Design and preparation of a novel fluorescent naphthalimide derivative supramolecular self-assembly system and its bioimaging application

ABSTRACT

A novel fluorescent naphthalimide derivative gelator (N-18) was designed and characterised which could form a stable gel in 1,4-dioxane/H₂O (2/1, v/v), methyl sulfoxide (DMSO), ethanol/H₂O (4/1, v/v), acetone/H₂O (2/1, v/v) and methanol. The self-assembly process of molecule N-18 in the five solvents was carefully investigated by the field emission scanning electron microscope, UV-vis absorption spectra, fluorescence emission spectra, fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD) and water contact angle experiments. Different structures from microbelts to helical nanofibers were formed in the self-assembly process. Hydrogen bonding and π–π stacking interaction were the mainly driving forces for the formation of gel. At the same time, the hydrophobic surface with the contact angles of 133°–142° was observed on the xerogel films N-18 from the above five solvents. Interestingly, molecule N-18 could be applied in bioimaging in a living cell.     

Microsphere-to-nanotube transition via in situ sonication triggered in a supramolecular self-assembly system based on triphenylamine derivative

A new gelator 1 containing triphenylamine was designed and synthesized, and formed stable gel in ethyl acetate. The self-assembly process of molecule 1 was thoroughly investigated. The solid microsphere structure formed in gel 1 could be turned into nanotube in the transition process of gel to gel via sonication. At the same time, the intermolecular hydrogen bond of self-assembly system was obviously enhanced under sonication. The XRD and water contact angle experiments results of xerogel 1 before and after sonication showed great difference. The hydrophobicity of xerogel 1 film was obviously decreased with the change of contact angle from 142° to 129° after sonication at 100 W for one minute. From the results, it was possible that the solid microsphere was re-dissolved and further reassembled into nanotube. To our knowledge, it was the first example that the solid sphere structure was changed into nanotube in self-assembly system via sonication.     

Novel CuS nanofibers using organogel as a template: controlled by binding sites

A new cholesterol organogelator 1 was synthesized, which was confirmed as an effective gelator for various organic solvents and could self-assemble into network fibers in some organic solvents. Moreover, gelator 1 could act as templates for the synthesis of various CuS nanofibers with different helical pitches. For example, when H(2)S was used as the sulfur source, straight and bending helical CuS nanofibers with a pitch of 100-200 nm could be fabricated in butyl acetate and benzene-butanol gel systems, respectively, while bending CuS nanofibers with a similar helical pitch (ca. 50 nm) could be obtained when thioacetamide was used as the sulfur source in both gel systems. It was first found that the morphologies of inorganic nanofibers could be controlled by the binding sites between the inorganic precursor and the organogel.     

Effect of Solvent and Molecular Structure on the Enhanced Fluorescence and Supramolecular Chirality of Schiff Bases in Organogels

The structures and properties of some Schiff base compounds doped in organogels were investigated. It was found that although individual Schiff bases could not form organogels with organic solvents, they can gel by mixing with an organogelator, N,N′-bisoctadecyl-L-Boc-glutamic-diamide, which formed transparent organogels in dimethyl sulfoxide (DMSO) or toluene (Tol). The enhancement of doping Schiff bases fluorescence in the organogel was observed in comparison with that of the corresponding solution. Furthermore, in the DMSO organogel, the induced chirality was obtained from the doping Schiff base with long alkyl chain. In contrast, the Schiff bases without long alkyl chain could not form supramolecular chiral assemblies in organogel. It was suggested that through gel formation the chirality of the gelator could be transferred to the Schiff base through hydrophobic interaction among the long alkyl chains.     

Construction of Novel Terbium Green Emissive Gels and Their Unique Thermal Degradation Processes

Abstract  

In this paper, four green luminescent gels were successfully formed in dimethyl sulfoxide as solvents. The gels are prepared by self-assembly of urea derivatives gelator N,N′-dioctadecylurea 1 and N-octadecylurea 2 in the presence of two terbium complexes. Very interestingly, the analysis of the peak intensities as function of temperature during heating treatments could be described by two linear equations at two stages. The best fit results were composed of two independent decay processes.     

Confinement effects on the self-assembly of 1,3:2,4-Di-p-methylbenzylidene sorbitol based organogel

1,3:2,4-di- p-methylbenzylidene sorbitol (MDBS) is a small organic molecule that is capable of inducing self-assembly in a wide variety of organic solvents and of forming organogels. In this paper, we present a novel approach to tune the network architectures of organogels by utilizing geometric confinement while varying the gelator concentration. Self-assembly of MDBS in propylene carbonate (PC) is investigated in a series of microchannels with widths varying from 20 to 80 mum and the gelator concentration varying from 2 to 7 wt %. We demonstrate by optical microscopy and scanning electron microscopy (SEM) that a transition from fibrillar structure to sheaflike spherulite structure occurs when (a) the channel width is increased for fixed gelator concentrations and (b) gelator concentration is increased for fixed channel widths. A phase diagram is built based on these observations. Polarized microscopy and transmission electron microscopy (TEM) images are also obtained for organogel under unconfined condition to display the spherulite structures viewed under different length scales. The thermal properties of the organogel are measured by differential scanning calorimetry (DSC) to verify the structural difference obtained under confined and unconfined conditions and the structure stability. Our results provide a novel strategy to control the topological structure of self-assembled systems and to modify their thermal properties via geometric confinement.     

Transformation from a heat-set organogel to a room-temperature organogel induced by alcohols

A unique transformation from a heat-set organogel to a room-temperature organogel induced by ethanol (EtOH) was reported here. When the system containing β-cyclodextrin, 4,4′-isopropylidenediphenol, N,N-dimethylacetamide and LiCl was heated to the gelling temperature (T _gel), a heat-set organogel would be formed. In contrast, a semitransparent organogel (room-temperature organogel) could be obtained by injecting EtOH into the system at ambient temperature. In this transformation process, EtOH played a role in the formation of hydrogen bonds, which was critical for the self-assembly. The influence of other guest molecules, solvents and alcohols on this transformation was also investigated. These organogels were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, thermal gravity analysis and differential thermal gravity. Further, the formation mechanism of the organogels was proposed based on the above measurements.     

Functional organogel based on a salicylideneaniline derivative with enhanced fluorescence emission and photochromism

A new organogelator based on a salicylideneaniline derivative with cholesterol moieties was synthesized, and it was proposed that it could gelate various organic solvents, such as 1-butanol, 1-octanol, butyl acetate, tetrachloromethane, benzene, toluene through combination with a gelation test. From the results of analysis by UV/Vis absorption, circular dichroism (CD), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) studies and semiempirical (AM1) calculations, we believed that the gelator molecules could self-assemble into left-handed helical nanofibers through unimolecular layer packing, which further twisted into the thicker fibers and constructed 3D networks in the gel phase. Interestingly, the organogel exhibited strong fluorescence enhancement relative to a solution of the same concentration because of the formation of J aggregations. Meanwhile, photochromism of the organogel could take place under UV-light irradiation. Both strong fluorescence emission and photochromism properties were concurrent in one system based on a salicylideneaniline derivative. It was suggested that the self-assembly of the functional organogelator could lead to unique photophysical properties.     

Utilizing dual responsive supramolecular gel to stabilize graphene oxide in apolar solvents

Here, we report a dual stimuli-responsive organogel which can stabilize graphene oxide (GO) in apolar solvents. The gelator 1-octadecyl-ureido-naphthalene (OUN) was synthesized, and it could form organogel in toluene and xylene. The resultant gels can respond to thermal and anion stimuli, bringing about fluorescent changes. Thin nanoribbons are entangled together to form three dimensional networks that can immobilize solvents in gel, providing large superficial area to interact with GO sheets. The addition of GO influences the gel properties, which are studied through rheological, fluorescent, and DSC measurements.     

Sol-gel phase transition of brucine-appended porphyrin gelator: a study by vibrational circular dichroism spectroscopy

A novel approach to study the sol-gel phase transition of a brucine–porphyrin based gelator, which uses vibrational circular dichroism (VCD) spectroscopy, is described. The gelation process leading to highly ordered chiral supramolecular assemblies was investigated in various solvents at the different temperatures and concentrations. The VCD spectra sensitively reveal the specific parts of molecule whose configuration is influenced by a sol-gel phase transition and chiral supramolecular aggregation and therefore indicate the parts of the molecule responsible for the chiral self-assembly formation. Temperature stability of the organogel studied is discussed on the basis of the VCD and IR absorption spectra. The scanning electron microscopy was used to visualize the structure of brucine–porphyrin conjugate in the gel phase.     

溶剂和分子结构对席夫碱分子在有机凝胶中的荧光增强和超分子手性的影响

研究了在有机胶凝剂中掺杂的席夫碱化合物的结构和性质. 实验发现, 虽然席夫碱分子单独不能在有机溶剂中形成凝胶, 当其与一种胶凝剂N,N’-双十八烷基-L-Boc-谷氨酸混合时, 它们在二甲基亚砜或甲苯中形成透明的有机凝胶. 与相应的溶液相比, 观察到在有机凝胶中的荧光增强现象, 并且这一增强与席夫碱的结构有密切关系. 在二甲基亚砜的有机凝胶中, 观察到带有长烷基链的席夫碱具有诱导手性. 表明通过凝胶的形成, 胶凝剂的手性能传递到带有长链的席夫碱上.     

Organogel of fluorescein-based derivative formation in the selected pH value

In this work, film structure was obtained by self-assembly of fluorescein derivative via sol–gel process. The self-assembly structure and the formation mechanism had been studied and certified by scanning electron microscopy, IR, UV–vis, fluorescence and X-ray diffraction experiment data. The UV–vis absorption and emission spectra of the compound 1 were changed with the change of the pH value in the solution state. This gelator had certain selectivity for pH value and formed gels.     

Super organogelator based on tetrathiafulvalene with four amide derivatives and its F4TCNQ charge-transfer complex

A new series of tetrathiafulvalene-based organogelators endowed with four hydrophobic chains incorporating amide groups was synthesised and characterised. The resulting transparent organogels were obtained with organic solvents such as cyclohexane, carbon tetrachloride and chlorobenzene. Additionally, the length of the alkyl chain influenced the gelation ability of organogels. Considering the results, we concluded that compounds were ‘super gelators’. Interestingly, the gelators reacted with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane to form charge-transfer (CT) complexes and binary organogels. ¹HNMR and FT-IR revealed that cooperation of hydrogen bonding, π–π and CT interactions was the main driving force for formation of the native and CT gels. The scanning electron microscopy images of native xerogels revealed characteristic gelation morphologies of three-dimensional cross-linking networks, whereas the morphologies of CT complex xerogels showed amorphous rod-like aggregates. X-ray powder diffraction studies suggested that both gelator and CT complex maintained lamellar molecular packing mode in organogel phase.     

Self-assembly of an Octa-uranate Cage Complex with a Rigid bis-Catechol Ligand

While the terminally protected tripeptide Boc-Phe-Gly-m-ABA-OMe I (m-ABA, meta-amino benzoic acid) is an excellent gelator of aromatic organic solvents, another similar tripeptide Boc-Leu-Gly-m-ABA-OMe II, where the Phe residue of peptide I is replaced by Leu, cannot form gels with the same solvents. The morphology of the gels of peptide I, characterised by the field-emission scanning electron microscopy and high-resolution transmission electron microscopy, reveals the formation of nanofibrous networks which are known to encapsulate solvent molecules to form gels. The wide-angle X-ray scattering studies of the gels suggest the β-sheet-mediated self-assembly of peptide I in the formation of a nanofibrous network, where π-stacking interactions of Phe play an important role in the self-assembly and gel formation. The dried gel of peptide I observed between crossed polarisers after binding with a physiological dye, Congo red, shows a bluish-green birefringence, a characteristic of amyloid fibrils.     

Gelation of a Highly Fluorescent Urea‐Containing Triarylmelamine Derivative: 2,4,6‐Tris(p‐N′‐Octadecylureido‐Anilino)Triazine in Organic Solvents

A new gelator of urea‐containing triazine derivatives was synthesized and tested in order to explore the gelation potential in different organic solvents. This compound has been found to form organogels with a variety of organic solvents such as decalin and other solvents. The resulting thermo‐reversible gel was characterized by using the dropping ball method and a number of other instruments. The melting temperature of the gel increased with the gel concentration. The intermolecular hydrogen bonding of gelation was demonstrated through an FT‐IR spectrometer. UV‐Vis and fluorescence analysis showed that the gel displayed various optical effects in different organic solvents. The blue fluorescence of the gel in decalin and the quenched effect of gel in CHCl³ were displayed, respectively. Morphological features in decalin and CHCl₃ were studied by applying atomic force microscopy (AFM), and the morphological features demonstrated that there were different aggregations in different solvents. In conductivity electrolyte experiments, the organogel electrolytes indicated high conductivity (σ) comparable to the corresponding NaClO₄/THF solution. The conductivity of gel electrolytes was increased with electrolyte salt.     

Synthesis and characterization of a new fluorinated macroinitiator and its diblock copolymer by AGET ATRP

A new fluorinated macroinitiator of poly 2,2,3,4,4,4-hexafluorobutyl methacrylate-Br (PHFMA-Br) was prepared via activator generated by electron transfer atom transfer radical polymerization (AGET ATRP), and then a series of fluorinated block copolymers with different fluorine content were successfully synthesized from the macroinitiator by the second step AGET ATRP. GPC, FTIR and ¹H NMR data obtained verified the synthesis. Contact angle measurement indicated that proper fluorine content could decrease the surface energy and increase the contact angle of the copolymer films. XPS characterization showed that the large difference in surface energy between the block and random copolymer film resulted from the difference of the fluorine content on the surface, although the fluorine content of the two copolymers in bulk was similar. The self-assembly behavior of the fluorinated block copolymer in selective solvents was evaluated by the TEM study, and the stable micelles with a core-shell structure were observed when the copolymer content was about 1 wt%.     

The remarkable role of hydrogen bond,halogen, and solvent effect on self-healing supramolecular gel

Self-healing supramolecular gels of low-molecular-weight (LMW) molecules are smart soft materials; however, the development of self-healing LMW gelator is still a challenging task because of the lack of in-depth studies about self-healing mechanisms of LMW gels and the solvent effect on gel properties. Therefore, herein a different perspective was used to study a family of D-gluconic acetal-based gelators with variable structural fragments in 14 different solvents, and a more detailed understanding of self-assembly and self-healing mechanism of supramolecular gels was attained. Based on the critical gelation concentration, phase transition temperature, and rheological data, A8 bearing an amide group in side chain and two chlorine atoms linked to benzene ring was found to be an outstanding gelator, which could form gels with good self-healing ability in a variety of solvents. Interestingly, A8 gel formed in n-BuOH demonstrates high transparency, good mechanical strength, self-supporting behavior, and great self-healing ability from mechanical damage. Based on the Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and theoretical calculation analysis, the self-assembly and self-healing mechanisms of A8 gel were proposed, indicating that a combination of hydrogen bonding and halogen effect was responsible for the efficient self-healing behavior of supramolecular gel. Furthermore, the analysis of solvent parameters indicated that the dispersion force of solvent favored gelators to self-assemble, hydrogen bonding donor ability of solvent mainly affected the formation of one-dimensional assembly, and hydrogen bonding receptor ability and polarity of solvent mainly influenced the supramolecular interactions among assemblies, significantly intervening the self-healing ability of gels. Overall, this study provides a new perspective to the understanding of gelator structure–property correlation in solvents and sheds light for future development of self-healing supramolecular gels.     

The curious case of 12-hydroxystearic acid — the Dr. Jekyll & Mr. Hyde of molecular gelators

A comprehensive review of the features driving self-assembly of 12-hydroxystearic acid (12-HSA), a low-molecular-weight gelator, and its applications in drug delivery and as other soft innovative materials are presented herein. 12-HSA is obtained via hydrogenation of ricinoleic acid naturally found in high concentrations in castor oil. The ability of 12-HSA to self-assemble is associated with the presence, position, and enantiomeric purity of the hydroxy group along the fatty acid chain. The polarity and position of the hydroxyl group facilitates more interaction possibilities leading to its exceptional self-assembly behavior giving rise to fibers, ribbons, and tubes in a variety of solvents. Upon self-assembly, 12-HSA undergoes crystallization resulting in the formation of high aspect ratio fibrillar structures due to noncovalent, intermolecular interactions forming self-spanning, three-dimensional networks (called self-assembled fibrillar networks) in both aqueous and organic solvents. Herein, emphasis is placed on emerging applications of 12-HSA supramolecular assemblies (i.e. responsive aqueous foams, gelled complex fluids, drug delivery systems, hydrogels, organogels, xerogels, and aerogel). The vast literature is compiled associated with 12-HSA self-assembly exploring supramolecular assemblies based on one ambidextrous gelator capable of assembling in aqueous and nonaqueous solvent.     

Dynamic light scattering and small-angle neutron scattering studies on organogels formed with a gelator

Small-angle neutron scattering (SANS) and light scattering studies were carried out on an organogel consisting of a gelator, coded P-1, and dimethyl sulfoxide (DMSO). The gelator was made of an oligosiloxane stem and about eight branches of an amino acid derivative combined with a long alkyl chain. The amino acid part, N-n-pentanoyl-L -isoleucylaminooctadecane, was responsible for intermolecular association via hydrogen bonding between amide groups. After the complete dissolution of P-1 in DMSO at 85 °C, the solution was cooled, and the variations of the scattered light intensity were monitored as a function of the temperature. The scattered intensity increased drastically at about 40 °C when the P-1 concentration (C) was 3.5 g/L, and this indicated gel formation. The SANS results showed that the scattering intensity function was a monotonically decreasing function, regardless of C. A master relationship of the scattering intensity was obtained with respect to C. These scattering studies disclosed the following facts. First, gelation could be monitored as an abrupt increase in the intensity. Second, the gel was composed of randomly oriented bundlelike clusters. Third, the structure factor could be reduced by the gelator concentration, and this indicated the presence of a self-similar structure across the gelation threshold. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1841–1848, 2004