Infrared Reflection-Absorption Spectroscopy of α-Keto Acids at the Air-Water Interface: Effects of Chain Length and Headgroup on Environmentally Relevant Surfactant Films.

A variety of organic surfactants are found at air-water interfaces in natural environments, including on the surfaces of aqueous aerosols. The structure and morphology of these organic films can have profound impacts on material transfer between the gas and condensed phases, the optical properties of atmospheric aerosol, and chemical processing at air-water interfaces. Combined, these effects can have significant impacts on climate via radiative forcing, but our understanding of organic films at air-water interfaces is incomplete. Here, we examine the impact of the polar headgroup and alkyl tail length on the structure and morphology of organic monolayers at the air-water interfaces. First, we focus on the substituted carboxylic acids, α-keto acids, using Langmuir isotherms and infrared reflection absorption spectroscopy (IR-RAS) to elucidate key structures and phase behaviors of α-keto acids with a range of surface activities. We show that the structure of α-keto acids, both soluble and insoluble, at water surfaces is a compromise between van der Waals interactions of the hydrocarbon tail and hydrogen bonding interactions involving the polar headgroup. Then, we use this new data set regarding α-keto acid films at water surfaces to examine the role of the polar headgroup on organic films using a similar substituted carboxylic acid (α-hydroxystearic acid), an unsubstituted carboxylic acid (stearic acid), and an alcohol (stearyl alcohol). We show that the polar headgroup and its hydrogen bonding interactions can significantly affect the orientation of amphiphiles at air-water interfaces. Here, we provide side-by-side comparisons of Langmuir isotherms and IR-RA spectra for a set of environmentally relevant organic amphiphiles with a range of alkyl tail lengths and polar headgroup structures.

A dual grafted fluorinated hydrocarbon amine weak anion exchange resin polymer for adsorption of perfluorooctanoic acid from water.

Perfluorooctanoic acid (PFOA) is a persistent and recalcitrant organic contaminant of exceptional environmental concern, and its removal from water has increasingly attracted global attention due to its wide distribution and strong bioaccumulation. Adsorption is considered an effective technique for PFOA removal and more efficient PFOA sorbents are still of interest. This study developed a dual grafted fluorinated hydrocarbon amine weak anion exchange (WAX) polymeric resin (Sepra-WAX-KelF-PEI) for PFOA removal from water. This polymer was synthesized by a two-step amine grafting reaction procedure involving first the reaction of the Sepra-WAX hydrocarbon polymer with poly(vinylidinefluoride-chlorotrifluoroethylene) (Kel-F 800) and then a second reaction with polyethyleneimine (PEI). Characterization of the synthesized polymers was performed using scanning electron microscopy and elemental analysis (F and Cl) by energy dispersive X-ray spectroscopy. The PFOA adsorption performance evaluations were conducted by packed column flow analyses with on-line detection. The results show the breakthrough of the Sepra-WAX-KelF-PEI synthesized with optimum stoichiometry was two times better than the starting anion exchange polymer Sepra-WAX, and six times better than powdered activated carbon, when using the same column size. The adsorption mechanisms of this novel adsorbent including hydrophobic interaction and electrostatic interaction were also clarified in this study. The adsorption kinetic parameters of the two optimum synthesized sorbents were determined using the Thomas model, the Yoon-Nelson model, and batch isotherm studies, and compared with those found with activated carbon and the starting WAX resin. Good agreement of the batch isotherm and column studies with respect to adsorption capacities trends between all three polymers (Sepra-WAX, Sepra-WAX-KelF, and Sepra-WAX-KelF-PEI) were noted.

Super-Resolution SERS Spectral Bioimaging.

Advances in nanotechnology enable the detection of trace molecules from the enhanced Raman signal generated at the surface of plasmonic nanoparticles. We have developed technology to enable super-resolution imaging of plasmonic nanoparticles, where the fluctuations in the surface enhanced Raman scattering (SERS) signal can be analyzed with localization microscopy techniques to provide nanometer spatial resolution of the emitting molecule's location. Additional work now enables the super-resolved SERS image and the corresponding spectrum to be acquired simultaneously. Here we will discuss how this approach can be applied to provide new insights into biological cells.

Enhanced Recovery After Surgery in Pediatric and Adolescent Gynecology: A Pilot Study.

STUDY OBJECTIVE: Enhanced recovery after surgery (ERAS) protocols have been successfully implemented in adult gynecology as well as adult and pediatric colorectal and urologic surgery with reduction in narcotic use, complications, return to the system (RTS), length of stay (LOS), and improved patient satisfaction. There are no studies evaluating the use of ERAS in pediatric and adolescent gynecology (PAG). The goals of this study are to present initial patient outcomes using ERAS in PAG patients undergoing intra-abdominal gynecologic surgery to prove efficacy, patient satisfaction, and decreased narcotic use. DESIGN: As a quality improvement measure in perioperative care, an ERAS protocol including preoperative, intraoperative, and postoperative components and a follow-up patient telephone call for pain assessment was implemented for all intra-abdominal gynecologic procedures. A retrospective study on implementation of ERAS components, outcomes, and patient satisfaction was then performed in participants meeting inclusion criteria. SETTING: Large academic children's hospital. PARTICIPANTS: Patients <25 years of age who underwent laparoscopic (LSC) or open abdominal (XLAP) gynecologic surgery using an ERAS protocol by the PAG service over a 12-month period. INTERVENTIONS: An ERAS protocol including preoperative, intraoperative, and postoperative components and follow-up patient telephone call for pain assessment was implemented for all major gynecologic surgeries performed by the PAG service. MAIN OUTCOME MEASURES: Patient satisfaction with the perioperative ERAS protocol along with components including pain management, narcotic use, LOS, RTS, and postoperative complications for various intra-abdominal gynecologic procedures. RESULTS: A total of 40 participants met inclusion criteria for the study. Thirty-four (85%) participants underwent LSC procedures and six (15%) underwent XLAP. Of the LSC patients, 95% were discharged on postoperative day 0, and all XLAP patients and one LSC patient were discharged on postoperative day 1. In all, 95% of patients were discharged from the hospital requiring only non-narcotic ERAS medications. There were no readmissions or postoperative complications. All patients were satisfied with their postoperative pain control at their follow-up telephone call and clinic visit. CONCLUSION: Implementation of a pediatric-specific ERAS protocol in children and adolescents undergoing gynecologic surgery is feasible and safe, and leads to less narcotic use without an increase in complications or decrease in patient satisfaction.

PagP activation in the outer membrane triggers R3 core oligosaccharide truncation in the cytoplasm of Escherichia coli O157:H7.

The Escherichia coli outer membrane phospholipid:lipid A palmitoyltransferase PagP is normally a latent enzyme, but it can be directly activated in outer membranes by lipid redistribution associated with a breach in the permeability barrier. We now demonstrate that a lipid A myristate deficiency in an E. coli O157:H7 msbB mutant constitutively activates PagP in outer membranes. The lipid A myristate deficiency is associated with hydrophobic antibiotic sensitivity and, unexpectedly, with serum sensitivity, which resulted from O-antigen polysaccharide absence due to a cytoplasmically determined truncation at the first outer core glucose unit of the R3 core oligosaccharide. Mutational inactivation of pagP in the myristate-deficient lipid A background aggravated the hydrophobic antibiotic sensitivity as a result of losing a partially compensatory increase in lipid A palmitoylation while simultaneously restoring serum resistance and O-antigen attachment to intact lipopolysaccharide. Complementation with either wild-type pagP or catalytically inactive pagPSer77Ala alleles restored the R3 core truncation. However, the intact lipopolysaccharide was preserved after complementation with an internal deletion pagPDelta5-14 allele, which mostly eliminates a periplasmic amphipathic alpha-helical domain but fully supports cell surface lipid A palmitoylation. Our findings indicate that activation of PagP not only triggers lipid A palmitoylation in the outer membrane but also separately truncates the R3 core oligosaccharide in the cytoplasm. We discuss the implication that PagP might function as an apical sensory transducer, which can be activated by a breach in the outer membrane permeability barrier.