Machine Learning Discrimination and Ultrasensitive Detection of Fentanyl Using Gold Nanoparticle-Decorated Carbon Nanotube-Based Field-Effect Transistor Sensors.

The opioid overdose crisis is a global health challenge. Fentanyl, an exceedingly potent synthetic opioid, has emerged as a leading contributor to the surge in opioid-related overdose deaths. The surge in overdose fatalities, particularly due to illicitly manufactured fentanyl and its contamination of street drugs, emphasizes the urgency for drug-testing technologies that can quickly and accurately identify fentanyl from other drugs and quantify trace amounts of fentanyl. In this paper, gold nanoparticle (AuNP)-decorated single-walled carbon nanotube (SWCNT)-based field-effect transistors (FETs) are utilized for machine learning-assisted identification of fentanyl from codeine, hydrocodone, and morphine. The unique sensing performance of fentanyl led to use machine learning approaches for accurate identification of fentanyl. Employing linear discriminant analysis (LDA) with a leave-one-out cross-validation approach, a validation accuracy of 91.2% is achieved. Meanwhile, density functional theory (DFT) calculations reveal the factors that contributed to the enhanced sensitivity of the Au-SWCNT FET sensor toward fentanyl as well as the underlying sensing mechanism. Finally, fentanyl antibodies are introduced to the Au-SWCNT FET sensor as specific receptors, expanding the linear range of the sensor in the lower concentration range, and enabling ultrasensitive detection of fentanyl with a limit of detection at 10.8 fg mL-1.

Crystallographic Mapping and Tuning of Water Adsorption in Metal-Organic Frameworks Featuring Distinct Open Metal Sites.

Crucial steps toward designing water sorption materials and fine-tuning their properties for specific applications include precise identification of adsorption sites and establishment of rigorous molecular-level insight into the water adsorption process. We report stepwise crystallographic mapping and density functional theory computations of adsorbed water molecules in ALP-MOF-1, a metal-organic framework decorated with distinct open metal sites and carbonyl functional groups that serve as water anchoring sites for seeding the nucleation of a complex water network. Identification of an unusual water adsorption step in ALP-MOF-1 motivated the tuning of metal ion composition to adjust water uptake. These studies provide direct evidence that the identity of the open metal sites in MOFs can dramatically affect water adsorption behavior between 0 and ∼20% RH and that multiple proximal water anchoring sites along the MOF skeleton facilitate water uptake which could be potentially useful for applications requiring rapid and energetically facile water sorption.

Real-Time Modulation of Hydrogen Evolution Activity of Graphene Electrodes Using Mechanical Strain.

This paper reports the effect of mechanically applied elastic strain on the hydrogen evolution reaction (HER) activity of graphene under acidic conditions. An applied tensile strain of 0.2% on a graphene electrode is shown to lead to a 1-3% increase in the HER current. The tensile strain increases HER activity, whereas compressive strain decreases it. Density functional theory (DFT) calculations using a periodic graphene slab model predict an increase in the adsorption energy of the H atom with growing tensile strain, consistent with an enhancement of the current density in HER, similar to that observed experimentally.

Heterogeneous Growth of UiO-66-NH2 on Oxidized Single-Walled Carbon Nanotubes to Form "Beads-on-a-String" Composites.

In this work, we demonstrate a facile synthesis of UiO-66-NH2 metal-organic framework (MOF)/oxidized single-walled carbon nanotubes (ox-SWCNTs) composite at room temperature. Acetic acid (HAc) was used as a modulator to manipulate the morphology of the MOF in these composites. With a zirconium oxide cluster (Zr) to 2-aminoteraphthalate linker (ATA) 1:1.42 ratio and acetic acid modulator, we achieved predominately heterogeneous MOF growth on the sidewalls of CNTs. Understanding the growth mechanism of these composites was facilitated by conducting DFT calculations to investigate the interactions between ox-SWCNTs and the MOF precursors. The synthesized composites combine both microporosity of the MOF and electrical conductivity of the SWCNTs. Gas sensing tests demonstrated higher response for UiO-66-NH2/ox-SWCNT hybrid toward dry air saturated with dimethyl methylphosphonate (DMMP) vapor compared to oxidized single-walled carbon nanotubes (ox-SWCNTs) alone.

Modification of Carbon Nitride/Reduced Graphene Oxide van der Waals Heterostructure with Copper Nanoparticles To Improve CO2 Sensitivity.

Carbon nitride/reduced graphene oxide (rGO) van der Waals heterostructures (vdWH) have previously shown exceptional oxygen sensitivity via a photoredox mechanism, making it a potential material candidate for various applications such as oxygen reduction reaction catalysis and oxygen sensing. In this work, the electronic structure of a carbon nitride/rGO composite is modified through the introduction of copper nanoparticles (NPs). When incorporated into a chemiresistor device, this vdWH displayed a newfound CO2 sensitivity. The effects of humidity and light were investigated and found to be crucial components for the CO2 sensitivity. Density functional theory calculations performed on a carbon nitride/copper NP@rGO model system found an enhanced stabilization of CO2 caused by H-bonds between the carbon nitride layer and chemisorbed CO2 on copper, pointing to the important role played by humidity. The synergetic effect between the carbon nitride layer interfaced with CuNP@rGO, in combination with humidity and light (395 nm) irradiation, is found to be responsible for the newfound sensitivity toward CO2.

Machine-Learning Identification of the Sensing Descriptors Relevant in Molecular Interactions with Metal Nanoparticle-Decorated Nanotube Field-Effect Transistors.

Carbon nanotube-based field-effect transistors (NTFETs) are ideal sensor devices as they provide rich information regarding carbon nanotube interactions with target analytes and have potential for miniaturization in diverse applications in medical, safety, environmental, and energy sectors. Herein, we investigate chemical detection with cross-sensitive NTFETs sensor arrays comprised of metal nanoparticle-decorated single-walled carbon nanotubes (SWCNTs). By combining analysis of NTFET device characteristics with supervised machine-learning algorithms, we have successfully discriminated among five selected purine compounds, adenine, guanine, xanthine, uric acid, and caffeine. Interactions of purine compounds with metal nanoparticle-decorated SWCNTs were corroborated by density functional theory calculations. Furthermore, by testing a variety of prepared as well as commercial solutions with and without caffeine, our approach accurately discerns the presence of caffeine in 95% of the samples with 48 features using a linear discriminant analysis and in 93.4% of the samples with only 11 features when using a support vector machine analysis. We also performed recursive feature elimination and identified three NTFET parameters, transconductance, threshold voltage, and minimum conductance, as the most crucial features to analyte prediction accuracy.

Uncondensed Graphitic Carbon Nitride on Reduced Graphene Oxide for Oxygen Sensing via a Photoredox Mechanism.

Melon, a polymeric, uncondensed graphitic carbon nitride with a two-dimensional structure, has been coupled with reduced graphene oxide (rGO) to create an oxygen chemiresistor sensor that is active under UV photoactivation. Oxygen gas is an important sensor target in a variety of areas including industrial safety, combustion process monitoring, as well as environmental and biomedical fields. Because of the intimate electrical interface formed between melon and rGO, charge transfer of photoexcited electrons occurs between the two materials when under UV (λ = 365 nm) irradiation. A photoredox mechanism wherein oxygen is reduced on the rGO surface provides the basis for sensing oxygen gas in the concentration range 300-100 000 ppm. The sensor response was found to be logarithmically proportional to oxygen gas concentration. DFT calculations of a melon-oxidized graphene composite found that slight protonation of melon leads to charge accumulation on the rGO layer and a corresponding charge depletion on the melon layer. This work provides an example of a metal-free system for solid-gas interface sensing via a photoredox mechanism.

Enhanced adsorption of CO2 at steps of ultrathin ZnO: the importance of Zn-O geometry and coordination.

The interaction between CO2 and ultrathin ZnO supported on Au(111) has been studied using temperature programmed desorption (TPD) and density functional theory (DFT) calculations. We find that CO2 binds weakly on the planar ZnO bilayer and trilayer surfaces, desorbing at T = 130 K. CO2 binds more strongly at the steps formed between ZnO bilayers and trilayers, desorbing at T = 285-320 K depending upon the CO2 exposure. The adsorption energies determined from DFT calculations for CO2 on the ZnO planar surfaces and at the steps are ∼5.8 and 19.0 kcal mol-1, respectively, agreeing with the apparent activation energies of desorption (Ed) estimated based on the TPD peaks at the limit of low CO2 exposures (7.7 and 19.5 kcal mol-1, respectively). The DFT calculations further identify that the most stable adsorption configuration of CO2 at the steps of ultrathin ZnO is facilitated by the geometry and coordination of the Zn cations and O anions near the step region. Specifically, the enhanced adsorption takes place via bonding of both the C and O atoms of the CO2 molecule to the tri-fold coordinated O anions at the trilayer edge and to the neighboring Zn cations on the bilayer terrace, respectively, leading to CO2 bending and formation of a carbonate-like species.

Atomic intercalation to measure adhesion of graphene on graphite.

The interest in mechanical properties of two-dimensional materials has emerged in light of new device concepts taking advantage of flexing, adhesion and friction. Here we demonstrate an effective method to measure adhesion of graphene atop highly ordered pyrolytic graphite, utilizing atomic-scale 'blisters' created in the top layer by neon atom intercalates. Detailed analysis of scanning tunnelling microscopy images is used to reconstruct atomic positions and the strain map within the deformed graphene layer, and demonstrate the tip-induced subsurface translation of neon atoms. We invoke an analytical model, originally devised for graphene macroscopic deformations, to determine the graphite adhesion energy of 0.221±0.011 J m-2. This value is in excellent agreement with reported macroscopic values and our atomistic simulations. This implies mechanical properties of graphene scale down to a few-nanometre length. The simplicity of our method provides a unique opportunity to investigate the local variability of nanomechanical properties in layered materials.

Tunable Lattice Constant and Band Gap of Single- and Few-Layer ZnO.

Single and few-layer ZnO(0001) (ZnO(nL), n = 1-4) grown on Au(111) have been characterized via scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and density functional theory (DFT) calculations. We find that the in-plane lattice constants of the ZnO(nL, n ≤ 3) are expanded compared to that of the bulk wurtzite ZnO(0001). The lattice constant reaches a maximum expansion of 3% in the ZnO(2L) and decreases to the bulk wurtzite ZnO value in the ZnO(4L). The band gap decreases monotonically with increasing number of ZnO layers from 4.48 eV (ZnO(1L)) to 3.42 eV (ZnO(4L)). These results suggest that a transition from a planar to the bulk-like ZnO structure occurs around the thickness of ZnO(4L). The work also demonstrates that the lattice constant and the band gap in ultrathin ZnO can be tuned by controlling the number of layers, providing a basis for further investigation of this material.

Indium Oxide-Single-Walled Carbon Nanotube Composite for Ethanol Sensing at Room Temperature.

Utilizing a sol-gel synthesis, indium oxide is grown on the surface of oxidized single-walled carbon nanotubes (SWCNT) to form a hybrid material with high conductivity and sensitivity toward certain organic vapors. The room-temperature sensing of dilute ethanol and acetone vapors on the surface of indium oxide/SWCNT hybrid material is studied using electrical conductance experiments in a nonoxidizing environment. Through testing of variously calcinated materials, it was observed that the degree of annealing greatly affects the material's response to acetone and ethanol, such that the intermediate calcination condition yields the best sensitivity. DFT simulations are used to study the interface between defective SWCNT and indium oxide, as well as the interaction between ethanol and acetone molecules with the indium oxide/SWCNT hybrid material.

Nano-gold corking and enzymatic uncorking of carbon nanotube cups.

Because of their unique stacked, cup-shaped, hollow compartments, nitrogen-doped carbon nanotube cups (NCNCs) have promising potential as nanoscale containers. Individual NCNCs are isolated from their stacked structure through acid oxidation and subsequent probe-tip sonication. The NCNCs are then effectively corked with gold nanoparticles (GNPs) by sodium citrate reduction with chloroauric acid, forming graphitic nanocapsules with significant surface-enhanced Raman signature. Mechanistically, the growth of the GNP corks starts from the nucleation and welding of gold seeds on the open rims of NCNCs enriched with nitrogen functionalities, as confirmed by density functional theory calculations. A potent oxidizing enzyme of neutrophils, myeloperoxidase (MPO), can effectively open the corked NCNCs through GNP detachment, with subsequent complete enzymatic degradation of the graphitic shells. This controlled opening and degradation was further carried out in vitro with human neutrophils. Furthermore, the GNP-corked NCNCs were demonstrated to function as novel drug delivery carriers, capable of effective (i) delivery of paclitaxel to tumor-associated myeloid-derived suppressor cells (MDSC), (ii) MPO-regulated release, and (iii) blockade of MDSC immunosuppressive potential.

Assessing the Performances of Dispersion-Corrected Density Functional Methods for Predicting the Crystallographic Properties of High Nitrogen Energetic Salts.

Several density functional methods with corrections for long-range dispersion interactions are evaluated for their capabilities to describe the crystallographic lattice properties of a set of 26 high nitrogen-content salts relevant for energetic materials applications. Computations were done using methods that ranged from adding atom-atom dispersion corrections with environment-independent and environment-dependent coefficients, to methods that incorporate dispersion effects via dispersion-corrected atom-centered potentials (DCACP), to methods that include nonlocal corrections. Among the functionals tested, the most successful is the nonlocal optPBE-vdW functional of Klimes and Michaelides that predicts unit cell volumes for all crystals of the reference set within the target error range of ±3% and gives individual lattice parameters with a mean average percent error of less than 0.81%. The DCACP, Grimme's D3, and Becke and Johnson's exchange-hole (XDM) methods, when used with the BLYP, PBE, and B86b functionals, respectively, are also quite successful at predicting the lattice parameters of the test set.

CO2 capture properties of lithium silicates with different ratios of Li2O/SiO2: an ab initio thermodynamic and experimental approach.

The lithium silicates have attracted scientific interest due to their potential use as high-temperature sorbents for CO2 capture. The electronic properties and thermodynamic stabilities of lithium silicates with different Li2O/SiO2 ratios (Li2O, Li8SiO6, Li4SiO4, Li6Si2O7, Li2SiO3, Li2Si2O5, Li2Si3O7, and α-SiO2) have been investigated by combining first-principles density functional theory with lattice phonon dynamics. All these lithium silicates examined are insulators with band-gaps larger than 4.5 eV. By decreasing the Li2O/SiO2 ratio, the first valence bandwidth of the corresponding lithium silicate increases. Additionally, by decreasing the Li2O/SiO2 ratio, the vibrational frequencies of the corresponding lithium silicates shift to higher frequencies. Based on the calculated energetic information, their CO2 absorption capabilities were extensively analyzed through thermodynamic investigations on these absorption reactions. We found that by increasing the Li2O/SiO2 ratio when going from Li2Si3O7 to Li8SiO6, the corresponding lithium silicates have higher CO2 capture capacity, higher turnover temperatures and heats of reaction, and require higher energy inputs for regeneration. Based on our experimentally measured isotherms of the CO2 chemisorption by lithium silicates, we found that the CO2 capture reactions are two-stage processes: (1) a superficial reaction to form the external shell composed of Li2CO3 and a metal oxide or lithium silicate secondary phase and (2) lithium diffusion from bulk to the surface with a simultaneous diffusion of CO2 into the shell to continue the CO2 chemisorption process. The second stage is the rate determining step for the capture process. By changing the mixing ratio of Li2O and SiO2, we can obtain different lithium silicate solids which exhibit different thermodynamic behaviors. Based on our results, three mixing scenarios are discussed to provide general guidelines for designing new CO2 sorbents to fit practical needs.

Photoinduced charge transfer and acetone sensitivity of single-walled carbon nanotube-titanium dioxide hybrids.

The unique physical and chemical properties of single-walled carbon nanotubes (SWNTs) make them ideal building blocks for the construction of hybrid nanostructures. In addition to increasing the material complexity and functionality, SWNTs can probe the interfacial processes in the hybrid system. In this work, SWNT-TiO2 core/shell hybrid nanostructures were found to exhibit unique electrical behavior in response to UV illumination and acetone vapors. By experimental and theoretical studies of UV and acetone sensitivities of different SWNT-TiO2 hybrid systems, we established a fundamental understanding on the interfacial charge transfer between photoexcited TiO2 and SWNTs as well as the mechanism of acetone sensing. We further demonstrated a practical application of photoinduced acetone sensitivity by fabricating a microsized room temperature acetone sensor that showed fast, linear, and reversible detection of acetone vapors with concentrations in few parts per million range.

Hybridization of phenylthiolate- and methylthiolate-adatom species at low coverage on the Au(111) surface.

Using scanning tunneling microscopy we observed reaction products of two chemisorbed thiolate species, methylthiolate and phenylthiolate, on the Au(111) surface. Despite the apparent stability, organometallic complexes of methyl- and phenylthiolate with the gold-adatom (RS-Au-SR, with R as the hydrocarbon group) undergo a stoichiometric exchange reaction, forming hybridized CH3S-Au-SPh complexes. Complementary density functional theory calculations suggest that the reaction is most likely mediated by a monothiolate RS-Au complex bonded to the gold surface, which forms a trithiolate RS-Au-(SR)-Au-SR complex as a key intermediate. This work therefore reveals the novel chemical reactivity of the low-coverage "striped" phase of alkanethiols on gold and strongly points to the involvement of monoadatom thiolate intermediates in this reaction. By extension, such intermediates may be involved in the self-assembly process itself, shedding new light on this long-standing problem.

Water Chain Formation on TiO2(110).

The adsorption of water on a reduced rutile TiO2(110)-(1×1) surface has been investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The STM measurements show that at a temperature of 50 K, an isolated water monomer adsorbs on top of a Ti(5f) atom on the Ti row in agreement with earlier studies. As the coverage increases, water molecules start to form one-dimensional chain structures along the Ti row direction. Supporting DFT calculations show that the formation of an H-bonded one-dimensional water chain is energetically favorable compared to monomer adsorption. In the chain, there are H-bonds between adjacent water molecules, and the water molecules also form H-bonds to neighboring bridging oxygens of TiO2(110). Thermal annealing at T = 190 K leads to the formation of longer chains facilitated by the diffusion of water on the surface. The results provide insight into the nature of the hydrogen bonding in the initial stage of wetting of TiO2.

Coadsorption properties of CO2 and H2O on TiO2 rutile (110): a dispersion-corrected DFT study.

Adsorption and reactions of CO(2) in the presence of H(2)O and OH species on the TiO(2) rutile (110)-(1×1) surface were investigated using dispersion-corrected density functional theory and scanning tunneling microscopy. The coadsorbed H(2)O (OH) species slightly increase the CO(2) adsorption energies, primarily through formation of hydrogen bonds, and create new binding configurations that are not present on the anhydrous surface. Proton transfer reactions to CO(2) with formation of bicarbonate and carbonic acid species were investigated and found to have barriers in the range 6.1-12.8 kcal/mol, with reactions involving participation of two or more water molecules or OH groups having lower barriers than reactions involving a single adsorbed water molecule or OH group. The reactions to form the most stable adsorbed formate and bicarbonate species are exothermic relative to the unreacted adsorbed CO(2) and H(2)O (OH) species, with formation of the bicarbonate species being favored. These results are consistent with single crystal measurements which have identified formation of bicarbonate-type species following coadsorption of CO(2) and water on rutile (110).

Density functional theory studies on the electronic, structural, phonon dynamical and thermo-stability properties of bicarbonates MHCO(3), M = Li, Na, K.

The structural, electronic, phonon dispersion and thermodynamic properties of MHCO(3) (M = Li, Na, K) solids were investigated using density functional theory. The calculated bulk properties for both their ambient and the high-pressure phases are in good agreement with available experimental measurements. Solid phase LiHCO(3) has not yet been observed experimentally. We have predicted several possible crystal structures for LiHCO(3) using crystallographic database searching and prototype electrostatic ground state modeling. Our total energy and phonon free energy (F(PH)) calculations predict that LiHCO(3) will be stable under suitable conditions of temperature and partial pressures of CO(2) and H(2)O. Our calculations indicate that the [Formula: see text] groups in LiHCO(3) and NaHCO(3) form an infinite chain structure through O⋯H⋯O hydrogen bonds. In contrast, the [Formula: see text] anions form dimers, [Formula: see text], connected through double hydrogen bonds in all phases of KHCO(3). Based on density functional perturbation theory, the Born effective charge tensor of each atom type was obtained for all phases of the bicarbonates. Their phonon dispersions with the longitudinal optical-transverse optical splitting were also investigated. Based on lattice phonon dynamics study, the infrared spectra and the thermodynamic properties of these bicarbonates were obtained. Over the temperature range 0-900 K, the F(PH) and the entropies (S) of MHCO(3) (M =Li, Na, K) systems vary as F(PH)(LiHCO(3)) > F(PH)(NaHCO(3)) > F(PH)(KHCO(3)) and S(KHCO(3)) > S(NaHCO(3)) > S(LiHCO(3)), respectively, in agreement with the available experimental data. Analysis of the predicted thermodynamics of the CO(2) capture reactions indicates that the carbonate/bicarbonate transition reactions for Na and K could be used for CO(2) capture technology, in agreement with experiments.

Welding of gold nanoparticles on graphitic templates for chemical sensing.

Controlled self-assembly of zero-dimensional gold nanoparticles and construction of complex gold nanostructures from these building blocks could significantly extend their applications in many fields. Carbon nanotubes are one of the most promising inorganic templates for this strategy because of their unique physical, chemical, and mechanical properties, which translate into numerous potential applications. Here we report the bottom-up synthesis of gold nanowires in aqueous solution through self-assembly of gold nanoparticles on single-walled carbon nanotubes followed by thermal-heating-induced nanowelding. We investigate the mechanism of this process by exploring different graphitic templates. The experimental work is assisted by computational studies that provide additional insight into the self-assembly and nanowelding mechanism. We also demonstrate the chemical sensitivity of the nanomaterial to parts-per-billion concentrations of hydrogen sulfide with potential applications in industrial safety and personal healthcare.