Quantum‐Dot‐Functionalized Poly(styrene‐co‐acrylic acid) Microbeads: Step‐Wise Self‐Assembly,Characterization, and Applications for Sub‐femtomolar Electrochemical Detection of DNA Hybridization

A novel nanoparticle label capable of amplifying the electrochemical signal of DNA hybridization is fabricated by functionalizing poly(styrene‐co‐acrylic acid) microbeads with CdTe quantum dots. CdTe‐tagged polybeads are prepared by a layer‐by‐layer self‐assembly of the CdTe quantum dots (diameter = 3.07 nm) and polyelectrolyte on the polybeads (diameter = 323 nm). The self‐assembly procedure is characterized using scanning and transmission electron microscopy, and X‐ray photoelectron, infrared and photoluminescence spectroscopy. The mean quantum‐dot coverage is (9.54 ± 1.2) × 10³ per polybead. The enormous coverage and the unique properties of the quantum dots make the polybeads an effective candidate as a functionalized amplification platform for labelling of DNA or protein. Herein, as an example, the CdTe‐tagged polybeads are attached to DNA probes specific to breast cancer by streptavidin–biotin binding to construct a DNA biosensor. The detection of the DNA hybridization process is achieved by the square‐wave voltammetry of Cd²⁺ after the dissolution of the CdTe tags with HNO₃. The efficient carrier‐bead amplification platform, coupled with the highly sensitive stripping voltammetric measurement, gives rise to a detection limit of 0.52 fmol L^?1 and a dynamic range spanning 5 orders of magnitude. This proposed nanoparticle label is promising, exhibits an efficient amplification performance, and opens new opportunities for ultrasensitive detection of other biorecognition events.     

Detection of Glioma‐Derived Exosomes with the Biotinylated Antibody‐Functionalized Titanium Nitride Plasmonic Biosensor

Titanium nitride (TiN), as an excellent alternative plasmonic supporting material compared to gold and silver, exhibits tunable plasmonic properties in the visible and near‐infrared spectra. However, label‐free surface plasmon resonance biosensing with TiN is seldom reported due to lack of proper surface functionalization protocols. Herein, this study reports biotinylated antibody‐functionalized TiN (BAF‐TiN) for high‐performance label‐free biosensing applications. The BAF‐TiN biosensor can quantitatively detect exosomes of 30–200 nm extracellular vesicles, isolated from a human glioma cell line. The limit of detection for an exosomal membrane protein with the BAF‐TiN biosensor is found to be 4.29 × 10^?3µg mL^?1 for CD63, an exosome marker, and 2.75 × 10^?3µg mL^?1 for epidermal growth factor receptor variant‐III, a glioma specific mutant protein, respectively. In conclusion, combining the biocompatibility, high stability, and excellent label‐free sensing performance of TiN, the BAF‐TiN biosensor could have great potential for the detection of cancer biomarkers, including exosomal surface proteins.     

Scissor‐Like Chiral Metamolecules for Probing Intracellular Telomerase Activity

A DNA‐driven gold (Au) heterodimer for intracellular telomerase detection is fabricated. The highly biocompatible and intracellularly stable probe shows an active chiroptical property in the visible region, due to the scissor‐like configuration formed by prolate nanoparticles. Importantly, the telomerase activity is specifically quantified using circular dichroism intensity in situ after internalization of the heterodimer into cancer cells. Moreover, the results clearly illustrate that this method has a remarkable linear range from 0.8 × 10^?12 to 32 × 10^?12 IU, and the limit of detection for telomerase activity is 1.7 × 10^?15 IU in a single HeLa cell. This strategy paves the way for chirality‐based ultrasensitive detection of intracellular cancer markers.     

Quantum‐Dot‐Tagged Bioresponsive Hydrogel Suspension Array for Multiplex Label‐Free DNA Detection

A novel hydrogel suspension array, which possesses the joint advantages of quantum‐dot‐encoded technology, bioresponsive hydrogels, and photonic crystal sensors with full multiplexing label‐free DNA detection capability is developed. The microcarriers of the suspension array are quantum‐dot‐tagged DNA‐responsive hydrogel photonic beads. In the case of label‐free DNA detection, specific hybridization of target DNA and the crosslinked single‐stranded DNA in the hydrogel grid will cause hydrogel shrinking, which can be detected as a corresponding blue shift in the Bragg diffraction peak position of the beads that can be used for quantitatively estimating the amount of target DNA. The results of the label‐free DNA detection show that the suspension array has high selectivity and sensitivity with a detection limit of 10^?9 M . This method has the potential to provide low cost, miniaturization, and simple and real‐time monitoring of hybridization reaction platforms for detecting genetic variations and sequencing genes.     

An Alternative Copolymer of Carbazole and Thieno[3,4b]‐Pyrazine: Synthesis and Mercury Detection

A donor‐π‐acceptor (D‐π‐A) alternative copolymer of carbazole and thieno[3,4b]‐pyrazine [P(CZ‐TPZ)] is synthesized through a Wittig–Horner reaction. In dilute THF solution, the absorption spectrum of P(CZ‐TPZ) shows two absorption peaks at 306 and 452 nm, respectively, and the PL spectrum of the polymer solution displays a PL peak maximum at 543 nm. The polymer possesses relatively high sensitivity and selectivity for Hg²⁺ detection. Upon addition of Hg²⁺ into its THF solution (containing 0.3% CH₃CN), P(CZ‐TPZ) exhibits a new absorption peak at 560～600 nm and its emission was quenched dramatically. The Hg²⁺ detection shows high selectivity in comparison with the other cations of Na⁺, K⁺, Mg²⁺, Ba²⁺, Al³⁺, Cu²⁺, Cd²⁺, Pb²⁺, Ni²⁺, Mn²⁺, and Co²⁺. The Hg²⁺ detection limit of the polymer solution by emission quenching is found to be 1 × 10^?7 mol L^?1. P(CZ‐TPZ) also shows a selective chromogenic behavior toward Hg²⁺ with color change of the solution from yellow to blue dark which can be detected with the naked eye, the detection limit reaches 1 × 10^?6 mol L^?1 with a 1 × 10^?4 mol L^?1 polymer solution. The absorption and PL spectral change can be resumed after adding thiourea, therefore the sensing ability of the polymer is re‐usable with the treatment of thiourea. The results indicate that P(CZ‐TPZ) is a promising chemosensor for the Hg²⁺ detection.     

Stimuli‐Responsive DNA‐Gated Nanoscale Porous Carbon Derived from ZIF‐8

Stimuli‐responsive nanoscale porous carbon derived from ZIF‐8 (NCZIF) gated by DNA capping units is reported. The NCZIF is first obtained by calcination of nano‐ZIF‐8 crystals under an inert atmosphere. It is further conjugated with amine‐modified single‐stranded DNA after carboxylation (DNA/NCZIF). The guest molecules are sealed in the pore of NCZIF by the formation of a DNA duplex structure on the surface of NCZIF. As proof of principle, two systems that can be, respectively, used for controlled drug delivery and biosensing are introduced. In the first system, the drug model (rhodamine 6G, Rh6G) is locked in the NCZIF by the DNA capping units composed of rich‐G sequences and its complementary DNA strand. The in vitro cellular experiments reveal that DNA/NCZIF has good biocompatibility and can controllably release Rh6G upon the K⁺‐stimuli in cells. In the second system, the signal probe (methylene blue, MB) is locked in the NCZIF and then released after the unlocking of the pores triggered by the dissociation of the aptamer‐hybrid capping units. The MB‐loaded DNA/NCZIF can linearly respond to target molecules in the range from 1 × 10^?9 to 10 × 10^?6 m and has good specificity.     

A Ratiometric Near‐Infrared Fluorescent Probe for Quantification and Evaluation of Selenocysteine‐Protective Effects in Acute Inflammation

Selenocysteine (Sec) is a primary kind of reactive selenium species in cells whose antioxidant roles in a series of liver diseases have been featured. However, it is difficult to determine Sec in living cells and in vivo due to its high reactivity and instability. This work reports a ratiometric near‐infrared fluorescent probe (Cy‐SS) for qualitative and quantitative determination of Sec in living cells and in vivo. The probe is composed of heptamethine cyanine fluorophore, the response unit bis(2‐hydroxyethyl) disulfide, and the liver‐targeting moiety d ‐galactose. Based on a detection mechanism of selenium–sulfur exchange reaction, the concentrations of Sec in HepG2, HL‐7702 cells, and primary mouse hepatocytes is determined as 3.08 ± 0.11 × 10^?6m , 4.03 ± 0.16 × 10^?6m and 4.34 ± 0.30 × 10^?6m , respectively. The probe can selectively accumulate in liver. The ratio fluorescence signal of the probe can be employed to quantitatively analyze the fluctuation of Sec concentrations in cells and mice models of acute hepatitis. The experimental results demonstrate that Sec plays important antioxidant and anti‐inflammatory roles during inflammatory process. And the levels of intracellular Sec have a close relationship with the degree of liver inflammation. The above imaging detections make this new probe a potential candidate for the accurate diagnosis of inflammation.     

N‐Type Self‐Assembled Monolayer Field‐Effect Transistors and Complementary Inverters

This work describes n‐type self‐assembled monolayer field‐effect transistors (SAMFETs) based on a perylene derivative which is covalently fixed to an aluminum oxide dielectric via a phosphonic acid linker. N‐type SAMFETs spontaneously formed by a single layer of active molecules are demonstrated for transistor channel length up to 100 μm. Highly reproducible transistors with electron mobilities of 1.5 × 10^?3 cm² V^?1 s^?1 and on/off current ratios up to 10⁵ are obtained. By implementing n‐type and p‐type transistors in one device, a complimentary inverter based solely on SAMFETs is demonstrated for the first time.     

A Multiwalled‐Carbon‐Nanotube‐Based Biosensor for Monitoring Microcystin‐LR in Sources of Drinking Water Supplies

A multiwalled carbon nanotube (MWCNT)‐based electrochemical biosensor is developed for monitoring microcystin‐LR (MC‐LR), a toxic cyanobacterial toxin, in sources of drinking water supplies. The biosensor electrodes are fabricated using vertically well‐aligned, dense, millimeter‐long MWCNT arrays with a narrow size distribution, grown on patterned Si substrates by water‐assisted chemical vapor deposition. High temperature thermal treatment (2500 °C) in an Ar atmosphere is used to enhance the crystallinity of the pristine materials, followed by electrochemical functionalization in alkaline solution to produce oxygen‐containing functional groups on the MWCNT surface, thus providing the anchoring sites for linking molecules that allow the immobilization of MC‐LR onto the MWCNT array electrodes. Addition of the monoclonal antibodies specific to MC‐LR in the incubation solutions offers the required sensor specificity for toxin detection. The performance of the MWCNT array biosensor is evaluated using micro‐Raman spectroscopy, including polarized Raman measurements, X‐ray photoelectron spectroscopy, cyclic voltammetry, optical microscopy, and Faradaic electrochemical impedance spectroscopy. A linear dependence of the electron‐transfer resistance on the MC‐LR concentration is observed in the range of 0.05 to 20 μg L^?1, which enables cyanotoxin monitoring well below the World Health Organization (WHO) provisional concentration limit of 1 μg L^?1 for MC‐LR in drinking water.     

Ultrasensitive Detection of Mitochondrial DNA Mutation by Graphene Oxide/DNA Hydrogel Electrode

Ultrasensitive detection of nucleic acid has attracted considerable attention recently in academic research and clinic diagnostics. Current approaches for DNA analysis involve complicated or expensive processes for labeling and often yield a high detection limit. In this study, a hydrogel electrode prepared from graphene oxide and fish sperm DNA is used for label?free mitochondrial DNA detection by impedimetric approach. The hydrogel has a bionic structure containing rich water and natural biomolecule fish sperm DNA that would benefit the adsorption and hybridization of DNA. Graphene oxide is a semiconductor and its conductivity can be improved by doping negatively charged DNA molecules. The result shows that the conductivity and impedance change of hydrogel electrode could be tuned by its length and component. The linear range for DNA detection by the optimized hydrogel is from 1.0 × 10^?9 to 1.0 × 10^?20 M with a detection limit of 1.0 × 10^?20 M. The result is ascribed to the bionic structure and tunable conductivity of hydrogel electrode. The hydrogel electrode has been used to detect the real DNA samples from patients of ovarian cancer with satisfactory results.     

Oxidized Porous Silicon Nanostructures Enabling Electrokinetic Transport for Enhanced DNA Detection

Nanostructured porous silicon (PSi) is a promising material for the label‐free detection of biomolecules, but it currently suffers from limited applicability due to poor sensitivity, typically in micromolar range. This work presents the design, operation concept, and characterization of a novel microfluidic device and assay that integrates an oxidized PSi optical biosensor with electrokinetic focusing for a highly sensitive label‐free detection of nucleic acids. Under proper oxidation conditions, the delicate nanostructure of PSi can be preserved, while providing sufficient dielectric insulation for application of high voltages. This enables the use of signal enhancement techniques, which are based on electric fields. Here, the DNA target molecules are focused using an electric field within a finite and confined zone, and this highly concentrated analyte is delivered to an on‐chip PSi Fabry–Pérot optical transducer, prefunctionalized with capture probes. Using reflective interferometric Fourier transform spectroscopy real‐time monitoring, a 1000‐fold improvement in limit of detection is demonstrated compared to a standard assay, using the same biosensor. Thus, a measured limit of detection of 1 × 10^?9 m is achieved without compromising specificity. The concepts presented herein can be readily applied to other ionic targets, paving way for the development of other highly sensitive chemical and biochemical assays.     

High‐Performance SiC Nanobelt Photodetectors with Long‐Term Stability Against 300 °C up to 180 Days

In the present work, high‐performance photodetectors (PDs) based on a single B‐doped 3C‐SiC nanobelt, which are synthesized via catalyst‐free pyrolysis of polymeric precursors of polysilazane, are reported. The as‐built PDs have a high responsivity and external quantum efficiency of 6.37 × 10⁵ A · W^?1 and 2.0 × 10⁸% under 405 nm light with a power density of 0.14 mW · cm^?2 at 5 V, respectively. The detectivity of the PDs is measured to be of 6.86 × 10¹⁴ Jones. Moreover, the B‐doped 3C‐SiC nanobelt PDs exhibit a long‐term stability against 300 °C up to 180 days, suggesting their promising applications to be served under harsh conditions.     

Cyano‐Substituted Oligo(p‐phenylene vinylene) Single Crystals: A Promising Laser Material

Organic crystals that combine high charge‐carrier mobility and excellent light‐emission characteristics are expected to be of interest for light‐emitting transistors and diodes, and may offer renewed hope for electrically pumped laser action. High‐luminescence‐efficiency cyano‐substituted oligo(p‐ phenylene vinylene) (CN‐DPDSB) crystals (η ≈ 95%) grown by the physical vapor transport method is reported here, with high mobilities (at ≈10^?2 cm² V^?1 s^?1 order of magnitude) as measured by time‐of‐flight. The CN‐DPDSB crystals have well‐balanced bipolar carrier‐transport characteristics (μ_hole≈ 2.5–5.5 × 10^?2 cm² V^?1 s^?1; μ_electron ≈ 0.9–1.3 × 10^?2 cm² V^?1 s^?1) and excellent optically pumped laser properties. The threshold for amplified spontaneous emission (ASE) is about 4.6 μJ per pulse (23 KW cm^?2), while the gain coefficient at the peak wavelength of ASE and the loss coefficient caused by scattering are ≈35 and ≈1.7 cm^?1, respectively. This indicates that CN‐DPDSB crystals are promising candidates for organic laser diodes.     

Photoluminescence Detection of Biomolecules by Antibody‐Functionalized Diatom Biosilica

Diatoms are single‐celled algae that make microscale silica shells called “frustules”, which possess intricate nanoscale features imbedded within periodic two‐dimensional pore arrays. In this study, antibody‐functionalized diatom biosilica frustules serve as a microscale biosensor platform for selective and label‐free photoluminescence (PL)‐based detection of immunocomplex formation. The model antibody rabbit immunoglobulin G (IgG) is covalently attached to the frustule biosilica of the disk‐shaped, 10‐µm diatom Cyclotella sp. by silanol amination and crosslinking steps to a surface site density of 3948 ± 499 IgG molecules µm^?2. Functionalization of the diatom biosilica with the nucleophilic IgG antibody amplifies the intrinsic blue PL of diatom biosilica by a factor of six. Furthermore, immunocomplex formation with the complimentary antigen anti‐rabbit IgG further increases the peak PL intensity by at least a factor of three, whereas a non‐complimentary antigen (goat anti‐human IgG) does not. The nucleophilic immunocomplex increases the PL intensity by donating electrons to non‐radiative defect sites on the photoluminescent diatom biosilica, thereby decreasing non‐radiative electron decay and increasing radiative emission. This unique enhancement in PL emission is correlated to the antigen (goat anti‐rabbit IgG) concentration, where immunocomplex binding follows a Langmuir isotherm with binding constant of 2.8 ± 0.7 × 10^?7 M .     

Poly[oligo(ethylene glycol) methacrylate‐co‐glycidyl methacrylate] Brush Substrate for Sensitive Surface Plasmon Resonance Imaging Protein Arrays

Surface plasmon resonance imaging (SPRi) is a unique microarray method for label‐free and multiplexed bio‐assays. However, it currently cannot be used to detect human serum samples due to its low sensitivity and poor specificity. A poly[oligo(ethylene glycol) methacrylate‐co‐glycidyl methacrylate] (POEGMA‐co‐GMA) brush was synthesized by surface‐initiated atom transfer radical polymerization (SI‐ATRP) and used as a unique supporting matrix for SPRi arrays to efficiently load probe proteins for high sensitivity while reducing nonspecific adsorptions for good selectivity. Results indicate that the polymer brush has a high protein loading capacity (1.8 protein monolayers), low non‐specific protein adsorption (below the SPR detection limit), and high immobilization stability. Three model biomarkers, α‐fetoprotein, carcinoembryonic antigen, and hepatitis B surface antigen were simultaneously detected in human serum samples by a SPRi chip for the first time, showing detection limits of 50, 20, and 100 ng mL^?1, respectively. This work demonstrates great potential for a SPRi biochip as a powerful label‐free and high‐throughput detection tool in clinical diagnosis and biological research. Since the SPR detection is limited by the sensing film thickness, this approach particularly offers a unique way to significantly improve the sensitivity in the SPR detecting thickness range.     

Extreme Two‐Phase Cooling from Laser‐Etched Diamond and Conformal,Template‐Fabricated Microporous Copper

This paper reports the first integration of laser‐etched polycrystalline diamond microchannels with template‐fabricated microporous copper for extreme convective boiling in a composite heat sink for power electronics and energy conversion. Diamond offers the highest thermal conductivity near room temperature, and enables aggressive heat spreading along triangular channel walls with 1:1 aspect ratio. Conformally coated porous copper with thickness 25 µm and 5 µm pore size optimizes fluid and heat transport for convective boiling within the diamond channels. Data reported here include 1280 W cm^?2 of heat removal from 0.7 cm² surface area with temperature rise beyond fluid saturation less than 21 K, corresponding to 6.3 × 10⁵ W m^?2 K^?1. This heat sink has the potential to dissipate much larger localized heat loads with small temperature nonuniformity (5 kW cm^?2 over 200 µm × 200 µm with <3 K temperature difference). A microfluidic manifold assures uniform distribution of liquid over the heat sink surface with negligible pumping power requirements (e.g., <1.4 × 10^?4 of the thermal power dissipated). This breakthrough integration of functional materials and the resulting experimental data set a very high bar for microfluidic heat removal.     

Temperature‐Induced Stacking to Create Cu2O Concave Sphere for Light Trapping Capable of Ultrasensitive Single‐Particle Surface‐Enhanced Raman Scattering

The fabrication of bowl or concave particles with “asymmetric centers” has drawn considerable attentions, in which multiple scattering occurs inside the particles and the ability of light scattering is distinctly enhanced. However, the limited variety of templates, the uncontrollable dimensions such as the size of concavity and the complex growth process have posed serious limitations to the reproducible construction of concave particles with desired geometries and their light‐trapping properties. Herein, a “temperature‐induced stacking” strategy is proposed to create controllable concavity Cu₂O spheres for the first time. Different sizes of F68 micelles can be formed through aggregation under different reaction temperatures, which can serve as soft template to tailor concave geometries of Cu₂O spheres. The as‐prepared Cu₂O concave sphere (CS) can serve as single‐particle (SP) surface‐enhanced Raman scattering (SERS) substrate for highly repeatable and consistent Raman spectra. The unique cavity of Cu₂O CS entraps light effectively, which also enhances the scattering length owing to multiple light scattering. Combined with slightly increased surface area and charge‐transfer process, Cu₂O CS exhibits remarkable single‐particle SERS performance, with an ultralow low detection limit (2 × 10^?8 mol L^?1) and metal comparable enhancement factor (2.8 × 10⁵).     

Organic Thin‐Film Transistors with Anodized Gate Dielectric Patterned by Self‐Aligned Embossing on Flexible Substrates

An upscalable, self‐aligned patterning technique for manufacturing high‐ performance, flexible organic thin‐film transistors is presented. The structures are self‐aligned using a single‐step, multi‐level hot embossing process. In combination with defect‐free anodized aluminum oxide as a gate dielectric, transistors on foil with channel lengths down to 5 μm are realized with high reproducibility. Resulting on‐off ratios of 4 × 10⁶ and mobilities as high as 0.5 cm² V^?1 s^?1 are achieved, indicating a stable process with potential to large‐area production with even much smaller structures.     

Long Minority‐Carrier Diffusion Length and Low Surface‐Recombination Velocity in Inorganic Lead‐Free CsSnI3 Perovskite Crystal for Solar Cells

Sn‐based perovskites are promising Pb‐free photovoltaic materials with an ideal 1.3 eV bandgap. However, to date, Sn‐based thin film perovskite solar cells have yielded relatively low power conversion efficiencies (PCEs). This is traced to their poor photophysical properties (i.e., short diffusion lengths (<30 nm) and two orders of magnitude higher defect densities) than Pb‐based systems. Herein, it is revealed that melt‐synthesized cesium tin iodide (CsSnI₃) ingots containing high‐quality large single crystal (SC) grains transcend these fundamental limitations. Through detailed optical spectroscopy, their inherently superior properties are uncovered, with bulk carrier lifetimes reaching 6.6 ns, doping concentrations of around 4.5 × 10¹⁷ cm^?3, and minority‐carrier diffusion lengths approaching 1 µm, as compared to their polycrystalline counterparts having ≈54 ps, ≈9.2 × 10¹⁸ cm^?3, and ≈16 nm, respectively. CsSnI₃ SCs also exhibit very low surface recombination velocity of ≈2 × 10³ cm s^?1, similar to Pb‐based perovskites. Importantly, these key parameters are comparable to high‐performance p‐type photovoltaic materials (e.g., InP crystals). The findings predict a PCE of ≈23% for optimized CsSnI₃ SCs solar cells, highlighting their great potential.     

Selective Determination of Dopamine on a Boron‐Doped Diamond Electrode Modified with Gold Nanoparticle/Polyelectrolyte‐coated Polystyrene Colloids

Negatively charged gold nanoparticles (AuNPs) and a polyelectrolyte (PE) have been assembled alternately on a polystyrene (PS) colloid by a layer‐by‐layer (LBL) self‐assembly technique to form three‐dimensional (Au/PAH)₄/(PSS/PAH)₄ multilayer‐coated PS spheres (Au/PE/PS multilayer spheres). The Au/PE/PS multilayer spheres have been used to modify a boron‐doped diamond (BDD) electrode. Cyclic voltammetry is utilized to investigate the properties of the modified electrode in a 1.0 M KCl solution that contains 5.0 × 10^?3 M K₃Fe(CN)₆, and the result shows a dramatically decreased redox activity compared with the bare BDD electrode. The electrochemical behaviors of dopamine (DA) and ascorbic acid (AA) on the bare and modified BDD electrode are studied. The cyclic voltammetric studies indicate that the negatively charged, three‐dimensional Au/PE/PS multilayer sphere‐modified electrodes show high electrocatalytic activity and promote the oxidation of DA, whereas they inhibit the electrochemical reaction of AA, and can effectively be used to determine DA in the presence of AA with good selectivity. The detection limit of DA is 0.8 × 10^?6 M in a linear range from 5 × 10^?6 to 100 × 10^?6 M in the presence of 1 × 10^?3 M AA.