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Vanoppen, B. Sels, P. Jacobs, A. B , , Personal page. Fingerprint steroids. Springer Netherlands. Springer Netherlands, Springer Netherlands, pp. Fujita N, Shinkai S. Some supramolecular assemblies can be used for sensing ions, gas or small organic molecules. For these applications, the interactions between sensors and target molecules could produce some special signals, such as electrical signals or fluorescence Che et al.
And the molecular sensing can be achieved by analyzing the changes of these signals. Notably, such sensing is dependent on both the molecular structures and the supramolecular properties of the sensors. The supramolecular gels containing porphyrin or phthalocyanine have been investigated for molecular sensing.
Based on this characteristic, the hydrogel exhibits rapid, significant and visual sensitivity to low concentrations of heavy metal ions Figure 11B. Moreover, the uptake and release of heavy metal ions can be recycled conveniently Jia et al. B Fluorescent intensity of PEG-diisocyanate-porphyrin hydrogels in different metal ion aqueous solutions 0. C Integrated semiconductor optoelectronic devices based on hydrogels for real-time and indicator-free detection of aqueous nitric oxide; Reprinted with permission from Chao et al. Reprinted with permission from Al-Sagur et al.
Copyright Elsevier. Another polymer hydrogel containing porphyrin derivative 54 has been prepared into complex devices for real-time and indicator-free detection of aqueous nitric oxide. The polymer hydrogel can be photoluminescence, which is sensing specific to NO. And the changes of photoluminescence can be further transformed into electric signal by the photodetector Figure 11C ; Chao et al.
Hassan et al. This complex system can be used for electrochemical detection of glucose with high sensitivity This biosensor based on polymer hydrogel has very fast response time 1 s and high storage stability Figure 11D ; Al-Sagur et al. Different polymer gels systems containing porphyrins have been developed for gas sensing.
For example, McShane et al. In this case, near-infrared emitting quantum dots can be employed as reference luminophores; while long-lifetime platinum II porphyrin phosphor was used as oxygen indicator Figure 12A. The hydrogel containing porphyrins for in vivo oxygen sensing has been developed by Lovell et al Huang et al. This hydrogel exhibits oxygen-responsive phosphorescence Figure 12B and can be stably implanted subcutaneously in mice for weeks without degradation, bleaching, or host rejection. When the matrix containing lots of identical dots included with different luminescent molecules, the fluorescent sensor membrane can be fabricated for sensing both pH value and O 2 at different emission wavelengths.
Wolfbeis et al. In this case, oxygen can be detected by Pt-porphyrin, while fluorescein isothiocyanate was used to sense pH. The dual sensing can be achieved via RGB red-green-blue method, wherein the fluorescence intensities can be imaged with a digital camera Figure 12D. Nevertheless, sensing cellular oxygen is attracting increased interests recently. By using porphyrin-based hydrogels, more versatile, flexible, and simple oxygen sensors can be fabricated.
Papkovsky et al. This system provides efficient delivery into the cell and subsequent sensing and high-resolution imaging of cellular oxygen in different detection modalities, including ratiometric intensity and phosphorescence lifetime Figure 12E. A Confocal images of microparticle-based ratiometric oxygen sensors green represents PtP emission; red represents QD emission ; Reprinted with permission from Collier et al. Left images were taken following anesthetization and right ones taken following high-pressure oxygen administration; Reprinted with permission from Huang et al. C Molecular structures of components within fluorescent sensor membrane for sensing both pH value and O 2 ; D Sensing process for both O2 and pH.
Reprinted with permission from Kondrashina et al. Metal porphyrins or phthalocyanines are good catalysts for different reactions. Many related systems, such as P, have been thoroughly investigated Feiters et al. On the other hand, catalyzing based on gels systems belong to supramolecular catalysis Feng et al. When molecules with catalytic properties were self-assembled into ordered nanostructures, their catalytic active centers can also form ordering aggregations.
Moreover, the confinement effect derives from self-assembled nanostructures could be very useful for improving the yields and stereoselectivity of chemical reactions. Importantly, the catalytic properties of supramolecular assemblies can be modulated upon changing the solvents and molecular building blocks.
In principle, the gels containing porphyrin or phthalocyanine components can be used for catalyzing. And the nature of gel systems should give the advantages for different applications. Although there is still small amount of corresponding results can be found in the literature, the ongoing works already cover different fields.
The gels systems containing porphyrin and phthalocyanine have been proved to be able to catalyze some special organic reactions. The photocatalyzing for degradation of contaminants and hydrogen production was also investigated. Moreover, the in vivo catalyzing strongly highlights the advantages of the gels. For catalyzing aerobic oxidation of olefins, Ghorbanloo et al. The activity for catalyzing aerobic oxidation of olefins was found to be dependent on substituent effect of reactants, temperature and the amount of catalysts.
And this catalytic hydrogel can be easily recovered from the reaction medium and could be reused for another seven runs without significant loss of activity Yazdely et al.
Aqueous gels made of chiral lipid - And porphyrin-amphiphiles - RMIT Research Repository
A Catalyst system comprised of anionic [Mn tetrakis 4-sulfonatophenyl porphyrin OAc ] [Mn TPPS OAc ] embedded within cationic cross-linked polymeric ionic liquid poly[ 3-acrylamidopropyl trimethylammonium chloride] ; Reprinted with permission from Yazdely et al. C Porphyrin-based imine gels for enhanced visible-light photocatalytic hydrogen production; Reprinted with permission from Liao et al.
D Dual enzyme gel with high antioxidant ability based on engineered seleno-ferritin and artificial superoxide dismutase; Reprinted with permission from Gao et al. E Molecular structure of hematin 62 , and subcutaneous in situ gelation catalyzed by hematin right. Reprinted with permission from Sakai et al. Chen et al. This system has excellent photocatalytic activity for rhodamine B photodegradation. And the hydrogels could be reused more than five times without losing any photodegradation ability Yuan and Chen, An excellent gel system showing enhanced visible light photocatalytic hydrogen production has been developed by Zhang et al.
These porphyrin-based imine gels offer chemical variety and hierarchically porous structures. And the properties of these catalysts can be easily medicated by changing porphyrin metal centers. The Pd gel enables efficient photocatalytic H 2 evolution via photoinjection of electrons from the light-harvesting gel network into the Pt nanoparticles.
Upon visible light irradiation, the Pd-porphyrin gels doped with Pt nanoparticles show very high efficiency for hydrogen production in aqueous sodium ascorbate solution 1. The catalytic properties of porphyrin-based gels have been utilized for tissue engineering depending on enzyme mimicking. Sakai et al. The gelatin derivative with phenolic hydroxyl moieties can form gel in the presence of both hematin and H 2 O 2 Sakai et al. By making gels containing porphyrin molecules, more complex catalytic systems with delicate nanostructures and functions can be achieved. In this case, the main catalytic components of glutathione peroxidase were put onto the surface of ferritin.
The resulting seleno-ferritin Se-Fn monomers can self-assemble into nanocomposites that exhibit remarkable GPx activity due to the well-organized multi-GPx catalytic centers. On the other hand, since some metal porphyrin molecules are good superoxide dismutase mimic, the gel system mimicking synergistic dual enzyme can be prepared by crosslinking seleno-ferritin nanocomposites with porphyrin Figure 13D ; Gao et al.
The supramolecular gels containing porphyrin or phthalocyanine building blocks could provide the porphyrin assemblies or phthalocyanine aggregates with nice nanostructures and tailored molecular packing modes. Different molecular packing modes could render the assemblies with varied spectral characteristics, special energy transfer or electron transfer properties.
Therefore, some unusual photophysical, photochemical or electrochemical properties of these assemblies can be expected. For example, Bai et al. These assemblies show great light response properties. In this case, the long-range order assembly of aromatic peptide can act as photoelectron acceptor and conductor to promote the production of photoelectrons by the light antenna porphyrin molecules.
And porphyrin can effectively reduce the resistance, facilitating the transfer of photoelectrons Figure 14A ; Feng et al. A Self-assembled peptide hydrogel with porphyrin as a dopant for enhanced photocurrent generation; Reprinted with permission from Feng et al. B Dopant-enabled supramolecular approach for controlled synthesis of nanostructured conductive polymer hydrogels; Reprinted with permission from Wang et al.
C Ultrasound-induced formation of phthalocyanine organogel for field-effect transistor applications. Reprinted with permission from Xu et al. On the other hand, when porphyrin or phthalocyanine molecules were doped into the supramolecular systems, they can also change the aggregation properties of other molecular building blocks. Polypyrrole is a type of conducting polymer.
Phthalocyanine favors the formation of polypyrrole nanofibers. The gels containing metal phthalocyanines not only can be good electric conductor, but also can be nice semiconductor. Xu et al. The corresponding gels can be further fabricated into field-effect transistor Figure 14C. Fabrication of supramolecular gels containing porphyrins or phthalocyanines molecules represents the efforts to build novel functional soft matters. In this case, functional molecular building blocks could organize into hierarchical nanostructures in a controlled manner.
Many interesting features and subsequently novel applications of these materials could be developed depending on ordered nanostructures. In principle, gels especially hydrogels can be considered as matter of life, due to many similarities between their nature and that of the organisms Li et al. However, making the supramolecular assemblies as complex as the nanostructures of some cell organelles is still very difficult. It is necessary to further understand the complex non-covalent interactions within various materials.
Although there are still big challenges to both controlling the nanostructures and improving performance of functional soft matters, the development of gels systems has provided unlimited expectation and possibility Weiss, And the fabrication of different gels systems should be more dependent on the principles and methods of biomimetic.
Nevertheless, considering the infinite constructing possibilities of supramolecular gels, functional gels containing the hierarchical assembly of porphyrins or phthalocyanines will be further developed in the field of chemistry, nanoscience, and biological applications. All authors listed have made a substantial, direct and intellectual contribution to the work, and approved it for publication.
Aqueous gels made of chiral lipid - And porphyrin-amphiphiles
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