Organic-Inorganic Hybrid Glasses of Atomically Precise Nanoclusters.

Organic-inorganic atomically precise nanoclusters provide indispensable building blocks for establishing structure-property links in hybrid condensed matter. However, robust glasses of ligand-protected nanocluster solids have yet to be demonstrated. Herein, we show [Cu4I4(PR3)4] cubane nanoclusters coordinated by phosphine ligands (PR3) form robust melt-quenched glasses in air with reversible crystal-liquid-glass transitions. Protective phosphine ligands critically influence the glass formation mechanism, modulating the glasses' physical properties. A hybrid glass utilizing ethyldiphenylphosphine-based nanoclusters, [Cu4I4(PPh2Et)4], exhibits superb optical properties, including >90% transmission in both visible and near-infrared wavelengths, negligible self-absorption, near-unity quantum yield, and high light yield. Experimental and theoretical analyses demonstrate the structural integrity of the [Cu4I4(PPh2Et)4] nanocluster, i.e., iodine-bridged tetranuclear cubane, has been fully preserved in the glass state. The strong internanocluster CH-π interactions found in the [Cu4I4(PPh2Et)4] glass and subsequently reduced structural vibration account for its enhanced luminescence properties. Moreover, this highly transparent glass enables performant X-ray imaging and low-loss waveguiding in fibers drawn above the glass transition. The discovery of "nanocluster glass" opens avenues for unraveling glass formation mechanisms and designing novel luminescent glasses of well-defined building blocks for advanced photonics.

Copper Organometallic Iodide Arrays for Efficient X-ray Imaging Scintillators.

Lead-free organic metal halide scintillators with low-dimensional electronic structures have demonstrated great potential in X-ray detection and imaging due to their excellent optoelectronic properties. Herein, the zero-dimensional organic copper halide (18-crown-6)2Na2(H2O)3Cu4I6 (CNCI) which exhibits negligible self-absorption and near-unity green-light emission was successfully deployed into X-ray imaging scintillators with outstanding X-ray sensitivity and imaging resolution. In particular, we fabricated a CNCI/polymer composite scintillator with an ultrahigh light yield of ∼109,000 photons/MeV, representing one of the highest values reported so far for scintillation materials. In addition, an ultralow detection limit of 59.4 nGy/s was achieved, which is approximately 92 times lower than the dosage for a standard medical examination. Moreover, the spatial imaging resolution of the CNCI scintillator was further improved by using a silicon template due to the wave-guiding of light through CNCI-filled pores. The pixelated CNCI-silicon array scintillation screen displays an impressive spatial resolution of 24.8 line pairs per millimeter (lp/mm) compared to the resolution of 16.3 lp/mm for CNCI-polymer film screens, representing the highest resolutions reported so far for organometallic-based X-ray imaging screens. This design represents a new approach to fabricating high-performance X-ray imaging scintillators based on organic metal halides for applications in medical radiography and security screening.

Evaporation-Induced Biomolecule Detection on Versatile Superhydrophilic Patterned Surfaces: Glucose and DNA Assay.

We introduce a droplet-based biomolecular detection platform using robust, versatile, and low-cost superhydrophilic patterned superhydrophobic surfaces. Benefitting from confinement and evaporation-induced shrinkage of droplets on wetted patterns, we show enrichment-based biomolecular detection using very low sample volumes. First, we developed a glucose assay using fluorescent polydopamine (PDA) based on enhancement of PDA emission by hydrogen peroxide (H2O2) produced in enzyme-mediated glucose oxidation reaction. Incubation in evaporating droplets resulted in brighter fluorescence compared to that in bulk solutions. Droplet assay was highly sensitive toward increasing glucose concentration while that in milliliter-volume solutions resulted in no fluorescence enhancement at similar time scales. This is due to droplet evaporation that increased the reaction rate by causing enrichment of PDA and glucose/glucose oxidase as well as increased concentration of H2O2 generated in shrinking droplet. Second, we chemically functionalized wetted patterns with single-stranded DNA and developed fluorescence-based DNA detection to demonstrate the adaptability of the patterned surfaces for a different class of assay. We achieved detection of glucose and DNA with concentration down to 130 µM and 200 fM, respectively. Patterned superhydrophobic surfaces with their simple production, sensitive response, and versatility present potential for bioanalysis from low sample volumes.

Label-Free Optical Biodetection of Pathogen Virulence Factors in Complex Media Using Microtoroids with Multifunctional Surface Functionality.

Early detection of pathogens or their virulence factors in complex media has a key role in early diagnosis and treatment of many diseases. Nanomolar and selective detection of Exotoxin A, which is a virulence factor secreted from Pseudomonas aeruginosa in the sputum of Cystic Fibrosis (CF) patients, can pave the way for early diagnosis of P. aeruginosa infections. In this study, we conducted a preliminary study to demonstrate the feasibility of optical biodetection of P. aeruginosa Exotoxin A in a diluted artificial sputum mimicking the CF respiratory environment. Our surface engineering approach provides an effective biointerface enabling highly selective detection of the Exotoxin A molecules in the complex media using monoclonal anti-Exotoxin A functionalized microtoroids. The highly resilient microtoroid surface toward other constituents of the sputum provides Exotoxin A detection ability in the complex media by reproducible measurements. In this study, the limit-of-detection of Exotoxin A in the complex media is calculated as 2.45 nM.

Tapered nanoscale chalcogenide fibers directly drawn from bulk glasses as optical couplers for high-index resonators.

We report production of air-clad tapered chalcogenide fibers by directly drawing bulk glasses between cleaved tips of tapered silica fibers. Exploiting these tapered fibers with nanoscale waists as evanescent optical couplers, we demonstrate phase-matched coupling of light into on-chip whispering gallery mode chalcogenide microresonators with coupling efficiencies as high as 95%. To the best of our knowledge, this is the first-time demonstration of critical coupling into high-index microresonators by using high-index tapered fibers. The tapered chalcogenide fibers can also be utilized as optical couplers for microresonators made of various high-index materials, as well as for nonlinear optical applications.

Oligonucleotide-based label-free detection with optical microresonators: strategies and challenges.

This review targets diversified oligonucleotide-based biodetection techniques, focusing on the use of microresonators of whispering gallery mode (WGM) type as optical biosensors mostly integrated with lab-on-a-chip systems. On-chip and microfluidics combined devices along with optical microresonators provide rapid, robust, reproducible and multiplexed biodetection abilities in considerably small volumes. We present a detailed overview of the studies conducted so far, including biodetection of various oligonucleotide biomarkers as well as deoxyribonucleic acids (DNAs), ribonucleic acids (RNAs) and proteins. We particularly advert to chemical surface modifications for specific and selective biosensing.

Binary coded identification of industrial chemical vapors with an optofluidic nose.

An artificial nose system for the recognition and classification of gas-phase analytes and its application in identifying common industrial gases is reported. The sensing mechanism of the device comprises the measurement of infrared absorption of volatile analytes inside the hollow cores of optofluidic Bragg fibers. An array of six fibers is used, where each fiber targets a different region of the mid-infrared in the range of 2-14 µm with transmission bandwidths of about 1-3 µm. The quenching in the transmission of each fiber due to the presence of analyte molecules in the hollow core is measured separately and the cross response of the array allows the identification of virtually any volatile organic compound (VOC). The device was used for the identification of seven industrial VOC vapors with high selectivity using a standard blackbody source and an infrared detector. The array response is registered as a unique six digit binary code for each analyte by assigning a threshold value to the fiber transmissions. The developed prototype is a comprehensive and versatile artificial nose that is applicable to a wide range of analytes.

Real-Time and Selective Detection of Single Nucleotide DNA Mutations Using Surface Engineered Microtoroids.

Mictoroids, as optical biosensors, can provide beneficial biosensing platforms to understand DNA alterations. These alterations could have significant clinical importance, such as the case of Pseudomonas aeruginosa, which is a commonly found pathogen in Cystic Fibrosis (CF) patients-causing poor prognosis by undergoing mutations during disease steps, gaining virulence and drug resistance. To provide a preliminary diagnosis platform for early-stage bacterial mutations, biosensing with a selective microtoroid surface was suggested. For this purpose, microtoroids with high quality factors were fabricated. The microtoroid surfaces were coated with (3-aminopropyl) triethoxysilane (APTES)/trimethylmethoxysilane (TMMS) mixed silane solution followed by EDC/NHS chemistry for covalent conjugation of DNA probes. Ethanolamine capping was applied to avoid unspecific interactions. The confocal studies confirmed homogeneous functionalization of the microtoroid surface. The DNA hybridization was demonstrated to be affected from the probe length. The optical biosensors showed a significant response (∼22 pm) to the complementary strand of the mutated type P. aeruginosa DNA, while showing substantially low and late response (∼5 pm) to the point mismatch strand. The limit of detection (LOD) for the complementary strand was calculated as 2.32 nM. No significant response was obtained for the noncomplementary strand. The results showed the microtoroids possessed selective surfaces in terms of distinguishing DNA alterations.

Nanosprings harvest light more efficiently.

Nanotechnology presents versatile architectural designs for the purpose of utilization as a building block of 1D optoelectronic nanodevices because current nanowire-based schemes require more effective solutions for low absorption capacity of nanoscale volumes. We report on the potential of nanospring absorbers as an alternative light-harvesting platform with significant advantages over conventional nanowires. Absorption capacity of nanospring geometry is found to be superior to cylindrical nanowire shape. Unlike nanowires, they are able to trap a larger amount of light thanks to characteristic periodic behavior that boosts light collection for the points matched with Mie resonances. Moreover, nanospring shape supplies compactness to a resulting device with area preservation as high as twofold. By considering that a nanospring array with optimal periods yields higher absorption than individual arrangements and core-shell designs, which further promote light collection due to unique antireflection features of shell layer, these nanostructures will pave the way for the development of highly efficient self-powered nanosystems.

Label-Free Biosensing with High Selectivity in Complex Media using Microtoroidal Optical Resonators.

Although label-free biosensors comprised of optical microcavities inherently possess the capability of resolving molecular interactions at individual level, this extreme sensitivity restricts their convenience for large scale applications by inducing vulnerability towards non-specific interactions that readily occur within complex media. Therefore, the use of optical microresonators for biosensing is mostly limited within strictly defined laboratory conditions, instead of field applications as early detection of cancer markers in blood, or identification of contamination in food. Here, we propose a novel surface modification strategy suitable for but not limited to optical microresonator based biosensors, enabling highly selective biosensing with considerable sensitivity as well. Using a robust, silane-based surface coating which is simultaneously protein resistant and bioconjugable, we demonstrate that it becomes possible to perform biosensing within complex media, without compromising the sensitivity or reliability of the measurement. Functionalized microtoroids are successfully shown to resist nonspecific interactions, while simultaneously being used as sensitive biological sensors. This strategy could pave the way for important applications in terms of extending the use of state-of-the-art biosensors for solving problems similar to the aforementioned.

A motion- and sound-activated, 3D-printed, chalcogenide-based triboelectric nanogenerator.

A multilayered triboelectric nanogenerator (MULTENG) that can be actuated by acoustic waves, vibration of a moving car, and tapping motion is built using a 3D-printing technique. The MULTENG can generate an open-circuit voltage of up to 396 V and a short-circuit current of up to 1.62 mA, and can power 38 LEDs. The layers of the triboelectric generator are made of polyetherimide nanopillars and chalcogenide core-shell nanofibers.

Superenhancers: novel opportunities for nanowire optoelectronics.

Nanowires play a crucial role in the development of new generation optoelectronic devices ranging from photovoltaics to photodetectors, as these designs capitalize on the low material usage, utilize leaky-mode optical resonances and possess high conversion efficiencies associated with nanowire geometry. However, their current schemes lack sufficient absorption capacity demanded for their practical applicability, and more efficient materials cannot find widespread usage in these designs due to their rarity and cost. Here we suggest a novel and versatile nanoconcentrator scheme utilizing unique optical features of non-resonant Mie (NRM) scattering regime associated with low-index structures. The scattering regime is highly compatible with resonant Mie absorption effect taking place in nanowire absorbers. This technique in its optimized forms can provide up to 1500% total absorption enhancement, 400-fold material save and is suitable for large-area applications with significant area preservation compared to thin-film of same materials. Proposed superenhancer concept with its exceptional features such as broadband absorption enhancement, polarization immunity and material-independent manner paves the way for development of efficient nanowire photosensors or solar thermophotovoltaic devices and presents novel design opportunities for self-powered nanosystems.

Nanoconfinement of pyrene in mesostructured silica nanoparticles for trace detection of TNT in the aqueous phase.

This article describes the preparation of pyrene confined mesostructured silica nanoparticles for the trace detection of trinitrotoluene (TNT) in the aqueous phase. Pyrene confined mesostructured silica nanoparticles were prepared using a facile one-pot method where pyrene molecules were first encapsulated in the hydrophobic parts of cetyltrimethylammonium micelles and then silica polymerized around these micelles. The resulting hybrid particles have sizes of around 75 nm with fairly good size distribution. Also, they are highly dispersible and colloidally stable in water. More importantly, they exhibit bright and highly stable pyrene excimer emission. We demonstrated that excimer emission of the particles exhibits a rapid, sensitive and visual quenching response against TNT. The detection limit for TNT was determined to be 12 nM. Furthermore, excimer emission of pyrene shows significantly high selectivity for TNT.

Anemone-like nanostructures for non-lithographic, reproducible, large-area, and ultra-sensitive SERS substrates.

The melt-infiltration technique enables the fabrication of complex nanostructures for a wide range of applications in optics, electronics, biomaterials, and catalysis. Here, anemone-like nanostructures are produced for the first time under the surface/interface principles of melt-infiltration as a non-lithographic method. Functionalized anodized aluminum oxide (AAO) membranes are used as templates to provide large-area production of nanostructures, and polycarbonate (PC) films are used as active phase materials. In order to understand formation dynamics of anemone-like structures finite element method (FEM) simulations are performed and it is found that wetting behaviour of the polymer is responsible for the formation of cavities at the caps of the structures. These nanostructures are examined in the surface-enhanced-Raman-spectroscopy (SERS) experiment and they exhibit great potential in this field. Reproducible SERS signals are detected with relative standard deviations (RSDs) of 7.2-12.6% for about 10,000 individual spots. SERS measurements are demonstrated at low concentrations of Rhodamine 6G (R6G), even at the picomolar level, with an enhancement factor of ∼10(11). This high enhancement factor is ascribed to the significant electric field enhancement at the cavities of nanostructures and nanogaps between them, which is supported by finite difference time-domain (FDTD) simulations. These novel nanostructured films can be further optimized to be used in chemical and plasmonic sensors and as a single molecule SERS detection platform.

Spontaneous high piezoelectricity in poly(vinylidene fluoride) nanoribbons produced by iterative thermal size reduction technique.

We produced kilometer-long, endlessly parallel, spontaneously piezoelectric and thermally stable poly(vinylidene fluoride) (PVDF) micro- and nanoribbons using iterative size reduction technique based on thermal fiber drawing. Because of high stress and temperature used in thermal drawing process, we obtained spontaneously polar γ phase PVDF micro- and nanoribbons without electrical poling process. On the basis of X-ray diffraction (XRD) analysis, we observed that PVDF micro- and nanoribbons are thermally stable and conserve the polar γ phase even after being exposed to heat treatment above the melting point of PVDF. Phase transition mechanism is investigated and explained using ab initio calculations. We measured an average effective piezoelectric constant as -58.5 pm/V from a single PVDF nanoribbon using a piezo evaluation system along with an atomic force microscope. PVDF nanoribbons are promising structures for constructing devices such as highly efficient energy generators, large area pressure sensors, artificial muscle and skin, due to the unique geometry and extended lengths, high polar phase content, high thermal stability and high piezoelectric coefficient. We demonstrated two proof of principle devices for energy harvesting and sensing applications with a 60 V open circuit peak voltage and 10 µA peak short-circuit current output.

Turn-on fluorescent dopamine sensing based on in situ formation of visible light emitting polydopamine nanoparticles.

Dopamine is the principle biomarker for diseases such as schizophrenia, Huntington's, and Parkinson's, and the need is urgent for rapid and sensitive detection methods for diagnosis and monitoring of such diseases. In this Article, we report a turn-on fluorescent method for rapid dopamine sensing which is based on monitoring the intrinsic fluorescence of in situ synthesized polydopamine nanoparticles. The assay uses only a common base and an acid, NaOH and HCl to initiate and stop the polymerization reaction, respectively, which makes the assay extremely simple and low cost. First, we studied the in situ optical properties of polydopamine nanoparticles, for the first time, which formed under different alkaline conditions in order to determine optimum experimental parameters. Then, under optimized conditions we demonstrated high sensitivity (40 nM) and excellent selectivity of the assay. With its good analytical figures of merit, the described method is very promising for detection of dopamine related diseases.

Robust Cassie state of wetting in transparent superhydrophobic coatings.

This paper investigates the stability of the Cassie state of wetting in transparent superhydrophobic coatings by comparing a single-layer microporous coating with a double-layer micro/nanoporous coating. Increasing pressure resistance of superhydrophobic coatings is of interest for practical use because high external pressures may be exerted on surfaces during operation. The Cassie state stability against the external pressure of coatings was investigated by squeezing droplets sitting on surfaces with a hydrophobic plate. Droplets on the single-layer coating transformed to the Wenzel state and pinned to the surface after squeezing, whereas droplets on the double-layer micro/nanoporous coating preserved the Cassie state and rolled off the surface easily. In addition, the contact angle and contact-line diameter of water droplets during evaporation from surfaces were in situ investigated to further understand the stability of coatings against Wenzel transition. A droplet on a microporous coating gradually transformed to the Wenzel state and lost its spherical shape as the droplet volume decreased (i.e., the internal pressure of the droplet increased). The contact line of the droplet during evaporation remained almost unchanged. In contrast, a water droplet on a double-layer surface preserved its spherical shape even at the last stages of the evaporation process, where pressure differences as high as a few thousand pascals were generated. For this case, the droplet contact line retracted during evaporation and the droplet recovered the initial water contact angle. The demonstrated method for the preparation of robust transparent superhydrophobic coatings is promising for outdoor applications such as self-cleaning cover glasses for solar cells and nonwetting windows.

Tailoring self-organized nanostructured morphologies in kilometer-long polymer fiber.

While nanowires and nanospheres have been utilized in the design of a diverse array of nanoscale devices, recent schemes frequently require nanoscale architectures of higher complexity. However, conventional techniques are largely unsatisfactory for the production of more intricate nanoscale shapes and patterns, and even successful fabrication methods are incompatible with large-scale production efforts. Novel top-down, iterative size reduction (ISR)-mediated approaches have recently been shown to be promising for the production of high-throughput cylindrical and spherical nanostructures, though more complex architectures have yet to be created using this process. Here we report the presence of a hitherto-undescribed transitory region between nanowire and nanosphere transformation, where a diverse array of complex quasi one-dimensional nanostructures is produced by Rayleigh-Plateau instability-mediated deformation during the progress of a combined ISR/thermal instability technique. Temperature-based tailoring of architecturally diverse, indefinitely long, globally parallel, complex nanostructure arrays with high uniformity and low size variation facilitates the development of in-fiber or free-standing nanodevices with significant advantages over on-chip devices.

Biomimicry of multifunctional nanostructures in the neck feathers of mallard (Anas platyrhynchos L.) drakes.

Biological systems serve as fundamental sources of inspiration for the development of artificially colored devices, and their investigation provides a great number of photonic design opportunities. While several successful biomimetic designs have been detailed in the literature, conventional fabrication techniques nonetheless remain inferior to their natural counterparts in complexity, ease of production and material economy. Here, we investigate the iridescent neck feathers of Anas platyrhynchos drakes, show that they feature an unusual arrangement of two-dimensional (2D) photonic crystals and further exhibit a superhydrophobic surface, and mimic this multifunctional structure using a nanostructure composite fabricated by a recently developed top-down iterative size reduction method, which avoids the above-mentioned fabrication challenges, provides macroscale control and enhances hydrophobicity through the surface structure. Our 2D solid core photonic crystal fibres strongly resemble drake neck plumage in structure and fully polymeric material composition, and can be produced in wide array of colors by minor alterations during the size reduction process.