Stereoselective Peterson olefinations from bench-stable reagents and N-phenyl imines.

The synthesis of bench-stable α,α-bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles (E/Z ∼1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N-benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N,N-bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained.

Risk Factors for Deterioration Events in the Pediatric Acute Care Setting.

OBJECTIVES: Rapid response system (RRS) activations resulting in emergency transfers (ETs) and codes outside the ICU are associated with increased mortality and length of stay. We aimed to evaluate the patient and care team characteristics of RRS activations resulting in ETs and codes outside the ICU (together classified as "deterioration events") versus those that did not result in a deterioration event. METHODS: For each RRS activation at our institution from 2019 to 2021, data were gathered on patient demographics and medical diagnoses, care team and treatment factors, and ICU transfer. Descriptive statistics, bivariate analyses, and multivariable logistic regression using a backward elimination model selection method were performed to assess potential risk factors for deterioration events. RESULTS: Over the 3-year period, 1765 RRS activations were identified. Fifty-three (3%) activations were deemed acute care codes, 64 (4%) were noncode ETs, 921 (52%) resulted in nonemergent transfers to an ICU, and 727 (41%) patients remained in an acute care unit. In a multivariable model, any complex chronic condition (adjusted odds ratio, 6.26; 95% confidence interval, 2.83-16.60) and hematology/oncology service (adjusted odds ratio, 2.19; 95% confidence interval, 1.28-3.74) were independent risk factors for a deterioration event. CONCLUSIONS: Patients with medical complexity and patients on the hematology/oncology service had a higher risk of deterioration events than other patients with RRS activations. Further analyzing how our hospital evaluates and treats these specific patient populations is critical as we develop targeted interventions to reduce deterioration events.

Impact of a Coordinated Sepsis Response on Time to Treatment in a Pediatric Emergency Department.

BACKGROUND: Sepsis is responsible for 75 000 pediatric hospitalizations annually, with an associated mortality rate estimated between 11% and 19%. Evidence supports the use of timely fluid resuscitation and antibiotics to decrease morbidity and mortality. Our emergency department did not meet the timeliness goals for fluid and antibiotic administration suggested by the 2012 Surviving Sepsis Campaign. METHODS: In November 2018, we implemented a sepsis response team utilizing a scripted communication tool and a dedicated sepsis supply cart to address timeliness barriers. Performance was evaluated using statistical process control charts. We conducted observations to evaluate adherence to the new process. Our aim was to meet the Surviving Sepsis Campaign's timeliness goals for first fluid and antibiotic administration (20 and 60 minutes, respectively) within 8 months of our intervention. RESULTS: We observed sustained decreases in mean time to fluids. We also observed a shift in the proportion of patients receiving fluids within 20 minutes. No shifts were observed for timely antibiotic administration. CONCLUSIONS: The implementation of a dedicated emergency department sepsis response team with designated roles and responsibilities, directed communication, and easily accessible supplies can lead to improvements in the timeliness of fluid administration in the pediatric population.

Sieving polymer synthesis by reversible addition fragmentation chain transfer polymerization.

Replaceable sieving polymers are the fundamental component for high resolution nucleic acids separation in CE. The choice of polymer and its physical properties play significant roles in influencing separation performance. Recently, reversible addition fragmentation chain transfer (RAFT) polymerization has been shown to be a versatile polymerization technique capable of yielding well defined polymers previously unattainable by conventional free radical polymerization. In this study, a high molecular weight PDMA at 765 000 gmol-1 with a PDI of 1.55 was successfully synthesized with the use of chain transfer agent - 2-propionic acidyl butyl trithiocarbonate (PABTC) in a multi-step sequential RAFT polymerization approach. This study represents the first demonstration of RAFT polymerization for synthesizing polymers with the molecular weight range suitable for high resolution DNA separation in sieving electrophoresis. Adjustment of pH in the reaction was found to be crucial for the successful RAFT polymerization of high molecular weight polymer as the buffered condition minimizes the effect of hydrolysis and aminolysis commonly associated with trithiocarbonate chain transfer agents. The separation efficiency of PABTC-PDMA was found to have marginally superior separation performance compared to a commercial PDMA formulation, POP™-CAP, of similar molecular weight range.

Synthesis of trisubstituted alkenes via direct oxidative arene-alkene coupling.

The use of an inorganic oxidant with an acetic acid/acetonitrile solvent combination has been identified as optimal for direct arene/1,2-disubstituted alkene oxidative couplings, providing an efficient route to trisubstituted alkenes. The acetonitrile cosolvent dramatically accelerates the rate of reaction, and an insoluble inorganic oxidant limits unwanted oxidation of substrates. The scope of this procedure is illustrated with arenes and alkenes containing electron-donating and -withdrawing substituents resulting in a general synthetic strategy to trisubstituted alkenes. In situ ESI-MS analysis of the reaction components has identified the key Pd intermediates in the Fujiwara-Moritani catalytic cycle.

Tautomerism and metal complexation of 2-acylmethyl-2-oxazolines: a combined synthetic, spectroscopic, crystallographic and theoretical treatment.

A synthetic, structural and theoretical investigation into the solid-state, solution and gas phase structure(s) of six 2-acylmethyl-4,4-dimethyl-2-oxazolines is reported. Four of these materials, viz.α-[(4,5-dihydro-4,4-dimethyl-2-oxazolyl)methylene]benzenemethanol (3a), α-[(4,5-dihydro-4,4-dimethyl-2-oxazolyl)methylene]-(4-nitrobenzene)methanol (3b), 1-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)-3,3-dimethyl-1-buten-2-ol (3d) and (E)-1-phenyl-2-((3aR)-3,3a,8,8a-tetrahydro-2H-indeno[1,2-d]oxazol-2-ylidene)ethanone (3f) have been characterised in the solid-state by single crystal X-ray diffraction studies. These data represent the first solid-state structural studies of this class of compounds and details the first synthesis and full characterisation of chiral derivative 3f. All four of these materials are shown to exist in the solid phase in the enamine tautomeric form (e.g., 3a is best described as 2-[4,4-dimethyl-2-oxazolidinylidene]-1-phenylethanone) and it is suggested (NMR, IR) that this isomeric form is likely also retained in solution (e.g., CDCl3) as the more stable isomer. An investigation of the relative gas phase stabilities of the three possible (i.e., the (Z)-enol, keto and enamine) isomers of all five compounds by DFT at the B3LYP/6-311G(d) level of theory confirms the latter as the most stable form. The energy differences between the enamine and keto tautomers have been calculated to be the lowest for derivative 3d. These results are compared and contrasted with the previously reported NMR studies of such compounds which have identified the keto form as being a minor (albeit solution) tautomer. Equilibrium solution tautomer distributions for 3d are found to be solvent dependent. The protonated form of 3a, isolated as the HSO4(-) salt (i.e.4a), has been further characterised in the solid state by single crystal X-ray diffraction. These data represent the first example of a protonated oxazoline to be structurally elucidated and confirms that upon protonation, the keto (oxazoline) tautomer is the energetically favoured form in the solid-state. This observation is further supported by DFT studies for the gas phase protonated forms of such materials. Further DFT (B3LYP/6-311G(d)) calculations employing the SM8 or SMD solvation models were then applied to address the observed solution isomeric distribution for 3d; these results corroborate the gas phase theoretical treatment and also yield values that predict the higher solution stability of the enamine form as observed, although they fail to account for the existence of the keto form as a minor solution state tautomer. To access the availability of an enol-form, via hypothetical de-protonation to the enolate, compound 3a was treated with hydrated Cu(NO3)2 in EtOH solution. The resulting isolated green-coloured product (5), the first metal derivative of this entire class of ligands, is best described (IR, X-ray diffraction) as a coordinated enolate complex, i.e., Cu(3a-H)2. Complex 5 crystallizes in the P21/c space group with four molecules in the unit cell. The coordination geometry around the formal Cu(2+) metal centre is determined to be highly distorted square planar in nature (τ4 = 0.442). TD-DFT is used to give a reasonable explanation for the intensity of the absorbance band observed in the visible region for solutions of 5. These latter experiments strongly suggest that the title class of compounds may have considerable potential as ligands in coordination chemistry and/or metal-mediated catalysis.

Reducing Intraoperative Hypothermia in Infants from the Neonatal Intensive Care Unit.

Infants from the neonatal intensive care unit (NICU) undergoing surgery in the operating room (OR) are at greater risk for hypothermia during surgery than afterward due to environmental heat loss, anesthesia, and inconsistent temperature monitoring. A multidisciplinary team aimed to reduce hypothermia (<36.1 °C) for infants at a level IV NICU at the beginning of the operation (first OR temperature) or at any time during the operation (lowest OR temperature) by 25%. Methods: The team followed preoperative, intraoperative (first, lowest, and last OR), and postoperative temperatures. It sought to reduce intraoperative hypothermia using the "Model for Improvement" by standardizing temperature monitoring, transport, and OR warming, including raising ambient OR temperatures to 74°F. Temperature monitoring was continuous, secure, and automated. The balancing metric was postoperative hyperthermia (>38 °C). Results: Over 4 years, there were 1235 operations: 455 in the baseline and 780 in the intervention period. The percentage of infants experiencing hypothermia upon OR arrival and at any point during the operation decreased from 48.7% to 6.4% and 67.5% to 37.4%, respectively. Upon return to the NICU, the percentage of infants experiencing postoperative hypothermia decreased from 5.8% to 2.1%, while postoperative hyperthermia increased from 0.8% to 2.6%. Conclusions: Intraoperative hypothermia is more prevalent than postoperative hypothermia. Standardizing temperature monitoring, transport, and OR warming reduces both; however, further reduction requires a better understanding of how and when risk factors contribute to hypothermia to avoid further increasing hyperthermia. Continuous, secure, and automated data collection improved temperature management by enhancing situational awareness and facilitating data analysis.

Sepsis Prediction in Hospitalized Children: Model Development and Validation.

BACKGROUND AND OBJECTIVES: Early recognition and treatment of pediatric sepsis remain mainstay approaches to improve outcomes. Although most children with sepsis are diagnosed in the emergency department, some are admitted with unrecognized sepsis or develop sepsis while hospitalized. Our objective was to develop and validate a prediction model of pediatric sepsis to improve recognition in the inpatient setting. METHODS: Patients with sepsis were identified using intention-to-treat criteria. Encounters from 2012 to 2018 were used as a derivation to train a prediction model using variables from an existing model. A 2-tier threshold was determined using a precision-recall curve: an "Alert" tier with high positive predictive value to prompt bedside evaluation and an "Aware" tier with high sensitivity to increase situational awareness. The model was prospectively validated in the electronic health record in silent mode during 2019. RESULTS: A total of 55 980 encounters and 793 (1.4%) episodes of sepsis were used for derivation and prospective validation. The final model consisted of 13 variables with an area under the curve of 0.96 (95% confidence interval 0.95-0.97) in the validation set. The Aware tier had 100% sensitivity and the Alert tier had a positive predictive value of 14% (number needed to alert of 7) in the validation set. CONCLUSIONS: We derived and prospectively validated a 2-tiered prediction model of inpatient pediatric sepsis designed to have a high sensitivity Aware threshold to enable situational awareness and a low number needed to Alert threshold to minimize false alerts. Our model was embedded in our electronic health record and implemented as clinical decision support, which is presented in a companion article.

Sepsis Prediction in Hospitalized Children: Clinical Decision Support Design and Deployment.

BACKGROUND: Following development and validation of a sepsis prediction model described in a companion article, we aimed to use quality improvement and safety methodology to guide the design and deployment of clinical decision support (CDS) tools and clinician workflows to improve pediatric sepsis recognition in the inpatient setting. METHODS: CDS tools and sepsis huddle workflows were created to implement an electronic health record-based sepsis prediction model. These were proactively analyzed and refined using simulation and safety science principles before implementation and were introduced across inpatient units during 2020-2021. Huddle compliance, alerts per non-ICU patient days, and days between sepsis-attributable emergent transfers were monitored. Rapid Plan-Do-Study-Act (PDSA) cycles based on user feedback and weekly metric data informed improvement throughout implementation. RESULTS: There were 264 sepsis alerts on 173 patients with an 89% bedside huddle completion rate and 10 alerts per 1000 non-ICU patient days per month. There was no special cause variation in the metric days between sepsis-attributable emergent transfers. CONCLUSIONS: An automated electronic health record-based sepsis prediction model, CDS tools, and sepsis huddle workflows were implemented on inpatient units with a relatively low rate of interruptive alerts and high compliance with bedside huddles. Use of CDS best practices, simulation, safety tools, and quality improvement principles led to high utilization of the sepsis screening process.

Binary Solvent Swap Processing in a Bubble Column in Batch and Continuous Modes.

A lab-scale bubble column was investigated as an alternative means to achieve a low-temperature binary solvent swap of solutions containing pharmaceutical materials at atmospheric pressure, for batch and continuous configurations. The rate of solvent evaporation was predicted by first-principles vapor-liquid equilibrium (VLE) thermodynamic modeling and compared to experimentally achieved results. For batch configurations, evaporation rates of up to 5 g/min were achieved at gas flow rates up to 2.5 L/min (0.21 m/s superficial velocity) and temperatures up to 50 °C. This achieved 99 mol % purity of the desired solvent within three "put and take" evaporations from a 50:50 starting mixture. The evaporation rate profiles for the duration of the experiments were calculated, and the changing concentration profile was predicted within satisfactory error margins of <5%. Continuous process modeling explored a multistage equilibrium configuration and could predict the approach to attaining steady-state operation for various operating conditions. All rates of evaporation and resulting changes in solution concentration were measured, and direct comparison of model predictions fell within instrumentation error margins, as previously. This underlined the capability of the model to provide accurate representations of predicted evaporation rates and binary solution concentration changes during operation.

Design and Optimization of the Single-Stage Continuous Mixed Suspension-Mixed Product Removal Crystallization of 2-Chloro-N-(4-methylphenyl)propenamide.

A continuously operated single-stage mixed suspension-mixed product removal (MSMPR) crystallizer was developed for the continuous cooling crystallization of 2-chloro-N-(4-methylphenyl)propanamide (CNMP) in toluene from 25 to 0 °C. The conversion of the previous batch to a continuous process was key to developing a methodology linking the synthesis and purification unit operations of CNMP and gave further insight in the development of continuous process trains for active pharmaceutical ingredient materials. By monitoring how parameters such as cooling and agitation rates influence particle size and the yield, two batch start-up strategies were compared. The second part of the study focused on developing and optimizing the continuous cooling crystallization of CNMP in the MSMPR crystallizer in relation to the yield by determining the effects of varying the residence time and the agitation rates. During the MSMPR operation, the plot of the focused beam reflectance measurement total counts versus time oscillates and reaches an unusual state of control. Despite the oscillations, the dissolved concentration was constant. The yield and production rate from the system were constant after two residence times, as supported by FTIR data. The overall productivity was higher at shorter residence times (τ), and a productivity of 69.51 g/h for τ = 20 min was achieved for the isolation of CNMP.

The impact of standardized huddle tools on case duration in pediatric microlaryngoscopy/bronchoscopy.

OBJECTIVE: Equipment necessary to perform pediatric microlaryngoscopy/bronchoscopy (MLB) varies considerably depending on the selected interventions. In procedures with equipment variability, surgical case length may be increased due to the need to procure items intraoperatively. We hypothesized that use of standardized huddle tools listing necessary equipment would be associated with a shortened case duration in MLB. METHODS: As part of a quality improvement initiative at our academic, tertiary care pediatric hospital, a standardized huddle sheet was created that listed options of equipment for MLB. Listed items included telescope/bronchoscope size, laryngoscope selection, interventional equipment, suspension, microscopes, and topical medications. The tool was completed by otolaryngology and shared with the circulating nurse at the beginning of the day so equipment needs could be anticipated. The tool was introduced to staff in November 2017 and to trainees in February 2018. To assess intervention impact, monthly median surgical case duration and room turnover time were retrospectively tracked using control chart analysis from March 2017 to June 2019. RESULTS: At baseline, the centerline case duration was 49 min. Two months following introduction of the huddle sheet to trainees, the centerline duration decreased to 43 min. This change was sustained throughout the period studied. No changes in room turnover time were observed during this period. CONCLUSIONS: Standardized huddle tool use prior to MLB was associated with a median decrease of 6 min of operating room time without a change in operating room turnover time. Use of similar tools in procedures with significant equipment variability may be beneficial.

Influenza-like illness in a community surrounding a school-based outbreak of 2009 pandemic influenza A (H1N1) virus-Chicago, Illinois, 2009.

In April 2009, following the first school closure due to 2009 pandemic influenza A (H1N1) (pH1N1) in Chicago, Illinois, area hospitals were inundated with patients presenting with influenza-like illness (ILI). The extent of disease spread into the surrounding community was unclear. We performed a household survey to estimate the ILI attack rate among community residents and compared reported ILI with confirmed pH1N1 cases and ILI surveillance data (ie, hospital ILI visits, influenza testing, and school absenteeism). The estimated ILI attack rate was 4.6% (95% confidence interval, 2.8%-7.4%), with cases distributed throughout the 5-week study period. In contrast, 36 (84%) of 43 confirmed pH1N1 cases were identified the week of the school closure. Trends in surveillance data peaked during the same week and rapidly decreased to near baseline. Public awareness and health care practices impact standard ILI surveillance data. Community-based surveys are a valuable tool to help assess the burden of ILI in a community.

Use of the vector index and geographic information system to prospectively inform West Nile virus interventions.

We sought to estimate West Nile virus (WNV) activity in mosquito populations weekly at the census tract level in Chicago, IL, and to provide this information graphically. Each week we calculated a vector index (VI) for each mosquito trap then generated tract estimates using geographic information systems. During June 29-September 13, 2008, a median of 527 (60%) of 874 possible tracts per week had a VI value. Overall, 94% of the weekly VI tract estimates were 0; among those with a VI estimate greater than 0, the median was 0.33 (range 0.003-3.5). Officials deemed risk levels and weather conditions appropriate for adulticide treatments on 3 occasions, resulting in the treatment of approximately 252 linear kilometers of residential streets and alleys. Our analysis successfully converted complex, raw surveillance data into a format that highlighted areas of elevated WNV activity and facilitated the determination of appropriate response procedures.

The impact of adulticide applications on mosquito density in Chicago, 2005.

The city of Chicago used ground ultra-low volume treatments of sumithrin (ANVIL 10+10) in areas with high West Nile virus infection rates among Culex mosquitoes. Two sequential treatments in Morbidity and Mortality Weekly Reports wk 31 and 32 decreased mean mosquito density by 54% from 2.5 to 1.1 mosquitoes per trap-day, whereas mosquito density increased by 153% from 1.3 to 3.3 mosquitoes per trap-day at the nonsprayed sites. The difference between these changes in mosquito density was statistically significant (confidence intervals for the difference in change: -4.7 to -1.9). Sequential adulticide treatments in September (wk 34 and 35) had no effect on mosquito density, probably because it was late in the season and the mosquitoes were presumably entering diapause and less active. Overall, there was significant decrease in mosquito density at the trap sites treated in all 4 wk (wk 31, 32, 34, and 35), suggesting that sustained sequential treatments suppressed mosquito density. Maximum likelihood estimates (MLE) of infection rate estimates varied independently of adulticide treatments, suggesting that the adulticide treatments had no direct effect on MLE. Mosquito trap counts were low, which was probably due to large numbers of alternative oviposition sites, especially catch basins competing with the gravid traps.

Leveraging community concerns regarding meningococcal disease to address racial and socioeconomic disparities in immunization coverage.

Following the death of 2 adolescents due to serogroup C invasive meningococcal disease (SCIMD) in April 2008, the Chicago Department of Public Health (CDPH) observed a high level of concern in 2 Chicago communities inferred to have low meningococcal vaccine (MCV) coverage rates. In response, CDPH promptly mobilized additional resources, administering 5,343 doses of MCV in 40 schools over 2 weeks and immunizing 44% of enrolled students aged 11 to 18 years. The number of eligible students vaccinated per school ranged from 9 to 466 (median, 112) and the proportion of age-eligible students receiving the vaccine ranged from 5% to 87% (median, 52%). The attributes of the SCIMD activity did not meet the definition of a community-based outbreak, but presented an opportunity to promptly intensify existing mechanisms for meningococcal vaccination of adolescents in the affected neighborhoods and overcome traditional barriers to vaccination.

Efficient Postoperative Disposition Selection in Pediatric Otolaryngology Patients: A Novel Approach.

OBJECTIVE: Pediatric patients undergoing surgery on the aerodigestive tract require a wide range of postoperative airway support that may be difficult predict in the preoperative period. Inaccurate prediction of postoperative resource needs leads to care inefficiencies in the form of unanticipated intensive care unit (ICU) admissions, ICU bed request cancellations, and overutilization of ICU resources. At our hospital, inefficient utilization of pediatric intensive care unit (PICU) resources was negatively impacting safety, access, throughput, and finances. We hypothesized that actionable key drivers of inefficient ICU utilization at our hospital were operative scheduling errors and the lack of predictability of intermediate-risk patients and that improvement methodology could be used in iterative cycles to enhance efficiency of care. Through testing this hypothesis, we aimed to provide a framework for similar efforts at other hospitals. STUDY DESIGN: Quality improvement initiative. METHODS: Plan, Do, Study, Act methodology (PDSA) was utilized to implement two cycles of change aimed at improving level-of-care efficiency at an academic pediatric hospital. In PDSA cycle 1, we aimed to address scheduling errors with surgical order placement restriction, creation of a standardized list of surgeries requiring PICU admission, and implementation of a hard stop for postoperative location in the electronic medical record surgical order. In the PDSA cycle 2, a new model of care, called the Grey Zone model, was designed and implemented where patients at intermediate risk of airway compromise were observed for 2-5 hours in the post-anesthesia care unit. After this observation period, patients were then transferred to the level of care dictated by their current status. Measures assessed in PDSA cycle 1 were unanticipated ICU admissions and ICU bed request cancellations. In addition to continued analysis of these measures, PDSA cycle 2 measures were ICU beds avoided, safety events, and secondary transfers from extended observation to ICU. RESULTS: In PDSA cycle 1, no significant decrease in unanticipated ICU admissions was observed; however, there was an increase in average monthly ICU bed cancellations from 36.1% to 45.6%. In PDSA cycle 2, average monthly unanticipated ICU admissions and cancelled ICU bed requests decreased from 1.3% to 0.42% and 45.6% to 33.8%, respectively. In patients observed in the Grey Zone, 229/245 (93.5%) were transferred to extended observation, avoiding admission to the ICU. Financial analysis demonstrated a charge differential to payers of $1.1 million over the study period with a charge differential opportunity to the hospital of $51,720 for each additional hospital transfer accepted due to increased PICU bed availability. CONCLUSIONS: Implementation of the Grey Zone model of care improved efficiency of ICU resource utilization through reducing unanticipated ICU admissions and ICU bed cancellations while simultaneously avoiding overutilization of ICU resources for intermediate-risk patients. This was achieved without compromising safety of patient care, and was financially sound in both fee-for-service and value-based reimbursement models. While such a model may not be applicable in all healthcare settings, it may improve efficiency at other pediatric hospitals with high surgical volume and acuity. LEVEL OF EVIDENCE: N/A Laryngoscope, 131:S1-S10, 2021.

Short-Duration Electronic Health Record Option Buttons to Reduce Prolonged Length of Antibiotic Therapy in Outpatients.

BACKGROUND: Prolonged antibiotic therapy may be associated with increased adverse events and antibiotic resistance. We deployed an intervention in the electronic health record (EHR) to reduce antibiotic duration for pediatric outpatients. METHODS: A preintervention and postintervention interrupted time series analysis of antibiotic duration for 7 antibiotics was performed for patients discharged from the ED and clinics of a children's hospital network from 2012 to 2018. In February 2015, clickable 5- and 7-day duration option buttons were deployed in the EHR for clindamycin, cephalexin, ciprofloxacin and levofloxacin, trimethoprim-sulfamethoxazole, amoxicillin, and cefdinir, with an additional 10-day option for the latter 2. Prescribers were able to enter a free-text duration. The option buttons were not announced, and were not linked to a specific diagnosis or quality improvement initiative. The primary outcome was proportion of prescriptions per month with duration of 10 days. Balancing secondary outcomes were reorders of the same agent, return to clinic, and inpatient admissions within 30 days. RESULTS: There were 54 315 prescriptions for the 7 antibiotics associated with 39 894 patients, 18 683 clinic visits, and 35 632 ED visits. Overall, a -5.1% (95% confidence interval [CI], -8.3% to -2.0%) change in the proportion of prescriptions with a 10-day duration was attributable to the intervention, with larger effects noted for clindamycin (-20.8% [95% CI, -26.9% to -14.7%]) and cephalexin (-9.9% [95% CI, -14.3% to -5.4%]). There was no increase in the reorders of the same agent, return clinical encounters, or inpatient admissions within 30 days. CONCLUSIONS: A simple intervention in the EHR can safely reduce duration of antibiotic therapy.

Characterization of tetra-aryl benzene isomers by using preparative gas chromatography with mass spectrometry, nuclear magnetic resonance spectroscopy, and X-ray crystallographic methods.

The present study describes a preparative gas chromatographic (GC) approach employed to study a series of products arising from reaction of phenylacetylene with para-substituted aryl-iodides under Sonogashira catalysis conditions. GC analysis resolves the isomers from each reaction; however, it cannot provide structural details (their MS data are virtually identical). Since classical liquid chromatography cannot resolve the isomers, preparative-scale GC is the only practical approach to provide further spectroscopic characterization of the isomers. The products are well separated by GC so a single thick-film capillary column is adequate for this case, with operation up to approximately +300 degrees C. By collection of 50+ repeat injections, sufficient material could be isolated for (1)H NMR spectral analysis of the isomers, and for one isomer (isomer I) of a number of analogous related catalytic reaction mixtures, X-ray crystal structure determination enabled complete structural elucidation (absolute configuration) of the substitution pattern of the structure of this isomer. This confirmed isomer I to be the 2-para-aryl-substituted 1,3,5-triphenylbenzene product in all cases. (1)H NMR spectra of isomer I products generally had similar patterns but differed markedly from the second major isomer product (isomer II).

Binuclear intermediates in oxidation reactions: [(Me(3)SiC[triple bond]C)Me(2)(bipy)Pt-PtMe(2)(bipy)](+) in the oxidation of Pt(II)Me(2)(bipy) (bipy = 2,2'-bipyridine) by IPh(C[triple bond]CSiMe(3))(OTf) (OTf = triflate).

A study of the reaction of PtMe(2)(bipy) with IPh(C[triple bond]CSiMe(3))(OTf) at low temperature in acetone, leading to detection of the Pt-Pt-bonded cation [Pt(2)Me(4)(C[triple bond]CSiMe(3))(bipy)(2)](+), an intermediate in the oxidation of Pt(II) to Pt(IV), is reported. The cation is assessed as Pt(III)-Pt(III) <--> Pt(IV)-Pt(II), and at the other extreme may be regarded as a cationic alkynylplatinum(IV) center, "[Pt(IV)Me(2)(C[triple bond]CSiMe(3))(bipy)](+)", stabilized by "Pt(II)Me(2)(bipy)" as a donor ligand. The detection and isolation of the [Pt(2)Me(4)(C[triple bond]CSiMe(3))(bipy)(2)](+) cation provides a number of insights into the mechanisms of oxidation reactions.