Spatially Responsive Multicolor Lanthanide-MOF Heterostructures for Covert Photonic Barcodes

Micro/nanoscale photonic barcodes based on multicolor luminescent segmented heterojunctions hold potential for applications in information security. However, such multicolor heterojunctions reported thus far are exclusively based on static luminescent signals, thus restricting their application in advanced confidential information protection. Reported here is a strategy to design responsive photonic barcodes with heterobimetallic (Tb³⁺/Eu³⁺) metal—organic framework multicolor heterostructures. The spatial colors could be precisely controlled by thermally manipulating the energy-transfer process between the two lanthanides, thus achieving responsive covert photonic barcodes. Also demonstrated is that spatially resolved responsive barcodes with multi-responsive features could be created in a single heterostructure. These findings offer unique opportunities to purposely design highly integrated responsive microstructures and smart devices toward advanced anti-counterfeiting applications.     

Heteroepitaxial Growth of Multiblock Ln‐MOF Microrods for Photonic Barcodes

Micro/nanoscale multicolor barcodes with unique identifiability and a small footprint play significant roles in applications such as multiplexed labeling and tracking systems. Now, a strategy is reported to design multicolor photonic barcodes based on 1D Ln‐MOF multiblock heterostructures, where the domain‐controlled emissive colors and different block lengths constitute the fingerprint of a corresponding heterostructure. The excellent heteroepitaxial growth characteristics of MOFs enable the effective modulation of the coding structures, thereby remarkably increasing the encoding capacity. The as‐prepared multicolor barcodes enable an efficient authentication and exhibit great potential in fulfilling the functions of anti‐counterfeiting, information security, and so on. The results will pave an avenue to novel hybrid MOFs for optical data recording and security labels.     

Methods to array photonic crystal microcavities for high throughput high sensitivity biosensing on a silicon-chip based platform

We experimentally demonstrate a method to create large-scale chip-integrated photonic crystal sensor microarrays by combining the optical power splitting characteristics of multi-mode interference (MMI) power splitters and transmission drop resonance characteristics of multiple photonic crystal microcavities arrayed along the length of the same photonic crystal waveguide. L13 photonic crystal microcavities are employed which show high Q values (~9300) in the bio-ambient phosphate buffered saline (PBS) as well as high sensitivity, experimentally demonstrated to ~98 atto-grams. Two different probe antibodies were specifically detected simultaneously with a control sample, in the same experiment.     

Energy Transfer‐Assisted Whispering Gallery Mode Lasing in Conjugated Polymer/Europium Hybrid Microsphere Resonators

Lanthanide metal complexes display luminescence with narrow bandwidth. Here, we present coupling of the luminescence from europium ion (Eu³⁺) with whispering gallery modes (WGMs) in conjugated polymer microsphere resonators. Self‐assembly of fluorene–terpyridine alternating copolymer, coordinated by Eu³⁺ (F8tpy‐Eu³⁺), forms well‐defined microspheres with an average diameter of 3.2 μm. Upon focused laser excitation, a microsphere of F8tpy copolymer displays WGM photoluminescence (PL) at a wide spectral range from 420 to 680 nm. In contrast, F8tpy‐Eu³⁺ hybrid microspheres exhibit sharp WGM PL at a narrow spectral range of 615–630 nm, which is characteristic of luminescence from Eu³⁺. The PL behavior indicates that photoinduced energy transfer from F8tpy to Eu³⁺ occurs efficiently. Furthermore, the intensity of the PL peak increases nonlinearly upon strong pumping, indicating that a lasing action appears with the threshold of 1.85 mJ cm^?2. These results will pave the way for developing microlasers and photonic devices from soft organic materials.     

Whispering‐Gallery‐Mode Microlaser Based on Self‐Assembled Organic Single‐Crystalline Hexagonal Microdisks

Whispering‐gallery‐mode (WGM) resonators of semiconductor microdisks have been applied for achieving low‐threshold and narrow‐linewidth microlasers, but require sophisticated top‐down processing technology. Organic single‐crystalline hexagonal microdisks (HMDs) of p‐distyrylbenzene (DSB) self‐assembled from solution can function as WGM microresonators with a cavity quality factor (Q) of 210. Both multiple‐ and single‐mode lasing had been achieved using DSB HMDs with an edge length of 4.3 and 1.2 μm, respectively. These organic microdisks fabricated by bottom‐up self‐assembly approach may offer potential applications as low‐threshold microlaser sources for photonic circuit integration.     

High refractive index hyperbranched polyvinylsulfides for planar one‐dimensional all‐polymer photonic crystals

We report on the growth and characterization of one‐dimensional (1D) planar all‐polymer photonic crystals (PhC) with high dielectric contrast (Δn = 0.3) prepared by spin coating using hyperbranched polyvinylsulfide polymers (HB‐PVS) as high refractive index material and cellulose acetate as low refractive index material. Solution processable HB‐PVS show a near ultraviolet absorption inducing an increased refractive index in the visible‐near infrared (n = 1.68, λ = 1000 nm). HBPVS:Cellulose Acetate Distributed Bragg Reflectors show a very clear fingerprint of the photonic band gap possessing the expected polarized dispersion properties as a function of the incidence angle. Moreover, engineered microcavities tuned on the weak fluorescence spectrum of the HB‐PVS show directional fluorescence enhancement effects due to spectral redistribution of the emission oscillator strength. The combination of all these properties testifies the high optical quality of the obtained photonic structures thus indicating HB‐PVS as an interesting material for the preparation of such PhC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 73–80     

Sample illumination configurations for spatially resolved Raman spectrometry using a charge-coupled device detector

In this paper two simple configurations for sample illumination using a charge-coupled device (CCD) detector have been shown. The choice of an appropriate sample illumination can be crucial to obtain spatial and spectral information of complex samples. It is demonstrated that simultaneous Raman spectra of a heterogeneous sample of three compounds can be obtained using a vertical sample illumination. Spatially resolved resonant Raman and surface-enhanced resonant Raman spectra of a complex (Ni-PAPH) have been observed with a low integration time. Dividing the CCD in two region; and with horizontal multiline sample illumination (argon-ion laser at 488 nm and HeNe laser at 632.8 nm) spatially resolved fluorescence spectra of a homogeneous mixture of dyes have been obtained. The total image was acquired in only 1 s.     

P(HEMA-co-AM)胶体晶体膜的制备及其性能

将聚苯乙烯胶体晶体嵌入丙烯酰胺(AM)与甲基丙烯酸羟乙酯(HEMA)的交联共聚膜中,制备了共聚物P(AM-co-HEMA)胶体晶体膜.研究了单体配比及交联剂N,N'-亚甲基双(丙烯酰胺)(MBA)对胶体晶体膜的光子带隙峰位置、拉伸强度和断裂伸长率的影响.结果表明:当n(HEMA)/n(AM)≤2.33时,光子带隙峰较明...     

Vibrational spectroscopic encoding of polystyrene-based resin beads: converting the encoding peaks into barcodes

A detailed approach is described for the vibrational spectroscopic encoding of polystyrene-based resin beads by converting the infrared absorption peaks suitable for encoding (encoding peaks) into barcodes. Based on combining the FT-IR measurements and the quantum-chemical computations, the vibrational characteristics of p-tert-butylstyrene monomer, polystyrene and poly(p-tert-butylstyrene) resin beads are analyzed, which are helpful for the selection of encoding peaks. The vibrational spectroscopic encoding of polystyrene-based resin beads could be obtained by converting the wavenumber, intensity and full width at half maximum (FWHM) of the encoding peaks into barcodes automatically through a computer program designed in our laboratory.     

A three-layer egg-configurated Bragg microcavity of polyglycerol coated cholesteric-liquid-crystal encapsulated by hollow-glass-microsphere

ABSTRACT

This letter reports the optical pumped lasing behaviours of a three-layer Bragg resonance cavity consisting of dye-doped cholesteric liquid crystal (DDCLC) microdroplet, polyglycerol-2 and hollow glass microsphere. The function of PG2 is to control the parallel anchoring of the liquid crystal (LC) molecules on the surface of the LC microdroplet. The whispering-gallery mode (WGM), radial Bragg (photonic bandgap, PBG) mode and Bragg WGM (BWGM) are observed in DDCLC microspheres with different helical pitches and LC refractive indices. The formation mechanisms of six types of lasing emission conditions are analysed in detail. The study results present the prospect of controlling the output mode of the laser. Furthermore, such solid shell-based DDCLC microspheres have outstanding potential applications in miniaturised 3D Bragg lasers, sensors, and integrated and tunable optical devices.     

Inhibition and exaltation of emission in layer-controlled colloidal photonic architectures

We described the engineering and characterization of photonic colloidal crystals based on silica spheres with incorporated YVO₄:Eu luminescent nanoparticles. These structures exhibit strong angle-dependent luminescent properties. The controlled incorporation of a planar defect in the periodic structures gives rise to the creation of a pass band in the pseudo-gap. In the energy range of this pass band, we observed a strong increase in combination with a sharp width of the emission spectrum, which opens new possibilities for the design of low-threshold and/or single mode photonic crystal lasers.     

Spatially resolved ultra-trace analysis of elements combining resonance ionization with a MALDI-TOF spectrometer

A combined setup for spatially resolved mass analysis of trace amounts of elements and macromolecules is presented. Using a MALDI-TOF mass spectrometer, a laser spectroscopic setup for resonant ionization of neutral atoms has been implemented. This allows for an efficient and selective detection of trace elements by means of resonance ionization mass spectrometry (RIMS). The instrumental scheme is described, and methodological developments are presented. In a first application pure, laser desorption/ionization with TOF-MS was used to measure mass distributions of cosmic nanodiamonds. For further applications regarding the spatially resolved ultra-trace analysis of elements in solid samples, an implanted target was used to characterize both laser desorption/ionization and laser desorption/resonance ionization for the detection of trace elements within. A perspective of the setup is given and future investigations are outlined.     

Frequency shifts due to the interference of resolved peaks in magnitude-mode Fourier-transform ion cyclotron resonance mass spectra

We have obtained relationships for frequency shifts resulting from the interference of spectral components for the magnitude mode Fourier transform. The approximation of a weak perturbation of well resolved peaks has been used. Both the low- and high-pressure limits for Fourier-transform ion cyclotron resonance (FTICR) operation have been considered. We have found that the shifts can be either negative or positive, depending on the initial phase and/or the choice of the time-domain interval. The magnitude of shifts generally does not exceed the peak width. In the approximation of small perturbations the shifts produced by multiple peaks are additive. We have compared theoretical results with experimental shifts for isotopic clusters of multiply charged insulin. Up to 1 ppm frequency variations were experimentally observed for the insulin 5+ charge state, consistent with theoretical estimates. The peak interference is of particular significance in the case of bio-molecular mass spectra having a large number of peaks and covering a considerable dynamic range (i.e., relative abundance). We conclude that the common mass measurement procedure based on the location of the magnitude mode maxima of well resolved peaks can result in systematic mass measurement errors. The relationships obtained provide corrections for the frequency shifts and thus improve the mass measurement accuracy.     

Dual enzyme electrochemical coding for detecting DNA hybridization

Enzyme-based hybridization assays for the simultaneous electrochemical measurements of two DNA targets are described. Two encoding enzymes, alkaline phosphatase and beta-galactosidase, are used to differentiate the signals of two DNA targets in connection to chronopotentiometric measurements of their electroactive phenol and alpha-naphthol products. These products yield well-defined and resolved peaks at +0.31 V (alpha-naphthol) and +0.63 V (phenol) at the graphite working electrode (vs. Ag/AgCl reference). The position and size of these peaks reflect the identity and level of the corresponding target. The dual target detection capability is coupled to the amplification feature of enzyme tags (to yield fmol detection limits) and with an efficient magnetic removal of non-hybridized nucleic acids. Proper attention is given to the choice of the substrates (for attaining well resolved peaks), to the activity of the enzymes (for obtaining similar sensitivities), and to the selection of the enzymes (for minimizing cross interferences). The new bioassay is illustrated for the simultaneous detection of two DNA sequences related to the BCRA1 breast-cancer gene in a single sample in connection to magnetic beads bearing the corresponding oligonucleotide probes. Prospects for electrochemical coding of multiple DNA targets are discussed.     

Bicomponent Microneedle Array Biosensor for Minimally‐Invasive Glutamate Monitoring

This article describes the design of a new and attractive minimally‐invasive bicomponent microneedle sensing device for the electrochemical monitoring of the excitatory neurotransmitter glutamate and glucose. The new device architecture relies on the close integration of solid and hollow microneedles into a single biosensor array device containing multiple microcavities. Such microcavities facilitate the electropolymeric entrapment of the recognition enzyme within each microrecess. The resulting microneedle biosensor array can be employed as a minimally‐invasive on‐body transdermal patch, obviating the extraction/sampling of the biological fluid, thereby simplifying device requirements. The new concept is demonstrated for the electropolymeric entrapment of glutamate oxidase and glucose oxidase within a poly(o‐phenylenediamine) (PPD) thin film. The PPD‐based enzyme entrapment methodology enables the effective rejection of coexisting electroactive interferents without compromising the sensitivity or response time of the device. The resulting microneedle‐based glutamate and glucose biosensors thus exhibit high selectivity, sensitivity, speed, and stability in both buffer and undiluted human serum. High‐fidelity glutamate measurements down to the 10 µM level are obtained in serum. The attractive recess design also serves to protect the enzyme layer upon insertion into the skin. This simple, yet robust microneedle design is well‐suited for diverse biosensing applications in which real‐time metabolite monitoring is a core requirement.     

Elucidating the fine details of cholesteric liquid crystal shell reflection patterns

ABSTRACT

Clusters of planar-aligned short-pitch cholesteric liquid crystal spheres generate dynamic colourful patterns due to multiple selective reflections from the radially oriented cholesteric helices in neighbour shells at varying distances. These photonic communication patterns were widely investigated for the cases of both droplets and shells, demonstrating not only intriguing optical phenomena but also potential for applications as new optical elements for photonics, sensing or security pattern generation. However, the optics of these clusters is truly complex and until now only the strongest and most fundamental reflections have been analysed and explained. In this report, we elucidate the origin of a number of more subtle reflections and we explain the extension in space of various spots as well as their internal colour variations.     

Spatially-resolved analysis of nanoparticle nucleation and growth in a microfluidic reactor

Microfluidic systems provide a unique platform for investigation of fundamental reaction processes, which is critical to understanding how to control nanostructure synthesis on a production scale. We have examined the synthesis of cysteine-capped CdS quantum dot nanocrystals (CdS-Cys) between two interdiffusing reagent streams in a continuous-flow microfluidic reactor. Using spatially resolved photoluminescence imaging and spectroscopy of the microreactor, we have acquired kinetic and mechanistic data on the CdS-Cys nanoparticle nucleation and growth, and observed a binary shift in the particle emission spectrum from a higher (2.9 eV) to lower (2.5 eV) energy emission peak within the first second of residence time. Several reactor models have been tested against the spatially and spectrally resolved signals, which suggest that homogeneous reaction and particle nucleation are diffusion-limited and occur only at the boundary between the two laminar streams, while a slower activation process occurs on a longer (seconds) time scale. The results provide direct insight into the rapid processes that occur during crystallization in microfluidic mixing channels, and demonstrate the potential of using controlled microfluidic environments with spatially resolved monitoring to conduct fundamental studies of nanocrystal nucleation and growth.     

Facile microfluidic fabrication of monodispersed self-coupling microcavity with fine tunability

Whispering gallery mode (WGM) resonators have received extensive attention because of their nonlinear optical application in lasers and sensors. Optical microcavities are excellent candidates for constructing powerful microlasers and label-free biosensors, owing to their low optical losses and small size. However, most of these microcavity syntheses rely on sophisticated fabrication methods and cannot be manipulated easily. To achieve facile and versatile microcavity fabrication, we present a robust microfluidics method for monodispersed self-coupling optical microcavity fabrication with a fine tunability. The microcavity polydispersity was less than 3%. The optical microcavity size could be varied from 10 to 30 µm with a steady quality factor (Q) of approximately 1000. The lowest laser threshold that we obtained was 0.82 µJ with a microcavity size of 20 µm. The doped fluorescent dye concentration can be tuned precisely from 0.001 to 0.05 wt% to explore an optimized fluorescent background. The experimental results and theoretical simulation match well in terms of Q and the electrometric resonance field intensity. Compared with previous precise and practical fabrication methods, we have demonstrated a facile approach for versatile optical microcavity fabrication. This method can vary the microcavity materials, size, doped fluorescent dye concentration, WGM resonance spectrum, Q factor, and laser threshold easily to adapt to various circumstances and specific applications.     

Spatially and electrically tunable random lasing based on a polymer-stabilised blue phase liquid crystal-wedged cell

ABSTRACT

We demonstrate a spatially and electrically tunable random lasing based on polymer-stabilized blue phase liquid crystal (PS-BPLC)-wedged cell. The spatially tunable random lasers can be obtained from the laser dye-doped PS-BPLC-wedged cell through changing the pump positions, where the emission wavelength of the random laser can be tuned due to the thickness gradient of the wedged cell, which affects the scattering mean free path. Additionally, applying different electric fields can also tune the laser emission wavelength. The changing of refractive index due to the Kerr effect leads to a change in the scattering mean free path, resulting in shift of lasing wavelength. This PS-BPLC-wedged cell device has a great potential in applications of speckle-free imaging, document coding, biomedicine and other photonic devices.     

Preparation and characterization of Pb<Subscript>0.56</Subscript>Sr<Subscript>0.44</Subscript>Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>O<Subscript>3</Subscript> inverse opal

Pb_0.56Sr_0.44Zr_0.52Ti_0.48O₃ (PSZT) inverse opal photonic crystals (PCs) have been synthesized by a process of self-assembly in combination with a sol–gel procedure. PSZT inverse opals show pure perovskite structure with good orders in three dimensions. The evident photonic band gaps have been observed in the transmittance spectra with a blue-shift phenomenon due to the decrease of opal template periods. PSZT inverse opals also exhibit the reflection peaks in basic agreement with the calculated results. This three-dimensional (3D) ordered PSZT inverse opals have shown interesting optical characteristics and potential applications in optoelectronic and photonic devices.