Microwave-assisted synthesis of ZnS@CuInxSy for photocatalytic degradation of coloured and non-coloured pollutants.

Copper indium sulfide (CuInS2) exhibits strong visible light absorption and thus has the potential for good photocatalytic activity; however, rapid charge recombination limits its practical usage. An intriguing strategy to overcome this issue is to couple CuInS2 with another semiconductor to form a heterojunction, which can improve the charge carrier separation and, hence, enhance the photocatalytic activity. In this study, photocatalysts comprising CuInS2 with a secondary CuS phase (termed CuInxSy) and CuInxSy loaded with ZnS (termed ZnS@CuInxSy) were synthesized via a microwave-assisted method. Structural and morphological characterization revealed that the ZnS@CuInxSy photocatalyst comprised tetragonal CuInS2 containing a secondary phase of hexagonal CuS, coupled with hexagonal ZnS. The effective band gap energy of CuInxSy was widened from 2.23 to 2.71 as the ZnS loading increased from 0 to 30%. The coupling of CuInxSy with ZnS leads to long-lived charge carriers and efficient visible-light harvesting properties, which in turn lead to a remarkably high activity for the photocatalytic degradation of brilliant green (95.6% in 5 h) and conversion of 4-nitrophenol to 4-nitrophenolate ions (95.4% in 5 h). The active species involved in these photocatalytic processes were evaluated using suitable trapping agents. Based on the obtained results, photocatalytic mechanisms are proposed that emphasize the importance of h+, O2•-, and OH- in photocatalytic processes using ZnS@CuInxSy.

Effect of CdS loading on the properties and photocatalytic activity of MoS2 nanosheets.

Molybdenum sulfide (MoS2) and modified MoS2 with different percentages of CdS (10%, 30%, and 50% CdS@MoS2) were successfully synthesized and characterized. The photocatalytic performance of the MoS2 and CdS@MoS2 was evaluated by degrading brilliant green (BG), methylene blue (MB), and rhodamine B (RhB) dyes under visible light irradiation. Amongst the synthesized photocatalysts, 50% CdS@MoS2 exhibited the highest photocatalytic activity, degrading 97.6%, 90.3%, and 75.5% of BG, MB, and RhB dyes, respectively within 5 h. The active species involved in the degradation processes were investigated. All trapping agents inhibited BG and MB degradation to a similar extent, indicating that all of the probed active species play an important role in the degradation of BG and MB. In contrast, h+ and O2•- were found to be the main reactive species in the photocatalytic RhB degradation. A potential mechanism for the photocatalytic degradation of dyes using CdS@MoS2 has been proposed. This work highlights the potential of CdS@MoS2 as a photocatalyst for more efficient water remediation applications.

Doped Ceria Nanomaterials: Preparation, Properties, and Uses.

Doping is a powerful strategy for enhancing the performance of ceria (CeO2) nanomaterials in a range of catalytic, photocatalytic, biomedical, and energy applications. The present review summarizes recent developments in the doping of ceria nanomaterials with metal and non-metal dopants for selected applications. The most important metal dopants are grouped into s, p, d, and f block elements, and the relevant synthetic methods, novel properties, and key applications of metal doped ceria are collated and critically discussed. Non-metal dopants are similarly examined and compared with metal dopants using the same performance criteria. The review reveals that non-metal (N, S, P, F, and Cl) doped ceria has mainly been synthesized by calcination and hydrothermal methods, and it has found applications mostly in photocatalysis or as a cathode material for LiS batteries. In contrast, metal doped ceria nanomaterials have been prepared by a wider range of synthetic routes and evaluated for a larger number of applications, including as catalysts or photocatalysts, as antibacterial agents, and in devices such as fuel cells, gas sensors, and colorimetric detectors. Dual/co-doped ceria containing both metals and non-metals are also reviewed, and it is found that co-doping often leads to improved properties compared with single-element doping. The review concludes with a future outlook that identifies unaddressed issues in the synthesis and applications of doped ceria nanomaterials.

Structure-Activity Relationships of Cationic Lipidoids against Escherichia coli.

Membrane-active molecules provide a promising strategy to target and kill pathogenic bacteria. Understanding how specific molecular features drive interactions with membrane components and subsequently cause disruption that leads to antimicrobial activity is a crucial step in designing next-generation treatments. Here, we test a library of lipid-like compounds (lipidoids) against Gram-negative bacteria Escherichia coli to garner in-depth structure-activity relationships using antimicrobial assays. Modular lipidoid molecules were synthesized in high-throughput, such that we could analyze 104 compounds with variable combinations of hydrophobic tails and cationic headgroups. Antibacterial activity was strongly correlated to specific structural features, including tail hydrophobicity and headgroup charge density, and also to the overall molecular shape and propensity for self-assembly into curved liquid crystalline phases. Dye permeabilization assays showed that E. coli membranes were permeabilized by lipidoids, confirming their membrane-active nature. The reduced permeabilization, as compared to Gram-positive Bacillus subtilis, alludes to the challenge of permeabilizing the additional outer membrane layer of E. coli. The effect of headgroup solubility in gemini-type lipidoids was also demonstrated, revealing that a headgroup with a more hydrophilic spacer between amine groups had enhanced activity against B. subtilis but not E. coli. This provides insight into features enabling outer membrane penetration and governing selectivity between bacterial species.

Combinatorial Screening of Cationic Lipidoids Reveals How Molecular Conformation Affects Membrane-Targeting Antimicrobial Activity.

The search for next-generation antibacterial compounds that overcome the development of resistance can be facilitated by identifying how to target the cell membrane of bacteria. Understanding the key molecular features that enable interactions with lipids and lead to membrane disruption is therefore crucial. Here, we employ a library of lipid-like compounds (lipidoids) comprising modular structures with tunable hydrophobic and hydrophilic architecture to shed light on how the chemical functionality and molecular shape of synthetic amphiphilic compounds determine their activity against bacterial membranes. Synthesized from combinations of 8 different polyamines as headgroups and 13 acrylates as tails, 104 different lipidoids are tested for activity against a model Gram-positive bacterial strain (Bacillus subtilis). Results from the combinatorial screening assay show that lipidoids with the most potent antimicrobial properties (down to 2 µM) have intermediate tail hydrophobicity (i.e., c log P values between 3 and 4) and lower headgroup charge density (i.e., longer spacers between charged amines). However, the most important factor appeared to be the ability of a lipidoid to self-assemble into an inverse hexagonal liquid crystalline phase, as observed by small-angle X-ray scattering (SAXS) analysis. The lipidoids active at lowest concentrations, which induced the most significant membrane damage during propidium iodide (PI) permeabilization assays, were those that aggregated into highly curved inverse hexagonal liquid crystal phases. These observations suggest that the introduction of strong curvature stress into the membrane is one way to maximize membrane disruption and lipidoid antimicrobial activity. Lipidoids that demonstrated the ability to furnish this phase consisted of either (i) branched or linear headgroups with shorter linear tails or (ii) cyclic headgroups with 4 bulky nonlinear tails. On the contrary, lipidoids previously observed to adopt disc-like conformations that pack into bicontinuous cubic phases were significantly less effective against B. subtilis. The discovery of these structure-property relationships demonstrates that it is not simply a balance of hydrophobic and hydrophilic moieties that govern membrane-active antibacterial activity, but also their intrinsic curvature and collective behavior.

Bactericidal Activity to Escherichia coli: Different Modes of Action of Two 24-Mer Peptides SAAP-148 and OP-145, Both Derived from Human Cathelicidine LL-37.

OP-145 and SAAP-148, two 24-mer antimicrobial peptides derived from human cathelicidin LL-37, exhibit killing efficacy against both Gram-positive and Gram-negative bacteria at comparable peptide concentrations. However, when it comes to the killing activity against Escherichia coli, the extent of membrane permeabilization does not align with the observed bactericidal activity. This is the case in living bacteria as well as in model membranes mimicking the E. coli cytoplasmic membrane (CM). In order to understand the killing activity of both peptides on a molecular basis, here we studied their mode of action, employing a combination of microbiological and biophysical techniques including differential scanning calorimetry (DSC), zeta potential measurements, and spectroscopic analyses. Various membrane dyes were utilized to monitor the impact of the peptides on bacterial and model membranes. Our findings unveiled distinct binding patterns of the peptides to the bacterial surface and differential permeabilization of the E. coli CM, depending on the smooth or rough/deep-rough lipopolysaccharide (LPS) phenotypes of E. coli strains. Interestingly, the antimicrobial activity and membrane depolarization were not significantly different in the different LPS phenotypes investigated, suggesting a general mechanism that is independent of LPS. Although the peptides exhibited limited permeabilization of E. coli membranes, DSC studies conducted on a mixture of synthetic phosphatidylglycerol/phosphatidylethanolamine/cardiolipin, which mimics the CM of Gram-negative bacteria, clearly demonstrated disruption of lipid chain packing. From these experiments, we conclude that depolarization of the CM and alterations in lipid packing plays a crucial role in the peptides' bactericidal activity.

Influence of metal salts (Al, Ca, and Mg) on the work function and hole extraction at carbon counter electrodes in perovskite solar cells.

Hole transport material-free carbon-based perovskite solar cells (HTM-free C-PSCs) are recognized as a cost-effective and stable alternative to conventional perovskite solar cells. However, the significant energy level misalignment between the perovskite layer and the carbon counter electrode (CE) results in ineffective hole extraction and unfavorable charge recombination, which decreases the power conversion efficiency (PCE). Here, we report the introduction of metal salts (Al, Ca, and Mg) into graphite/carbon black (Gr/CB) CEs to modify the work function and enhance the hole selectivity of the CE. This modification leads to improved energy level alignment, efficient hole extraction, and reduced charge recombination. The PCE of the HTM-free C-PSC based on Al-modified Gr/CB as the CE material reached 9.91%, which is approximately 12% higher than that of devices employing unmodified Gr/CB CEs. This work demonstrates that by directly incorporating metal salts into the Gr/CB CE, the energy level alignment and hole extraction at the perovskite/carbon interface can be improved. This presents a viable method for enhancing the PCE of HTM-free C-PSCs.

Multiple Routes to Bicontinuous Cubic Liquid Crystal Phases Discovered by High-Throughput Self-Assembly Screening of Multi-Tail Lipidoids.

Bicontinuous cubic phases offer advantageous routes to a broad range of applied materials ranging from drug delivery devices to membranes. However, a priori design of molecules that assemble into these phases remains a technological challenge. In this article, a high-throughput synthesis of lipidoids that undergo protonation-driven self-assembly (PrSA) into liquid crystalline (LC) phases is conducted. With this screening approach, 12 different multi-tail lipidoid structures capable of assembling into the bicontinuous double gyroid phase are discovered. The large volume of small-angle X-ray scattering (SAXS) data uncovers unexpected design criteria that enable phase selection as a function of lipidoid headgroup size and architecture, tail length and architecture, and counterion identity. Surprisingly, combining branched headgroups with bulky tails forces lipidoids to adopt unconventional pseudo-disc conformations that pack into double gyroid networks, entirely distinct from other synthetic or biological amphiphiles within bicontinuous cubic phases. From a multitude of possible applications, two examples of functional materials from lipidoid liquid crystals are demonstrated. First, the fabrication of gyroid nanostructured films by interfacial PrSA, which are rapidly responsive to the external medium. Second, it is shown that colloidally-dispersed lipidoid cubosomes, for example, for drug delivery, are easily assembled using top-down solvent evaporation methods.

Stimuli-Responsive Polymer Coatings for the Rapid and Tunable Contact Transfer of Plasmid DNA to Soft Surfaces.

We report the design and characterization of thin polymer-based coatings that promote the contact transfer of DNA to soft surfaces under mild and physiologically relevant conditions. Past studies reveal polymer multilayers fabricated using linear poly(ethylene imine) (LPEI), poly(acrylic acid) (PAA), and plasmid DNA promote contact transfer of DNA to vascular tissue. Here, we demonstrate that changes in the structure of the polyamine building blocks of these materials can have substantial impacts on rates and extents of contact transfer. We used two hydrogel-based substrate models that permit identification and manipulation of parameters that influence contact transfer. We used a planar gel model to characterize films having the structure (cationic polymer/PAA/cationic polymer/plasmid DNA)x fabricated using either LPEI or one of three poly(ß-amino ester)s as polyamine building blocks. The structure of the polyamine influenced subsequent contact transfer of DNA significantly; in general, films fabricated using more hydrophilic polymers promoted transfer more effectively. This planar model also permitted characterization of the stabilities of films transferred onto secondary surfaces, revealing rates of DNA release to be slower than rates of release prior to transfer. We also used a three-dimensional hole-based hydrogel model to evaluate contact transfer of DNA from the surfaces of inflatable catheter balloons used in vascular interventions and selected a rapid-transfer coating for proof-of-concept studies to characterize balloon-mediated contact transfer of DNA to peripheral arterial tissue in swine. Our results reveal robust and largely circumferential transfer of DNA to the luminal walls of peripheral arteries using inflation times as short as 15 to 30 s. The materials and approaches reported here provide new and useful tools for promoting rapid, substrate-mediated contact transfer of plasmid DNA to soft surfaces in vitro and in vivo that could prove useful in a range of fundamental and applied contexts.

Hydrocarbon-Based Statistical Copolymers Outperform Block Copolymers for Stabilization of Ethanol-Water Foams.

Well-defined block copolymers have been widely used as emulsifiers, stabilizers, and dispersants in the chemical industry for at least 50 years. In contrast, nature employs amphiphilic proteins as polymeric surfactants whereby the spatial distribution of hydrophilic and hydrophobic amino acids within the polypeptide chains is optimized for surface activity. Herein, we report that polydisperse statistical copolymers prepared by conventional free-radical copolymerization can provide superior foaming performance compared to the analogous diblock copolymers. A series of predominantly (meth)acrylic comonomers are screened to identify optimal surface activity for foam stabilization of aqueous ethanol solutions. In particular, all-acrylic statistical copolymers comprising trimethylhexyl acrylate and poly(ethylene glycol) acrylate, P(TMHA-stat-PEGA), confer strong foamability and also lower the surface tension of a range of ethanol-water mixtures to a greater extent than the analogous block copolymers. For ethanol-rich hand sanitizer formulations, foam stabilization is normally achieved using environmentally persistent silicone-based copolymers or fluorinated surfactants. Herein, the best-performing fully hydrocarbon-based copolymer surfactants effectively stabilize ethanol-rich foams by a mechanism that resembles that of naturally-occurring proteins. This ability to reduce the surface tension of low-surface-energy liquids suggests a wide range of potential commercial applications.

Molybdenum Disulfide-Based Nanomaterials for Visible-Light-Induced Photocatalysis.

Visible-light-responsive photocatalytic materials have a multitude of important applications, ranging from energy conversion and storage to industrial waste treatment. Molybdenum disulfide (MoS2) and its variants exhibit high photocatalytic activity under irradiation by visible light as well as good stability and recyclability, which are desirable for all photocatalytic applications. MoS2-based materials have been widely applied in various fields such as wastewater treatment, environmental remediation, and organic transformation reactions because of their excellent physicochemical properties. The present review focuses on the fundamental properties of MoS2, recent developments and remaining challenges, and key strategies for tackling issues related to the utilization of MoS2 in photocatalysis. The application of MoS2-based materials in visible-light-induced catalytic reactions for the treatment of diverse kinds of pollutants including industrial, environmental, pharmaceutical, and agricultural waste are also critically discussed. The review concludes by highlighting the prospects of MoS2 for use in various established and emerging areas of photocatalysis.

Graphite/Carbon Black Counter Electrode Deposition Methods to Improve the Efficiency and Stability of Hole-Transport-Layer-Free Perovskite Solar Cells.

The interfacial compatibility between the graphite/carbon black composite counter electrode (Gr/CB CE) and the perovskite layer is a crucial determinant of the performance of the hole-transport-layer-free carbon-based perovskite solar cells, and judicious selection of the Gr/CB CE application method is essential for achieving an optimum contact. In this work, three different types of Gr/CB CEs application methods are investigated: (1) deposition of Gr/CB on the fluorine-doped tin oxide (FTO) substrate, followed by clamping to the perovskite layer, (2) direct deposition of Gr/CB onto the perovskite layer, and (3) deposition of Gr/CB onto the PbI2 precursor layer, followed by immersion in methylammonium iodide solution for the in situ conversion of PbI2 to perovskite. The results revealed that Method 3 produced superior Gr/CB-perovskite contacts, resulting in up to 8.81% power conversion efficiency. The devices prepared using Method 3 also exhibited the best stability in the air, retaining 71.1% of their original efficiency after 1600 h of continuous testing. These results demonstrate that Gr/CB CEs can be considered excellent alternatives to the costly noble metals often employed in perovskite solar cells (PSCs) when deposited using a suitable technique.

Highly Stretchable Conductive Covalent Coacervate Gels for Electronic Skin.

Highly stretchable electrically conductive hydrogels have been extensively researched in recent years, especially for applications in strain and pressure sensing, electronic skin, and implantable bioelectronic devices. Herein, we present a new cross-linked complex coacervate approach to prepare conductive hydrogels that are both highly stretchable and compressive. The gels involve a complex coacervate between carboxylated nanogels and branched poly(ethylene imine), whereby the latter is covalently cross-linked by poly(ethylene glycol) diglycidyl ether (PEGDGE). Inclusion of graphene nanoplatelets (Gnp) provides electrical conductivity as well as tensile and compressive strain-sensing capability to the hydrogels. We demonstrate that judicious selection of the molecular weight of the PEGDGE cross-linker enables the mechanical properties of these hydrogels to be tuned. Indeed, the gels prepared with a PEGDGE molecular weight of 6000 g/mol defy the general rule that toughness decreases as strength increases. The conductive hydrogels achieve a compressive strength of 25 MPa and a stretchability of up to 1500%. These new gels are both adhesive and conformal. They provide a self-healable electronic circuit, respond rapidly to human motion, and can act as strain-dependent sensors while exhibiting low cytotoxicity. Our new approach to conductive gel preparation is efficient, involves only preformed components, and is scalable.

Shape-shifting thermoreversible diblock copolymer nano-objects via RAFT aqueous dispersion polymerization of 4-hydroxybutyl acrylate.

2-Hydroxypropyl methacrylate (HPMA) is a useful model monomer for understanding aqueous dispersion polymerization. 4-Hydroxybutyl acrylate (HBA) is an isomer of HPMA: it has appreciably higher aqueous solubility so its homopolymer is more weakly hydrophobic. Moreover, PHBA possesses a significantly lower glass transition temperature than PHPMA, which ensures greater chain mobility. The reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of HBA using a poly(ethylene glycol) (PEG113) precursor at 30 °C produces PEG113-PHBA200-700 diblock copolymer nano-objects. Using glutaraldehyde to crosslink the PHBA chains allows TEM studies, which reveal the formation of spheres, worms or vesicles under appropriate conditions. Interestingly, the partially hydrated highly mobile PHBA block enabled linear PEG113-PHBA x spheres, worms or vesicles to be reconstituted from freeze-dried powders on addition of water at 20 °C. Moreover, variable temperature 1H NMR studies indicated that the apparent degree of hydration of the PHBA block increases from 5% to 80% on heating from 0 °C to 60 °C indicating uniform plasticization. In contrast, the PHPMA x chains within PEG113-PHPMA x nano-objects become dehydrated on raising the temperature: this qualitative difference is highly counter-intuitive given that PHBA and PHPMA are isomers. The greater (partial) hydration of the PHBA block at higher temperature drives the morphological evolution of PEG113-PHBA260 spheres to form worms or vesicles, as judged by oscillatory rheology, dynamic light scattering, small-angle X-ray scattering and TEM studies. Finally, a variable temperature phase diagram is constructed for 15% w/w aqueous dispersions of eight PEG113-PHBA200-700 diblock copolymers. Notably, PEG113-PHBA350 can switch reversibly from spheres to worms to vesicles to lamellae during a thermal cycle.

Reduction in Schedule II opioid prescribing by primary care -providers, orthopedic and general surgeons, and pain -management specialists following the implementation of a State House Bill and an Institutional Controlled Substance Task Force.

OBJECTIVE: Prescription opioid misuse represents a social and economic challenge in the United States. We evaluated Schedule II opioid prescribing practices by primary care providers (PCPs), orthopedic and general surgeons, and pain management specialists. DESIGN: Prospective evaluation of prescribing practices of PCPs, orthopedic and general surgeons, and pain management specialists over 5 years (October 1, 2014-September 30, 2019) in an outpatient setting. METHODS: An analysis of Schedule II opioid prescribing following the implementation of federal and state guidelines and evidence-based standards at our institution. RESULTS: There were significantly more PCPs, orthopedic and general surgeons, and pain management specialists with a significantly increased number who prescribed Schedule II opioids, whereas there was a simultaneous significant decline in the average number of Schedule II opioid prescriptions per provider, Schedule II opioid pills prescribed per provider, and Schedule II opioid pills prescribed per patient by providers. The average number of Schedule II opioid prescriptions with a quantity >90 and Opana/Oxycontin prescriptions per PCP, orthopedic surgeon, and pain management specialist significantly decreased. The total morphine milligram equivalent (MME)/day of Schedule II opioids ordered by PCPs, orthopedic and general surgeons, and pain management specialists significantly declined. The ages of the providers remained consistent throughout the study. CONCLUSIONS: This study reports the implementation of federal and state regulations and institutional evidence-based guidelines into primary care and medical specialty practices to reduce the number of Schedule II opioids prescribed. Further research is warranted to determine alternative therapies to Schedule II opioids that may alleviate a patient's pain without initiating or exacerbating a potentially lethal opioid addiction.

Small-Angle X-Ray Scattering Studies of Block Copolymer Nano-Objects: Formation of Ordered Phases in Concentrated Solution During Polymerization-Induced Self-Assembly.

We report that polymerization-induced self-assembly (PISA) can be used to prepare lyotropic phases comprising diblock copolymer nano-objects in non-polar media. RAFT dispersion polymerization of benzyl methacrylate (BzMA) at 90 °C using a trithiocarbonate-capped hydrogenated polybutadiene (PhBD) steric stabilizer block in n-dodecane produces either spheres or worms that exhibit long-range order at 40 % w/w solids. NMR studies enable calculation of instantaneous copolymer compositions for each phase during the BzMA polymerization. As the PBzMA chains grow longer when targeting PhBD80 -PBzMA40 , time-resolved small-angle X-ray scattering reveals intermediate body-centered cubic (BCC) and hexagonally close-packed (HCP) sphere phases prior to formation of a final hexagonal cylinder phase (HEX). The HEX phase is lost on serial dilution and the aligned cylinders eventually form disordered flexible worms. The HEX phase undergoes an order-disorder transition on heating to 150 °C and a pure HCP phase forms on cooling to 20 °C.

Soft Materials that Intercept, Respond to, and Sequester Bacterial Siderophores.

We report the design and characterization of Fe-containing soft materials that respond to, interface with, and/or sequester Fe-chelating 'siderophores' that bacteria use to scavenge for iron and regulate iron homeostasis. We demonstrate that metal-organic network coatings fabricated by crosslinking tannic acid with iron(III) are stable in bacterial growth media, but erode upon exposure to biologically relevant concentrations of enterobactin and deferoxamine B, two siderophores produced by Gram-negative and Gram-positive bacteria, respectively. Our results are consistent with changes in network stability triggered by the extraction of iron(III) and reveal rates of siderophore-induced disassembly to depend upon both siderophore concentration and affinity for iron(III). These coatings also disassemble when incubated in the presence of cultures of wild-type Escherichia coli. Assays using genetically modified strains of E. coli reveal the erosion of these materials by live cultures to be promoted by secretion of enterobactin and not from other factors resulting from bacterial growth and metabolism. This stimuli-responsive behavior can also be exploited to design coatings that release the Fe-chelating antibiotic ciprofloxacin into bacterial cultures. Finally, we report the discovery of Fe-containing polymer hydrogels that avidly sequester and scavenge enterobactin from surrounding media. The materials reported here are (i) capable of interfacing or interfering with mechanisms that bacteria use to maintain iron homeostasis, either by yielding iron to or by sequestering iron-scavenging agents from bacteria, and can (ii) respond dynamically to or report on the presence of populations of iron-scavenging bacteria. Our results thus provide new tools that could prove useful for microbiological research and enable new stimuli-responsive strategies for interfacing with or controlling the behaviors of communities of iron-scavenging bacteria.

Multidisciplinary approach to enhancing provider well-being in a metropolitan medical group in the United States.

BACKGROUND: Physician burnout refers to depersonalization, emotional exhaustion, and a sense of lower personal accomplishment. Affecting approximately 50% of physicians in the United States, physician burnout negatively impacts both the physician and patient. Over a 3-year-period, this prospective study evaluated the multidisciplinary approach to decreasing provider burnout and improving provider well-being in our metropolitan community. METHODS: A multidisciplinary Well-Being Task Force was established at our Institution in 2017 to assess the myriad factors that may play a role in provider burnout and offer solutions to mitigate the stressors that may lead to decreased provider well-being. Four multifaceted strategies were implemented: (1) provider engagement & growth; (2) workflow/office efficiencies; (3) relationship building; and (4) communication. Providers at our Institution took the Mayo Clinic's well-being index survey on 3 occasions over 3 years. Their scores were compared to those of providers nationally at baseline and at 1 and 2 years after implementing organizational and individualized techniques to enhance provider well-being. Lower well-being index scores reflected better well-being. RESULTS: The average overall well-being index scores of our Institution's providers decreased from 1.76 at baseline to 1.32 2 years later compared to an increase in well-being index scores of physicians nationally (1.73 to 1.85). Both male and female providers' average well-being index scores at our Institution decreased over the 3 years of this study, from 1.72 to 1.58 for males and 1.78 to 1.21 for females, while physicians' scores nationally increased for both genders. The average well-being index scores were highest for providers at our Institution who graduated from medical school less than 5 years earlier (2.0) and who graduated 15-24 years earlier (2.3), whereas the average lowest scores were observed in providers who graduated ≥25 years earlier (1.37). Obstetricians/gynecologists and internal medicine physicians had the highest average well-being index scores (2.48 and 2.4, respectively) compared to other medical specialties. The turnover rate of our Institution's providers was 5.6% in 2017 and 3.9% in 2019, reflecting a 30% decrease. CONCLUSION: This study serves as a model to reduce provider burnout and enhance well-being through both organizational and individual interventions.

Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids.

We report the aqueous lyotropic mesophase behaviors of protonated amine-based "lipidoids," a class of synthetic lipid-like molecules that mirrors essential structural features of the multitail bacterial amphiphile lipid A. Small-angle X-ray scattering (SAXS) studies demonstrate that the protonation of the tetra(amine) headgroups of six-tail lipidoids in aqueous HCl, HNO3, H2SO4, and H3PO4 solutions variably drives their self-assembly into lamellar (Lα) and inverse micellar (III) lyotropic liquid crystals (LLCs), depending on acid identity and concentration, amphiphile tail length, and temperature. Lipidoid assemblies formed in H2SO4(aq) exhibit rare inverse body-centered cubic (BCC) and inverse face-centered cubic (FCC) micellar morphologies, the latter of which unexpectedly coexists with zero mean curvature Lα phases. Complementary atomistic molecular dynamics (MD) simulations furnish detailed insights into this unusual self-assembly behavior. The unique aqueous lyotropic mesophase behaviors of ammonium lipidoids originate in their dichotomous ability to adopt both inverse conical and chain-extended molecular conformations depending on the number of counterions and their identity, which lead to coexisting supramolecular assemblies with remarkably different mean interfacial curvatures.

Synthesis of High χ-Low N Diblock Copolymers by Polymerization-Induced Self-Assembly.

Polymerization-induced self-assembly (PISA) enables the scalable synthesis of functional block copolymer nanoparticles with various morphologies. Herein we exploit this versatile technique to produce so-called "high χ-low N" diblock copolymers that undergo nanoscale phase separation in the solid state to produce sub-10 nm surface features. By varying the degree of polymerization of the stabilizer and core-forming blocks, PISA provides rapid access to a wide range of diblock copolymers, and enables fundamental thermodynamic parameters to be determined. In addition, the pre-organization of copolymer chains within sterically-stabilized nanoparticles that occurs during PISA leads to enhanced phase separation relative to that achieved using solution-cast molecularly-dissolved copolymer chains.