Ultrasensitive Graphene Field-Effect Biosensors Based on Ferroelectric Polarization of Lithium Niobate for Breast Cancer Marker Detection.

Herein, we present a novel ultrasensitive graphene field-effect transistor (GFET) biosensor based on lithium niobate (LiNbO3) ferroelectric substrate for the application of breast cancer marker detection. The electrical properties of graphene are varied under the electrostatic field, which is generated through the spontaneous polarization of the ferroelectric substrate. It is demonstrated that the properties of interface between graphene and solution are also altered due to the interaction between the electrostatic field and ions. Compared with the graphene field-effect biosensor based on the conventional Si/SiO2 gate structure, our biosensor achieves a higher sensitivity to 64.7 mV/decade and shows a limit of detection down to 1.7 fM (equivalent to 12 fg·mL-1) on the detection of microRNA21 (a breast cancer marker). This innovative design combining GFETs with ferroelectric substrates holds great promise for developing an ultrahigh-sensitivity biosensing platform based on graphene that enables rapid and early disease diagnosis.

Silicon flower structures by maskless plasma etching.

Silicon nano/microstructures are widely utilized in the semiconductor industry, and plasma etching is the most prominent method for fabricating silicon nano/microstructures. Among the variety of silicon nano/microstructures, black silicon with light-trapping properties has garnered broad interest from both the scientific and industrial communities. However, the fabrication mechanism of black silicon remains unclear, and the light absorption of black silicon only focuses on the near-infrared region thus far. Herein, we demonstrate that black silicon can be fabricated from individual flower-like silicon microstructures. Using fluorocarbon gases as etchants, silicon flower microstructures have been formed via maskless plasma etching. Black silicon forming from silicon flower microstructures exhibits strong absorption with wavelength from 0.25 µm to 20 µm. The result provides novel insight into the understanding of the plasma etching mechanism in addition to offering further significant practical applications for device manufacturing.

Hydrophobic Wafer-Scale High-Reproducibility SERS Sensor Based on Silicon Nanorods Arrays Decorated with Au Nanoparticles for Pesticide Residue Detection.

High sensitivity and reproducibility are highly desirable to a SERS sensor in diverse detection applications. Moreover, it is a great challenge to determine how to promote the target molecules to be more concentrated on the hotspots of the SERS substrate by engineering a surface with switching interfacial wettability. Along these lines, wafer-scale uniformly hydrophobic silicon nanorods arrays (SiNRs) decorated with Au nanoparticles were designed as the SERS substrate. Typically, the SERS substrate was fabricated by enforcing the polystyrene (PS) sphere self-assembly, as well as the plasma etching and the magnetron sputtering techniques. Consequently, the SERS substrate was treated by soaking within a n-dodecyl mercaptan (NDM) solution at different times in order to obtain adjustable wettabilities. By leveraging the electromagnetic enhancement resulted from the Au nanostructures and enrichment effect induced by the hydrophobicity, the SERS substrate is endowed with efficient SERS capabilities. During the detection of malachite green (MG), an ultralow relative standard deviation (RSD) 4.04-6.14% is achieved and the characteristic signal of 1172 cm-1 can be detected as low as 1 ng/mL. The proposed SiNRs' structure presents outstanding SERS activity with sensitivity and reproducibility rendering thus an ideal candidate for potential application in analytical detection fields.

Sandwich magnetically imprinted immunosensor for electrochemiluminescence ultrasensing diethylstilbestrol based on enhanced luminescence of Ru@SiO2 by CdTe@ZnS quantum dots.

A molecularly imprinted magnetic sensor with electroluminescent tags (MIP-ECL sensor) was developed for ultrasensing diethylstilbestrol (DES). A strategy is exploited to enhance ECL emission of the [Ru(bpy)3]2 +-tripropyl amine (TPrA) system by CdTe@ZnS quantum-dots (QDs) through energy transfer. Magnetically molecularly imprinted nanoparticles (MMIPs NPs) based on Fe3O4@SiO2 carriers are artificial, easily reproducible, and could replace easily inactivated first antibodies for capturing more DES molecules. Functionalized bio-conjugates of single antibody-CdTe@ZnS (Ab-CdTe@ZnS) are for the first time loaded on signal labels of Ru(bpy)32 +-doped silica nanocomposites (Ru@SiO2) for signal amplification. The final bio-conjugated signal probes are denoted as Ab-DES/CdTe@ZnS-Ru@SiO2. MMIPs beads that have captured antigens are bio-conjugated with antibody-labeled luminescent probes by specific immunoreactive reaction, and then the luminescent immunocomplex generates ECL signal on the magnetic electrode. The logarithm of ECL intensities depend linearly on the logarithm of DES concentrations in the range from 4.8 × 10- 4 to 36.0 nM with a detection limit of 0.025 pM. This novel assay is much more sensitive than other MIP sensors, and achieves lower cost and more enhanced stability than other immunosensors. The sensor is significantly potential and has been applied to DES detection in actual environment.

Preparation of porous Co3O4 and its response to ethanol with low energy consumption.

Co3O4 is a promising p-type semiconductor for ethanol detection. In this work, ethanol detection sensors were fabricated with nanostructured Co3O4, which exhibited higher selectivity and lower operating temperature. The Co3O4 was synthesised using ZIF-67 as a sacrificial precursor. The T400-Co3O4 that was obtained by calcining ZIF-67 at 400 °C showed the best sensing performance. Its response to 100 ppm ethanol vapor was 221.99 at a low optimal operating temperature (200 °C). Moreover, T400-Co3O4 achieved a low detection limit (1 ppm), remarkable repeatability, and higher selectivity compared to ammonia, carbon monoxide, acetone, hydrogen, methane, methanol, and nitrogen dioxide. The enhanced sensing performance was mainly attributed to three factors: (1) the adsorption/desorption of active adsorbed oxygen molecules (e.g. O- and O2-) and abundant oxygen vacancies, which increased the number of active sites; (2) the catalytic activity of Co3+, which greatly increased the reaction route and decreased the activation energy; and (3) the effective diffusion of gas molecules, which increased the effect of collisions between gas molecules and the material surface. This work provides an effective means to fabricate sensitive ethanol gas sensors with low energy consumption.

Fabrication, Characterization, and Application of Large-Scale Uniformly Hybrid Nanoparticle-Enhanced Raman Spectroscopy Substrates.

Surface-enhanced Raman spectroscopy (SERS) substrates with high sensitivity and reproducibility are highly desirable for high precision and even molecular-level detection applications. Here, large-scale uniformly hybrid nanoparticle-enhanced Raman spectroscopy (NERS) substrates with high reproducibility and controllability were developed. Using oxygen plasma treatment, large-area and uniformly rough polystyrene sphere (URPS) arrays in conjunction with 20 nm Au films (AuURPS) were fabricated for SERS substrates. Au nanoparticles and clusters covered the surface of the URPS arrays, and this increased the Raman signal. In the detection of malachite green (MG), the fabricated NERS substrates have high reproducibility and sensitivity. The enhancement factor (EF) of Au nanoparticles and clusters was simulated by finite-difference time-domain (FDTD) simulations and the EF was more than 104. The measured EF of our developed substrate was more than 108 with a relative standard deviation as low as 6.64%-13.84% over 15 points on the substrate. The minimum limit for the MG molecules reached 50 ng/mL. Moreover, the Raman signal had a good linear relationship with the logarithmic concentration of MG, as it ranged from 50 ng/mL to 5 µg/mL. The NERS substrates proposed in this work may serve as a promising detection scheme in chemical and biological fields.

Fabrication of alignment polycaprolactone scaffolds by combining use of electrospinning and micromolding for regulating Schwann cells behavior.

In the present study, a new approach for fabricating micropatterned polycaprolactone (PCL) scaffolds with ridge/groove structure on the surface was developed by combining use of electrospinning and micromolding method. A series of physicochemical properties, including morphology, wettability, component, crystal pattern and mechanical properties, of prepared PCL scaffolds were characterization, respectively. Stability of the micropatterned PCL scaffolds was measured using phosphate buffer solution immersion for a certain period. Then, the regulating effects of the micropatterned PCL scaffolds on attachment, orientation and normal biological function of Schwann cells were evaluated. And the protein adsorption behavior in various PCL scaffolds was also detected. The results showed that the micropatterned PCL scaffolds demonstrated a porous micro/nano complex structure with enhanced hydrophobicity and mechanical properties as a function of electrospun flow-rate of PCL solution. The micropatterned PCL scaffolds possessed good stability and could effectively regulate the attachment and orientation of Schwann cells at the early stage after cell culture. Importantly, the electrospun flow-rate of PCL solution was found to play an important role in scaffold properties, cell behavior and protein adsorption. The micropatterned scaffolds with a flow-rate of PCL solution at 0.12 mL h-1 demonstrated the better regulation on Schwann cells attachment and alignment without negatively affect the normal biological function of the cells. To the best of our knowledge, this is the first report of combining use of electrospinning and micromolding method for preparing artificial nerve implants. The study is anticipated to have potential application in peripheral nerve and other tissue engineering. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 3123-3134, 2018.

Characterization of immobilized tyrosinase - an enzyme that is stable in organic solvent at 100 °C.

Tyrosinase is a copper-containing enzyme present in plant and animal tissues, which catalyzes the production of melanin and other pigments. In organic solvent, tyrosinase can convert N-acetyl-l-tyrosine ethyl ester (insoluble in aqueous) to a derivative of l-dopamine (a drug used for the treatment of Parkinson's disease). Thus, the performances of tyrosinase in organic solvent have attracted scientific attention since 1980. In this work, we investigated the stability of immobilized tyrosinase at high temperature in anhydrous organic solvent. Triethylaminoethyl cellulose (TEAE-Cellulose) performed the best out of six immobilization platforms. The dry immobilized tyrosinase became extremely thermostable in organic solvent, and the half-life of the dry immobilized tyrosinase in organic solvent is strongly related to the polarity of the organic solvent than their log P value. The immobilized tyrosinase loses its activity instantaneously in aqueous solution at 100 °C, but it keeps enzymatic activity within 10 min in hydrophilic methanol and over one month in hydrophobic hexane (log P: 4.66, non-polar) even incubating at 100 °C. This research provides valuable information for the design of new biocatalysts.