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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

Ultrasensitive and selective non-enzymatic electrochemical glucose sensor based on hybrid material of graphene nanosheets/graphene nanoribbons/nickel nanoparticle

Highlights: • Nickel nanoparticles incorporated graphene nanosheets/graphene nanoribbons (GS/GNR/Ni) composite was synthesized by in-situ chemical reduction route and the as prepared GS/GNR/Ni modified glassy carbon electrode (GCE) was applied to detect glucose. • The fabricated GS/GNR/Ni/GCE modified electrode exhibits outstanding performance for non-enzymatic glucose sensing with sensitivity (2.3 mA/mM cm{sup 2}), linear range (5 nM - 5 mM) and detection limit (2.5 nM). • GS/GNR/Ni/GCE modified electrode exhibited a high selectivity towards glucose against the interferents, such as ascorbic acid (AA), uric acid (UA), dopamine and sucrose. - Abstract: A fast, highly sensitive and selective non-enzymatic electrochemical glucose sensor based on graphene sheet/graphene nanoribbon/nickel nanoparticles (GS/GNR/Ni) hybrid material modified electrode was fabricated. The hybrid material was synthesized via facile in-situ chemical reduction and characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy. The GS/GNR/Ni/GCE showed high electrochemical activity towards the oxidation of glucose in a 0.1 M NaOH solution. At an applied potential of +0.5 V, it displayed wide linear amperometric response towards glucose from the range of 5 nM–5 mM, with a detection limit of 2.5 nM and sensitivity of 2.3 mA/mM cm{sup 2}. Moreover, the modified electrode was relatively insensitive to commonly interfering species such as dopamine, ascorbic acid, sucrose, uric acid and Cl{sup −} ions. The fabricated sensor with better reproducibility, good long term stability, makes it a promising electrode for the development of effective glucose sensor.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Trapping-Micro-LC-FAIMS/dCV-MS Strategy for Ultrasensitive and Robust Targeted Quantification of Protein Drugs and Biomarkers

The sensitivity of LC-MS in quantifying target proteins in plasma/tissues is significantly hindered by co-eluted matrix interferences. While antibody-based immuno-enrichment effectively reduces interferences, developing and optimizing antibodies are often time-consuming and costly. Here, in this study, by leveraging the orthogonal separation capability of Field Asymmetric Ion Mobility Spectrometry (FAIMS), we developed a FAIMS/differential-compensation-voltage (FAIMS/dCV) method for antibody-free, robust, and ultra-sensitive quantification of target proteins directly from plasma/tissue digests. By comparing the intensity-CV profiles of the target vs. co-eluted endogenous interferences, the FAIMS/dCV approach identifies the optimal CV for quantification of each target protein, thus maximizing the signal-to-noise ratio (S/N). Compared to quantification without FAIMS, this technique dramatically reduces endogenous interferences, showing a median improvement of the S/N by 14.8-fold for the quantification of 17 representative protein drugs and biomarkers in plasma or tissues and a 5.2-fold median increase in S/N over conventional FAIMS approach, which uses the peak CV of each target. We also discovered that the established CV parameters remain consistent over months and are matrix-independent, affirming the robustness of the developed FAIMS/dCV method and the transferability of the method across matrices. The developed method was successfully demonstrated in three applications: the quantification of monoclonal antibodies with sub-ng/mL LOQ in plasma, an investigation of the time courses of evolocumab and its target PCSK9 in a preclinical setting, and a clinical investigation of low abundance obesity-related biomarkers. This innovative and easy-to-use method has extensive potential in clinical and pharmaceutical research, particularly where sensitive and high-throughput quantification of protein drugs and biomarkers is required.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deep-Dive Targeted Quantification for Ultrasensitive Analysis of Proteins in Nondepleted Human Blood Plasma/Serum and Tissues

Mass spectrometry-based targeted proteomics (e.g., selected reaction monitoring, SRM) is emerging as an attractive alternative to immunoassays for protein quantification. Recently we have made significant progress in SRM sensitivity for enabling quantification of low ng/mL to sub-ng/mL level proteins in nondepleted human blood plasma/serum without affinity enrichment. However, precise quantification of extremely low abundant but biologically important proteins (e.g., ≤100 pg/mL in blood plasma/serum) using targeted proteomics approaches still remains challenging. To address this need, we have developed an antibody-independent Deep-Dive SRM (DD-SRM) approach that capitalizes on multidimensional high-resolution reversed-phase liquid chromatography (LC) separation for target peptide enrichment combined with precise selection of target peptide fractions of interest, significantly improving SRM sensitivity by ~5 orders of magnitude when compared to conventional LC-SRM. Application of DD-SRM to human serum and tissue has been demonstrated to enable precise quantification of endogenous proteins at ~10 pg/mL level in nondepleted serum and at <10 copies per cell level in tissue. Thus, DD-SRM holds great promise for precisely measuring extremely low abundance proteins or protein modifications, especially when high-quality antibody is not available.

Environmental Molecular Sciences Laboratory↗

Picoflow Liquid Chromatography–Mass Spectrometry for Ultrasensitive Bottom-Up Proteomics Using 2-μm-i.d. Open Tubular Columns

In many areas of applications key objectives of chemical separations and analysis are to minimize the sample quantity while maximizing the chemical information obtained. Increasing measurement sensitivity is especially critical for proteomics research, especially when processing trace samples and where multiple measurements are desired. A rich collection of technologies has been developed, but the resulting sensitivity remains insufficient for achieving in-depth coverage of proteomic samples as small as single cells. In this paper, we combine picoliter-scale liquid chromatography (picoLC) with mass spectrometry (MS) to address this issue. The picoLC employs 2-µm-i.d. open tubular column to reduce the sample input needed to greatly increase the sensitivity achieved using electrospray ionization (ESI) with MS. With this picoLC-MS system, we show that we can identify ~1000 proteins reliably using only 30 pg of tryptic peptides, representing a 10–100-fold sensitivity improvement compared with the state-of-the-art liquid chromatography (LC) or capillary electrophoresis (CE)-MS methods. PicoLC-MS extends the limit of separation science and is expected to be a powerful tool for single cell proteomics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boron Doping and Defect Engineering of Graphene Aerogels for Ultrasensitive NO 2 Detection

In this study, boron-doped and defect-engineered graphene aerogels are prepared using triphenyl boron as a boron precursor and subsequent heat treatments. The boron chemistry and concentration in the graphene lattice are found to be highly dependent on the temperature used to activate boron. At 1500 °C, boron is incorporated at 3.2 atom % through a combination of B–C, B–N, and B–O bonds. At 1750 °C, the boron concentration decreases to 0.7 atom % and is predominantly incorporated through B–N bonding. Higher temperatures result in complete expulsion of boron from the lattice, leaving behind defects that are found to be beneficial for NO 2 gas detection. The gas sensing properties are explored to gain insight into the impact of boron chemistry on the sensing performance. A highly sensitive and selective conductometric NO 2 sensor is fabricated on a low-power microheater. Defect-engineered graphene aerogels with no boron remaining have superior gas detection properties. At an optimum sensing temperature of 240 °C, the defect-engineered aerogel has a theoretical detection limit of 7 ppb for NO 2 and response and recovery times of 100 and 300 s, respectively, with excellent selectivity over ammonia and hydrogen. Lastly, the superior gas sensing performance of defect-engineered graphene aerogels has remarkable implications for their performance in catalysis and energy storage applications.

36 MATERIALS SCIENCE↗

Ultrasensitive Tip- and Antenna-Enhanced Infrared Nanoscopy of Protein Complexes

Surface enhanced infrared absorption (SEIRA) us-ing resonant plasmonic nanoantennas enables zeptomolar detection sensitivity of (bio)analytes, although with diffraction limited spa-tial resolution. In contrast, infrared scattering-scanning near-field optical microscopy (IR s-SNOM) allows simultaneous imaging and spectroscopy with nanometer spatial resolution through vibrational coupling to the antenna mode of a probe tip. Herein, we combine these two approaches to image distributions of ferritin protein com-plexes adsorbed onto IR-resonant Au nanoantennas. The joint tip- and antenna-enhancement yields single protein complex sensitivity due to coupling with the vibrational modes of the bioanalytes. The coupling is revealed through IR s-SNOM spectra in the form of Fano lineshapes, which can be modelled using coupled harmonic oscillators. The role of the antenna resonance frequency on the cou-pling strength and the sensitivity is explored. Inhomogeneities in protein density within the film can be detected at single protein complex level. This work paves the way for single protein identi-fication and imaging through a combination of tip- and antenna-enhanced IR nanoscopy.

O'Callahan, Brian T.↗

Ultrasensitive Photothermal Spectroscopy: Harnessing the Seebeck Effect for Attogram-Level Detection

Molecular-level spectroscopy is crucial for sensing and imaging applications, yet detecting and quantifying minuscule quantities of chemicals remain a challenge, especially when they surface adsorb in low numbers. Here, we introduce a photothermal spectroscopic technique that enables the high selectivity sensing of adsorbates with an attogram detection limit. Our approach utilizes the Seebeck effect in a microfabricated nanoscale thermocouple junction, incorporated into the apex of a microcantilever. We observe minimal thermal mass exhibited by the sensor, which maintains exceptional thermal insulation. The temperature variation driving the thermoelectric junction arises from the nonradiative decay of molecular adsorbates’ vibrational states on the tip. We demonstrate the detection of photothermal spectra of physisorbed trinitrotoluene (TNT) and dimethyl methylphosphonate (DMMP) molecules, as well as representative polymers, with an estimated mass of 10 -18 g.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗