Ultrasensitive Solution-Processed Broadband PbSe Photodetectors through Photomultiplication Effect
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Abstract Optical devices are highly attractive for biosensing as they can not only enable quantitative measurements of analytes but also provide information on molecular structures. Unfortunately, typical refractive index-based optical sensors do not have sufficient sensitivity to probe the binding of low-molecular-weight analytes. Non-optical devices such as field-effect transistors can be more sensitive but do not offer some of the significant features of optical devices, particularly molecular fingerprinting. We present optical conductivity-based mid-infrared (mid-IR) biosensors that allow for sensitive and quantitative measurements of low-molecular-weight analytes as well as the enhancement of spectral fingerprints. The sensors employ a hybrid metasurface consisting of monolayer graphene and metallic nano-antennas and combine individual advantages of plasmonic, electronic and spectroscopic approaches. First, the hybrid metasurface sensors can optically detect target molecule-induced carrier doping to graphene, allowing highly sensitive detection of low-molecular-weight analytes despite their small sizes. Second, the resonance shifts caused by changes in graphene optical conductivity is a well-defined function of graphene carrier density, thereby allowing for quantification of the binding of molecules. Third, the sensor performance is highly stable and consistent thanks to its insensitivity to graphene carrier mobility degradation. Finally, the sensors can also act as substrates for surface-enhanced infrared spectroscopy. We demonstrated the measurement of monolayers of sub-nanometer-sized molecules or particles and affinity binding-based quantitative detection of glucose down to 200 pM (36 pg/mL). We also demonstrated enhanced fingerprinting of minute quantities of glucose and polymer molecules.
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The discovery of the RNA-guided DNA nuclease CRISPR-Cas9 has enabled the targeted editing of genomes from diverse organisms, but the permanent and inheritable nature of genome modification also poses immense risks. The potential for accidental exposure, malicious use, or undesirable persistence of Cas9 therapeutics and off-target genome effects highlight the need for detection assays. Here we report a centrifugal microfluidic platform for the measurement of both Cas9 protein levels and nuclease activity. Because Cas9 from many bacterial species have been adapted for biotechnology applications, we developed the capability to detect Cas9 from the widely-used S. pyogenes, as well as S. aureus, N. meningitidis, and S. thermophilus using commercially-available antibodies. Further, we show that the phage-derived anti-CRISPR protein AcrIIC1, which binds to Cas9 from several species, can be used as a capture reagent to broaden the species range of detection. Finally, as genome modification generally requires Cas9 nuclease activity, a fluorescence-based sedimentation nuclease assay was also incorporated to allow the sensitive and simultaneous measurement of both Cas9 protein and activity in a single biological sample.
Gravimetric, direct-current electrical, and electrical impedance sensing modes were used to measure response of high surface area 2D Ti 3 C 2 MXene film to water vapor pressures spanning 3 orders of magnitude (20 mTorr–20 Torr). The Ti 3 C 2 film exhibited reproducible reversible response in 0.1%–95% relative humidity (RH) range with a detection limit of <20 mTorr H 2 O partial pressure (<0.1% RH). DC electrical current-based sensing with 3 mV operating voltage and 0.8 pW power consumption was demonstrated. The highest normalized sensitivity was shown for gravimetric sensing modalities which scale with the overtone number, reaching highest sensitivity of about 12 Hz/% RH at the 9th crystal overtone (45 MHz oscillation).
Here, we report on the combination of nanodroplet sample preparation, ultra-low-flow nanoLC, high-field asymmetric ion mobility spectrometry (FAIMS), and the latest-generation Orbitrap Eclipse Tribrid mass spectrometer for greatly improved single-cell proteome profiling. FAIMS effectively filtered out singly charged ions for more effective MS analysis of multiply charged peptides, resulting in an average of 1056 protein groups identified from single HeLa cells without MS1-level feature matching. This is 2.3 times more identifications than without FAIMS and a far greater level of proteome coverage for single mammalian cells than has been previously reported for a label-free study. Differential analysis of single microdissected motor neurons and interneurons from human spinal tissue indicated a similar level of proteome coverage, and the two subpopulations of cells were readily differentiated based on single-cell label-free quantification.
In this work, ordered porous thin films of reduced graphene oxide and tin oxide (rGO/SnO 2 ) were synthesized by a polystyrene sphere monolayer colloidal crystal template method, and their gas-sensing properties were systematically studied. The formed amorphous SnO 2 and partially reduced graphene oxide were analyzed using several complementary material characterization techniques. Further, the results show that the incorporation of rGO significantly improved the humidity sensitivity and the electrical conductivity of the sensor relative to the pristine SnO 2 thin film. Fast response time and excellent selectivity towards humidity were also achieved for the rGO/SnO 2 composite film. The long-term stability of the rGO/SnO 2 sensor was confirmed by comparing its performance to a commercial humidity sensor. The enhanced sensor performance is attributed to the synergistic effects of the incorporation of rGO and the ordered porous structure of the composite film.
Ubiquitous carbon nanomaterials have great potential for emerging technologies, but they also pose a threat to human health at the end of their lifecycle, especially when they are introduced into waste or ground waters. Graphene field-effect transistors (GFET) and real time in situ confocal Raman microscopy (CRM) were employed to detect a submonolayer of carbon quantum dots (CQDs) in water. An effective GFET channel was formed on exfoliated and chemical vapor deposited (CVD) graphene. The adsorption of CQDs was monitored by measuring conductance changes in GFETs. The graphene channel was functionalized with (3-aminopropyl) triethoxysilane (APTES), which allowed for easy observation of a shift in the charge neutrality point (CNP) when the graphene channel was exposed to CQDs. The affinity of the CQD's carboxyl terminal groups to the aminofunctionalized channel enabled a highly sensitive CQD detection based on changes in the GFET conductivity. The adsorption of the CQDs induced a positive shift of the CNP with a limit of detection at concentrations of 239 ppm and 62 ppm for the exfoliated and CVD graphene, respectively. A supporting study of graphene functionalization and CQD adsorption was performed by real time in situ CRM, ellipsometry, and ex situ X-ray photoelectron spectroscopy. © 2019 Author(s).
InSe, a member of the layered materials family, is a superior electronic and optical material which retains a direct bandgap feature from the bulk to atomically thin few-layers and high electronic mobility down to a single layer limit. We, for the first time, exploit strain to drastically modify the bandgap of two-dimensional (2D) InSe nanoflakes. We demonstrated that we could decrease the bandgap of a few-layer InSe flake by 160 meV through applying an in-plane uniaxial tensile strain to 1.06% and increase the bandgap by 79 meV through applying an in-plane uniaxial compressive strain to 0.62%, as evidenced by photoluminescence (PL) spectroscopy. The large reversible bandgap change of ~239 meV arises from a large bandgap change rate (bandgap strain coefficient) of few-layer InSe in response to strain, ~154 meV/% for uniaxial tensile strain and ~140 meV/% for uniaxial compressive strain, representing the most pronounced uniaxial strain-induced bandgap strain coefficient experimentally reported in 2D materials. We developed a theoretical understanding of the strain-induced bandgap change through first-principles DFT and GW calculations. We also confirmed the bandgap change by photoconductivity measurements using excitation light with different photon energies. In conclusion, the highly tunable bandgap of InSe in the infrared regime should enable a wide range of applications, including electro-mechanical, piezoelectric and optoelectronic devices.
Organic materials that conduct both electrons and ions are integral to implantable bioelectronics because of their conformable nature. There is a dearth of these materials that are highly sensitive to cations, which are the majority ions on the surface of neurons. This manuscript offers a solution using an extended ribbon structure that is defect-free, providing high electronic mobility along its fused backbone, while the edge structure of these ribbons promotes high ionic conductivity. We incorporated these mixed ion/electron conductors into neural probes and implanted them in a rodent brain where they offer a suite of useful properties: high cation sensitivity, stability over several weeks after implantation, and biocompatibility. These materials represent an innovative class of implantable biosensors.
ABSTRACT While functional gene arrays (FGAs) have greatly expanded our understanding of complex microbial systems, specificity, sensitivity, and quantitation challenges remain. We developed a new generation of FGA, GeoChip 5.0, using the Agilent platform. Two formats were created, a smaller format (GeoChip 5.0S), primarily covering carbon-, nitrogen-, sulfur-, and phosphorus-cycling genes and others providing ecological services, and a larger format (GeoChip 5.0M) containing the functional categories involved in biogeochemical cycling of C, N, S, and P and various metals, stress response, microbial defense, electron transport, plant growth promotion, virulence, gyrB , and fungus-, protozoan-, and virus-specific genes. GeoChip 5.0M contains 161,961 oligonucleotide probes covering >365,000 genes of 1,447 gene families from broad, functionally divergent taxonomic groups, including bacteria (2,721 genera), archaea (101 genera), fungi (297 genera), protists (219 genera), and viruses (167 genera), mainly phages. Computational and experimental evaluation indicated that designed probes were highly specific and could detect as little as 0.05 ng of pure culture DNAs within a background of 1 μg community DNA (equivalent to 0.005% of the population). Additionally, strong quantitative linear relationships were observed between signal intensity and amount of pure genomic (∼99% of probes detected; r > 0.9) or soil (∼97%; r > 0.9) DNAs. Application of the GeoChip to a contaminated groundwater microbial community indicated that environmental contaminants (primarily heavy metals) had significant impacts on the biodiversity of the communities. This is the most comprehensive FGA to date, capable of directly linking microbial genes/populations to ecosystem functions. IMPORTANCE The rapid development of metagenomic technologies, including microarrays, over the past decade has greatly expanded our understanding of complex microbial systems. However, because of the ever-expanding number of novel microbial sequences discovered each year, developing a microarray that is representative of real microbial communities, is specific and sensitive, and provides quantitative information remains a challenge. The newly developed GeoChip 5.0 is the most comprehensive microarray available to date for examining the functional capabilities of microbial communities important to biogeochemistry, ecology, environmental sciences, and human health. The GeoChip 5 is highly specific, sensitive, and quantitative based on both computational and experimental assays. Use of the array on a contaminated groundwater sample provided novel insights on the impacts of environmental contaminants on groundwater microbial communities.
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Stability and optimal concentrations of reagents were studied in bioluminescence assay of ATP levels. Luciferase enzyme was prepared and purified using Sephadex G-100. Interdependencies between enzyme and luciferin concentrations in presence of optimal Mg are illustrated. Optimal ionic strength was confirmed to be 0.05 M for the four buffers tested. Adapted features of the R- and H-systems are summarized, as well as the percentages of ATP pools released from representative microbes by heat and chloroform.
Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.
A standard gas-dilution method was used to determine the selective response of the reversal electron attachment detector to carbon tetrachloride concentrations in nitrogen. Data are provided that determine the lowest concentration of sample detectable with the present instrumental configuration as being below 1.0 part per trillion by volume. The incorporation of a 90-deg electrostatic deflector with the quadrupole mass spectrometer is shown to be vital, and with it, negative-ion quadrupole mass spectrometry is used to characterize the ionization process. Observations are also made of the reversal electron attachment response to nitrobenzene. The analytical potential of reversal electron capture negative-ion mass spectrometry is examined, and areas for future development are discussed.
The problem we are addressing concerns the astronauts, and their exposure to radiation during spaceflight. The amount of this radiation is a variable depending on solar events and orbital characteristics. Our goal is to measure the total integrated quantity of radiation damage to the cell nucleus in astronauts or other people exposed to radiation. In my lab, we are turning up the microscope from the level of the chromosome, about eight orders of magnitude, to the molecular level. It is well known that radiation causes DNA and chromosome damage. We are developing methods to measure a specific molecular lesion. The lesion that we have selected to measure is thymidine diol, which is created by hydroxyl radicals adding across the 5.6 double bond of thymidine in DNA.