Publications by authors named "Carnes K"

Article Synopsis
  • - The study investigates how bromoform (CHBr) behaves when exposed to near-infrared (NIR) light, focusing on its breakdown and isomerization in cationic states through advanced imaging techniques.
  • - It is observed that the dissociation process, particularly when forming HBr and Br fragments, occurs with a delay compared to the faster breakdown of the C-Br bond.
  • - Molecular dynamics simulations indicate that this delay results from temporary isomerization processes involving H- and Br-migrations before the final fragments are produced.
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We have measured the photodissociation of few-keV OD molecular ions into either D + O or O + D final products. The three-dimensional momentum imaging measurements of the light and massive fragments in coincidence were enabled by using an upgraded two-detector setup. In this work, we show that absorption of a single 790 or 395 nm photon excites the OD from its electronic ground state to the B state, which dissociates to the O(S) + D dissociation limit.

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An essential problem in photochemistry is understanding the coupling of electronic and nuclear dynamics in molecules, which manifests in processes such as hydrogen migration. Measurements of hydrogen migration in molecules that have more than two equivalent hydrogen sites, however, produce data that is difficult to compare with calculations because the initial hydrogen site is unknown. We demonstrate that coincidence ion-imaging measurements of a few deuterium-tagged isotopologues of ethanol can determine the contribution of each initial-site composition to hydrogen-rich fragments following strong-field double ionization.

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Introduction: Medicaid, a joint federal-state program, finances health care for eligible low-income individuals and families in the United States. Medicaid patients use disproportionately more emergency room (ER) services than other patients in the United States. Inadequate provider communication during primary care visits might be one reason for this well-documented phenomenon.

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Importance: Postoperative opioid prescriptions are associated with delayed recovery, perioperative complications, opioid use disorder, and diversion of overprescribed opioids, which places the community at risk of opioid misuse or addiction.

Objective: To assess a protocol for eliminating postdischarge opioid prescriptions after major urologic cancer surgery.

Design, Setting, And Participants: This cohort study of the no opioid prescriptions at discharge after surgery (NOPIOIDS) protocol was conducted between May 2017 and June 2021 at a tertiary referral center.

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We investigate the two- and three-body fragmentation of tribromomethane (bromoform, CHBr) resulting from multiple ionization by 28-femtosecond near-infrared laser pulses with a peak intensity of 6 × 10 W cm. The analysis focuses on channels consisting exclusively of ionic fragments, which are measured by coincidence momentum imaging. The dominant two-body fragmentation channel is found to be Br + CHBr.

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The Coulomb explosion of tribromomethane (bromoform, CHBr) induced by 28 fs near-infrared laser pulses is investigated by three-dimensional coincidence ion momentum imaging. We focus on the fragmentation into three, four, and five ionic fragments measured in coincidence and present different ways of visualizing the three-dimensional momentum correlations. We show that the experimentally observed momentum correlations for 4- and 5-fold coincidences are well reproduced by classical Coulomb explosion simulations and contain information about the structure of the parent molecule that could be used to differentiate structural isomers formed, for example, in a pump-probe experiment.

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Purpose: Opioid prescriptions after surgery are major contributors to the opioid abuse epidemic. Several measures designed to limit opioid prescriptions at discharge have been evaluated. We conducted a comprehensive review and meta-analysis of the effectiveness of various types of interventions in reducing opioid prescriptions after urological surgery.

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Introduction: Erenumab, a first-in-class monoclonal antibody targeting the calcitonin gene-related peptide pathway, was approved by the US Food and Drug Administration in 2018 for the prevention of migraine in adults. There is limited data available on its impact in real-world settings. The study aim was to characterize the real-world treatment profiles, clinical outcomes, and healthcare resource utilization of patients prescribed erenumab from select major US headache centers.

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Introduction/objective: 24-h urine collections are recommended for motivated first-time stone formers. Given that children have a lifetime potential for recurrences, metabolic work-up has been recommended. 24-hour urine collections can be problematic, especially in children.

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Time-resolved donor-detected Förster resonance energy transfer (trDDFRET) allows the observation of molecular interactions of dye-labeled biomolecules in the ∼10-100 Å region. However, we can observe longer-range interactions when using time-resolved acceptor-detected FRET (trADFRET), since the signal/noise ratio can be improved when observing the acceptor emission. Therefore, we propose a new methodology based on trADFRET to construct a new fluorescence lifetime microscopy (FLIM-trADFRET) technique to observe biological machinery in the range of 100-300 Å in vivo, the last frontier in biomolecular medicine.

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Introduction: Enhanced recovery after surgery protocols are designed to limit the use of opioids during inpatient stay to facilitate recovery and early discharge. It is not clear whether the enhanced recovery after surgery related limitations on opioids are associated with opioid prescribing at discharge. We wished to evaluate whether the enhanced recovery after surgery efforts had an impact on opioid prescriptions given after discharge following major urological cancer surgery.

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The Stopped-Flow apparatus (SF) tracks molecular events by mixing the reactants in sub-millisecond regimes. The reaction of intrinsically or extrinsically labeled biomolecules can be monitored by recording the fluorescence, (), anisotropy, (), polarization, (), or FRET, (), traces at nanomolar concentrations. These kinetic measurements are critical to elucidate reaction mechanisms, structural information, and even thermodynamics.

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Using the CDOH isotopologue of methanol, the ratio of DH to D formation is manipulated by changing the characteristics of the intense femtosecond laser pulse. Detection of DH indicates a formation process involving two hydrogen atoms from the methyl side of the molecule and a proton from the hydroxyl side, while detection of D indicates local formation involving only the methyl group. Both mechanisms are thought to involve a neutral D moiety.

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An adaptive closed-loop system employing coincidence time-of-flight feedback is used to determine the optimal pulse shapes for manipulating the branching ratio of NO dications following double ionization by an intense laser pulse. Selection between the long-lived NO and the dissociative N + O final states requires control of the vibrational population distribution in the transient NO. The ability to both suppress and enhance NO relative to N + O is observed, with the effectiveness of shaped pulses surpassing near Fourier transform-limited pulses by about an order of magnitude in each direction, depending on the pulse energy.

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We have investigated the femtosecond laser-induced fragmentation of CH ion beam targets in various initial configurations, including acetylene (linear HCCH), vinylidene (HCC), and cis/ trans. The initial configuration is shown to have a tremendous impact on the branching ratio of acetylene-like (CH + CH ) and vinylidene-like (C + CH ) dissociation of a specific CH molecular ion. In particular, whereas CH generated from CH, a linear HCCH target, exhibits comparable levels of acetylene-like and vinylidene-like fragmentation, vinylidene or cis/ trans configuration ion beams preferably undergo vinylidene-like fragmentation, with an acetylene branching ratio ranging from 13.

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The high affinity (KD ~ 10-15 M) of biotin for avidin and streptavidin is the essential component in a multitude of bioassays with many experiments using biotin modifications to invoke coupling. Equilibration times suggested for these assays assume that the association rate constant (kon) is approximately diffusion limited (109 M-1s-1) but recent single molecule and surface binding studies indicate that they are slower than expected (105 to 107 M-1s-1). In this study, we asked whether these reactions in solution are diffusion controlled, which reaction model and thermodynamic cycle describes the complex formation, and if there are any functional differences between avidin and streptavidin.

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Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here, the mechanistic details and femtosecond time-resolved dynamics of H formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H roaming prior to H formation are uncovered.

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A key question concerning the three-body fragmentation of polyatomic molecules is the distinction of sequential and concerted mechanisms, i.e., the stepwise or simultaneous cleavage of bonds.

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Strong-field laser-matter interactions often lead to exotic chemical reactions. Trihydrogen cation formation from organic molecules is one such case that requires multiple bonds to break and form. We present evidence for the existence of two different reaction pathways for H formation from organic molecules irradiated by a strong-field laser.

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Much of our intuition about strong-field processes is built upon studies of diatomic molecules, which typically have electronic states that are relatively well separated in energy. In polyatomic molecules, however, the electronic states are closer together, leading to more complex interactions. A combined experimental and theoretical investigation of strong-field ionization followed by hydrogen elimination in the hydrocarbon series CD, CD and CD reveals that the photofragment angular distributions can only be understood when the field-dressed orbitals rather than the field-free orbitals are considered.

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The transition between two distinct ionization mechanisms in femtosecond laser fields at 785 nm is observed for C molecules. The transition occurs in the investigated intensity range from 3 to 20 TW/cm and is visualized in electron kinetic energy spectra below the one-photon energy (1.5 eV) obtained via velocity map imaging.

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Background: The advent of adverse local tissue reactions seen in metal-on-metal bearings, and the recent recognition of trunnionosis, have led many surgeons to recommend ceramic-on-polyethylene articulations for primary total hip arthroplasty. However, to our knowledge, there has been little research that has considered whether the increased cost of ceramic provides enough benefit over cobalt-chromium to justify its use. The primary purpose of this study was to compare the cost-effectiveness of ceramic-on-polyethylene implants and metal-on-polyethylene implants in patients undergoing total hip arthroplasty.

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