Initial-site characterization of hydrogen migration following strong-field double-ionization of ethanol.

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. These site-specific probabilities produce benchmarks for calculations and answer outstanding questions about photofragmentation of ethanol dications; e.g., establishing that the central two hydrogen atoms are 15 times more likely to abstract the hydroxyl proton than a methyl-group proton to form H[Formula: see text] and that hydrogen scrambling, involving the exchange of hydrogen between different sites, is important in H2O+ formation. The technique extends to dynamic variables and could, in principle, be applied to larger non-cyclic hydrocarbons.

Implementation and Assessment of No Opioid Prescription Strategy at Discharge After Major Urologic Cancer Surgery.

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. Patients undergoing open or minimally invasive radical cystectomy, radical or partial nephrectomy, and radical prostatectomy were sorted into the control group (usual opioids), the lead-in group (reduced opioids), and the NOPIOIDS group (no opioid prescriptions). Interventions: The NOPIOIDS group received a preadmission educational handout, postdischarge instructions for using nonopioid analgesics, and no routine opioid prescriptions. The lead-in group received a postdischarge instruction sheet and reduced opioid prescriptions at prescribers' discretion. The control group received opioid prescriptions at prescribers' discretion. Main Outcomes and Measures: Primary outcome measures included rate and dose of opioid prescriptions at discharge and for 30 days postdischarge. Additional outcome measures included patient-reported pain and satisfaction level, unplanned health care utilization, and postoperative complications. Results: Of 647 opioid-naive patients (mean [SD] age, 63.6 [10.0] years; 478 [73.9%] male; 586 [90.6%] White), the rate of opioid prescriptions at discharge for the control, the lead-in, and the NOPIOIDS groups was 80.9% (157 of 194), 57.9% (55 of 95), and 2.2% (8 of 358) (Kruskal-Wallis test of medians: P < .001), and the overall median (IQR) tablets prescribed was 14 (10-20), 4 (0-5.3), and 0 (0-0) per patient in the control, lead-in, and NOPIOIDS groups, respectively (Kruskal-Wallis test of medians: P < .001). In the NOPIOIDS group, median and mean opioid dose was 0 tablets for all procedure types, with the exception of kidney procedures (mean [SD], 0.5 [1.7] tablets). Patient-reported pain surveys were received from 358 patients (72.6%) in the NOPIOIDS group, demonstrating low pain scores (mean [SD], 2.5 [0.86]) and high satisfaction scores (mean [SD], 86.6 [3.8]). There was no increase in postoperative complications in the group with no opioid prescriptions. Conclusions and Relevance: This perioperative protocol, with emphasis on nonopioid alternatives and patient instructions, may be safe and effective in nearly eliminating the need for opioid prescriptions after major abdominopelvic cancer surgery without adversely affecting pain control, complications, or recovery.

Two- and three-body fragmentation of multiply charged tribromomethane by ultrafast laser pulses.

We investigate the two- and three-body fragmentation of tribromomethane (bromoform, CHBr3) resulting from multiple ionization by 28-femtosecond near-infrared laser pulses with a peak intensity of 6 × 1014 W cm-2. 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+ + CHBr2+. Weaker HBr+ + CBr2+, CHBr+ + Br2+, CHBr2+ + Br2+, and Br+ + CHBr22+ channels, some of which require bond rearrangement prior to or during the fragmentation, are also observed. The dominant three-body fragmentation channel is found to be Br+ + Br+ + CHBr+. This channel includes both concerted and sequential fragmentation pathways, which we identify using the native frames analysis method. We compare the measured kinetic energy release and momentum correlations with the results of classical Coulomb explosion simulations and discuss the possible isomerization of CHBr3 to BrCHBr-Br (iso-CHBr3) prior to the fragmentation.

Strong-Field-Induced Coulomb Explosion Imaging of Tribromomethane.

The Coulomb explosion of tribromomethane (bromoform, CHBr3) 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. Our results thus provide a clear path toward visualizing structural dynamics in polyatomic molecules by strong-field-induced Coulomb explosion imaging.

Interventions to Reduce Opioid Prescriptions following Urological Surgery: A Systematic Review and Meta-Analysis.

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. MATERIALS AND METHODS: A systematic review including MEDLINE®, Web of Science™ and Cochrane databases was conducted to identify studies on opioid prescriptions and urological surgery. Twenty-two studies met the inclusion criteria, of which 19 were used for quantitative analysis for reduction in opioid prescriptions. Additional outcomes included opioid consumption and satisfaction with analgesia. RESULTS: Of the 8,318 patients, 53% were in the pre- and 47% in the post-intervention cohort. Overall mean reduction/patient in prescribed opioids was -67.59 (95% CI 54.23 to 80.94) morphine milligram equivalents (MME). Direct interventions, implemented by providers within their local department or hospital, were more effective in reducing prescribed opioids compared to indirect, or systemic, interventions, at -76.68 MME (95% CI 60.04 to -93.31) vs -46.72 MME (95% CI 24.20 to -69.23; p=0.04). Opioid consumption significantly decreased post-intervention with a mean reduction of -18.31 MME (95% CI 7.89 to 28.72). Patient satisfaction with analgesia remained unchanged between the pre- and post-intervention groups. CONCLUSIONS: Successful reduction in opioid prescriptions, without compromising pain control, can be achieved through a variety of interventions. Direct interventions appear to have a greater impact than indirect interventions in reducing opioid prescriptions. Despite the reduction, unused, excess prescription opioids were still noted, which provides an opportunity for further control on opioid prescriptions.

24-Hour urine collection for first time pediatric stone formers: Is it worth it?

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. We sought to study the benefits of 24-h urine collections in children with stones. STUDY DESIGN: We performed a single center, retrospective chart review of the most recent pediatric nephrolithiasis patients under age 18 at our center who supplied their first 24-h urine collection. We assessed whether 24-h urine results led to a change in management and if those patients were adherent to the recommendations. RESULTS: Seventy pediatric nephrolithiasis patients who had 24-h urine collection were reviewed. Recommendations other than standard dietary and fluid intake changes were made in 8/70 (11%). A low citrate/calcium ratio (327 vs. 525, p < 0.03) and whether the test was ordered by nephrology vs. urology (26% vs. 2%, p < 0.003) were predictive of an additional recommendation. Of the 8 patients who had changes recommended only 1/8 completed a repeat 24-h urine collection, 3/8 never returned for followed up and 2/8 stopped the medicines prior to follow up. There was no difference in early stone recurrence rates, 55% of the studies were incorrectly collected, and total costs are estimated at $9800. DISCUSSION: Our study aimed to evaluate the impact and value of 24-h urine collection in first time pediatric stone formers. We found that 24-h urine collections altered management from standard dietary recommendations in only 11% of cases. These collections were fraught with challenges - 55% of our samples appeared to be incorrectly collected, there was at least one abnormality noted in 100% of collections, these tests are expensive, and patients were poorly compliant with recommendations based on test results. Additionally, changes made based on the 24-h urine results seemed to vary depending on who evaluated the test results. Among cases in which changes were made, nephrologists made alterations at a far greater rate than urologists did. We do acknowledge there are several limitations to our study. First, this is a retrospective chart review. Second, for the urology patients, we were only able to review patient records that were available due to a transition from one electronic medical record to another, resulting in a loss of some earlier patient records. We highly doubt that those records we could not review were significantly different than those we did review. Third, this is a single center design and includes the practice patterns of the providers here. We acknowledge that our local practice patterns may or may not be reflective of national practice patterns, however, most clinicians are likely faced with similar interpretation issues and poor rates of compliance and could benefit from guidelines. CONCLUSION: 24-h urine collection for first time pediatric stone formers is expensive, difficult to accomplish and infrequently leads to treatment changes. Our data suggest it adds little for most children with stones and may be better reserved for those children with recurrent stone disease.

Impact of Enhanced Recovery after Surgery Protocols on Opioid Prescriptions at Discharge after Major Urological Cancer Surgery.

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. METHODS: We reviewed the opioid prescription data following hospital discharge after major urological cancer surgery from 2016 to 2018, including cystectomy, renal surgery (total, partial) and prostatectomy. Patient calls and refill requests were recorded for 30 days after discharge. Multivariable analysis was performed to evaluate the effect of various factors on normalized opioid tablets given at discharge. RESULTS: A total of 409 patients met the inclusion criteria, with 207 before and 202 after ERAS protocols. Following enhanced recovery after surgery, potent opioid (oxycodone, hydrocodone) prescriptions decreased by 53% while tramadol use increased by more than four-fold (p <0.001). Reduction in opioid prescriptions was noted for prostatectomy (30%, p <0.001), cystectomy (27%, p=0.02) and all renal procedures (32%, p <0.001) after enhanced recovery after surgery protocol. On multivariable analysis, enhanced recovery after surgery protocol was an independent predictor of reduced opioids given at discharge. CONCLUSIONS: Enhanced recovery after surgery protocol implementation was associated with a significant decrease in the opioid prescriptions at discharge after all major urological cancer procedures. Prescribing patterns shifted away from more potent opioids. These findings provide a benchmark for further interventions and reduction in the outpatient opioid prescriptions after open and minimally invasive surgery. KEY WORDS: enhanced recovery after surgery; opioid epidemic; pain management; medication therapy management; analgesics, opioid.

H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields.

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 H3+ 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 H2 roaming prior to H3+ formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H3+ formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H3+, the most important ion in interstellar chemistry, through H2 roaming occurring in ionic species.

Mechanisms and time-resolved dynamics for trihydrogen cation (H3+) formation from organic molecules in strong laser fields.

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 H3+ formation from organic molecules irradiated by a strong-field laser. Assignment of the two pathways was accomplished through analysis of femtosecond time-resolved strong-field ionization and photoion-photoion coincidence measurements carried out on methanol isotopomers, ethylene glycol, and acetone. Ab initio molecular dynamics simulations suggest the formation occurs via two steps: the initial formation of a neutral hydrogen molecule, followed by the abstraction of a proton from the remaining CHOH2+ fragment by the roaming H2 molecule. This reaction has similarities to the H2 + H2+ mechanism leading to formation of H3+ in the universe. These exotic chemical reaction mechanisms, involving roaming H2 molecules, are found to occur in the ~100 fs timescale. Roaming molecule reactions may help to explain unlikely chemical processes, involving dissociation and formation of multiple chemical bonds, occurring under strong laser fields.

Carrier-envelope-phase stabilized terawatt class laser at 1 kHz with a wavelength tunable option.

We demonstrate a chirped-pulse-amplified Ti:Sapphire laser system operating at 1 kHz, with 20 mJ pulse energy, 26 femtosecond pulse duration (0.77 terawatt), and excellent long term carrier-envelope-phase (CEP) stability. A new vibrational damping technique is implemented to significantly reduce vibrational noise on both the laser stretcher and compressor, thus enabling a single-shot CEP noise value of 250 mrad RMS over 1 hour and 300 mrad RMS over 9 hours. This is, to the best of our knowledge, the best long term CEP noise ever reported for any terawatt class laser. This laser is also used to pump a white-light-seeded optical parametric amplifier, producing 6 mJ of total energy in the signal and idler with 18 mJ of pumping energy. Due to preservation of the CEP in the white-light generated signal and passive CEP stability in the idler, this laser system promises synthesized laser pulses spanning multi-octaves of bandwidth at an unprecedented energy scale.

A Cost-Benefit Analysis of Medical Scribes and Electronic Medical Record System in an Academic Urology Clinic.

INTRODUCTION: Electronic medical records have introduced an additional level of complexity to the patient-provider encounter and medical scribes may offer a solution. We examined how a medical scribe system could support an academic urology clinic. To assess the financial feasibility of this model, we analyzed the additional costs associated with adding medical scribes and we discuss the potential benefits of this system. METHODS: We measured total patient wait and interaction times with staff, and estimated the additional staff required to maintain an increased patient load if medical scribes were introduced. We then calculated the average revenue per patient during the most recent 9 months of data to estimate the minimum increase in the number of patient visits needed to offset the additional staffing needs. RESULTS: Mean ± SD total wait time was 23 minutes 28 seconds ± 13 minutes 4 seconds. Average monthly expenses would increase by $17,452.50 for 6 additional staff members, including 1 nursing assistant, 1 patient service specialist, 1 nurse and 3 scribes. There was an average of 666 monthly office visits and average net revenue to the department was $107.78 per patient visit. The increase in the number of patient visits required to break even would be 162 additional patients per month, representing a 24.3% increase. Additional downstream revenue was considered. CONCLUSIONS: A medical scribe system in the example of an academic urology clinic setting could increase patient flow and decrease the burden on medical providers by reducing computer charting. This model is only financially prudent if the increased expenses are offset by additional revenue from increased patient visits.

Susceptibility of domestic cats to chronic wasting disease.

Domestic and nondomestic cats have been shown to be susceptible to feline spongiform encephalopathy (FSE), almost certainly caused by consumption of bovine spongiform encephalopathy (BSE)-contaminated meat. Because domestic and free-ranging nondomestic felids scavenge cervid carcasses, including those in areas affected by chronic wasting disease (CWD), we evaluated the susceptibility of the domestic cat (Felis catus) to CWD infection experimentally. Cohorts of 5 cats each were inoculated intracerebrally (i.c.) or orally (p.o.) with CWD-infected deer brain. At 40 and 42 months postinoculation, two i.c.-inoculated cats developed signs consistent with prion disease, including a stilted gait, weight loss, anorexia, polydipsia, patterned motor behaviors, head and tail tremors, and ataxia, and the cats progressed to terminal disease within 5 months. Brains from these two cats were pooled and inoculated into cohorts of cats by the i.c., p.o., and intraperitoneal and subcutaneous (i.p./s.c.) routes. Upon subpassage, feline CWD was transmitted to all i.c.-inoculated cats with a decreased incubation period of 23 to 27 months. Feline-adapted CWD (Fel(CWD)) was demonstrated in the brains of all of the affected cats by Western blotting and immunohistochemical analysis. Magnetic resonance imaging revealed abnormalities in clinically ill cats, which included multifocal T2 fluid attenuated inversion recovery (FLAIR) signal hyperintensities, ventricular size increases, prominent sulci, and white matter tract cavitation. Currently, 3 of 4 i.p./s.c.- and 2 of 4 p.o. secondary passage-inoculated cats have developed abnormal behavior patterns consistent with the early stage of feline CWD. These results demonstrate that CWD can be transmitted and adapted to the domestic cat, thus raising the issue of potential cervid-to-feline transmission in nature.

Calibration of electron spectrometer resolution in attosecond streak camera.

We report a new method for determining the energy resolution of time-of-flight spectrometers for detecting photoelectrons produced with attosecond XUV pulses. By measuring the width of the 2s2p autoionization line of helium, we found the resolution of our spectrometer to be approximately 0.6 eV for electrons at 35.5 eV. Furthermore, the resolution in the 10 to 35 eV range was determined by applying a retarding potential at the entrance of the drift tube.

Disentangling the volume effect through intensity-difference spectra: application to laser-induced dissociation of H2+.

An intensity-difference spectrum method is developed to disentangle the intensity volume effect inherent in focused laser beam interaction with gas-phase matter. This method is applicable to a Gaussian beam of constant axial intensity, which keeps the exact contribution from a predetermined intensity range and eliminates the contributions from lower intensities. We apply this method to the angularly resolved kinetic energy release spectrum of laser-induced dissociation of H2+. The difference spectrum at higher intensities is found to be dominated by the bond-softening process, and the distribution shifts to lower energy and becomes narrower with increasing intensity.