Construction and Research of Multiple Stimuli-Responsive 2D Photonic Crystal DNA Hydrogel Sensing Platform with Double-Network Structure and Signal Self-Expression.

The stimuli-responsive DNA hydrogel has attracted wide attention in the fields of chemical and biological sensing. However, it is still a challenge to integrate characteristics with low-cost, high mechanical strength, and signal self-expression into a DNA hydrogel simultaneously. Herein, a stimuli-responsive 2D photonic crystal double network DNA hydrogel (2D PhC DN-DNA hydrogel) sensing platform is developed via combining the signal self-expression of 2D PhC array with the selective recognition of polyacrylamide (PAM)/DNA DN hydrogel. The change of DNA configuration induced by specific target triggers the change of 2D PhC DN-DNA hydrogel volume, leading to a shift of the Debye diffraction ring diameter. In order to verify the feasibility of this strategy, the 2D PhC DN-DNA hydrogel with C-rich sequences is chosen as a proof-of-concept. The results indicate that the hydrogel has good detection performance for pH and Ag+/Cys. And the Debye diffraction ring diameter of the hydrogel is correlated with the concentration of the Ag+/Cys in the range of 0.5-20 µM. Compared with previously pure DNA hydrogel sensing platform, the 2D PhC DN-DNA hydrogel features low-cost preparation process and label-free determination. Meanwhile, only a laser pointer and a ruler are needed for the determination of targets, which shows that the hydrogel has application prospect in the development of portable response equipment.

Interpenetrating porous photonic crystal balls for rapid naked eye detection of uranyl ions.

There is an increasing need to develop simple yet effective sensors with high sensitivity, high selectivity, rapid response, and low cost for on-site detection of UO22+ in the environment in planned or emergency situations. Herein, we develop a UO22+ responsive interpenetrating porous photonic crystal ball (IPPCB) sensor by template replication and a two-step activation method. The amidoxime group and carboxyl group in the hydrogel drive the shrinkage of the hydrogel network through the coordination with UO22+, which reduces the lattice spacing, thereby changing the structure color and shifting the reflection peak position. Therefore, we can perform a semi-quantitative analysis of UO22+ with the naked eye or a fiber spectrometer. Benefiting from the sensor's spherical symmetry and periodic interpenetrating porous structure, the sensor can provide angle-independent, fast (12 min), and sensitive (minimum detection concentration of 1 nM) detection of UO22+. Moreover, IPPCBs have high selectivity and excellent regeneration performance, which can be applied to real sample detection.

Control of Liquid Crystal Microarray Optical Signals Using a Microspectral Mode Based on Photonic Crystal Structures.

Herein, a novel liquid crystal microarray (LCM) film with optical regulation ability is first constructed by combining liquid crystals (LC) and the highly ordered microporous structure of inverse opal photonic crystals (IOPhCs). The LCM films are fabricated by infiltrating LC molecules into the LC polymer with the structure of IOPhCs, and their properties are very different from those without the LC. Interestingly, the optical property of LCM films can be controlled by changing the orientation of LC molecules, which varies with the interfacial force. In combination with polarization images, spectral reflection peak, circular dichroism spectra, potential difference, and fluorescence images of LCM films, the mechanism of this change is investigated. It is found that the exposed basic group of single-stranded DNA is the key to the change of the optical property of LC microarrays. Meanwhile, the optical signals of LC microarrays based on the PhCs provide a novel LC signal mode for an LC sensing system (microspectral signal mode), and it can be recorded by a fiber-optic spectrometer, which is a great improvement on LC sensing signals. Therefore, the LC microarray sensing signal can be used for accurate analysis of targets by the change of the reflection peak intensity of PhCs. When the LC molecules are induced by different aptamers, the LC microarray sensing interface can be further used for the determination of different targets, such as cocaine and Hg2+. The research on LCM films is of significant value for the development of LC sensing technology and also shows great application prospects in biochemical sensing fields.

A two-dimensional photonic crystal hydrogel biosensor for colorimetric detection of penicillin G and penicillinase inhibitors.

A simple penicillinase functionalized two-dimensional photonic crystal hydrogel (2DPPCH) biosensor was developed for colorimetric detection of penicillin G and penicillinase inhibitors. The penicillinase can specifically recognize penicillin G and catalyze it to produce penicilloic acid, which decreases the pH of the hydrogel microenvironment and shrinks the pH-sensitive hydrogel. The particle spacing decrease of the 2D photonic crystal array induced by the hydrogel shrinkage further causes a blue-shift in the diffraction wavelength. While the hydrolysis reaction is repressed upon treatment with clavulanate potassium (a kind of penicillinase inhibitor), no significant change in the diffraction wavelength is found. The detection of targets can be achieved by measuring the Debye diffraction ring diameter or observing the structural color change in the visible region. The lowest detectable concentrations for penicillin G and clavulanate potassium are 1 µM and 0.1 µM, respectively. Moreover, the 2DPPCH is proved to exhibit high selectivity and an excellent regeneration property, and it shows satisfactory performance for penicillin G analysis in real water samples.

A self-healing smart photonic crystal hydrogel sensor for glucose and related saccharides.

A self-healing smart PhC hydrogel sensor that combines the optical property of photonic crystal and the dynamic regeneration property of boronate ester bond has been prepared for determination of glucose and related saccharides using Debye diffraction ring detection. The boronate ester bond formed through phenylboronic acid and dopamine endows the hydrogel network self-healing ability, and the tensile stress of the healing hydrogel can recover to 94.4%; this excellent self-healing property can effectively improve the reliability and lifetime of the hydrogel. Due to the high bonding capacity between 1,2- and 1,3-diol and phenylboronic acid, the hydrogel sensor has a good recognition ability for glucose and related saccharides. The reaction between the monosaccharides and the phenylboronic acid group makes the sensor swell and the diameter of the Debye diffraction ring decrease. The sensor shows good reuse and responsive ability for saccharides; the RSD of the recoverability assays is 4.3%. The determination range of the sensor to glucose is 0.5 to 12 mM. The sensor also has good response to glucose in urine, exhibiting potential application value in the preliminary screening of diabetes. Although the sensor has poor selectivity for specific monosaccharides, the process of measuring the Debye ring makes the determination no longer rely on expensive and complicated equipment and greatly simplifies the determining process and reduces the cost of determination, which shows a broad application prospect. The boronate ester bond formed through phenylboronic acid and dopamine results in the self-healing property of hydrogel network, which can effectively improve the reliability and lifetime of hydrogel. And due to the high bonding capacity between 1,2- and 1,3-diol and phenylboronic acid, the smart hydrogel sensor has a good recognition ability for glucose and related saccharides. The reaction between the monosaccharides and the phenylboronic acid group breaks the original boronate ester bond; this will lead to a decrease in cross-linking density of the PhC hydrogel sensor and further makes the sensor swell and the diameter of the Debye diffraction ring decrease.

A responsive photonic crystal film sensor for the ultrasensitive detection of uranyl ions.

As an effective nuclear energy resource, uranium plays an important role in industry and energy but the wastes of uranium also cause radioactive contamination, which is harmful to the environment and the human body. Herein, a responsive photonic crystal (PC) film sensor for the ultrasensitive and label-free detection of uranyl ions (UO22+) has been proposed, which is easy to construct and does not need to be combined with a hydrogel. The PC film is not pH-sensitive because it is obtained by the self-assembly of methyl methacrylate-acrylonitrile co-polymeric nanospheres (PMMA-AN). These nanospheres were modified with amidoxime groups, which have a good coordination ability with UO22+. The bindings between nanospheres and UO22+ change the refractive index and disturb the face-centered cubic structure of the film, which leads to a decrease in the diffraction peak intensity of the PC film. The sensor works in the concentration range of 10 pM to 100 µM for UO22+ determination and the decreased intensities of the diffraction peaks are linearly correlated with the logarithm of UO22+ concentration in the range from 1 nM to 100 µM. Moreover, the sensor shows good selectivity for UO22+ and can also perform the determination of UO22+ in a real sample. The responsive PC film sensor shows great potential in the label-free and ultrasensitive detection of UO22+.

Low-angle-dependent CdS@SiO2 photonic crystal hydrogel material for visual detection and removal of uranyl ions.

A low-angle-dependent photonic crystal hydrogel (LAD-PCH) material was developed to simultaneously detect and remove uranyl ions (UO22+). Different from traditional SiO2 photonic crystal hydrogel with the problem of angle dependency, the LAD-PCH material overcomes the restriction of observation direction. The LAD-PCH is a composite material with the photonic crystal array of 180-nm monodisperse CdS@SiO2 particles embedded into the functional hydrogel. As one UO22+ can bind to multiple carboxyl groups and amide groups, the functional hydrogel fabricated by acrylic acid and acrylamide will shrink after chelating. These changes in the hydrogel volume alter the array spacing and trigger a blue shift of diffraction wavelength and naked-eye visual color changes of LAD-PCH. The color can vary from orange-red to orange, yellow, green, and cyan, corresponding to the determination range of 100 pM-100 µM. The LAD-PCH material detects UO22+ sensitively as the lowest detectable concentration is about 100 pM, and removes UO22+ high-efficiently as the maximum adsorption capacity of U(VI) is about 1010 mg g-1 at 298 K. This LAD-PCH material is convenient and has potential to simultaneously monitor and remove UO22+ from uranium-polluted water. Schematic representation of the low-angle-dependent photonic crystal hydrogel (LAD-PCH) material for UO22+ detection and removal: The structural colors of LAD-PCH material overcome the restriction of observation angles. After the ligands complex with UO22+, the networks of LAD-PCH show different degrees of shrinkage; these volume changes of hydrogel trigger obvious naked-eye visual color changes of LAD-PCH.

Sensing of cocaine using polarized optical microscopy by exploiting the conformational changes of an aptamer at the water/liquid crystal interface.

Liquid crystals (LCs) have the ability to transduce and amplify a molecular stimulus into optical signals due to their elastic and birefringence properties. An aptamer-based LC sensor for cocaine is described here. 3-Morpholinopropanesulfonic acid with amphipathic structure was used to establish recognition sites at a water/LC interface for the detection of cocaine. The cocaine-binding aptamer is formed at the interface. The conformation of the aptamer undergoes a change on binding cocaine, and this triggers the LCs anchoring transition from homeotropic to planar. Binding can also be detected by polarized optical microscopy. The fluorescence spectroscopy and circular dichroism results are used to prove that the conformation of aptamer changed from a hairpin structure to a special three-way junction structure on binding of cocaine at the interface. The assay works in the 1 nM to 10 µM cocaine concentration range and is specific. Graphical abstract Schematic representation of aptamer-based liquid crystal (LC) biosensor for the detection of cocaine. In this interface biosensing system, after the aptamer binding with cocaine, the conformation of aptamer at the aqueous/LC interface was changed from a hairpin structure to a special three-way junction structure. This triggered the Liquid crystals (LCs) anchoring transition from homeotropic to planar and the sign-on optical signal could be obtained by polarizing optical microscope (POM) in real-time.

Molecularly imprinted photonic hydrogel sensor for optical detection of L-histidine.

A molecularly imprinted photonic hydrogel (MIPH) is described for the optical determination of L-histidine (L-His). The inverse opal structure of MIPH was obtained by placing silica particles (230 nm) in molecularly imprinted polymer on a glass slide. After being fully etched by hydrofluoric acid, this inverse opal structure brings about a high specific surface and plentiful binding sites for L-His. If L-His is absorbed by the modified MIPH, its average effective refraction coefficient is increased. This causes the Bragg diffraction peak to be red-shifted by about 34 nm as the concentration of L-His increases from 0 to 100 nM. Much smaller diffraction peak shifts are obtained for other amino acids. The detection limit of this method is 10 pM. The response time towards L-His is as short as 60 s. In addition, the sensor can be recovered by treatment with 0.1 M acetic acid/methanol. It was applied to the determination of L-His in drinks sample. Graphical abstract After absorbing L-histidine, the average effective refractive index of this molecularly imprinted photonic hydrogel (MIPH) is increased, and the Bragg diffraction peak is shifted. The shift of the diffraction peak can be used for the detection of L-His.

Label-Free Photonic Crystal-Based ß-Lactamase Biosensor for ß-Lactam Antibiotic and ß-Lactamase Inhibitor.

A simple, label-free, and visual photonic crystal-based ß-lactamase biosensor was developed for ß-lactam antibiotic and ß-lactamase inhibitor in which the penicillinase (a ß-lactamase) was immobilized on the pH-sensitive colloidal crystal hydrogel (CCH) film to form penicillinase colloidal crystal hydrogel (PCCH) biosensing film. The hydrolysis of penicillin G (a ß-lactam antibiotic) can be catalyzed by penicillinase to produce penicilloic acid, leading to a pH decrease in the microenvironment of PCCH film, which causes the shrink of pH-sensitive CCH film and triggers a blue-shift of the diffraction wavelength. Upon the addition of ß-lactamase inhibitor, the hydrolysis reaction is suppressed and no clear blue-shift is observed. The concentrations of ß-lactam antibiotic and ß-lactamase inhibitor can be sensitively evaluated by measuring the diffraction shifts. The minimum detectable concentrations for penicillin G and clavulanate potassium (a ß-lactamase inhibitor) can reach 1 and 0.1 µM, respectively. Furthermore, the proposed method is highly reversible and selective, and it allows determination of penicillin G in fish pond water samples.

Construction of hybridization chain reaction induced optical signal directed change of photonic crystals-DNA hydrogel sensor and its visual determination for aflatoxin B1.

Herein, we have introduced hybridization chain reaction (HCR) into the photonic crystals (PhCs) hydrogel, for the first time, realizing HCR for inducing the change of the optical signal of PhCs hydrogel and using this hydrogel as a sensor for determination of the aflatoxin B1 (AFB1). By using specific sequences as the cross-linker, the extension of the cross-linker by HCR drives the swelling of the hydrogel, and the optical property of 2D PhCs array converts this swelling into a change of the Debye diffraction ring. Moreover, by further selecting the aptamer to construct the cross-linker, the hydrogel is also endowed with a unique capability for AFB1, making the hydrogel a novel sensor based on the signal amplification strategy. The results show that the designed hairpin DNAs can effectively trigger the HCR and cause the swelling of hydrogel, and the hydrogel sensor has a good determination performance and high specific recognition for AFB1.

Partial induced reorientation of 5CB in a liquid crystal microarray and a signal-on sensing assay for the detection of aflatoxin B1.

Herein, a signal-on liquid crystal microarray (LCM) sensor is designed for the first time with a micro-spectral optical sensing signal. Depending on the change of the orientation of the LC molecules in the LCM films and the intensity of the spectral peaks of the PhCs, the signal-on LCM biosensor achieves the detection of AFB1 and the Partial Response Mechanism (PSM) of the LCM films is discovered.