Population and Energy Transfer Dynamics in an Open Excitonic Quantum Battery.

In a previous study, we proposed an open quantum network model of a quantum battery (QB) that possesses dark states owing to its structural exchange symmetries. While in a dark state, the QB is capable of storing an exciton without any environment-induced population losses. However, when the structural exchange symmetry is broken, the QB begins to discharge the exciton towards its exit site. In this article, we start by demonstrating that this QB is not only loss-free with respect to exciton population during the storage phase, but also with respect to the QB energy. We then explore the exciton population and energy transfer dynamics of the QB during the discharge phase over a wide range of site energies, bath temperatures, and bath reorganization energies. Our results shed light on how to optimize the QB's population and energy transfer dynamics for different purposes.

Robotic assistance in lumbar fusion surgery: trends and patterns from 2016-2019.

PURPOSE: Robotic-assisted spine surgery is an emerging field that is growing in utilization. Intraoperative robotic surgical units cost upwards of $600,000 for medical facilities to purchase. Despite significant cost barriers, these devices are highly marketable for hospitals and physicians. METHODS: The Nationwide Inpatient Sample database from 2016 to 2019 was reviewed. Inclusion criteria were patients over 18 years of age who underwent elective lumbar spinal fusion. Trends of robotic-assisted lumbar fusion were examined over time, as well as stratified based on patient and surgical characteristics. RESULTS: A total of 176,377 patients met the inclusion criteria. The overall rate of robotic-assisted lumbar fusion was 1.2% (2,131/174,246). Patients with private insurance were more likely to receive robotic-assisted lumbar fusion (40.3% vs. 37.5%; p < 0.05). Stratifying by race, whites were more likely to receive robotic-assisted lumbar fusion (84.1% vs. 79.5%; p < 0.05). Patients who underwent robotic-assisted lumbar fusion were significantly more likely to have a diagnosis of spondylolisthesis compared to those that underwent non-robotic-assisted lumbar fusion (25.9% vs. 22.0%; p < 0.05). Patients with lumbar fusion done via the anterior approach were more likely to have robotic-assisted surgery compared to other approaches (25.2% vs. 21.3; p < 0.05). Overall, there was a steady increase in its use over time, with patients who underwent lumbar fusion procedures four times more likely to receive robotic assistance in 2019 compared to 2016 (OR: 4.0; 95% CI: 3.5-4.6; p < 0.0001). Robotic-assisted lumbar fusion was associated with higher inpatient costs ($170,036.40 vs. $139,026.10; p < 0.0001) despite having equivalent length of stay (3.31 ± 2.6 vs.3.37 ± 2.6; p = 0.06). CONCLUSION: Robotic-assisted lumbar fusion is on the rise. Patients who had private insurance, were diagnosed with spondylolisthesis, and who had lumbar fusion via the anterior approach were more likely to undergo lumbar fusion using robotic assistance.

Tuning Structural and Optical Properties of Porphyrin-based Hydrogen-Bonded Organic Frameworks by Metal Insertion.

Herein, a simple way of tuning the optical and structural properties of porphyrin-based hydrogen-bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB-5 (p-H8 -TPPA (5,10,15,20-Tetrakis[p-phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu-, Ni-, Pd-, and Zn-GTUB-5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal-induced structural changes, viz., changes in the metal-to-nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu-, Zn-, and Pd- GTUB-5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π- orbitals on the porphyrin linkers, while that of Ni-GTUB-5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal-insertion can be used to optimize HOFs for optoelectronics and small-molecule capture applications.

Coordination-Induced Band Gap Reduction in a Metal-Organic Framework.

Herein, we report on the synthesis of a microporous, three-dimensional phosphonate metal-organic framework (MOF) with the composition Cu3 (H5 -MTPPA)2 ⋅ 2 NMP (H8 -MTPPA=methane tetra-p-phenylphosphonic acid and NMP=N-methyl-2-pyrrolidone). This MOF, termed TUB1, has a unique one-dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m2 /g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin-dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta-gap for the trigonal bipyramidal copper atoms is 3.72 eV.

Cerebrospinal fluid (CSF) leak after elective lumbar spinal fusion: Who is at risk?

PURPOSE: CSF leaks are a known complication of lumbar fusion surgery. There is a scarcity of literature describing the incidence and risk factors associated with this complication. The aim of this study was to identify patients who are at risk of developing postoperative CSF leak. METHODS: The Nationwide Inpatient Sample database was used to identify patients who had lumbar fusion in the US from 2002 to 2014. Inpatient outcomes included the incidence and risk of developing CSF leak based on selected patient-specific characteristics. Secondary outcomes included average length of stay, mean costs, and mortality rates. All statistical analyses were conducted based on multivariate regression models using the SPSS software. RESULTS: A total of 439,220 patients who underwent elective lumbar fusion procedures were identified. Of these patients, 2.6% (11,636 /439,220) were found to have CSF leak. Independent important risk factors for CSF leak development included: older age (OR: 1.025; 95% CI: 1.02-1.03; p < 0.0001), posterior approach (OR: 1.71; 95% CI: 1.59-1.85; p < 0.0001) compared to anterior approach, chronic deficiency anemia (OR: 1.21; 95% CI:1.14-1.30; p < 0.0001), obesity (OR: 1.22; 95% CI: 1.15-1.30; p < 0.0001), and pulmonary circulatory disease (OR: 1.44; 95% CI: 1.18-1.75; p < 0.0001). CSF leak was associated with increased length of stay (5.39 ± 3.86 vs. 3.74 ± 2.55; p < 0.0001), hospitalization costs (120,129.0 ± 88,123.5 vs. 89,226.8 ± 65,350.3; p < 0.0001) and mortality (0.3% vs. 0.1%; p < 0.05). CONCLUSION: Spine surgeons should be aware of certain patient and procedure-specific characteristics that increase the risk of developing postoperative CSF leak after lumbar fusion in order to improve patient outcomes.

Quantum bath effects on nonequilibrium heat transport in model molecular junctions.

Quantum-classical dynamics simulations enable the study of nonequilibrium heat transport in realistic models of molecules coupled to thermal baths. In these simulations, the initial conditions of the bath degrees of freedom are typically sampled from classical distributions. Herein, we investigate the effects of sampling the initial conditions of the thermal baths from quantum and classical distributions on the steady-state heat current in the nonequilibrium spin-boson model-a prototypical model of a single-molecule junction-in different parameter regimes. For a broad range of parameter regimes considered, we find that the steady-state heat currents are ∼1.3-4.5 times larger with the classical bath sampling than with the quantum bath sampling. Using both types of sampling, the steady-state heat currents exhibit turnovers as a function of the bath reorganization energy, with sharper turnovers in the classical case than in the quantum case and different temperature dependencies of the turnover maxima. As the temperature gap between the hot and cold baths increases, we observe an increasing difference in the steady-state heat currents obtained with the classical and quantum bath sampling. In general, as the bath temperatures are increased, the differences between the results of the classical and quantum bath sampling decrease but remain non-negligible at the high bath temperatures. The differences are attributed to the more pronounced temperature dependence of the classical distribution compared to the quantum one. Moreover, we find that the steady-state fluctuation theorem only holds for this model in the Markovian regime when quantum bath sampling is used. Altogether, our results highlight the importance of quantum bath sampling in quantum-classical dynamics simulations of quantum heat transport.

A Nanotubular Metal-Organic Framework with a Narrow Bandgap from Extended Conjugation*.

A one-dimensional nanotubular metal-organic framework (MOF) [Ni(Cu-H4 TPPA)]⋅2 (CH3 )2 NH2 + (H8 TPPA=5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin) constructed by using the arylphosphonic acid H8 TPPA is reported. The structure of this MOF, known as GTUB-4, was solved by using single-crystal X-ray diffraction and its geometric accessible surface area was calculated to be 1102 m2 g-1 , making it the phosphonate MOF with the highest reported surface area. Due to the extended conjugation of its porphyrin core, GTUB-4 possesses narrow indirect and direct bandgaps (1.9 eV and 2.16 eV, respectively) in the semiconductor regime. Thermogravimetric analysis suggests that GTUB-4 is thermally stable up to 400 °C. Owing to its high surface area, low bandgap, and high thermal stability, GTUB-4 could find applications as electrodes in supercapacitors.

Nonequilibrium heat transport in a molecular junction: A mixed quantum-classical approach.

In a recent study [J. Liu et al., J. Chem. Phys. 149, 224104 (2018)], we developed a general mixed quantum-classical framework for studying heat transport through molecular junctions, in which the junction molecule is treated quantum mechanically and the thermal reservoirs to which the molecule is coupled are treated classically. This framework yields expressions for the transferred heat and steady-state heat current, which could be calculated using a variety of mixed quantum-classical dynamics methods. In this work, we use the recently developed "Deterministic Evolution of Coordinates with Initial Decoupled Equations" (DECIDE) method for calculating the steady-state heat current in the nonequilibrium spin-boson model in a variety of parameter regimes. Our results are compared and contrasted with those obtained using the numerically exact multilayer multiconfiguration time-dependent Hartree approach, and using approximate methods, including mean field theory, Redfield theory, and adiabatic mixed quantum-classical dynamics. Despite some quantitative differences, the DECIDE method performs quite well, is capable of capturing the expected trends in the steady-state heat current, and, overall, outperforms the approximate methods. These results hold promise for DECIDE simulations of nonequilibrium heat transport in realistic models of nanoscale systems.

Heat transfer statistics in mixed quantum-classical systems.

The modelling of quantum heat transfer processes at the nanoscale is crucial for the development of energy harvesting and molecular electronic devices. Herein, we adopt a mixed quantum-classical description of a device, in which the open subsystem of interest is treated quantum mechanically and the surrounding heat baths are treated in a classical-like fashion. By introducing such a mixed quantum-classical description of the composite system, one is able to study the heat transfer between the subsystem and bath from a closed system point of view, thereby avoiding simplifying assumptions related to the bath time scale and subsystem-bath coupling strength. In particular, we adopt the full counting statistics approach to derive a general expression for the moment generating function of heat in systems whose dynamics are described by the quantum-classical Liouville equation (QCLE). From this expression, one can deduce expressions for the dynamics of the average heat and heat current, which may be evaluated using numerical simulations. Due to the approximate nature of the QCLE, we also find that the steady state fluctuation symmetry holds up to order ℏ for systems whose subsystem-bath couplings and baths go beyond bilinear and harmonic, respectively. To demonstrate the approach, we consider the nonequilibrium spin boson model and simulate its time-dependent average heat and heat current under various conditions.

Mixed Quantum-Classical Simulations of Transient Absorption Pump-Probe Signals for a Photo-Induced Electron Transfer Reaction Coupled to an Inner-Sphere Vibrational Mode.

In a previous study (Martinez, F.; Hanna, G. Chem. Phys. Lett. 2013, 573, 77-83), we demonstrated the ability of two approximate solutions of the quantum-classical Liouville equation (QCLE) for qualitatively capturing the electronic dynamics in the pump-probe transient absorption (TA) signal of a model of a condensed phase photoinduced electron transfer reaction whose ground and excited donor states have the same equilibrium geometry. However, the question remained as to the ability of these solutions to treat the more complex situation in which the electronic states are coupled to a low-frequency inner-sphere harmonic vibrational mode (representing an intramolecular mode of the donor-acceptor complex) that shifts their equilibrium geometries with respect to each other and thereby gives rise to signatures of vibrational dynamics in the TA signal. Thus, in this study, we investigated this situation by treating the vibrational mode both quantum mechanically and classically within the context of the approximate Poisson bracket mapping equation (PBME) and forward-backward trajectory solutions (FBTS) of the QCLE. Depending on the definition of the quantum subsystem, both PBME and FBTS are capable of qualitatively capturing several of the main features in the exact TA signal and quantitatively capturing the characteristic time scale of the vibrational dynamics, despite the moderately strong subsystem-bath coupling in this model. Particularly, we found that treating the vibrational mode quantum mechanically using either PBME or FBTS better captures the signatures of the vibrational dynamics, while treating it classically using FBTS better captures the decay in the signal. These findings underscore the utility of the PBME and FBTS approaches for efficiently modeling and interpreting TA signals.

New insights into the nonadiabatic state population dynamics of model proton-coupled electron transfer reactions from the mixed quantum-classical Liouville approach.

In a previous study [F. A. Shakib and G. Hanna, J. Chem. Phys. 141, 044122 (2014)], we investigated a model proton-coupled electron transfer (PCET) reaction via the mixed quantum-classical Liouville (MQCL) approach and found that the trajectories spend the majority of their time on the mean of two coherently coupled adiabatic potential energy surfaces. This suggested a need for mean surface evolution to accurately simulate observables related to ultrafast PCET processes. In this study, we simulate the time-dependent populations of the three lowest adiabatic states in the ET-PT (i.e., electron transfer preceding proton transfer) version of the same PCET model via the MQCL approach and compare them to the exact quantum results and those obtained via the fewest switches surface hopping (FSSH) approach. We find that the MQCL population profiles are in good agreement with the exact quantum results and show a significant improvement over the FSSH results. All of the mean surfaces are shown to play a direct role in the dynamics of the state populations. Interestingly, our results indicate that the population transfer to the second-excited state can be mediated by dynamics on the mean of the ground and second-excited state surfaces, as part of a sequence of nonadiabatic transitions that bypasses the first-excited state surface altogether. This is made possible through nonadiabatic transitions between different mean surfaces, which is the manifestation of coherence transfer in MQCL dynamics. We also investigate the effect of the strength of the coupling between the proton/electron and the solvent coordinate on the state population dynamics. Drastic changes in the population dynamics are observed, which can be understood in terms of the changes in the potential energy surfaces and the nonadiabatic couplings. Finally, we investigate the state population dynamics in the PT-ET (i.e., proton transfer preceding electron transfer) and concerted versions of the model. The PT-ET results confirm the participation of all of the mean surfaces, albeit in different proportions compared to the ET-PT case, while the concerted results indicate that the mean of the ground- and first-excited state surfaces only plays a role, due to the large energy gaps between the ground- and second-excited state surfaces.

Molecular dynamics simulations predict an accelerated dissociation of H2CO3 at the air-water interface.

The dissociation and decomposition reactions of carbonic acid (H2CO3) in bulk water have been thoroughly studied, but little is known about its reactivity at the air-water interface. Herein, we investigate the dissociation reaction of H2CO3 at the air-water interface using ab initio molecular dynamics and metadynamics. Our results indicate that H2CO3 (pKa = 3.45) dissociates faster at the water surface than in bulk water, in contrast to recent experiments and simulations which have shown that HNO3 (pKa = -1.3) has a lower propensity to dissociate at the water surface than in bulk water. We find that the water surface allows for a more structured solvation environment around H2CO3 than in bulk water, which contributes to a decrease in the dissociation energy barrier via a stabilization of the transition state relative to the undissociated acid. Given its decreased kinetic stability at the air-water interface, H2CO3 may play an important role in the acidification of atmospheric aerosols and water droplets.

An analysis of model proton-coupled electron transfer reactions via the mixed quantum-classical Liouville approach.

The nonadiabatic dynamics of model proton-coupled electron transfer (PCET) reactions is investigated for the first time using a surface-hopping algorithm based on the solution of the mixed quantum-classical Liouville equation (QCLE). This method provides a rigorous treatment of quantum coherence/decoherence effects in the dynamics of mixed quantum-classical systems, which is lacking in the molecular dynamics with quantum transitions surface-hopping approach commonly used for simulating PCET reactions. Within this approach, the protonic and electronic coordinates are treated quantum mechanically and the solvent coordinate evolves classically on both single adiabatic surfaces and on coherently coupled pairs of adiabatic surfaces. Both concerted and sequential PCET reactions are studied in detail under various subsystem-bath coupling conditions and insights into the dynamical principles underlying PCET reactions are gained. Notably, an examination of the trajectories reveals that the system spends the majority of its time on the average of two coherently coupled adiabatic surfaces, during which a phase enters into the calculation of an observable. In general, the results of this paper demonstrate the applicability of QCLE-based surface-hopping dynamics to the study of PCET and emphasize the importance of mean surface evolution and decoherence effects in the calculation of PCET rate constants.

Computational study of the one- and two-dimensional infrared spectra of a proton-transfer mode in a hydrogen-bonded complex dissolved in a polar nanocluster.

The signatures of nanosolvation on the one- and two-dimensional (1D and 2D) IR spectra of a proton-transfer mode in a hydrogen-bonded complex dissolved in polar solvent molecule nanoclusters of varying size are elucidated by using mixed quantum-classical molecular dynamics simulations. For this particular system, increasing the number of solvent molecules successively from N=7 to N=9 initiates the transition of the system from a cluster state to a bulk-like state. Both the 1D and 2D IR spectra reflect this transition through pronounced changes in their peak intensities and numbers, but the time-resolved 2D IR spectra also manifest spectral features that uniquely identify the onset of the cluster-to-bulk transition. In particular, it is observed that in the 1D IR spectra, the relative intensities of the peaks change such that the number of peaks decreases from three to two as the size of the cluster increases from N=7 to N=9. In the 2D IR spectra, off-diagonal peaks are observed in the N=7 and N=8 cases at zero waiting time, but not in the N=9 case. It is known that there are no off-diagonal peaks in the 2D IR spectrum of the bulk version of this system at zero waiting time, so the disappearance of these peaks is a unique signature of the onset of bulk-like behavior. Through an examination of the trajectories of various properties of the complex and solvent, it is possible to relate the emergence of these off-diagonal peaks to an interplay between the vibrations of the complex and the solvent polarization dynamics.

A mixed quantum-classical Liouville study of the population dynamics in a model photo-induced condensed phase electron transfer reaction.

We apply two approximate solutions of the quantum-classical Liouville equation (QCLE) in the mapping representation to the simulation of the laser-induced response of a quantum subsystem coupled to a classical environment. These solutions, known as the Poisson Bracket Mapping Equation (PBME) and the Forward-Backward (FB) trajectory solutions, involve simple algorithms in which the dynamics of both the quantum and classical degrees of freedom are described in terms of continuous variables, as opposed to standard surface-hopping solutions in which the classical degrees of freedom hop between potential energy surfaces dictated by the discrete adiabatic state of the quantum subsystem. The validity of these QCLE-based solutions is tested on a non-trivial electron transfer model involving more than two quantum states, a time-dependent Hamiltonian, strong subsystem-bath coupling, and an initial energy shift between the donor and acceptor states that depends on the strength of the subsystem-bath coupling. In particular, we calculate the time-dependent population of the photoexcited donor state in response to an ultrafast, on-resonance pump pulse in a three-state model of an electron transfer complex that is coupled asymmetrically to a bath of harmonic oscillators through the optically dark acceptor state. Within this approach, the three-state electron transfer complex is treated quantum mechanically, while the bath oscillators are treated classically. When compared to the more accurate QCLE-based surface-hopping solution and to the numerically exact quantum results, we find that the PBME solution is not capable of qualitatively capturing the population dynamics, whereas the FB solution is. However, when the subsystem-bath coupling is decreased (which also decreases the initial energy shift between the donor and acceptor states) or the initial shift is removed altogether, both the PBME and FB results agree better with the QCLE-based surface-hopping results. These findings highlight the challenges posed by various conditions such as a time-dependent external field, the strength of the subsystem-bath coupling, and the degree of asymmetry on the accuracy of the PBME and FB algorithms.

The use of virtual interviews and new trends in orthopedic surgery residency match.

This retrospective cross-sectional study sought to determine if there was a change in geographical trends in the orthopedic surgery residency match with the use of virtual interviews. Due to the COVID-19 pandemic, visiting rotations at outside institutions were restricted and all residency interviews were conducted virtually for the 2021 match. Given these restrictions, it was hypothesized that applicants would match at a higher rate to their medical school-affiliated residency programs, or geographically nearby their medical school. Data was collected from residency program website and social media accounts to determine if the use of virtual interviews correlated with a decreased rate of matching at outside institutions. During the 2021 match, applicants who applied to orthopedic surgery in 2021 were more likely to match at their medical school-affiliated institution (OR, 1.46; 95% CI, 1.18-1.80; p < 0.01) compared to applicants during previous years. However, match rates were not different in terms of geographical regions. Virtual interviews are more cost-effective for both applicants and programs, however, this study demonstrates there are associated changes with this new interview structure. The utility of virtual interviews as a standard method in the future should take this change in trend into consideration.

Comparing severe COVID-19 outcomes of first and second/third waves: a prospective single-centre cohort study of health-related quality of life and pulmonary outcomes 6 months after infection.

OBJECTIVE: We aimed to compare long-term outcomes in intensive care unit (ICU) survivors between the first and second/third waves of the COVID-19 pandemic. More specifically, to assess health-related quality of life (HRQL) and respiratory health 6 months post-ICU and to study potential associations between patient characteristic and treatment variables regarding 6-month outcomes. DESIGN: Prospective cohort study. SETTING: Single-centre study of adult COVID-19 patients with respiratory distress admitted to two Swedish ICUs during the first wave (1 March 2020-1 September 2020) and second/third waves (2 September 2020- 1 August 2021) with follow-up approximately 6 months after ICU discharge. PARTICIPANTS: Critically ill COVID-19 patients who survived for at least 90 days. MAIN OUTCOME MEASURES: HRQL, extent of residual changes on chest CT scan and pulmonary function were compared between the waves. General linear regression and multivariable logistic regression were used to present mean score differences (MSD) and ORs with 95% CIs. RESULTS: Of the 456 (67%) critically ill COVID-19 patients who survived at least 90 days, 278 (61%) were included in the study. Six months after ICU discharge, HRQL was similar between survivors in the pandemic waves, except that the second/third wave survivors had better role physical (MSD 20.2, 95% CI 7.3 to 33.1, p<0.01) and general health (MSD 7.2, 95% CI 0.7 to 13.6, p=0.03) and less bodily pain (MSD 12.2, 95% CI 3.6 to 20.8, p<0.01), while first wave survivors had better diffusing capacity of the lungs for carbon monoxide (OR 1.9, 95% CI 1.1 to 3.5, p=0.03). CONCLUSIONS: This study indicates that even though intensive care treatment strategies have changed with time, there are few differences in long-term HRQL and respiratory health seems to remain at 6 months for patients surviving critical COVID-19 in the first and second/third waves of the pandemic.

Surgical prophylaxis in pediatric orthopedic patients with penicillin allergy: a multicentered retrospective prognostic study.

Up to 20% of orthopedic surgeons still avoid the use of cephalosporins in patients with penicillin allergies despite its reported safety in the adult and general surgery pediatric population. The primary objective is to determine the incidence of adverse effects and allergic reactions when using cephalosporins in pediatric orthopedic patients labeled as penicillin-allergic as compared to those without previously reported penicillin allergy. A multicenter retrospective chart review was performed across three level 1 trauma centers from January 2013 to February 2020 to identify penicillin-allergic as well as non-penicillin-allergic pediatric patients treated for orthopedic injuries. Data were collected regarding patient demographics, antibiotic administered, timing of antibiotic administration, reported drug allergy, and described allergic reaction. Postoperative or intraoperative allergic reactions to antibiotics, surgical site infections, and complications were recorded. A total of 2289 surgeries performed by four fellowship-trained surgeons were evaluated. Eighty-five patients diagnosed with penicillin allergy were identified and underwent 95 surgeries and 95 patients without previously reported penicillin allergy underwent 95 surgeries. One patient, with a documented history of anaphylaxis to cefazolin, sustained an anaphylactic reaction intraoperatively to cefazolin. There were no other reported reactions, surgical site infections, or complications. There was no statistically significant difference in rate of allergic reaction in patients with previously reported penicillin allergy treated with cefazolin and those with no previous reported reaction (P > 0.05). Prophylaxis with cephalosporins is not associated with increased risk for allergic reaction. Cephalosporins can be safely administered to pediatric patients with penicillin allergy undergoing orthopedic intervention. Level of evidence: Level II, Multicenter Retrospective Prognostic Study.

Electric scooter sharing systems: An analysis of injury patterns associated with their introduction.

BACKGROUND: With the increasing popularity of electric scooters (ES) and the introduction of ES sharing systems in 2017, hospitals are seeing more ES-related injuries. The effects of sharing systems on traumatic injuries are lacking in the literature. We, therefore, sought to describe trends in ES injuries. METHODS: The Nationwide Inpatient Sample was queried for patients hospitalized with ES-related injuries in the United States from 2015 to 2019. Admissions due to ES were divided into two cohorts: before (≤2017) and after (>2018) the introduction of sharing systems. Patients were stratified by injuries sustained, age, gender, and race. Inpatient hospital charges and length of stay were compared. Exclusion criteria included patients older than 65 and patients with neurological disorders. Traumatic injuries were compared after adjusting for age, gender, and race in a multivariate logistic regression analysis. RESULTS: During the study period, there were 686 admissions, of which 220 remained due to exclusion criteria. There was a consistent increase in ES-related injuries over the years (r = 0.91, p = 0.017). Patients who were injured after the introduction of sharing systems were more likely to sustain facial fractures (OR, 2.63; 95%CI, 1.30-5.32; p = 0.007) after controlling for age, gender, and race. The incidence of lumbar and pelvic fractures was higher following the introduction of such systems (7.1% vs. 0%; p<0.05). CONCLUSIONS: The introduction of ES sharing systems resulted in increased incidence of facial, pelvic, and lumbar fractures. Federal and state regulations need to be implemented to mitigate the detrimental effects of ES sharing systems.

Explaining the structure of the OH stretching band in the IR spectra of strongly hydrogen-bonded dimers of phosphinic acid and their deuterated analogs in the gas phase: a computational study.

We present a simulation of the OH stretching band in the gas-phase IR spectra of strongly hydrogen-bonded dimers of phosphinic acid and their deuterated analogs [(R(2)POOH(D), with R = CH(2)Cl, CH(3)], which is based on a model for a centrosymmetric hydrogen-bonded dimer that treats the high-frequency OH stretches harmonically and the low-frequency intermonomer (i.e., O···O) stretches anharmonically. This model takes into account the following effects: anharmonic coupling between the OH and O···O stretching modes; Davydov coupling between the two hydrogen bonds in the dimer; promotion of symmetry-forbidden OH stretching transitions; Fermi resonances between the fundamental of the OH stretches and the overtones of the in- and out-of-plane bending modes involving the OH groups; direct relaxation of the OH stretches; and indirect relaxation of the OH stretches via the O···O stretches. Using a set of physically sound parameters as input into this model, we have captured the main features in the experimental OH(D) bands of these dimers. The effects of key parameters on the spectra are also elucidated. By increasing the number and strength of the Fermi resonances and by promoting symmetry-forbidden OH stretching transitions in our simulations, we directly see the emergence of the ABC structure, which is a characteristic feature in the spectra of very strongly hydrogen-bonded dimers. However, in the case of the deuterated dimers, which do not exhibit the ABC structure, the Fermi resonances are found to be much weaker. The results of this model therefore shed light on the origin of the ABC structure in the IR spectra of strongly hydrogen-bonded dimers, which has been a subject of debate for decades.