A systematic investigation on the impact of the level of oxidation at sulfur and the configuration of <i>R</i>/<i>S</i>-sulfoxide on the solid structure

Zhou, Yanan; Ma, Hongzhi; Zhou, Yang; Wu, Chwan-Hwa; Sun, Tong

doi:10.1039/d1ce00346a

Cited by 3 publications

(3 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Although a single crystal of Fmoc‐C Bzl ‐( S )‐O suitable for X‐ray structural analysis has not been obtained, the crystal structure of Fmoc‐C Bzl ‐( R )‐O demonstrated the importance of the chirality of the sulfoxide moiety for effective 1D self‐assembly through hydrogen bonding interactions between the alkyl sulfoxide groups. [ 53 ]…”

Section: Resultsmentioning

confidence: 99%

“…Although a single crystal of Fmoc-C Bzl -(S)-O suitable for X-ray structural analysis has not been obtained, the crystal structure of Fmoc-C Bzl -(R)-O demonstrated the importance of the chirality of the sulfoxide moiety for effective 1D selfassembly through hydrogen bonding interactions between the alkyl sulfoxide groups. [53] To further investigate the supramolecular assembly mode, infrared (IR) spectral measurements were performed on xerogel samples prepared from Fmoc-C Bzl and Fmoc-C Bzl -(R)-O gels. Ammonium acetate buffer (50 mm, pH 7.0) was used to prepare the xerogels because Fmoc-C Bzl was insoluble in neither unbuffered nor deuterated water, making it difficult to prepare gel samples suitable for IR spectral measurements without freeze-drying.…”

Section: X-ray Single Crystal Analyses Of Fmoc-c Bzl and Fmoc-c Bzl -...mentioning

confidence: 99%

See 1 more Smart Citation

Oxidation‐Responsive Supramolecular Hydrogel Based on a Simple Fmoc‐Cysteine Derivative Capable of Showing Autonomous Gel–Sol–Gel Transitions

Shintani,

Katagiri,

Ikeda

2024

Adv Funct Materials

View full text Add to dashboard Cite

Aqueous soft matter, including supramolecular hydrogels capable of exhibiting stimuli–responsive macroscopic phase transitions, has attracted increasing attention for the exploration of functional soft materials. However, the investigation of supramolecular hydrogels that undergo autonomous and multiple macroscopic phase transitions (e.g., gel–sol–gel, sol–gel–sol) in response to the surrounding environment without repeated additions of stimuli has remained largely unexplored. In this study, the oxidation‐responsive autonomous gel–sol–gel transitions of supramolecular hydrogels fabricated via the self‐assembly of a simple fluorenylmethyloxycarbonyl (Fmoc)‐protected, benzylated cysteine (Fmoc‐CBzl) is presented. During the evaluation of the oxidation process of Fmoc‐CBzl, it is revealed that the oxidized products, two diastereomeric sulfoxides (Fmoc‐CBzl‐(R)‐O and Fmoc‐CBzl‐(S)‐O), exhibit significantly different self‐assembly propensities under aqueous conditions. It may be noteworthy that the chirality of sulfoxide is largely overlooked and not effectively used to modulate supramolecular, self‐assembled nanostructures. The difference in the self‐assembly propensities and kinetics of self‐assembly/disassembly as well as co‐assembly will contribute to oxidation‐responsive autonomous gel–sol–gel transitions.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: X-ray Single Crystal Analyses Of Fmoc-c Bzl and Fmoc-c Bzl -...mentioning

confidence: 99%

Oxidation‐Responsive Supramolecular Hydrogel Based on a Simple Fmoc‐Cysteine Derivative Capable of Showing Autonomous Gel–Sol–Gel Transitions

Shintani,

Katagiri,

Ikeda

2024

Adv Funct Materials

View full text Add to dashboard Cite

show abstract

“…Although a single crystal of Fmoc-C Bzl -(S)-O suitable for Xray structural analysis has not been obtained, the crystal structure of Fmoc-C Bzl -(R)-O demonstrated the importance of the chirality of the sulfoxide moiety for effective 1D self-assembly through hydrogen bonding interactions between the alkyl sulfoxide groups. [53] To further investigate the supramolecular assembly mode, infrared (IR) spectral measurements were performed on xerogel samples prepared from Fmoc-C Bzl and Fmoc-C Bzl -(R)-O gels. Ammonium acetate buffer (50 mM, pH 7.0) was used to prepare the xerogels because Fmoc-C Bzl was insoluble in neither unbuffered nor deuterated water, making it difficult to prepare gel samples suitable for IR spectral measurements without freeze-drying.…”

Section: Introductionmentioning

confidence: 99%

Oxidation-Responsive Supramolecular Hydrogel Based on a Simple Fmoc-Cysteine Derivative Capable of Showing Autonomous Gel–sol–gel Transitions

Shintani,

Katagiri,

Ikeda

2023

Preprint

View full text Add to dashboard Cite

Aqueous soft matter, including supramolecular hydrogels capable of exhibiting stimuli–responsive macroscopic phase transitions, has attracted increasing attention for the exploration of functional soft materials. However, the investigation of supramolecular hydrogels that undergo autonomous and multiple macroscopic phase transitions (e.g., gel–sol–gel, sol–gel–sol) in response to the surrounding environment without repeated additions of stimuli has remained largely unexplored. In this study, we present the oxidation-responsive autonomous gel–sol–gel transitions of supramolecular hydrogels fabricated via the self-assembly of a simple fluorenylmethyloxycarbonyl (Fmoc)-protected, benzylated cysteine (Fmoc-CBzl). During the evaluation of the oxidation process of Fmoc-CBzl, we found that the oxidized products, two diastereomeric sulfoxides (Fmoc-CBzl-(R)-O and Fmoc-CBzl-(S)-O), exhibit significantly different self-assembly propensities under aqueous conditions. The difference in the self-assembly propensities and kinetics of self-assembly/disassembly may contribute to oxidation-responsive autonomous gel–sol–gel transitions. Notably, the chirality of sulfoxide has been largely overlooked and not effectively used to modulate supramolecular, self-assembled nanostructures.

show abstract

Molecular and crystal structures of six poly(arylsulfinyl)- and poly(arylsulfanyl)ferrocenes

Blockhaus,

Sünkel

2024

Acta Crystallogr C Struct Chem

View full text Add to dashboard Cite

Starting from (p-tolylsulfinyl)ferrocene (1), a mixture of the complete series [CpFe{C5H5–n (SOTol-p) n }] (n = 2–4) (2–4) in all regioisomers was obtained. After chromatographic separation, crystals of 1,2-bis[(4-methylbenzene)sulfinyl]ferrocene, 2a, and 1,3-bis[(4-methylbenzene)sulfinyl]ferrocene, 2b, both [Fe(C5H5)(C19H17O2S2)], as well as of 1,2,3-tris[(4-methylbenzene)sulfinyl]ferrocene, [Fe(C5H5)(C26H23O3S3)], 3a, and 1,2,3,4-tetrakis[(4-methylbenzene)sulfinyl]ferrocene ethyl acetate 0.75-solvate, [Fe(C5H5)(C33H29O4S4)]·0.75C4H8O2, 4, could be isolated. Their molecular and crystal structures are compared with each other and also with the so far unreported structures of related 1,2-bis(phenylsulfanyl)ferrocene, [Fe(C5H5)(C17H13S2)], 5, and 1,2,3,4-tetrakis(phenylsulfanyl)ferrocene, [Fe(C5H5)(C29H21S4)], 6. In all the sulfinyl structures, the O atoms of the S=O groups are in equatorial positions, except for that in tetrasubstituted 4. All the arene rings of these compounds (except for one ring in 4) are in axial positions directed away from the Fe atom, mostly in a near perpendicular orientation with respect to the plane of the cyclopentadienyl ring. The main intermolecular interactions in the crystals are C—H...H—C, C—H...π and C—H...O, while C—H...S interactions are much less important, except for tetrasulfanyl compound 6. π–π interactions (intramolecular) are only important in compound 3a. Hirshfeld analysis shows that dispersion terms are dominant for the interaction energies of all six compounds. In general, the calculated total interaction energies increase with increasing number of substituents and are higher for the sulfinyl than for the sulfanyl groups.

show abstract

A systematic investigation on the impact of the level of oxidation at sulfur and the configuration of R/S-sulfoxide on the solid structure

Abstract: The current research on the crystals of sulfides, sulfoxides and sulfones either solely studied its different oxidation state or limited to the study of diastereomeric sulfoxides, but rarely combined the...

Cited by 3 publications

References 52 publications

Oxidation‐Responsive Supramolecular Hydrogel Based on a Simple Fmoc‐Cysteine Derivative Capable of Showing Autonomous Gel–Sol–Gel Transitions

Oxidation‐Responsive Supramolecular Hydrogel Based on a Simple Fmoc‐Cysteine Derivative Capable of Showing Autonomous Gel–Sol–Gel Transitions

Oxidation-Responsive Supramolecular Hydrogel Based on a Simple Fmoc-Cysteine Derivative Capable of Showing Autonomous Gel–sol–gel Transitions

Molecular and crystal structures of six poly(arylsulfinyl)- and poly(arylsulfanyl)ferrocenes

Contact Info

Product

Resources

About