Time-resolved photoemission electron microscopy (PEEM) has established itself as a versatile experimental technique to unravel the ultrafast electron dynamics of materials with nanometer-scale resolution. However, the approach of performing PEEM-based, pixel-by-pixel lifetime mapping has not been reported thus far. Herein, we describe in detail the data pre-processing procedure and an algorithm to perform time-trace fittings of each pixel.
View Article and Find Full Text PDFObjectives: To evaluate the proficiency of a HIPAA-compliant version of GPT-4 in identifying actionable, incidental findings from unstructured radiology reports of Emergency Department patients. To assess appropriateness of artificial intelligence (AI)-generated, patient-facing summaries of these findings.
Materials And Methods: Radiology reports extracted from the electronic health record of a large academic medical center were manually reviewed to identify non-emergent, incidental findings with high likelihood of requiring follow-up, further sub-stratified as "definitely actionable" (DA) or "possibly actionable-clinical correlation" (PA-CC).
Background: Food allergy (FA), which is a condition that has no effective cure and can result in severe life-threatening allergic reactions, remains a global public health concern; however, little is known about how FAs are currently managed in the Asia-Pacific region.
Objective: The main objective of this survey was to evaluate the epidemiology of FA, as well as the availability of resources and practices for management of FA and anaphylaxis by health care providers across Asia.
Methods: From June 2022 to September 2022, a questionnaire-based survey comprising 66 questions was electronically sent to member societies of the Asia Pacific Association of Allergy Asthma and Clinical Immunology by using Survey Monkey.
The dynamic role of the intramolecular hydrogen bond in the S relaxation of -2-chlorophenol (2-CP) or -2-chlorothiophenol (2-CTP) has been investigated in a state-specific manner. Whereas ultrafast internal conversion is dominant for 2-CP, the H-tunneling competes with internal conversion for 2-CTP even at the S origin. The S-S internal conversion rate of 2-CTP could be directly measured from the S lifetimes of 2-CTP- (Cl-CH-SD) as the D-tunneling is kinetically blocked, allowing distinct estimations of tunneling and internal conversion rates with increasing the energy.
View Article and Find Full Text PDFSince the start of the 2019 coronavirus pandemic, interest in digital therapeutics (DTx) has increased. Temporomandibular disorder (TMD) fundamentally requires cognitive behavioral therapy (CBT), including physical self-regulation. An application that records TMD pain and parafunctional activities for CBT has recently been developed.
View Article and Find Full Text PDFMode-dependent H atom tunneling dynamics of the O-H bond predissociation of the S phenol has been theoretically analyzed. As the tunneling is governed by the complicated multi-dimensional potential energy surfaces that are dynamically shaped by the upper-lying S(ππ*)/S(πσ*) conical intersection, the mode-specific tunneling dynamics of phenol (S) has been quite formidable to be understood. Herein, we have examined the topography of the potential energy surface along the particular S vibrational mode of interest at the nuclear configurations of the S minimum and S/S conical intersection.
View Article and Find Full Text PDFAllergic rhinitis (AR) is an IgE-mediated inflammatory disease of the upper airway. AR affects the patients' quality of life, is a known risk factor for asthma and a socio-economic burden. Allergen-specific immunotherapy (AIT), comprising sublingual immunotherapy (SLIT) and subcutaneous immunotherapy (SCIT), involves administering increasing doses of the causative allergen to induce clinical and immunologic tolerance to the allergens.
View Article and Find Full Text PDFThe S-H bond tunneling predissociation dynamics of thiophenol and its -substituted derivatives (2-fluorothiophenol, 2-methoxythiophenol, and 2-chlorothiphenol) in S (ππ*) where the H atom tunneling is mediated by the nearby S (πσ*) state (which is repulsive along the S-H bond extension coordinate) have been investigated in a state-specific way using the picosecond time-resolved pump-probe spectroscopy for the jet-cooled molecules. The effects of the specific vibrational mode excitations and the SH/SD substitutions on the S-H(D) bond rupture tunneling dynamics have been interrogated, giving deep insights into the multidimensional aspects of the S/S conical intersection, which also shapes the underlying adiabatic tunneling potential energy surfaces (PESs). The semiclassical tunneling rate calculations based on the Wentzel-Kramers-Brillouin (WKB) approximation or Zhu-Nakamura (ZN) theory have been carried out based on the ab initio PESs calculated in the (one, two, or three) reduced dimensions to be compared with the experiment.
View Article and Find Full Text PDFThe effective solution to avoid machinery damage caused by resonance has been perplexing the field of engineering as a core research direction since the resonance phenomenon was discovered by Euler in 1750. Numerous attempts have been performed to reduce the influence of resonance since the earlier of last century, by introducing a nonlinear structure or a closed-loop control system. However, the existed methodologies cannot eliminate resonance completely even extra problems were introduced inevitably, which means the technical choke-point of resonance-free remains unsolved.
View Article and Find Full Text PDFThe milk fat globule membrane (MFGM) has been recognized as a milk component for more than 60 years, but its exact benefits remain unknown. Research on human MFGM has revealed that the membrane holds a host of bioactive components with potential benefits for the brain-immune-gut (BiG) axis in early life. Gangliosides and sphingomyelin, components within the MFGM, have been included in infant formulas for many years.
View Article and Find Full Text PDFThe S-state decaying rates of the three different benzenediols, catechol, resorcinol, and hydroquinone, and their 1:1 water clusters have been state-specifically measured using the picosecond time-resolved parent ion transients obtained by the pump (excitation) and probe (ionization) scheme. The S lifetime of catechol is found to be short, giving τ ∼ 5.9 ps at the zero-point level.
View Article and Find Full Text PDFMolecular structures in the electronically excited (S) and cationic (D) states of 2-fluorothioanisole (2-FTA) have been precisely refined from the real-time dynamics of the femtosecond (fs) wavepacket prepared by the coherent excitation of the Franck-Condon active out-of-plane torsional modes in the S ← S transition at 285 nm. The simulation to reproduce the experiment in terms of the beating frequencies gives the nonplanar geometry of 2-FTA in S, where the out-of-plane dihedral angle (φ) of the S-CH moiety is 51° with respect to the molecular plane. The behavior of the fs wavepacket in terms of the amplitudes and phases with the change of the probe (ionization) wavelength (λ = 300-330 nm) provides the otherwise veiled structure of the cationic D state.
View Article and Find Full Text PDFThe dynamic role of the conical intersection "seam" coordinate has been first revealed in the H fragmentation reaction of -cresol conformers. One of the (3 - 8) dimensional seam coordinates of the S(ππ*)/S(πσ*) conical intersection has been identified as the CH torsional potential function. The tunneling dynamics of the reactive flux is dictated by its nuclear layout with respect to the CH torsional angle, as the multidimensional tunneling barrier is dynamically shaped along the conical intersection seam.
View Article and Find Full Text PDFProlongation of the picosecond Raman pump laser pulse in the femtosecond stimulated Raman spectroscopy (FSRS) setup is essential for achieving the high spectral resolution of the time-resolved vibrational Raman spectra. In this work, the 2nd-order diffraction has been firstly employed in the double-pass grating filter technique for realizing the FSRS setup with the sub-5 cm spectral resolution. It has been experimentally demonstrated that our new FSRS setup gives rise to a highly-resolved Raman spectrum of the excited trans-stilbene, which is much improved from those reported in the literatures.
View Article and Find Full Text PDFDynamic shaping of the adiabatic tunneling barrier in the S-H bond extension coordinate of several ortho-substituted thiophenols has been found to be mediated by low-frequency out-of-plane vibrational modes, which are parallel to the coupling vector of the branching plane comprising the conical intersection. The S-H predissociation tunneling rate () measured when exciting to the S zero-point level of 2-methoxythiophenol (44 ps) increases abruptly, to ≈ (22 ps), at the energy corresponding to excitation of the 152 cm out-of-plane vibrational mode and then falls back to ≈ (40 ps) when the in-plane mode is excited at 282 cm. Similar resonance-like peaks in plots of S tunneling rate versus internal energy are observed when exciting the corresponding low-frequency out-of-plane modes in the S states of 2-fluorothiophenol and 2-chlorothiophenol.
View Article and Find Full Text PDFFermi resonances in the first electronically excited (S) state of phenol have been observed in real time. Quantum beats associated with coherent superposition of Fermi resonant eigenstates are manifested as temporal oscillations of the ionization cross sections of which the amplitudes are strongly dependent on the total ionization energy. This indicates that coherently excited eigenstates are effectively decomposed into their zeroth-order states, providing the unique opportunity for the investigation of nonstationary state dynamics in real-time.
View Article and Find Full Text PDFState-selective deactivation rates of N-methylpyrrole in the S state have been measured by using the picosecond pump-probe method. The S decay time leading to the N-CH bond dissociation is found to be strongly mode-dependent as manifested in both S decay and methyl-fragment growth dynamics. Time-resolved velocity-map ion images of the ˙CH fragment, as far as the fragment of the Gaussian-shaped high kinetic energy distribution is concerned, suggest that the N-CH cleavage reaction might occur through an intermediate.
View Article and Find Full Text PDFMultidimensional facets of the hydrogen tunneling dynamics of phenol excited in S (ππ*) have been unraveled to give particular S vibronic states strongly coupled or actively decoupled to the O-H tunneling coordinate. Strong mode-dependent variation of the tunneling rate measured with picosecond lasers indicates that tunneling probability is extremely sensitive to low-frequency vibrational modes seemingly orthogonal to the O-H elongation coordinate unless the rate of energy randomization exceeds that of tunneling. The multidimensional nature of tunneling has also been manifested in efficient internal-to-translational energy transfers observed at S vibronic modes strongly coupled to the tunneling coordinate, giving insights into otherwise the formidable multidimensional map of tunneling process.
View Article and Find Full Text PDFEpidermal growth factor (EGF) stimulates cell growth, proliferation, and survival. The biological benefits of EGF have been utilized in medical uses for improving wound healing as well as in today's skin cosmetics. EGF has been found in urine, saliva, milk, and plasma, but its efficient isolation remains a difficult task.
View Article and Find Full Text PDFLooking into temporal dynamics of the reactive flux that is precisely located at the well-characterized conical intersection has been one of chemists' longstanding goals. We report here real-time nonadiabatic bifurcation dynamics in the S-CH bond predissociation of thioanisole (CHSCH) in the first electronically excited state (S). It is found that two distinct adiabatic and nonadiabatic reaction pathways are activated simultaneously only when the vibronic state near the first conical intersection is optically accessed.
View Article and Find Full Text PDFRhythmic arylalkylamine N-acetyltransferase (AANAT) synthesis is a prominent circadian-controlled response that occurs in most mammals. AANAT is the core enzyme in melatonin production; because melatonin participates in many physiological processes, the regulation of AANAT is an important research topic. In this study, we focused on the role of heterogeneous ribonucleoprotein R (hnRNP R) in the translation of AANAT.
View Article and Find Full Text PDFConical intersection seam comprised of crossing surfaces of two lowest excited states of dimethyl sulfide (DMS) has been directly accessed by the one-photon excitation from the ground equilibrium state. Since the S-C bond rupture takes place promptly, the molecular structure on the excited state effectively belongs to C(S) symmetry. Namely, excited states of 1(1)B1 and 1(1)A2 in C(2)V become 1(1)A'' and 2(1)A'' states in C(S), respectively, and the optical transition from the ground equilibrium state to the dissociating molecule at the conical intersection seam is symmetry-allowed to facilitate the nonadiabatic transition on the 2(1)A'' state, leading eventually to the CH3S + CH3 products.
View Article and Find Full Text PDFPercolation generally refers to the phenomenon of abrupt variations in electrical, magnetic, or optical properties caused by gradual volume fraction changes of one component across a threshold in bicomponent systems. Percolation behaviors have usually been observed in macroscopic systems, with most studies devoted to electrical percolation. We report on our observation of plasmonic percolation in Au nanorod core-Pd shell nanostructures.
View Article and Find Full Text PDFThe mouse PERIOD1 (mPER1) protein, along with other clock proteins, plays a crucial role in the maintenance of circadian rhythms. mPER1 also provides an important link between the circadian system and the cell cycle system. Here we show that the circadian expression of mPER1 is regulated by rhythmic translational control of mPer1 mRNA together with transcriptional modulation.
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