Visualizing individual molecules with chemical recognition is a longstanding target in catalysis, molecular nanotechnology and biotechnology. Molecular vibrations provide a valuable 'fingerprint' for ...such identification. Vibrational spectroscopy based on tip-enhanced Raman scattering allows us to access the spectral signals of molecular species very efficiently via the strong localized plasmonic fields produced at the tip apex. However, the best spatial resolution of the tip-enhanced Raman scattering imaging is still limited to 3-15 nanometres, which is not adequate for resolving a single molecule chemically. Here we demonstrate Raman spectral imaging with spatial resolution below one nanometre, resolving the inner structure and surface configuration of a single molecule. This is achieved by spectrally matching the resonance of the nanocavity plasmon to the molecular vibronic transitions, particularly the downward transition responsible for the emission of Raman photons. This matching is made possible by the extremely precise tuning capability provided by scanning tunnelling microscopy. Experimental evidence suggests that the highly confined and broadband nature of the nanocavity plasmon field in the tunnelling gap is essential for ultrahigh-resolution imaging through the generation of an efficient double-resonance enhancement for both Raman excitation and Raman emission. Our technique not only allows for chemical imaging at the single-molecule level, but also offers a new way to study the optical processes and photochemistry of a single molecule.
Chemical enhancement is an important mechanism in surface-enhanced Raman spectroscopy. It is found that mildly reduced graphene oxide (MR-GO) nanosheets can significantly increase the chemical ...enhancement of the main peaks by up to 1 order of magnitude for adsorbed Rhodamine B (RhB) molecules, in comparison with the mechanically exfoliated graphene. The observed enhancement factors can be as large as ∼10(3) and show clear dependence on the reduction time of graphene oxide, indicating that the chemical enhancement can be steadily controlled by specific chemical groups. With the help of X-ray photoelectron spectra, these chemical species are identified and the origin of the observed large chemical enhancement can thus be revealed. It is shown that the highly electronegative oxygen species, which can introduce a strong local electric field on the adsorbed molecules, are responsible for the large enhancement. In contrast, the local defects generated by the chemical reduction show no positive correlation with the enhancement. Most importantly, the dramatically enhanced Raman spectra of RhB molecules on MR-GO nanosheets reproduce all important spectral fingerprints of the molecule with a negligible frequency shift. Such a unique noninvasive feature, along with the other intrinsic advantages, such as low cost, light weight, easy availability, and flexibility, makes the MR-GO nanosheets very attractive to a variety of practical applications.
Objective
Advanced parental age has raised additional concern as a risk factor of autism. We conducted a meta‐analysis of observational studies investigating the association between advanced parental ...age and risk of autism.
Method
PubMed, EMBASE, and Web of Science were searched for reports published up to November 11, 2015. Risk estimates from individual studies were pooled using random‐effects models.
Results
Twenty‐seven studies were included in the meta‐analysis. Compared with the reference points, the lowest parental age category was associated with a reduced risk of autism in the offspring, with adjusted odds ratios (ORs) 0.89 (95% confidence intervals CIs 0.75–1.06) and 0.81 (95% CI 0.73–0.89) for mother and father, respectively, and the highest parental age category was associated with an increased risk of autism in the offspring, with adjusted ORs 1.41 (95% CI 1.29–1.55) and 1.55 (95% CI 1.39–1.73) for mother and father respectively. Dose–response meta‐analysis indicated that an increase of 10 years in maternal and paternal age was associated with an 18% and 21% higher risk of autism.
Conclusion
Advanced parental age was associated with an increased risk of autism in the offspring. More mechanistic studies are needed to further explain this positive association.
We report a rational design of CaHPO(4)-α-amylase hybrid nanobiocatalytic system based on allosteric effect and an explanation of the increase in catalytic activity when certain enzymes are ...immobilized in specific nanomaterials. Employing a calcification approach in aqueous solutions, we acquired such new nanobiocatalytic systems with three different morphologies, i.e., nanoflowers, nanoplates, and parallel hexahedrons. Through studying enzymatic performance of these systems and free α-amylase with/without Ca(2+), we demonstrated how two factors, allosteric regulation and morphology of the as-synthesized nanostructures, predominantly influence enzymatic activity. Benefiting from both the allosteric modulation and its hierarchical structure, CaHPO(4)-α-amylase hybrid nanoflowers exhibited dramatically enhanced enzymatic activity. As a bonus, the new system we devised was found to enjoy higher stability and durability than free α-amylase plus Ca(2+).
Context. Solar active region (AR) 12673 in 2017 September produced the two largest flares in Solar Cycle 24: the X9.3 flare on September 6 and the X8.2 flare on September 10. Aims. We attempt to ...investigate the evolutions of the two large flares and their associated complex magnetic system in detail. Methods. Combining observations from the Solar Dynamics Observatory and results of nonlinear force-free field (NLFFF) modeling, we identify various magnetic structures in the AR core region and examine the evolution of these structures during the flares. Results. Aided by the NLFFF modeling, we identify a double-decker flux rope configuration above the polarity inversion line (PIL) in the AR core region. The north ends of these two flux ropes were rooted in a negative- polarity magnetic patch, which began to move along the PIL and rotate anticlockwise before the X9.3 flare on September 6. The strong shearing motion and rotation contributed to the destabilization of the two magnetic flux ropes, of which the upper one subsequently erupted upward due to the kink-instability. Then another two sets of twisted loop bundles beside these ropes were disturbed and successively erupted within five minutes like a chain reaction. Similarly, multiple ejecta components were detected as consecutively erupting during the X8.2 flare occurring in the same AR on September 10. We examine the evolution of the AR magnetic fields from September 3 to 6 and find that five dipoles emerged successively at the east of the main sunspot. The interactions between these dipoles took place continuously, accompanied by magnetic flux cancellations and strong shearing motions. Conclusions. In AR 12673, significant flux emergence and successive interactions between the different emerging dipoles resulted in a complex magnetic system, accompanied by the formations of multiple flux ropes and twisted loop bundles. We propose that the eruptions of a multi-flux-rope system resulted in the two largest flares in Solar Cycle 24.
Highlights • Regional and network functional changes could be seen in the early stage of SCI. • Functional changes were associated with clinical symptom severity in SCI patients. • Functional ...reorganization may reflect a compensatory role in the recovery of SCI.
Unambiguous chemical identification of individual molecules closely packed on a surface can offer the possibility to address single chemical species and monitor their behaviour at the individual ...level. Such a degree of spatial resolution can in principle be achieved by detecting their vibrational fingerprints using tip-enhanced Raman scattering (TERS). The chemical specificity of TERS can be combined with the high spatial resolution of scanning probe microscopy techniques, an approach that has stimulated extensive research in the field. Recently, the development of nonlinear TERS in a scanning tunnelling microscope has pushed the spatial resolution down to ∼0.5 nm, allowing the identification of the vibrational fingerprints of isolated molecules on Raman-silent metal surfaces. Although the nonlinear TERS component is likely to help sharpen the optical contrast of the acquired image, the TERS signal still contains a considerable contribution from the linear term, which is spatially less confined. Therefore, in the presence of different adjacent molecules, a mixing of Raman signals may result. Here, we show that using a nonlinear scanning tunnelling microscope-controlled TERS set-up, two different adjacent molecules that are within van der Waals contact and of very similar chemical structure (a metal-centred porphyrin and a free-base porphyrin) on a silver surface can be distinguished in real space. In addition, with the help of density functional theory simulations, we are also able to determine their adsorption configurations and orientations on step edges and terraces.
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