Abstract
Formation of nanofibers and nanovesicles in the self-assembled state of small amphiphilic molecules has applications in versatile fields such as tissue engineering, controlled delivery of drug molecules, etc. This paper demonstrated the self-aggregation behavior of three synthesized 6-acylamino nicotinic acid amphiphiles named 6-octanoylamino-nicotinic acid (OANA), 6-decanoylamino-nicotinic acid (DANA) and 6-dodecanoylamino-nicotinic acid (DDANA) in water and basic aqueous solution. The result showed that the amphiphiles successfully self-organize into vesicles and twisted ribbons in water. FT-IR study revealed existence of mixtures of handedness in the fibrous structures. CD spectroscopy and TEM study elucidated formation of chiral structures through aggregation. Results showed that DDANA forms thermoreversible hydrogel in aqueous solutions of NaOH and Na2CO3, whereas other two amphiphiles form hydrogel only in the presence of NaOH. Morphological investigation revealed that the hydrogel is formed due to self-assembly of fibrils of micron length. The elastic fibrillar networks are quite stable to external forces. Existence of bilayer columnar square packing arrangement in the self-assembled state was recognized by XRD measurement. Spectroscopy and theoretical studies established that hydrogen bonding interactions are responsible to self-assemble the amphiphilic molecules. The amphiphiles are efficient phase selective gelators of mineral oils in water–mineral oil mixtures and excellent remover of rhodamine 6G, eosin Y and rose bengal from water. The amphiphiles successfully create reproducible fiber mat applicable in tissue engineering field.
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Adhikari B, Palui G, Banerjee A (2009) Self-assembling tripeptide based hydrogels and their use in removal of dyes from waste-water. Soft Matter 5:3452–3460. https://doi.org/10.1039/B905985G
Adochitei A, Drochioiu G (2011) Rapid characterization of peptide secondary structure by FT-IR spectroscopy. Rev Roum Chim 56:783–791
Ahmed EM (2015) Hydrogel: preparation, characterization, and applications—a review. J Adv Res 6:105–121. https://doi.org/10.1016/j.jare.2013.07.006
Appel EA, del Barrio JL, Xian J, Scherman OA (2012) Supramolecular polymeric hydrogels. Chem Soc Rev 41:6195–6214. https://doi.org/10.1039/C2CS35264H
Baker RJ, Colavita PE, Murphy DM, Platts JA, Wallis JD (2012) Fluorine-fluorine interactions in the solid state: an experimental and theoretical study. J Phys Chem A 116:1435–1444. https://doi.org/10.1021/jp2099976
Basak S, Nandi N, Banerjee A (2014) Selective binding of hydrogen chloride and its trapping through supramolecular gelation. Chem Commun 50:6917–6919. https://doi.org/10.1039/c4cc02300e
Bernet A, Behr M, Schmidt HW (2011) Supramolecular nanotube-based fiber mats by self-assembly of a tailored amphiphilic low molecular weight hydrogelator. Soft Matter 7:1058–1065. https://doi.org/10.1039/C0SM00456A
Bhattacharya S, Samanta SK (2012) Unusual salt-induced color modulation through aggregation-induced emission switching of a bis-cationic phenylenedivinylene-based π hydrogelator. Chem Eur J 18:16632–16641. https://doi.org/10.1002/chem.201201940
Bhattacharyya T, Kumar YP, Dash J (2017) Supramolecular hydrogel inspired from DNA structures mimics peroxidase activity. ACS Biomater Sci Eng 3:2358–2365. https://doi.org/10.1021/acsbiomaterials.7b00563
Buerkle LE, von Recum HA, Rowan SJ (2012) Toward potential supramolecular tissue engineering scaffolds based on guanosine derivatives. Chem Sci 3:564–572. https://doi.org/10.1039/C1SC00729G
Chen J, Kampf JW, McNeil AJ (2010) Comparing molecular gelators and nongelators based on solubilities and solid-state interactions. Langmuir 26:13076–13080. https://doi.org/10.1021/la102500u
Das D, Pal S (2015) Modified biopolymer-dextrin based crosslinked hydrogels: application in controlled drug delivery. RSC Adv 5:25014–25050. https://doi.org/10.1039/C4RA16103C
Dasgupta A, Mondal JH, Das D (2013) Peptide hydrogels. RSC Adv 3:9117–9149. https://doi.org/10.1039/C3RA40234G
Deng S, Xu H, Jiang X, Yin J (2013) Poly(vinyl alcohol) (PVA)-enhanced hybrid hydrogels of hyperbranched poly(ether amine) (hPEA) for selective adsorption and separation of dyes. Macromolecules 46:2399–2406. https://doi.org/10.1021/ma302330w
Dixon DA, Dobbs KD, Valentini JJ (1994) Amide-water and amide-amide hydrogen bond strengths. J Phys Chem 98:13435–13439. https://doi.org/10.1021/j100102a001
Dong R, Pang Y, Su Y, Zhu X (2015) Supramolecular hydrogels: synthesis, properties and their biomedical applications. Biomater Sci 3:937–954. https://doi.org/10.1039/C4BM00448E
Dou C, Li D, Gao H, Wang C, Zhang H, Wang Y (2010) Sonication-induced molecular gels based on mono-cholesterol substituted quinacridone derivatives. Langmuir 26:2113–2118. https://doi.org/10.1021/la902663z
Duan P, Zhu X, Liu M (2011) Isomeric effect in the self-assembly of pyridine-containing L-glutamic lipid: substituent position controlled morphology and supramolecular chirality. Chem Commun 47:5569–5571. https://doi.org/10.1039/c1cc10813a
Dutta S, Das D, Dasgupta A, Das PK (2010) Amino acid based low-molecular-weight ionogels as efficient dye-adsorbing agents and templates for the synthesis of TiO2 nanoparticles. Chem Eur J 16:1493–1505. https://doi.org/10.1002/chem.200901917
Fu IW, Markegard CB, Nguyen HD (2015) Solvent effects on kinetic mechanisms of self-assembly by peptide amphiphiles via molecular dynamics simulations. Langmuir 31:315–324. https://doi.org/10.1021/la503399x
George SJ, Ajayaghosh A, Jonkheijm P, Schenning APHJ, Meijer EW (2004) Coiled-coil gel nanostructures of oligo- (p- phenylenevinylene)s: gelation-induced helix transition in a higher- order supramolecular self-assembly of a rigid π-conjugated system. Angew Chem Int Ed 43:3422–3425. https://doi.org/10.1002/anie.200453874
Ghosh A, Dey J (2008) Effect of hydrogen bonding on the physicochemical properties and bilayer self-assembly formation of N-(2-Hydroxydodecyl)-L-alanine in aqueous solution. Langmuir 24:6018–6026. https://doi.org/10.1021/la800232x
Ghosh M, Halperin-Sternfeld M, Grigoriants I, Lee J, Nam KT, Adler-Abramovich L (2017) Arginine-presenting peptide hydrogels decorated with hydroxyapatite as biomimetic scaffolds for bone regeneration. Biomacromol 18:3541–3550. https://doi.org/10.1021/acs.biomac.7b00876
Gomes RF, Neto de Azevedo AC, Pereira AGB, Muniz EC, Fajardo AR, Rodrigues FHA (2015) Fast dye removal from water by starch-based nanocomposites. J Colloid Interface Sci 454:200–209. https://doi.org/10.1016/j.jcis.2015.05.026
Guchhait S, Roy S (2019) Efficient peptide based gelators for aromatic organic solvents and vegetable oils: application in phase selective gelation and dye entrapment. J Sol-Gel Sci Technol 89:852–865. https://doi.org/10.1007/s10971-018-4875-8
Haldar S, Karmakar K (2015) A systematic understanding of gelation self-assembly: solvophobically assisted supramolecular gelation via conformational reorientation across amide functionality on a hydrophobically modulated dipeptide based ambidextrous gelator, N-n-acyl-(L)Val-X(OBn), (X = 1, ω-amino acid). RSC Adv 5:66339–66354. https://doi.org/10.1039/C5RA10209J
Haris PI, Chapman D (1995) The Conformational analysis of peptides using fourier-transform ir spectroscopy. Biopolymers 37:251–263. https://doi.org/10.1002/bip.360370404
Jones CD, Steed JW (2016) Gels with sense: supramolecular materials that respond to heat, light and sound. Chem Soc ReV 45:6546–6596. https://doi.org/10.1039/C6CS00435K
Jäger CM, Hirsch A, Schade B, Ludwig K, Böttcher C, Clark T (2010) Self-assembly of structurally persistent micelles is controlled by specific-ion effects and hydrophobic guests. Langmuir 26(13):10460–10466
Kalyanasundaram K, Thomas JK (1977) Environmental effects on vibronic band intensities in pyrene monomer fluorescence and their application in studies of micellar systems. J Am Chem Soc 99:2039–2044. https://doi.org/10.1021/ja00449a004
Kameta N, Yoshida K, Masuda M, Shimizu T (2009) Supramolecular nanotube hydrogels: remarkable resistance effect of confined proteins to denaturants. Chem Mater 21:5892–5898. https://doi.org/10.1021/cr030072j
Kar B, Roy S (2016) Effect of amide bonds on the self-assembly of two synthesized sulphonamido group based amphiphiles: application in formation of stable silver nanoparticles. ChemistrySelect 1:4794–4802. https://doi.org/10.1002/slct.201600984
Lehn JM (1990) Perspectives in supramolecular chemistry: from molecular recognition towards molecular information-processing and self-organization. Angew Chem Int Ed Engl 29:1304–1319. https://doi.org/10.1002/anie.199013041
Lim GS, Jung BM, Lee SJ, Song HH, Kim C, Chang JY (2007) Synthesis of polycatenar-type organogelators based on chalcone and study of their supramolecular architectures. Chem Mater 19:460–467. https://doi.org/10.1021/cm061282q
Luisi PL (2015) Chemistry constraints on the origin of life. Isr J Chem 55:906–918. https://doi.org/10.1002/ijch.201400177
Maiti M, Roy A, Roy S (2013) Effect of pH and oxygen atom of the hydrophobic chain on the self-assembly property and morphology of the pyridyl boronic acid based amphiphiles. Langmuir 29:13329–21333. https://doi.org/10.1021/la403379g
Maiti M, Roy A, Roy S (2014) Effect of pH and amphiphile concentration on the gel-emulsion of sodium salt of 2-dodecylpyridine-5-boronic acid: entrapment and release of vitamin B12. Colloids Surfaces A Physicochem Eng Aspects 461:76–84. https://doi.org/10.1016/j.colsurfa.2014.07.030
Maity S, Das P, Reches M (2015) Inversion of supramolecular chirality by sonication-induced organogelation. Sci Rep 5:16365. https://doi.org/10.1038/srep16365
Manchineella S, Govindaraju T (2012) Hydrogen bond directed self-assembly of cyclic dipeptide derivatives: gelation and ordered hierarchical architectures. RSC Adv 2:5539–5542. https://doi.org/10.1039/C2RA20342A
Martinez-Felipe A, Brebner F, Zaton D, Concellon A, Ahmadi S, Piñol M, Oriol L (2018) Molecular recognition via hydrogen bonding in supramolecular complexes: a fourier transform infrared spectroscopy study. Molecules 23:2278. https://doi.org/10.3390/molecules23092278
Milli L, Zanna N, Merlettini A, Di Giosia M, Calvaresi M, Focarete ML, Tomasini C (2016) Pseudopeptide-based hydrogels trapping methylene blue and eosin Y. Chem Eur J 22:1–8. https://doi.org/10.1002/chem.201601861
Mondal S, Bairi P, Das S, Nandi AK (2019) Phase selective organogel from an imine based gelator for use in oil spill recovery. J Mater Chem A 7:381–392. https://doi.org/10.1039/c8ta09732a
Nakashima T, Kimizuka N (2002) Light-harvesting supramolecular hydrogels assembled from short-legged cationic L-glutamate derivatives and anionic fluorophores. Adv Mater 14:1113–1116. https://doi.org/10.1002/1521-4095(20020816)14:16<1113:AID-ADMA1113>3.0.CO;2-U
Nandi N, Gayen K, Ghosh S, Bhunia D, Kirkham S, Sen SK, Ghosh S, Hamley IW, Banerjee A (2017) Amphiphilic peptide-based supramolecular, noncytotoxic, stimuli-responsive hydrogels with antibacterial activity. Biomacromol 18:3621–3629. https://doi.org/10.1021/acs.biomac.7b01006
Nandi SK, Maji K, Haldar D (2018) Self-healing hydrogel from a dipeptide and HCl sensing. ACS Omega 3:3744–3751. https://doi.org/10.1021/acsomega.8b00358
Naskar J, Palui G, Banerjee A (2009) Tetrapeptide-based hydrogels: for encapsulation and slow release of an anticancer drug at physiological pH. J Phys Chem B 113:11787–11792. https://doi.org/10.1021/jp904251j
Podder D, Roy Chowdhury S, Nandi SK, Haldar D (2019) Tripeptide based super-organogelators: structure and function. New J Chem 43:3743–3749. https://doi.org/10.1039/c8nj05578e
Ray S, Das AK, Banerjee A (2007) pH-responsive, bolaamphiphile-based smart metallo-hydrogels as potential dye-adsorbing agents, water purifier, and vitamin B12 carrier. Chem Mater 19:1633–1639. https://doi.org/10.1021/cm062672f
Rodríguez-Llansola F, Miravet JF, Escuder B (2009) A supramolecular hydrogel as a reusable heterogeneous catalyst for the direct aldol reaction. Chem Commun. https://doi.org/10.1039/B916250J
Rosenlehner K, Schade B, Böttcher C, Jäger CM, Clark T, Heinemann FW, Hirsch A (2010) Sodium effect on self-organization of amphiphilic carboxylates: formation of structured micelles and superlattices. Chem Eur J 16:9544–9554. https://doi.org/10.1002/chem.201001150
Roy S, Dey J (2005) Spontaneously formed vesicles of sodium N-(11-Acrylamidoundecanoyl)-glycinate and L-Alaninate in water. Langmuir 21:10362–10369. https://doi.org/10.1021/la051206m
Roy A, Roy S (2016) Spontaneous formation of vesicles by self-assembly of nicotinyl amino acid amphiphiles: application as “turn-on” fluorescent sensors for the selective detection of trace-level Hg(II) in water. Ind Eng Chem Res 55:10104–10113. https://doi.org/10.1021/acs.iecr.6b02603
Roy A, Maiti M, Roy S (2012) Spontaneous formation of vesicles by sodium 2-dodecylnicotinate in water. Langmuir 28:12696–12703. https://doi.org/10.1021/la302484x
Roy A, Maiti M, Nayak RR, Roy S (2013a) Effect of amide hydrogen bonding on spontaneously formed gel-emulsions by two pyridyl carboxylic acid based amphiphiles, sodium salt of 2-dodecylpyridine- 5-carboxylic acid and sodium salt of [2-dodecylpyridine-5-carboxylic]glycine: entrapment and release of vitamin B12. J Mater Chem B 1:5588–5601. https://doi.org/10.1039/C3TB20970A
Roy S, Baral A, Banerjee A (2013b) An amino-acid-based self-healing hydrogel: modulation of the self- healing properties by incorporating carbon-based nanomaterials. Chem Eur J 19:14950–14957. https://doi.org/10.1002/chem.201301655
Safiullina AS, Ziganshina SA, Lyadov NM, Klimovitskii AE, Ziganshin MA, Gorbatchuk VV (2019) Role of water in the formation of unusual organogels with cyclo(leucyl–leucyl). Soft Matter 15:3595–3606. https://doi.org/10.1039/c9sm00465c
Sambri L, Cucinotta F, De Paoli G, Stagni S, De Cola L (2010) Ultrasound-promoted hydrogelation of terpyridine derivatives. New J Chem 34:2093–2096. https://doi.org/10.1039/C0NJ00391C
Sangeetha NM, Maitra U (2005) Supramolecular gels: Functions and uses. Chem Soc ReV 34:821–836. https://doi.org/10.1039/B417081B
Shinitzky M, Dianoux AC, Gitler C, Weber G (1971) Microviscosity and order in the hydrocarbon region of micelles and membranes determined with fluorescent probes I Synthetic micelles. Biochemistry 10:2106–2113. https://doi.org/10.1021/bi00787a023
Skilling KJ, Citossi F, Bradshaw TD, Ashford M, Kellam B, Marlow M (2014) Insights into low molecular mass organic gelators: a focus on drug delivery and tissue engineering applications. Soft Matter 10:237–256. https://doi.org/10.1039/C3SM52244J
Smith DK (2010) Supramolecular gels: building bridges. Nat Chem 2:162–163. https://doi.org/10.1038/nchem.566
Song S, Song A, Feng L, Wei G, Dong S, Hao J (2014) Fluorescent hydrogels with tunable nanostructure and viscoelasticity for formaldehyde removal. ACS Appl Mater Interfaces 6:18319–18328. https://doi.org/10.1021/am505701u
Tabata Y, Ikada Y (1998) Protein release from gelatin matrices. AdV Drug DeliVery ReV 31:287–301. https://doi.org/10.1016/S0169-409X(97)00125-7
Vass E, Hollosi M, Besson F, Buchet R (2003) Vibrational Spectroscopic detection of β- and γ-turns in synthetic and natural peptides and proteins. Chem Rev 103:1917–1954. https://doi.org/10.1021/cr000100n
Vollhardt D, Gehlert U (2002) Chiral discrimination in 1-stearylamine-glycerol monolayers. J Phys Chem B 106:4419–4423. https://doi.org/10.1021/jp0125294
Whitesides GM, Mathias JP, Seto CT (1991) Molecular self-assembly and nanochemistry—a chemical strategy for the synthesis of nanostructures. Science 254:1312–1319. https://doi.org/10.1126/science.1962191
Wu J, Wang Y, Chen K, Li F, Yan L, Tang L (2007) Preparation of a hydrogen bonded supramolecular hydrogels with two dimensional aggregate structure. Acta Polym Sin 7:397–400. https://doi.org/10.3724/SP.J.1105.2007.00397
Xu Z, Peng J, Yan N, Yu H, Zhang S, Liu K, Fang Y (2013) Simple design but marvelous performances: molecular gels of superior strength and self-healing properties. Soft Matter 9:1091–1099. https://doi.org/10.1039/C2SM27208C
Yoshii T, Onogi S, Shigemitsu H, Hamachi I (2015) Chemically reactive supramolecular hydrogel coupled with a signal amplification system for enhanced analyte sensitivity. J Am Chem Soc 137:3360–3365. https://doi.org/10.1021/ja5131534
Yuran S, Razvag Y, Reches M (2012) Coassembly of aromatic dipeptides into biomolecular necklaces. ACS Nano 6:9559–9566. https://doi.org/10.1021/nm302983e
Zafar A, Geib SJ, Hamuro Y, Carr AJ, Hamilton AD (2000) Hydrogen bonding control of molecular self-assembly: aggregation behavior of acylaminopyridine-carboxylic acid derivatives in solution and the solid state. Tetrahedron 56:8419–8427. https://doi.org/10.1016/S0040-4020(00)00733-X
Zhu YY, Jiang L, Li ZT (2009) Intramolecular six-membered N-H⋯Br and N–H⋯I hydrogen bonding in aromatic amides in the absence of competing interactions. CrystEngComm 11:235–238. https://doi.org/10.1039/B814859G
Zurcher DM, Adhia YJ, Romero JD, McNeil AJ (2014) Modifying a known gelator scaffold for nitrite detection. Chem Commun 50:7813–7816. https://doi.org/10.1039/C4CC02504K
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SD is thankful to UGC [20/12/2015(ii)EU-V] for a fellowship. DST FIST program and UGC SAP program of the department and instrumental facilities of USIC, Vidyasagar University, are acknowledged.
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Das, S., Roy, S. 6-acylamino nicotinic acid-based hydrogelators applicable in phase selective gelation, reproducible mat formation and toxic dye removal. Chem. Pap. 74, 4267–4282 (2020). https://doi.org/10.1007/s11696-020-01234-x
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DOI: https://doi.org/10.1007/s11696-020-01234-x