Deciphering the conformational preference and ionization dynamics of tetrahydrofuran: Insights from advanced spectroscopic techniques.

Tetrahydrofuran (THF) has garnered significant attention due to its pivotal role in biological and chemical processes. The diverse array of conformations exhibited by THF profoundly impacts its reactivity and interactions with other molecules. Understanding these conformational preferences is crucial for comprehending its molecular behavior. In this study, we utilize infrared (IR) resonant vacuum ultraviolet photoionization/mass-analyzed threshold ionization (VUV-PI/MATI) mass spectroscopies to capture distinctive vibrational spectra of individual conformers, namely, "twisted" and "bent," within THF. Our conformer-specific vibrational spectra provide valuable insights into the relative populations of these two conformers. The analysis reveals that the twisted (C2) conformer is more stable than the bent (CS) conformer by 17 ± 15 cm-1. By precisely tuning the VUV photon energy to coincide with vibrational excitation via IR absorption, we selectively ionize specific conformers, yielding two-photon IR + VUV-PI/MATI spectra corresponding to the twisted and bent conformers. This investigation conclusively affirms that both the twisted and bent conformers coexist in the neutral state, while only the twisted conformer exists in the cationic state. These findings not only bridge gaps in existing knowledge but also provide profound insights into the behavior of this pivotal molecule in the realms of biology and medicine.

Unraveling the Conformational Preference of Morpholine: Insights from Infrared Resonant Vacuum Ultraviolet Photoionization Mass Spectroscopy.

The preference for different conformations in morpholine has a notable effect on its behavior and reactivity in organic synthesis. Herein, we explored the intricate conformational properties of morpholines through a combination of advanced mass spectrometric techniques and theoretical calculations. Notably, we employed infrared (IR) resonant vacuum ultraviolet (VUV) mass-analyzed threshold ionization spectroscopy to measure the unique vibrational spectra of the distinct conformers (Chair-Eq and Chair-Ax) in morpholine for the first time. Through precise VUV photon energy adjustments to coincide with the vibrational excitation via IR absorption, we effectively pinpointed the adiabatic ionization thresholds corresponding to the Chair-Eq (65 442 ± 4 cm-1) and Chair-Ax (65 333 ± 4 cm-1) conformers. This allowed us to accurately determine the conformational stability between the two conformers (109 ± 4 cm-1). By shedding light on the conformational properties of morpholine, this study brings far-reaching implications to the fields of organic synthesis and pharmaceutical research.

Conformational diversity and environmental implications of trans-2-pentenal.

This study investigates the conformational intricacies of trans-2-pentenal (trans-2PA), a significant biogenic volatile organic compound. To unveil its potential implications in atmospheric chemistry and environmental pollution, we employ advanced infrared resonant vacuum ultraviolet mass-analysed threshold ionisation spectroscopy. Through this method, we identify the major conformers within trans-2PA, encompassing trans-s-trans (tt-) and trans-s-cis (tc-) structures with planar (cis) and non-planar (gauche) configurations introduced by a methyl group. In a pioneering spectroscopic examination, we analyze trans-2PA in both the neutral and cationic states. This approach allows us to gain a comprehensive understanding of its molecular behavior. Our conformer-specific vibrational spectra not only reveal the relative populations of the main conformers, notably tt-cis and tt-gauche conformers, but also shed light on atmospheric oxidation processes and lower tropospheric organic aerosol formation mechanisms. Our findings expand the understanding of the role of trans-2PA in environmental and biological contexts. Additionally, they contribute to a broader understanding of its influence on air quality, climate, and atmospheric dynamics. The collaboration between advanced experimental techniques and computational methods fortifies the scientific underpinning of this study, opening doors to further exploration in the realms of atmospheric chemistry and environmental science.

Conformational Structures of Neutral and Cationic Pivaldehyde Revealed by IR-Resonant VUV-MATI Mass Spectroscopy.

Pivaldehyde, which is an unwanted by-product released with engine exhaust, has received considerable research attention because of its hydrocarbon oxidations at atmospheric temperature. To gain insight into the conformer-specific reaction dynamics, we investigated the conformational structures of the pivaldehyde molecule in neutral (S0) and cationic (D0) states using the recently invented IR-resonant VUV-MATI mass spectroscopy. Additionally, we constructed the two-dimensional potential energy surfaces (2D PESs) associated with the conformational transformations in the S0 and D0 states to deduce the conformations corresponding to the measured vibrational spectra. The 2D PESs indicated the presence of only the eclipsed conformation in the global minima of both states, unlike those in propanal and isobutanal. However, comparing the IR-dip VUV-MATI spectra from two intense peaks in the VUV-MATI spectrum with the anharmonic IR simulations revealed the correspondence between the gauche conformer on the S0 state and the measured IR spectra. Furthermore, Franck-Condon analysis confirmed that most peaks in the VUV-MATI spectrum are attributed to the adiabatic ionic transitions between the neutral gauche and cationic eclipsed conformers in pivaldehyde. Consequently, electron removal from the highest occupied molecular orbital, consisting of the nonbonding orbital of the oxygen atom in pivaldehyde, promoted the formyl-relevant modes in the induced cationic eclipsed conformer.

Determination of the highest occupied molecular orbital and conformational structures of morpholine based on its conformer-specific photoionization dynamics.

Morpholine, a heterocycle composed of an ether and amine, is commonly used as a precursor in many organic synthesis processes because of the nucleophilicity induced by the lone-pair electrons of the nitrogen atom within its ring. Herein, we investigated the conformer-specific photoionization dynamics of morpholine under molecular-beam conditions using high-resolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) mass spectroscopy. Two-dimensional potential energy surfaces (2D PESs) associated with the conformational changes in the neutral (S0) and cationic (D0) ground states were constructed to identify the conformer(s) corresponding to the obtained VUV-MATI spectrum. The 2D PESs indicated that the chair and twisted boat forms with equatorial and axial NH conformations (four conformers with the following relative energies: Chair-Eq < Chair-Ax ≪ Twisted boat-Ax < Twisted boat-Eq) of morpholine lie on the global minimum of the S0 state. However, only the axial-like NH conformation in each form (stable Chair-Ax-like+˙ and Twisted boat-Ax-like+˙ conformers) exists in the D0 state. Accordingly, vibration assignment was performed based on Franck-Condon (FC) analyses of the adiabatic ionic transitions from each Chair-Eq and Chair-Ax conformer to the Chair-Ax-like+˙ conformer. The FC analyses revealed that only the Chair-Ax conformer contributes to the ionic transitions to the Chair-Ax-like+˙ conformer owing to the large FC factors, whose adiabatic ionization energy was determined to be 8.1003 ± 0.0005 eV. Consequently, adiabatic ionization arises because of electron removal from the highest occupied molecular orbital consisting of the nonbonding orbital of the N atom in the Chair-Ax conformer.

Development and Verification of Conformer-Specific Vibrational Spectroscopy.

Conformers have similar vibrational structures both in neutral (S0) and cationic (D0) states owing to the comparable force fields between their nuclei. Nevertheless, there is a continuous development of vibrational spectroscopic techniques to rigorously identify individual conformers in the designated molecule but only in the S0 state. We developed an inventive conformer-specific vibrational spectroscopic technique to measure identifiable vibrational spectra of individual conformers in both S0 and D0 states. We measured isomer-specific vibrational spectra in both states for gas-phase acetone and oxetane isomers from a solution with azeotropic composition to verify the proposed techniques that are based on infrared (IR) resonant vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. The measured IR dip VUV-MATI and IR hole-burn VUV-MATI spectra for each isomer, which correspond to isomer-specific vibrational spectra in both states, can be represented by IR-resonant VUV photoionization and one-photon VUV-MATI spectra of the binary mixture, respectively, under supersonic expansion conditions. The partial pressures of the individual isomers in the binary mixture with different mole fractions estimated according to the relative peak intensities in the measured spectra provide insights on solute-solvent interactions. We suggest that the verified IR-resonant VUV-MATI spectroscopy can form the basis of effective schemes toward conformational chemistry.

One-photon VUV-MATI and two-photon IR+VUV-MATI spectroscopic determination of oxetane cation ring-puckering vibrations and conformation.

The conformational structures of heterocyclic compounds are of considerable interest to chemists and biochemists as they are often the constituents of natural products. Among saturated four-membered heterocycles, the conformational structure of oxetane is known to be slightly puckered in equilibrium because of a low interconversion barrier in its ring-puckering potential, unlike cyclobutane and thietane. We measured the one-photon vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) and two-photon IR+VUV-MATI spectra of oxetane for the first time to determine the ring-puckering potential of the oxetane cation and hence its conformational structure in the D0 (ground) state. Remarkably, negative anharmonicity and large amplitudes were observed for the ring-puckering vibrational mode progression in the low-frequency region of the observed MATI spectra. We were able to successfully analyze the progression in the MATI spectra through the Franck-Condon simulations, using modeled potential energy functions for the ring-puckering modes in the S0 and D0 states. Considering that the interconversion barrier and puckered angle for the ring-puckering potential on the S0 state were found to be 15.5 cm-1 and 14°, respectively, the cationic structure is expected to be planar with C2v symmetry. Our results revealed that the removal of an electron from the nonbonding orbitals on the oxygen atom in oxetane induced the straightening of the puckered ring in the cation owing to an increase in ring strain. Consequently, we conclude that this change in the conformational structure upon ionization generated the ring-puckering vibrational mode progression in the MATI spectra.

Identification of individual conformers in C4H6O isomers using conformer-specific vibrational spectroscopy.

We measured the conformer-specific vibrational spectra of C4H6O isomers in neutral and cationic states using IR resonant vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy for the first time. Notably, the measured IR dip and hole-burn VUV-MATI spectra for each isomer represent the identifiable vibrational spectra of individual conformers in both states. Furthermore, we estimated the relative populations of individual conformers in crotonaldehyde (CA) and methyl vinyl ketone (MVK) isomers using the IR dip intensity, the corresponding Franck-Condon factor, and the IR absorption cross section. Our analysis revealed that the compositional ratio of s-trans to s-cis conformers in the CA isomer remained at 95.8 : 4.2 even under supersonic expansion, whereas that in the MVK isomer was determined as 90.6 : 9.4, which is consistent with previous research. These findings reveal that the conformational stability of each isomer depends on the position of the methyl group relative to the carbonyl group.

Conformer-specific VUV-MATI spectroscopy of methyl vinyl ketone: stabilities and cationic structures of the s-trans and s-cis conformers.

Methyl vinyl ketone (MVK), a volatile compound with photochemical activity, has received considerable attention in the fields of environmental chemistry and atmospheric chemistry. We explored the conformational stabilities of MVK in the neutral S0 and the cationic D0 states using conformer-specific vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy, which provided identifiable vibrational spectra for cationic MVK conformers. Based on the origin bands of the two individual conformers of MVK identified in the MATI spectra under different supersonic expansion conditions, the accurate adiabatic ionization energies of the s-trans and the s-cis conformers were determined to be 77 867 ± 4 (9.6543 ± 0.0005 eV) and 78 222 ± 4 cm-1 (9.6983 ± 0.0005 eV), respectively. The identifiable vibrational spectra of the two cationic conformers were further confirmed using vibrational assignments based on the Franck-Condon fit. Accordingly, precise cationic structures of the MVK conformers could be determined. The structural changes of the two conformers upon ionization could be attributed to the removal of an electron from the highest occupied molecular orbital of each conformer, which consists of nonbonding molecular orbitals on the oxygen atom in the carbonyl group interacting with the σ orbitals in the molecular plane. Consequently, the s-trans conformer was preferred by 48 ± 18 and 403 ± 18 cm-1 in the neutral ground S0 and the cationic D0 states, respectively, which was supported by density-corrected density functional theory calculations and natural bond orbital analysis.

The Risk Prediction of Coronary Artery Lesions through the Novel Hematological Z-Values in 4 Chronological Age Subgroups of Kawasaki Disease.

Background and Objectives: Most cases of Kawasaki disease (KD) occur between the ages of 6 months and 5 years. Differences in immunological reaction and CAL (coronary artery lesion) by the age subgroups classified according to the prevalence of KD and those particularly in the earlier life of KD should be investigated. Materials and Methods: The laboratory data of 223 infantile and 681 non-infantile KD cases from 2003 to 2018 at Korea University Hospital were retrospectively analyzed. Patients with KD were divided into infants and non-infants and further subdivided into four subgroups by age. The age-adjusted Z-values were compared among the subgroups. Febrile controls were identified as patients with fever for >5 days and who showed some of the KD symptoms. Results: IVIG (intravenous immunoglobulin) resistance at the age of 6 months or less was significantly lower than that at the ages of 7-12 months and 13-60 months (respectively, p < 0.05). The significant risk factors for CAL in total KD patients were age, incomplete KD, post-IVIG fever, IVIG resistance, convalescent Z-eosinophil, and subacute platelet (p < 0.05). The significant risk factors for CAL at the age of 6 months or less were IVIG resistance, acute Z-neutrophil, subacute Z-neutrophil, subacute NLR (neutrophil to lymphocyte ratio), and subacute platelet (respectively, p < 0.05). Conclusion: Younger age and incomplete presentation in KD can be independent risk factors for CAL. The immune reactions of KD at a younger age are more tolerated compared with those at older ages during the acute phase. The immune response at the age of 6 months or less showed immune tolerance in terms of incomplete presentation and IVIG responsiveness. The risk factors such as IVIG resistance, subacute platelet, subacute NLR, and acute or subacute Z-neutrophil at the age of 6 months or less can be very useful parameters to predict CAL in young, incomplete KD.

Identification and composition of conformational isomers and their cations in crotonaldehyde by VUV-MATI spectroscopy.

Crotonaldehyde is a simple α,ß-unsaturated aldehyde that reacts stereochemically with nucleophilic reagents according to its conformational structure. Identifiable vibrational spectra of the cationic crotonaldehyde conformers were measured using one-photon vacuum ultraviolet mass-analysed threshold ionization (VUV-MATI) spectroscopy. From the 0-0 bands for the individual conformers confirmed by Franck-Condon (FC) simulations, the precise adiabatic ionization energies were determined to be 9.7501 ± 0.0004 eV (78 640 ± 3 cm-1), 9.7620 ± 0.0004 eV (78 736 ± 3 cm-1), 9.7122 ± 0.0004 eV (78 334 ± 3 cm-1), and 9.6480 ± 0.0004 eV (77 816 ± 3 cm-1) for the trans-s-trans (tt)-, trans-s-cis (tc)-, cis-s-trans (ct)-, and cis-s-cis (cc)-crotonaldehyde, respectively. The complete vibrational assignments were accomplished for the peaks observed in the VUV-MATI spectrum from the calculated vibrational frequencies and the FC factors according to the dipole selection rules for one-photon absorption. In addition, the composition at ambient temperature was determined to be 1.000 (93.0%): 0.037 (3.4%): 0.036 (3.4%): 0.002 (0.2%) for the tt-/tc-/ct-/cc-conformers from the relative intensities of the 0-0 bands in the MATI spectrum normalized with the calculated dipole transition probabilities as proven by the NMR data for the trans- and cis-stereoisomers. This study ascertained the existence of the s-cis conformers of crotonaldehyde for the first time.

Breast abscess caused by Staphylococcus aureus in 2 adolescent girls with atopic dermatitis.

Atopic dermatitis (AD) is a chronic inflammatory skin disease in children. Patients with AD experience a high rate of colonization of the skin surface by Staphylococcus aureus. Because of a skin barrier defect, there is a potential risk of staphylococcal invasive infection in patients with AD. Here, we present 2 cases of breast abscess caused by S. aureus in 2 adolescent girls with severe AD. Methicillin-sensitive S. aureus was identified from the breast abscess material. They were treated with appropriate antibiotics, however surgical drainage of the abscess was needed in case 1. Identical strains were found from the breast abscess material as well as the lesional and the nonlesional skin of the patients through matrixassisted laser desorption/ionization time-of-flight analysis. We characterized the differential abundance of Firmicutes phylum in patients' skin in microbiota analysis. In particular, S. aureus, a member of Firmicutes, differed significantly between the lesional and the normal-appearing skin. Our cases demonstrate the potential severity of bacterial deep tissue infection in AD and the dysbiosis of skin microbiota may be involved in inflammation in AD.

Photodissociation Dynamics of Benzaldehyde-d5 at 205 nm:The H Atom Production Channel.

Photodissociation dynamics of benzaldehyde-d5 (C6D5CHO) at 205 nm was investigated by measuring laser-induced fluorescence spectra of fragment H atoms. From the Doppler-broadened spectra, center-of-mass translational energy release into the C6D5CO + H channel was obtained as 68.8 ± 5.8 kJ/mol with the absolute quantum yield, 0.17 ± 0.03. The observed translational energy was successfully estimated from two-dimensional potential energy surfaces along the C-H dissociation coordinate and the CCO bent angle and the out-of-plane H angle, respectively calculated at the B3LYP/cc-pVDZ level. The dissociation of H should take place along the triplet surface via intersystem crossing from S1 after internal conversion from the initially excited S3 state and on the triplet surface, the dissociation proceeds along the CCO bent-linear-bent configuration with H being planar to nonplanar pathway.

Conformational structures of the tetrahydrofuran cation determined using one-photon mass-analyzed threshold ionization spectroscopy.

One-photon vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy was used to characterize the essential conformations of tetrahydrofuran (THF) and thus determine the stereochemistry of the furanose ring constituting the backbones of DNA and RNA. Since the VUV-MATI spectrum of THF exactly corresponds to the vibrational spectrum of the gas-phase THF cation, the above cation was detected using time-of-flight mass spectrometry featuring the delayed pulsed-field ionization of the target in high Rydberg states by scanning the wavelength of the VUV pulse across the region of the vibrational spectrum. The position of the 0-0 band in the recorded VUV-MATI spectrum was extrapolated to the zero-field limit, allowing the adiabatic ionization energy of THF to be accurately estimated to be 9.4256 ± 0.0004 eV. The above ionization was assigned to a transition between C2-symmetric neutral (S0) and cationic (D0) ground states. The potential energy surfaces associated with molecular pseudorotation in the above states were constructed at the B3LYP/aug-cc-pVDZ level, being in good agreement with experimental observations. The twisted (C2-symmetric) and bent (CS-symmetric) conformers of the S0 state were predicted to be separated by a small interconversion barrier, whereas the D0 state exclusively existed in the C2 conformation. Based on the above, the peaks in the MATI spectrum were successfully assigned based on the Franck-Condon factors and vibrational frequencies calculated by varying the geometrical parameters of the C2 conformation, which determines the precise molecular structure of the THF cation.

Dynamics of H Atom Production from Photodissociation of Acetic Acid-d(1).

Detailed dissociation dynamics of H(D) from acetic acid-d1 (CH3COOD) has been investigated upon electronic excitation to the (1)(n,π*), S1 state at 205 nm by measuring laser-induced fluorescence spectra of the fragment H(D) atoms. In addition, quantum yields for the H(D) atom dissociation channels, CH3COO + D and CH2COOD + H, were measured, which are 0.07 ± 0.03 and 0.17 ± 0.03, respectively. From the Doppler broadened spectra, the center-of-mass translational energy releases into products were obtained. To determine the detailed dissociation dynamics, two-dimensional potential energy surfaces along the reaction coordinate including the coordinate directly coupled to the dissociation coordinate were examined by employing quantum chemical calculations. For the CH3COO + D channel, the coupled coordinate is the dihedral angle of D against the COO plane. The dissociation of D(H) from acetic acid should take place along the triplet surface via surface crossing from the initially excited S1 state. Along the triplet surface, an exit channel barrier exists, which originates from the structural difference between the T1 and the product asymptotes, especially the dihedral angle of D against the COO plane. The observed translational energy releases were successfully estimated by the barrier impulsive model based upon the calculated two-dimensional potential energy surfaces at the B3LYP/cc-pVDZ level of theory.

Is Transradial Cerebral Angiography Feasible and Safe? A Single Center's Experience.

OBJECTIVE: Although a transradial angiography is accepted as the gold standard for cardiovascular procedures, cerebral angiography has been performed via transfemoral approach in most institutions. The purpose of this study is to present our experience concerning the feasibility, efficacy, and safety of a transradial approach to cerebral angiography as an alternative to a transfemoral approach. METHODS: Between February 2007 and October 2009, a total of 1,240 cerebral angiographies were performed via a transradial approach in a single center. The right radial approach was used as an initial access route. The procedure continued only after the ulnar artery was proven to provide satisfactory collateral perfusion according to two tests (a modified Allen's test and forearm angiography). RESULTS: The procedural success rate was 94.8% with a mean duration of 28 minutes. All supra-aortic vessels were successfully catheterized with a success rate of 100%. The success rates of selective catheterization to the right vertebral artery, right internal carotid artery, left internal carotid artery, and left vertebral artery were 96.1%, 98.6%, 82.6% and 52.2%, respectively. The procedure was performed more than twice in 73 patients (5.9%), including up to 4 times in 2 patients. The radial artery occlusion was found in 4 patients (5.4%) on follow-up cerebral angiography, but no ischemic symptoms were observed in any of the cases. CONCLUSION: This study suggests that cerebral angiography using a transradial approach can be performed with minimal risk of morbidity. In particular, this procedure might be useful for follow-up angiographies and place less stress on patients.