepared using other standard crosslinkers, even disregarding toxicity. In this way, genipin is a very promising reagent in the design of biocatalysts.

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Section: Reactivity Of Genipin As Cross-linker Agentmentioning

confidence: 98%

Section: Chemisty Of Genipinmentioning

confidence: 99%

Section: Chemisty Of Genipinmentioning

confidence: 99%

Section: Chemisty Of Genipinmentioning

confidence: 99%

Section: Chemisty Of Genipinmentioning

confidence: 99%

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Genipin as An Emergent Tool in the Design of Biocatalysts: Mechanism of Reaction and Applications

et al. 2019

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High Capacity Functionalized Protein Superabsorbents from an Agricultural Co‐Product: A Cradle‐to‐Cradle Approach

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et al. 2020

Advanced Sustainable Systems

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Synthesis of superabsorbent particles from nontoxic wheat gluten (WG) protein, as an industrial co‐product, is presented. A natural molecular cross‐linker named genipin (a hydrogenated glycoside) is used together with a dianhydride (ethylenediaminetetraacetic EDTAD), to enable the preparation of a material with a network structure capable of swelling up to ≈4000% in water and ≈600% in saline solution. This represents an increase in swelling by over 10 times compared to the already highly absorbing gluten reference material. The carboxylation (using EDTAD) and the cross‐linking of the protein result in a hydrogel with liquid retention capacity as high as 80% of the absorbed water remaining in the WG network on extensive centrifugation, which is higher than that of commercial fossil‐based superabsorbents. The results also show that more polar forms of the reacted genipin are more effectively grafted onto the protein, contributing to the swelling and liquid retention. Microscopy of the materials reveals extensive nanoporosity (300 nm), contributing to rapid capillarity‐driven absorption. The use of proteins from agricultural industries for the fabrication of sustainable protein superabsorbents is herein described as an emerging avenue for the development of the next generation daily‐care products with a minimal environmental impact.

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22π-Electrons [1.1.1.1.1] pentaphyrin as a new photosensitizing agent for water disinfection: experimental and theoretical characterization

et al. 2016

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In view of their promising photosensitizing features, expanded porphyrins are gaining wide attention for their potential use in both photodynamic therapy (PDT) of cancer or as likely photoactivated agent for water disinfection. Herein, we report a joint experimental and theoretical investigation on the 20-(4'-carboxyphenyl)-2,13-dimethyl-3,12-diethyl-[22]pentaphyrin complex 4. The synthesis, NMR, UV-Vis and mass characterization of the new Author's Pre-Print Version 2 compound together with a detailed theoretical investigation of the photophysical properties are presented. In particular, type I-and type II-photoreactions have been explored by means of DFT and its TDDFT formulation characterizing the electronic absorption spectra, providing singlettriplet energy gap, vertical ionization potential and electron affinity. Results show that title compound is able to generate the cytotoxic singlet oxygen species supporting the application of the proposed molecule as a photoactivated agent for water disinfection. Supplementary Material. ESI-MS of PCCox, computed main Bond lengths (Å) and main dihedral angles (degrees) for PCCox, main vertical singlet electronic energies for several conformations of PCCox obtained with different XC functionals in methanol, computed UV-Vis Spectra, NMR computations.

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Structure of genipin in solution: a combined experimental and theoretical study

Cited by 15 publications

References 35 publications

Genipin as An Emergent Tool in the Design of Biocatalysts: Mechanism of Reaction and Applications

Genipin as An Emergent Tool in the Design of Biocatalysts: Mechanism of Reaction and Applications

High Capacity Functionalized Protein Superabsorbents from an Agricultural Co‐Product: A Cradle‐to‐Cradle Approach

22π-Electrons [1.1.1.1.1] pentaphyrin as a new photosensitizing agent for water disinfection: experimental and theoretical characterization

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