ABSTRACT
Machine learning (ML) approaches have enabled rapid and efficient molecular property predictions as well as the design of new novel materials. In addition to great success for molecular problems, ML techniques are applied to various chemical reaction problems that require huge costs to solve with the existing experimental and simulation methods. In this review, starting with basic representations of chemical reactions, we summarized recent achievements of ML studies on two different problems; predicting reaction properties and synthetic routes. The various ML models are used to predict physical properties related to chemical reaction properties (e. g. thermodynamic changes, activation barriers, and reaction rates). Furthermore, the predictions of reactivity, self-optimization of reaction, and designing retrosynthetic reaction paths are also tackled by ML approaches. Herein we illustrate various ML strategies utilized in the various context of chemical reaction studies.
Subject(s)
Machine Learning , ThermodynamicsABSTRACT
A theoretical protocol based on long-range corrected density functional theory is suggested for a highly accurate estimation of the two-electron two-proton (2e2p) reduction potential of ethyl 2-phenylazocarboxylate derivatives. Geometry optimization and single-point energy refinement with ωB97X-D are recommended. The impact of polarization and diffusion functions in the basis sets on the 2e2p reduction potential is discussed. Further improvements can be achieved by tuning the range-split parameter based on the linear relationship between the Hammett constant of phenyl substituents and the optimal ω value that most accurately reproduces the experiments. The suggested protocol can accurately predict the 2e2p reduction potential of five ethyl 2-phenylazocarboxylate derivatives. Based on these findings, 22 additional candidates are suggested to enlarge the electrochemical window and to increase the selectivity of 2e2p reactions. This study contributes to the development of a theoretical approach to accurately estimate the 2e2p reduction potential of azo groups.
ABSTRACT
Polymer membranes with excellent thermomechanical properties and good gas separation performance are desirable for efficient CO2 separation. A series of copolyimide membranes are prepared for the first time using PIM-PI-1, a hard segment with high CO2 permeability, and poly(ethylene glycol)/poly(propylene glycol) (PEG/PPG), a soft segment with high CO2 selectivity. Two different unit polymers are combined to compensate the limitations of each polymer (e.g., the fast aging and moderate selectivity of PIM-PI-1 and the poor mechanical properties and lower permeability of PEG/PPG). The corresponding PIM-(durene-PEG/PPG) membranes exhibit an excellent combination of mechanical properties and gas separation performance compared to the typical PI-PEG-based copolymer membrane. The improved mechanical property is attributed to the unique chain threading and the reinforcement between the spiro unit of PIM and the flexible PEG/PPG at the molecular level, which has not previously been exploited for membranes. The PIM-(durene-PEG/PPG) membranes show a high CO2 permeability of 350-669 Barrer and a high CO2/N2 selectivity of 33.5-40.3. The experimental results are further evaluated with theoretical results obtained from molecular simulation studies, and a very good agreement between the experimental results and simulation results is found. Moreover, the PIM-(durene-PEG/PPG) copolymer membranes display excellent anti-aging performance for up to 1 year.
ABSTRACT
We described a technology for immobilizing radioiodine in the sod-cages by the interzeolite transformation of iodine-containing LTA (zeolite A) and FAU (zeolites X and Y) into a sodalite (SOD) structure. The immobilization of iodine in the sod-cage was confirmed using diverse characterization methods including powder XRD, elemental analysis, SEM-EDS, 127I MAS NMR, and I 3d XPS. Although both zeolites A (Na-A) and X (Na-X) were well converted into SOD structure in the presence of NaI and AgI, the iodide anions were fixed in the sod-cages only when NaI was used. The ability to adsorb methyl iodide (CH3I) was evaluated for zeolites A and X in which Na+ and/or Ag+ ions were exchanged, and Ag+ and zeolite X showed better adsorption properties than Na+ and zeolite A, respectively. However, when both CH3I adsorption ability and the successive immobilization of iodine by interzeolite transformation were considered, Na-X was determined to be the best candidate of adsorbent among the studied zeolites. More than 98% of the iodine was successfully immobilized in the sod-cage in the SOD structure by the interconversion of Na-X following CH3I adsorption, although the Na-X zeolite exhibited half the CH3I adsorption capacity of Ag-X.
ABSTRACT
We report an optically patternable metamaterial (OPM) for ultraviolet nanolithography below the diffraction limit. The OPM features monolayered silver nanoislands embedded within a photosensitive polymer by using spin-coating of an ultrathin polymer, oblique angle deposition, and solid-state embedment of silver nanoislands. This unique configuration simultaneously exhibits both negative effective permittivity and high image contrast in the ultraviolet range, which enables the surface plasmon excitation for the clear photolithographic definition of minimum feature size of 70 nm (â² λ/5) beyond the near-field zone. This new metamaterial provides a new class of photoresist for ultraviolet nanolithography below the diffraction limit.
ABSTRACT
This work reports plasmon enhanced photoacoustic generation by using a three dimensional plasmonic absorber. The 3D plasmonic absorber comprises a thin polymer film on glass nanopillar arrays with nanogap-rich silver nanoislands. The 3D plasmonic absorber clearly shows 24.6 times higher enhancement of photoacoustic signals at an excitation wavelength of 630 nm than a simple polymeric absorber. The photoacoustic enhancement results from the volumetric electromagnetic field enhancement on a light-absorbing polymer through 3D plasmonic nanostructures. This novel photoacoustic absorber provides a new direction for highly efficient ultrasonic generation.
ABSTRACT
This work reports a facile wafer-level fabrication for nanogap-rich gold nanoislands for highly sensitive surface enhanced Raman scattering (SERS) by repeating solid-state thermal dewetting of thin gold film. The method provides enlarged gold nanoislands with small gap spacing, which increase the number of electromagnetic hotspots and thus enhance the extinction intensity as well as the tunability for plasmon resonance wavelength. The plasmonic nanoislands from repeated dewetting substantially increase SERS enhancement factor over one order-of-magnitude higher than those from a single-step dewetting process and they allow ultrasensitive SERS detection of a neurotransmitter with extremely low Raman activity. This simple method provides many opportunities for engineering plasmonics for ultrasensitive detection and highly efficient photon collection.
ABSTRACT
The on-chip integration of a preconcentration chamber for ultrasensitive surface-enhanced Raman scattering (SERS) is shown. Small molecules are preconcentrated using 3D volumetric electromagnetic hotspots. The experimental results demonstrate an enhancement of the SERS signals of over two orders of magnitude, which allows the fingerprinting of neurotransmitter molecules at the nanomolar level and furthers the selective detection of oppositely charged molecules. This on-chip integration will provide new directions for ultrasensitive SERS applications.
ABSTRACT
A quantitative correlation between plasmon resonance and surface enhanced Raman scattering (SERS) signals is revealed by using a novel active plasmonic method, that is, a deformable nanoplasmonic membrane. A single SERS peak has the maximum gain at the corresponding plasmon resonance wavelength, which has the maximum extinction product of an excitation and the corresponding Raman scattering wavelengths.
Subject(s)
Metal Nanoparticles/chemistry , Spectrum Analysis, Raman/methods , Surface Plasmon Resonance/methods , Electromagnetic Phenomena , Metal Nanoparticles/ultrastructure , Microscopy, Atomic Force , NanotechnologyABSTRACT
This work presents a nanoplasmonic photoconductive antenna (PCA) with metal nanoislands for enhancing terahertz (THz) pulse emission. The whole photoconductive area was fully covered with metal nanoislands by using thermal dewetting of thin metal film at relatively low temperature. The metal nanoislands serve as plasmonic nanoantennas to locally enhance the electric field of an ultrashort pulsed pump beam for higher photocarrier generation. The plasmon resonance of metal nanoislands was achieved at an excitation laser wavelength by changing the initial thickness of metal film. This nanoplasmonic PCA shows two times higher enhancement for THz pulse emission power than a conventional PCA. This work opens up a new opportunity for plasmon enhanced large-aperture THz photoconductive antennas.
ABSTRACT
Bridging the gap between ultrashort pulsed optical waves and terahertz (THz) waves, the THz photoconductive antenna (PCA) is a major constituent for the emission or detection of THz waves by diverse optical and electrical methods. However, THz PCA still lacks employment of advanced breakthrough technologies for high-power THz emission. Here, we report the enhancement of THz emission power by incorporating optical nanoantennas with a THz photoconductive antenna. The confinement and concentration of an optical pump beam on a photoconductive substrate can be efficiently achieved with optical nanoantennas over a high-index photoconductive substrate. Both numerical and experimental results clearly demonstrate the enhancement of THz wave emission due to high photocarrier generation at the plasmon resonance of nanoantennas. This work opens up many opportunities for diverse integrated photonic elements on a single PCA at THz and optical frequencies.
