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1.
Nanotechnology ; 32(16): 162003, 2021 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-33543734

RESUMEN

Quantum phenomena are typically observable at length and time scales smaller than those of our everyday experience, often involving individual particles or excitations. The past few decades have seen a revolution in the ability to structure matter at the nanoscale, and experiments at the single particle level have become commonplace. This has opened wide new avenues for exploring and harnessing quantum mechanical effects in condensed matter. These quantum phenomena, in turn, have the potential to revolutionize the way we communicate, compute and probe the nanoscale world. Here, we review developments in key areas of quantum research in light of the nanotechnologies that enable them, with a view to what the future holds. Materials and devices with nanoscale features are used for quantum metrology and sensing, as building blocks for quantum computing, and as sources and detectors for quantum communication. They enable explorations of quantum behaviour and unconventional states in nano- and opto-mechanical systems, low-dimensional systems, molecular devices, nano-plasmonics, quantum electrodynamics, scanning tunnelling microscopy, and more. This rapidly expanding intersection of nanotechnology and quantum science/technology is mutually beneficial to both fields, laying claim to some of the most exciting scientific leaps of the last decade, with more on the horizon.

2.
Annu Rev Phys Chem ; 2021 Jan 22.
Artículo en Inglés | MEDLINE | ID: mdl-33481640

RESUMEN

Because plasmonic metal nanostructures combine strong light absorption with catalytically active surfaces, they have become platforms for the light-assisted catalysis of chemical reactions. The enhancement of reaction rates by plasmonic excitation has been extensively discussed. This review focuses on a less discussed aspect: the induction of new reaction pathways by light excitation. Through commentary on seminal reports, we describe the principles behind the optical modulation of chemical reactivity and selectivity on plasmonic metal nanostructures. Central to these phenomena are excited charge carriers generated by plasmonic excitation, which modify the energy landscape available to surface reactive species and unlock pathways not conventionally available in thermal catalysis. Photogenerated carriers can trigger bond dissociation or desorption in an adsorbate-selective manner, drive charge transfer and multielectron redox reactions, and generate radical intermediates. Through one or more of these mechanisms, a specific pathway becomes favored under light. By improved control over these mechanisms, light-assisted catalysis can be transformational for chemical synthesis and energy conversion. Expected final online publication date for the Annual Review of Physical Chemistry, Volume 72 is April 2021. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

3.
Proc Inst Mech Eng H ; : 954411921990138, 2021 Jan 22.
Artículo en Inglés | MEDLINE | ID: mdl-33482709

RESUMEN

Post-treatment coronal hermetic seal of the root canal opening prevents the food or saliva which assist to achieve successful endodontic treatment. Gutta-percha is filled in the inner canal, that is, from cervical third to apical third. Gutta-percha does not provide the hermetic seal because it does not bound with dentine walls. Various new restorative materials have been developed in the last 6-7 decade but drawback related to the polymerization shrinkage of the composite resin remains a clinical problem. In general, dental composites having volumetric shrinkage of the material depends on its formulation and curing conditions. In this article, the effect of this polymerization shrinkage on the tooth structure has been studied.

4.
Nano Lett ; 2020 Dec 04.
Artículo en Inglés | MEDLINE | ID: mdl-33274940

RESUMEN

Superionic conductors are prime candidates for the electrolytes of all-solid-state batteries. Our understanding of the mechanism and performance of superionic conductors is largely based on their idealized lattice structures. But how do defects in the lattice affect ionic structure and transport in these materials? This is a question answered here by in situ transmission electron microscopy of copper selenide, a classic superionic conductor. Nanowires of copper selenide exhibit antiphase boundaries which are a form of a planar defect. We examine the lattice structure around an antiphase boundary and monitor with atomic resolution how this structure evolves in an ordered-to-superionic phase transition. Antiphase boundaries are found to act as barriers to the propagation of the superionic phase. Antiphase boundaries also undergo spatial diffusion and shape changes resulting from thermally activated fluctuations of the neighboring ionic structure. These spatiotemporal insights highlight the importance of collective ionic transport and the role of defects in superionic conduction.

5.
Angew Chem Int Ed Engl ; 59(50): 22480-22483, 2020 Dec 07.
Artículo en Inglés | MEDLINE | ID: mdl-32898311

RESUMEN

The photoexcitation of plasmonic nanoparticles has been shown to drive multistep, multicarrier transformations, such as the conversion of CO2 into hydrocarbons. But for such plasmon-driven chemistry to be precisely understood and modeled, the critical photoinitiation step in the reaction cascade must be identified. We meet this goal by measuring H/D and 12 C/13 C kinetic isotope effects (KIEs) in plasmonic photosynthesis. In particular, we found that the substitution of H2 O with D2 O slows hydrocarbon production by a factor of 5-8. This primary H/D KIE leads to the inference that hole-driven scission of the O-H bond in H2 O is a critical, limiting step in plasmonic photosynthesis. This study advances mechanistic understanding of light-driven chemical reactions on plasmonic nanoparticles.

6.
Acc Chem Res ; 53(9): 1773-1781, 2020 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-32786334

RESUMEN

ConspectusPlasmonic nanostructures have garnered widescale scientific interest because of their strong light-matter interactions and the tunability of their absorption across the solar spectrum. At the heart of their superlative interaction with light is the resonant excitation of a collective oscillation of electrons in the nanostructure by the incident electromagnetic field. These resonant oscillations are known as localized surface plasmon resonances (LSPRs). In recent years, the community has uncovered intriguing photochemical attributes of noble metal nanostructures arising from their LSPRs. Chemical reactions that are otherwise unfavorable or sluggish in the dark are induced on the nanostructure surface upon photoexcitation of LSPRs. This phenomenon has led to the birth of plasmonic catalysis. The rates of a variety of kinetically challenging reactions are enhanced by plasmon-excited nanostructures. While the potential utility for solar energy harvesting and chemical production is clear, there is a natural curiosity about the precise origin(s) of plasmonic catalysis. One explanation is that the reactions are facilitated by the action of the intensely concentrated and confined electric fields generated on the nanostructure upon LSPR excitation. Another mechanism of activation involves hot carriers transiently produced in the metal nanostructure by damping of LSPRs.In this Account, we visit a phenomenon that has received less attention but has a key role to play in plasmonic catalysis and chemistry. Under common chemical scenarios, plasmonic excitation induces a potential or a voltage on a nanoparticle. This photopotential modifies the energetics of a chemical reaction on noble metal nanoparticles. In a range of cases studied by our laboratory and others, light-induced potentials underlie the plasmonic enhancement of reaction kinetics. The photopotential model does not replace other known mechanisms, but it complements them. There are multiple ways in which an electrostatic photopotential is produced by LSPR excitation, such as optical rectification, but one that is most relevant in chemical media is asymmetric charge transfer to solution-phase acceptors. Electrons and holes produced in a nanostructure by damping of LSPRs are not removed at the same rate. As a result, the slower carrier accumulates on the nanostructure, and a steady-state charge is built up on the nanostructure, leading to a photopotential. Potentials of up to a few hundred millivolts have been measured by our laboratory and others. A photocharged nanoparticle is a source of carriers of a higher potential than an uncharged one. As a result, redox chemical reactions on noble metal nanoparticles exhibit lower activation barriers under photoexcitation. In electrochemical reactions on noble metal nanoparticles, the photopotential supplements the applied potential. In a diverse set of reactions, the photopotential model explains the photoenhancement of rates as well as the trends as a function of light intensity and photon energy. With further gains, light-induced potentials may be used as a knob for controlling the activities and selectivities of noble metal nanoparticle catalysts.

7.
Chem Soc Rev ; 2020 Jul 23.
Artículo en Inglés | MEDLINE | ID: mdl-32700702

RESUMEN

Single-molecule-level measurements are bringing about a revolution in our understanding of chemical and biochemical processes. Conventional measurements are performed on large ensembles of molecules. Such ensemble-averaged measurements mask molecular-level dynamics and static and dynamic fluctuations in reactivity, which are vital to a holistic understanding of chemical reactions. Watching reactions on the single-molecule level provides access to this otherwise hidden information. Sub-diffraction-limited spatial resolution fluorescence imaging methods, which have been successful in the field of biophysics, have been applied to study chemical processes on single-nanoparticle and single-molecule levels, bringing us new mechanistic insights into physiochemical processes. However, the scope of chemical processes that can be studied using fluorescence imaging is considerably limited; the chemical reaction has to be designed such that it involves fluorophores or fluorogenic probes. In this article, we review optical imaging modalities alternative to fluorescence imaging, which expand greatly the range of chemical processes that can be probed with nanoscale or even single-molecule resolution. First, we show that the luminosity, wavelength, and intermittency of solid-state photoluminescence (PL) can be used to probe chemical transformations on the single-nanoparticle-level. Next, we highlight case studies where localized surface plasmon resonance (LSPR) scattering is used for tracking solid-state, interfacial, and near-field-driven chemical reactions occurring in individual nanoscale locations. Third, we explore the utility of surface- and tip-enhanced Raman scattering to monitor individual bond-dissociation and bond-formation events occurring locally in chemical reactions on surfaces. Each example has yielded some new understanding about molecular mechanisms or location-to-location heterogeneity in chemical activity. The review finishes with new and complementary tools that are expected to further enhance the scope of knowledge attainable through nanometer-scale resolution chemical imaging.

8.
Angew Chem Int Ed Engl ; 59(5): 2085-2088, 2020 01 27.
Artículo en Inglés | MEDLINE | ID: mdl-31765516

RESUMEN

By the photoexcitation of localized surface plasmon resonances of metal nanoparticles, one can generate reaction equivalents for driving redox reactions. We show that, in such cases, there is a chemical potential contributed by the plasmonic excitation. This chemical potential is a function of the concentration of light, as we determine from the light-intensity-dependent activity in the plasmon-excitation-driven reduction of CO2 on Au nanoparticles. Our finding allows the treatment of plasmonic excitation as a reagent in chemical reactions; the chemical potential of this reagent is tunable by the light intensity.

9.
Nat Commun ; 10(1): 3285, 2019 Jul 23.
Artículo en Inglés | MEDLINE | ID: mdl-31337760

RESUMEN

The engineering of nanoscale features enables the properties of solid-state materials to be tuned. Here, we show the tunable preparation of cuprous sulfide nanocrystals ranging in internal structures from single-domain to multi-domain. The synthetic method utilizes in-situ oxidation to grow nanocrystals with a controlled degree of copper deficiency. Copper-deficient nanocrystals spontaneously undergo twinning to a multi-domain structure. Nanocrystals with twinned domains exhibit markedly altered crystallographic phase and phase transition characteristics as compared to single-domain nanocrystals. In the presence of twin boundaries, the temperature for transition from the ordered phase to the high-copper-mobility superionic phase is depressed. Whereas the superionic phase is stable in the bulk only above ca. 100 °C, cuprous sulfide nanocrystals of ca. 7 nm diameter and a twinned structure are stable in the superionic phase well below ambient temperature. These findings demonstrate twinning to be a structural handle for nanoscale materials design and enable applications for an earth-abundant mineral in solid electrolytes for Li-S batteries.

10.
Proc Inst Mech Eng H ; 233(8): 839-848, 2019 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-31165678

RESUMEN

During root canal shaping, pain could result from the high level of force or vibration generated. This could be related to file kinematics or geometry. In the present study, a comparison is made between forces and vibrations generated by endodontic files having three different kinematics. Square pillar resin blocks were used as simulated root canals to study forces and vibrations generated by the file having reciprocating motion (WaveOne Gold), transline motion (Self-Adjusting File), and rotary motion (2Shape). The forces and vibrations were measured using the dynamometer and accelerometer, respectively. Recorded time domain signals were processed in MATLAB to calculate the root mean square value. A one-way analysis of variance and Tukey's test for post hoc comparison at 95% confidence interval were applied over the root mean square data of different files. From a statistical analysis of the file systems, the null hypotheses could not be accepted (P < 0.05) as 95% of the confidence interval. Differences between the means were statistically significant. The root mean square values of force and vibration for WaveOne Gold significantly exceeded those of Self-Adjusting File, 2Shape1, and 2Shape2 while the root mean square values of vibration for 2Shape1 and 2Shape2 were significantly less than the Self-Adjusting File; however, the root mean square value of force for the 2Shape2 was significantly more than for the Self-Adjusting File. Under the present experimental conditions, significant differences in the root mean square values of force and vibration of the three endodontic files of different kinematics have been observed. The WaveOne Gold file system generated higher apical force and vibration than the transline and rotary file system.


Asunto(s)
Preparación del Conducto Radicular/instrumentación , Vibración , Fenómenos Biomecánicos , Dolor/etiología , Preparación del Conducto Radicular/efectos adversos , Rotación
11.
J Phys Chem B ; 123(29): 6253-6259, 2019 07 25.
Artículo en Inglés | MEDLINE | ID: mdl-31246466

RESUMEN

An understanding of the thermodynamic properties of elementary chemical steps of a reaction is important for the development of fundamental reaction theories and for effective industrial practice. In this work, temperature-variable single-molecule fluorescence microscopy was employed to study a reversible redox chemical process and reveal the thermodynamics of chemical elementary reactions at a single-molecule level. Activation energies of pure elementary steps were measured on the level of single molecules and found to be heterogeneously distributed across the population of individual molecules. The activation parameters measured across the population of individual molecules also exhibited a compensation effect and an isokinetic relationship. These results constitute a new single-molecule-level perspective into a chemical reaction.

12.
Angew Chem Int Ed Engl ; 58(26): 8794-8798, 2019 Jun 24.
Artículo en Inglés | MEDLINE | ID: mdl-31038831

RESUMEN

Localized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel-cell-relevant reaction. The electrocatalyst consists of Pdx Ag alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible-light plasmonic response of Ag. The alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the Pdx Ag NTs.

13.
Nat Commun ; 10(1): 2022, 2019 05 01.
Artículo en Inglés | MEDLINE | ID: mdl-31043604

RESUMEN

Photochemical conversion of CO2 into fuels has promise as a strategy for storage of intermittent solar energy in the form of chemical bonds. However, higher-energy-value hydrocarbons are rarely produced by this strategy, because of kinetic challenges. Here we demonstrate a strategy for green-light-driven synthesis of C1-C3 hydrocarbons from CO2 and H2O. In this approach, plasmonic excitation of Au nanoparticles produces a charge-rich environment at the nanoparticle/solution interface conducive for CO2 activation, while an ionic liquid stabilizes charged intermediates formed at this interface, facilitating multi-step reduction and C-C coupling. Methane, ethylene, acetylene, propane, and propene are photosynthesized with a C2+ selectivity of ~50% under the most optimal conditions. Hydrocarbon turnover exhibits a volcano relationship as a function of the ionic liquid concentration, the kinetic analysis of which coupled with density functional theory simulations provides mechanistic insights into the synergy between plasmonic excitation and the ionic liquid.

14.
Nat Commun ; 10(1): 1505, 2019 04 03.
Artículo en Inglés | MEDLINE | ID: mdl-30944324

RESUMEN

Solid-solid phase transitions are processes ripe for the discovery of correlated atomic motion in crystals. Here, we monitor an order-disorder transition in real-time in nanoparticles of the super-ionic solid, Cu2-xSe. The use of in-situ high-resolution transmission electron microscopy allows the spatiotemporal evolution of the phase transition within a single nanoparticle to be monitored at the atomic level. The high spatial resolution reveals that cation disorder is nucleated at low co-ordination, high energy sites of the nanoparticle where cationic vacancy layers intersect with surface facets. Time-dependent evolution of the reciprocal lattice of individual nanoparticles shows that the initiation of cation disorder is accompanied by a ~3% compression of the anionic lattice, establishing a correlation between these two structural features of the lattice. The spatiotemporal insights gained here advance understanding of order-disorder transitions, ionic structure and transport, and the role of nanoparticle surfaces in phase transitions.

15.
Angew Chem Int Ed Engl ; 58(25): 8410-8415, 2019 Jun 17.
Artículo en Inglés | MEDLINE | ID: mdl-31016822

RESUMEN

Cuprous selenide nanocrystals have hallmark attributes, especially tunable localized surface plasmon resonances (LSPRs) and super-ionic behavior. These attributes of cuprous selenide are now integrated with a one-dimensional morphology. Essentially, Cu2 Se nanowires (NWs) of micrometer-scale lengths and about 10 nm diameter are prepared. The NWs exhibit a super-ionic phase that is stable at temperatures lower than in the bulk, owing to compressive lattice strain along the radial dimension of the NWs. The NWs can be switched between oxidized and reduced forms, which have contrasting phase transition and LSPR characteristics. This work thus makes available switchable, one-dimensional waveguides and ion-conducting channels.

16.
ACS Nano ; 12(8): 8330-8340, 2018 Aug 28.
Artículo en Inglés | MEDLINE | ID: mdl-30089207

RESUMEN

Photocatalytic reduction of carbon dioxide (CO2) by visible light has the potential to mimic plant photosynthesis and facilitate the renewable production of storable fuels. Accomplishing desirable efficiency and selectivity in artificial photosynthesis requires an understanding of light-driven pathways on photocatalyst surfaces. Here, we probe with single-nanoparticle spatial resolution the dynamics of a plasmonic silver (Ag) photocatalyst under conditions of visible light-driven CO2 reduction. In situ surface-enhanced Raman spectroscopy captures discrete adsorbates and products formed dynamically on single photocatalytic nanoparticles, most prominent among which is a surface-adsorbed hydrocarboxyl (HOCO*) intermediate critical to further reduction of CO2 to carbon monoxide (CO) and formic acid (HCOOH). Density functional theory simulations of the captured adsorbates reveal the mechanism by which plasmonic excitation activates physisorbed CO2 leading to the formation of HOCO*, indicating close interplay between photoexcited states and adsorbate/metal interactions.

17.
Nat Commun ; 9(1): 3056, 2018 08 03.
Artículo en Inglés | MEDLINE | ID: mdl-30076295

RESUMEN

Ethylene epoxidation is used to produce 2 × 107 ton per year of ethylene oxide, a major feedstock for commodity chemicals and plastics. While high pressures and temperatures are required for the reaction, plasmonic photoexcitation of the Ag catalyst enables epoxidation at near-ambient conditions. Here, we use surface-enhanced Raman scattering to monitor the plasmon excitation-assisted reaction on individual sites of a Ag nanoparticle catalyst. We uncover an unconventional mechanism, wherein the primary step is the photosynthesis of graphene on the Ag surface. Epoxidation of ethylene is then promoted by this photogenerated graphene. Density functional theory simulations point to edge defects on the graphene as the sites for epoxidation. Guided by this insight, we synthesize a composite graphene/Ag/α-Al2O3 catalyst, which accomplishes ethylene photo-epoxidation under ambient conditions at which the conventional Ag/α-Al2O3 catalyst shows negligible activity. Our finding of in situ photogeneration of catalytically active graphene may apply to other photocatalytic hydrocarbon transformations.

18.
Proc Inst Mech Eng H ; 232(8): 787-795, 2018 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-30014778

RESUMEN

In cases of teeth with unusual morphology like calcified pulp canal, guided endodontic treatment is suggested. An endodontic guide which navigates burs according to a preplanned path is used. Existing approaches of endodontic guide design are based on visual observation and analysis of tomographic scan of teeth. Hence, they are time-consuming and expert-dependent. Computer-aided design-based methodology was employed to design and fabricate a customized endodontic guide. A cone beam computed tomographic scan with MIMICS software was used to create a solid model of the teeth. The solid model generated was sliced through the developed program in MATLAB. The geometric centers of consecutive slices were joined to plot the root canals central axis. To gauge the optimum bur angulation for guide design, a straight line fitted in the data set of the geometric center helped create minimally invasive access. Methodology involved simulated verification of the drill path to judge the accuracy and feasibility of root canal access cavity preparation. Next, endodontic guides for extracted teeth were designed and fabricated using a three-dimensional printer, followed by guided root canal access cavity preparation for extracted teeth. To validate the proposed methodology, using a MATLAB image processing tool box, the deviation between the prepared root canal access cavity axis and root canal axis was analyzed in radiographs of post-treated teeth. The deviation between the tool path axis and root canal axis in simulated root canals was found to be not more than 0.210 ± 0.04 mm. The deviation between the axis of the planned root canal access cavity and the prepared root canal access cavity was 0.07 ± 0.02 mm. The proposed method reveals encouraging results for endodontic guide design.


Asunto(s)
Diseño Asistido por Computadora , Cavidad Pulpar/cirugía , Preparación del Conducto Radicular/métodos , Programas Informáticos , Tomografía Computarizada de Haz Cónico , Cavidad Pulpar/diagnóstico por imagen , Diseño de Equipo , Preparación del Conducto Radicular/instrumentación
19.
Nano Lett ; 18(7): 4370-4376, 2018 07 11.
Artículo en Inglés | MEDLINE | ID: mdl-29932665

RESUMEN

Conversion of solar energy into liquid fuel often relies on multielectron redox processes that include highly reactive intermediates, with back reaction routes that hinder the overall efficiency of the process. Here, we reveal that these undesirable reaction pathways can be minimized, rendering the photocatalytic reactions more efficient, when charge carriers are harvested from a multiexcitonic state of a semiconductor photocatalyst. A plasmonic antenna, comprising Au nanoprisms, was employed to accomplish feasible levels of multiple carrier excitations in semiconductor nanocrystal-based photocatalytic systems (CdSe@CdS core-shell quantum dots and CdSe@CdS seeded nanorods). The antenna's near-field amplifies the otherwise inherently weak biexciton generation in the semiconductor. The two-electron photoreduction of Pt and Pd metal precursors served as model reactions. In the presence of the plasmonic antenna, these photocatalyzed two-electron reactions exhibited enhanced yields and kinetics. This work uniquely relies on a nonlinear enhancement that has potential for large amplification of photocatalytic activity in the presence of a plasmonic near-field.

20.
Angew Chem Int Ed Engl ; 57(30): 9315-9319, 2018 Jul 20.
Artículo en Inglés | MEDLINE | ID: mdl-29863294

RESUMEN

The search for ion-conductive solid electrolytes for Li+ batteries is an important scientific and technological challenge with economic and sustainable energy implications. In this study, nanocrystals (NCs) of the ion conductor copper selenide (Cu2-y Se) were doped with Li by the process of cation exchange. Li2x Cu2-2x Se alloy NCs were formed at intermediate stages of the reaction, which was followed by phase segregation into Li2 Se and Cu2 Se domains. Li-doped Cu2-y Se NCs and Li2 Se NCs exhibit a possible SI phase at moderately elevated temperatures and warrant further ion-conductance tests. These findings may guide the design of nanostructured super-ionic electrolytes for Li+ transport.

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