Metal/Ion Interactions Induced p-i-n Junction in Methylammonium Lead Triiodide Perovskite Single Crystals.

Hybrid perovskites, as emerging multifunctional semiconductors, have demonstrated dual electronic/ionic conduction properties. We report a metal/ion interaction induced p-i-n junction across slightly n-type doped MAPbI3 single crystals with Au/MAPbI3/Ag configuration based on interface dependent Seebeck effect, Hall effect and time-of-flight secondary ion mass spectrometry analysis. The organic cations (MA+) interact with Au atoms, forming positively charged coordination complexes at Au/MAPbI3 interface, whereas iodine anions (I-) can react with Ag contacts, leading to interfacial ionic polarization. Such metal/ion interactions establish a p-doped region near the Au/MAPbI3 interface due to the formation of MA+ vacancies, and an n-doped region near the Ag/MAPbI3 interface due to formation of I- vacancies, consequently forming a p-i-n junction across the crystal in Au/MAPbI3/Ag configuration. Therefore, the metal/ion interaction plays a role in determining the surface electronic structure and semiconducting properties of hybrid perovskites.

Development of a Novel Leak-Free Constant-Pressure Cylinder for Certified Reference Materials of Liquid Hydrocarbon Mixtures.

Liquid hydrocarbon mixtures such as liquefied petroleum gas and liquefied natural gas are becoming integral parts of the world's energy system. Certified reference materials (CRMs) of liquid hydrocarbon mixtures are necessary to allow assessment of the accuracy and traceability of the compositions of such materials. A piston-type constant-pressure cylinder (PCPC) comprising chambers for a pressurizing gas (helium) and liquid (hydrocarbons) separated by a piston can be used to develop accurate and traceable liquid hydrocarbon mixture CRMs. The development of accurate CRMs relies on the maintenance of their composition. However, a PCPC might allow hydrocarbons to leak owing to the imperfect seal of the piston. In this study, a novel leak-free bellows-type constant-pressure cylinder (BCPC) is designed and evaluated by comparison with PCPCs. Liquid hydrocarbon mixtures consisting of ethane, propane, propene, isobutane, n-butane, 1-butene, and isopentane were prepared in both types of constant pressure cylinders and then monitored to check leakages between the gas and liquid chambers. Overall, notable leakage occurred from and into both chambers in the PCPCs, whereas no leakage occurred in the BCPCs in the three months after their gravimetric preparation. The BCPCs maintained no leakage even 10 months after their preparation, whereas the PCPCs showed significantly increasing leakage during the same period.

Improving mechanical properties of carbon nanotube fibers through simultaneous solid-state cycloaddition and crosslinking.

Individual carbon nanotubes (CNTs) exhibit exceptional mechanical properties. However, difficulties remain in fully realizing these properties in CNT macro-assemblies, because the weak inter-tube forces result in the CNTs sliding past one another. Herein, a simple solid-state reaction is presented that enhances the mechanical properties of carbon nanotube fibers (CNTFs) through simultaneous covalent functionalization and crosslinking. This is the first chemical crosslinking proposed without the involvement of a catalyst or byproducts. The specific tensile strength of CNTFs obtained from the treatment employing a benzocyclobutene-based polymer is improved by 40%. Such improvement can be attributed to a reduced number of voids, impregnation of the polymer, and the formation of covalent crosslinks. This methodology is confirmed using both multiwalled nanotube (MWNT) powders and CNTFs. Thermogravimetric analysis, differential scanning calorimetry, x-ray photoelectron spectroscopy, and transmission electron microscopy of the treated MWNT powders confirm the covalent functionalization and formation of inter-tube crosslinks. This simple one-step reaction can be applied to industrial-scale production of high-strength CNTFs.

CO2 Outgassing from an Urbanized River System Fueled by Wastewater Treatment Plant Effluents.

Continuous underway measurements were combined with a basin-scale survey to examine human impacts on CO2 outgassing in a highly urbanized river system in Korea. While the partial pressure of CO2 (pCO2) was measured at 15 sites using syringe equilibration, 3 cruises employing an equilibrator were done along a 30 km transect in the Seoul metropolitan area. The basin-scale survey revealed longitudinal increases in surface water pCO2 and dissolved organic carbon (DOC) in the downstream reach. Downstream increases in pCO2, DOC, fluorescence index, and inorganic N and P reflected disproportionately large contributions from wastewater treatment plant (WWTP) effluents carried by major urban tributaries. Cruise transects exhibited strong localized peaks of pCO2 up to 13 000 µatm and 13CO2 enrichment along the confluences of tributaries at an average flow, whereas CO2 pulses were dampened by increased flow during the monsoon period. Fluctuations in pCO2 along the eutrophic reach downstream of the confluences reflected environmental controls on the balance between photosynthesis, biodegradation, and outgassing. The results underscore WWTP effluents as an anthropogenic source of nutrients, DOC, and CO2 and their influences on algal blooms and associated C dynamics in eutrophic urbanized river systems, warranting further research on urbanization-induced perturbations to riverine metabolic processes and carbon fluxes.

Unexpected Molecular Weight Effect in Polymer Nanocomposites.

The properties of the interfacial layer between the polymer matrix and nanoparticles largely determine the macroscopic properties of polymer nanocomposites (PNCs). Although the static thickness of the interfacial layer was found to increase with the molecular weight (MW), the influence of MW on segmental relaxation and the glass transition in this layer remains to be explored. In this Letter, we show an unexpected MW dependence of the interfacial properties in PNC with attractive polymer-nanoparticle interactions: the thickness of the interfacial layer with hindered segmental relaxation decreases as MW increases, in sharp contrast to theoretical predictions. Further analyses reveal a reduction in mass density of the interfacial layer with increasing MW, which can elucidate these unexpected dynamic effects. Our observations call for a significant revision of the current understandings of PNCs and suggest interesting ways to tailor their properties.

Synthesis and photoluminescent properties of geometrically hindered cis-tris(diphenylaminofluorene) as precursors to light-emitting devices.

A novel highly luminescent tris-fluorenyl ring-interconnected chromophore tris(DPAF-C9) was synthesized using a C3 symmetrical triaminobenzene core as the synthon. This structure bears three light-harvesting 2-diphenylamino-9,9-dialkylfluorenyl (DPAF) ring moieties with each attached by two branched 3',5',5'-trimethylhexyl (C9) arms. A major stereoisomer was chromatographically isolated and characterized to possess a 3D structural configuration of cis-conformer in a cup-form. Molecular calculation at B3LYP/6-31G* level revealed the unexpected stability of this cis-cup-conformer of tris(DPAF-C9) better than that of the stereoisomer in a propeller-form and the trans-conformer. The structural geometry is proposed to be capable of minimizing the aggregation related self-quenching effect in the condensed phase. Fluorescence emission wavelength of tris(DPAF-C9) was found to be in a close range to that of PVK that led to its potential uses as the secondary blue hole-transporting material for enhancing the device property toward the modulation of PLED performance.

Net global warming potential index rather than soil carbon stock change could provide better understanding of the carbon balance in soil systems.

This study was conducted to determine the soil organic carbon (SOC) stock change factor for green manure crops that was developed by the Intergovernmental Panel on Climate Change (IPCC) Tier 2 method and compare this with the net global warming potential (GWP) index that is used to evaluate the contribution of green manuring to global warming. Four treatments were barley (Hordeum vulgare L.; B), hairy vetch (Vicia villosa R.; HV), a barley/hairy vetch mixture (BHV) and a conventional treatment (C). The aboveground biomass of green manure crops was incorporated into the soil on 25 May 2018, 26 April 2019, 29 April 2020, 30 April 2021 and 2 May 2022. Maize (Zea mays L.) was transplanted as the subsequent crop after the incorporation of green manures. SOC stock decreased with green manures, even though carbon input with green manures, including B, HV and BHV, was greater than that with C. The mean value of the SOC stock change factor for green manure crops, including B, HV and BHV was 0.627 and was significantly lower than that of the C. However, the net GWP also decreased with the incorporation of green manure crops, and the mean value of the relative net GWP index across B, HV and BHV was 0.853. These conflicting results were caused by different estimation methods between annual SOC change (△SOC) and net GWP. The estimation of SOC stock change using △SOC suggested by the IPCC method may overestimate the contribution of green manure crops to global warming. The net GWP method with comprehensive input and output of carbon in the soil system could provide a better understanding of the carbon balance in soil systems. In the current study, the comparison of △SOC and net GWP was conducted for at one site of upland soil for 5 years. Therefore, further research on estimating the effect of green manure crops on net GWP in various types of soil for longer years should be conducted.

Obesity and inflammation influence pharmacokinetic profiles of PEG-based nanoparticles.

Most patients that will be treated with soft nanoparticles (NPs) will be obese. Yet, NP testing, which begins with pharmacokinetic (PK) and toxicity studies, is carried out almost exclusively in lean rodents having healthy livers and low inflammation. To address this knowledge gap, we determined the PK and toxicity of tail-vein-injected, PEG-based cylindrical nanoparticles (CNPs) and PEGylated liposomes (PLs) as a function of obesity, liver health, and inflammation in leptin-deficient ob/ob and wild-type C57BL/6 J mice. CNPs localized faster to obese livers than to healthy livers within 24 h of injection. PLs localized faster to obese livers than to healthy livers but only 30 min post-injection. Afterwards PL localization to lean livers was higher than localization to obese livers. Overall, PL liver signal peaked ∼6 h post-injection in lean mice, ∼24 h post-injection in heavy mice, and âˆ¼ 48 h post-injection in obese mice. CNPs and PLs were non-toxic to mouse livers as assessed by histology; they reduced many cytokine and chemokine levels that were elevated by obesity. Liver macrophage depletion reduced CNP and PL liver localization as expected; liver sinusoidal endothelial cell (LSEC) depletion reduced PL liver localization but surprisingly increased CNP liver localization. The intensity of RAW264.7 macrophages was higher after CNP incubations than with PL incubations; conversely, the intensity of LSECs was higher after PL incubations than with CNP incubations. This shows the potential for key differences in NP-liver interactions. Triggering inflammation by administering lipopolysaccharide (LPS) to mice increased CNP liver localization but decreased PL liver localization. The results show that obesity and inflammation in a mouse model and in vitro affect soft PEG-based NP interaction with macrophages and LSECs, but also that these NPs can reduce pro-inflammatory pathways increased by obesity.

Uni-molecular hollow micelles from amphiphilic homopolymer poly(2-(4-vinylphenyl)pyridine).

Amphiphilic homopolymer poly(2-(4-vinylphenyl)pyridine) (PVPPy) forms hollow micelles with uni-molecular thickness in a tetrahydrofuran/water (95/5 v/v) azeotropic solvent. Depending on the pH of the media, the micelles may be transformed to vesicles.

Elongated PEO-based nanoparticles bind the high-density lipoprotein (HDL) receptor scavenger receptor class B I (SR-BI).

Targeting cell-surface receptors with nanoparticles (NPs) is a crucial aspect of nanomedicine. Here, we show that soft, flexible, elongated NPs with poly-ethylene-oxide (PEO) exteriors and poly-butadiene (PBD) interiors - PEO-PBD filomicelles - interact directly with the major high-density lipoprotein (HDL) receptor and SARS-CoV-2 uptake factor, SR-BI. Filomicelles have a ~ 6-fold stronger interaction with reconstituted SR-BI than PEO-PBD spheres. HDL, and the lipid transport inhibitor, BLT-1, both block the uptake of filomicelles by macrophages and Idla7 cells, the latter are constitutively expressing SR-BI (Idla7-SR-BI). Co-injections of HDL and filomicelles into wild-type mice reduced filomicelle signal in the liver and increased filomicelle plasma levels. The same was true with SCARB1-/- mice. SR-BI binding is followed by phagocytosis for filomicelle macrophage entry, but only SR-BI is needed for entry into Idla7-SR-BI cells. PEO-PBD spheres did not interact strongly with SR-BI in the above experiments. The results show elongated PEO-based NPs can bind cells via cooperativity among SR-BI receptors on cell surfaces.

Nitrous oxide emission and sweet potato yield in upland soil: Effects of different type and application rate of composted animal manures.

The aims of this study were to determine type and application rate of composted animal manure to optimize sweet potato yield relative to N2O emissions from upland soils. To this end, the study was conducted on upland soils amended with different types and rates of composted animal manure and located at two geographically different regions of South Korea. Field trials were established at Miryang and Yesan in South Korea during the sweet potato (Ipomoea batatas) growing season over 2 years: 2017 (Year 1) and 2018 (Year 2). Three composted animal manures (chicken, cow, and pig) were applied at the rates of 0, 10, and 20 Mg ha-1 to upland soils in both locations. In both Years and locations, manure type did not affected significantly cumulative N2O emissions from soil during the sweet potato growing season or the belowground biomass of sweet potato. However, application rate of animal manures affected significantly the cumulative N2O emission, nitrogen (N) in soil, and belowground biomass of sweet potato. An increase in cumulative N2O emission with application rates of animal manures was related to total N and inorganic N concentration in soil. The belowground biomass yield of sweet potato but also the cumulative N2O emission increased with increasing application rate of composted animal manures up to 7.6 and 16.0 Mg ha-1 in Miryang and Yesan, respectively. To reduce N2O emission from arable soil while increasing crop yield, composted animal manures should be applied at less than application rate that produce the maximum belowground biomass of sweet potato.

Effect of solvent composition on transformation of micelles to vesicles of rod-coil poly(n-hexyl isocyanate-block-2-vinylpyridine) diblock copolymers.

The self-aggregation behavior of an amphiphilic rod-coil block copolymer of poly(n-hexyl isocyanate-block-2-vinylpyridine) (PHIC(189)-b-P2VP(228)) (f(P2VP) = 0.78, M(n) = 24.5K) in a tetrahydrofuran (THF)/water system was examined using dynamic light scattering (DLS), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). The presence of a certain amount of water in the THF-based polymer solution induced a morphological transition from spherical solid micelles to open mouth platelike vesicles. The size of the aggregates increased with an increase in water content in the mixed solvent of THF/water. In the range of 30-40% water, the polymer formed vesicles with an interdigitated architecture of poly(n-hexyl isocyanate) (PHIC) at the center of the membrane and with the poly(2-vinylpyridine) (P2VP) block forming the outer layers and pointing toward the solvent. However, at higher water contents, the thickness of the bilayer increased due to the rearrangement of the vesicle membrane from a flip-flop to a lamellar architecture. After the degradation of the PHIC from the vesicles at basic pH, hollow spherical aggregates remained stable. After removing the THF from the mixed solvent using dialysis, large-sized compound vesicles were formed.

The fabrication of nanopatterns with Au nanoparticles-embedded micelles via nanoimprint lithography.

We fabricated nanopatterns with Au nanoparticles-embedded micelles (Au-micelles) by self-assembly of block copolymers via nanoimprint lithography. The micelle structure prepared by self-assembled block copolymers was used as a template for the synthesis of Au nanoparticles (Au NPs). Au NPs were synthesized in situ inside the micelles of polystyrene-block-poly(2-vinylpyridine) (PS- b-P2VP). Au-micelles were arranged on the trenches of the polymer template, which was imprinted by nanoimprint lithography. The fabrication of line-type and dot-type nanopatterns was carried out by the combined method. In addition, multilayer nanopatterns of the Au-micelles were also proposed.

Different elution modes and field programming in gravitational field-flow fractionation. Effect of channel angle.

Gravitational field-flow fractionation (GrFFF) has been shown to be useful for separation and characterization of various types of micrometer-sized particles. It has been recognized however that GrFFF is less versatile than other members of FFF because the external field (Earth's gravity) in GrFFF is relatively weak and is not tunable (constant), which makes the force acting on the particles constant. A few approaches have been suggested to control the force acting on particles in GrFFF. They include (1) changing the angle between the Earth's gravitational field and the longitudinal axis of the channel, and (2) the use of carrier liquid having different densities. In the hyperlayer mode of GrFFF, the hydrodynamic lift force (HLF) also act on particles. The existence of HLF allows other means of changing the force acting on the particles in GrFFF. They include (1) the flow rate programming, or (2) the use of channels having non-constant cross-section. In this study, with polystyrene latex beads used as model particles, the channel angle was varied to study its effect on elution parameters (such as selectivity, band broadening and resolution) in the steric or in the hyperlayer mode of GrFFF. In addition, the effects of the channel thickness and the flow rate on the elution parameters were also investigated. It was found that, in the steric mode, the resolution decreases as the flow rate increases due to increased zone broadening despite of the increase in the selectivity. At a constant volumetric flow rate, both the zone broadening and the selectivity increase as the channel thickness increases, resulting in the net increase in the resolution. It was also found that the retention time decreases as the channel angle increases in both up- and down-flow positions. The zone broadening tends to increase almost linearly with the channel angle, while no particular trends were found in selectivity. As a result, the resolution decreases as the channel angle increases.

Perchlorate production by ozone oxidation of chloride in aqueous and dry systems.

Overwhelming evidence now exists that perchlorate is produced through natural processes and can be ubiquitously found at environmentally relevant concentrations in arid and semi-arid locations. A number of potential production mechanisms have been hypothesized and ClO(4)(-) production by ozone oxidation of surface bound Cl(-) was demonstrated. However, no information concerning the impact of concentration, final reaction products distribution, impact of reaction phase, or oxidation of important oxychlorine intermediates has been reported. Using IC-MS-MS analysis and replicate oxidation experiments, we show that exposing aqueous solutions or Cl(-) coated sand or glass surfaces to O(3) (0.96%) generated ClO(4)(-) with molar yields of 0.007 and 0.01% for aqueous Cl(-) solutions and 0.025 and 0.42% for Cl(-) coated sand and glass, respectively. Aqueous solutions of Cl(-) produced less ClO(4)(-) than Cl(-) coated sand or glass as well as a higher ratio of ClO(3)(-) to ClO(4)(-). Reduction of the initial Cl(-) mass resulted in substantially higher molar yields of ClO(4)(-) and ClO(3)(-). In addition, alkaline absorbers that captured gaseous products contained substantial quantities of Cl(-), ClO(3)(-), and ClO(4)(-). Solutions of possible oxychlorine intermediates (OCl(-) and ClO(3)(-)) exposed to O(3) produced only scant amounts of ClO(4)(-) while a ClO(2)(-) solution exposed to O(3) produced substantial molar yields of ClO(4)(-) (4% molar yield). Scanning electron microscopy coupled with energy energy-dispersive X-ray analysis demonstrated a significant loss of Cl(-) and an increase in oxygen on the Cl(-) coated silica sand exposed to O(3). While the experimental conditions are not reflective of natural conditions this work clearly demonstrates the relative potential of Cl(-) precursors in perchlorate production and the likely importance of dry aerosol oxidation over solution phase reactions. It also suggests that ClO(2)(-) may be a key intermediate while ClO(3)(-) and OCl(-) are unlikely to play a significant role.

Single-step process to improve the mechanical properties of carbon nanotube yarn.

Carbon nanotube (CNT) yarns exhibit low tensile strength compared to conventional high-performance carbon fibers due to the facile sliding of CNTs past one another. Electron beam (e-beam) irradiation was employed for in a single-step surface modification of CNTs to improve the mechanical properties of this material. To this end, CNT yarns were simultaneously functionalized and crosslinked using acrylic acid (AA) and acrylonitrile (AN) in an e-beam irradiation process. The chemical modification of CNT yarns was confirmed by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and scanning electron microscopy (SEM). The best improvement in mechanical properties was achieved on a sample treated with an aqueous solution of AA and subsequent irradiation. CNT yarn treatment with AA enhanced the strength (444.5 ± 68.4 MPa) by more than 75% and the modulus (21.5 ± 0.6 GPa) by more than 144% as compared to untreated CNT yarn (strength 251 ± 26.5 MPa and modulus 8.8 ± 1.2 GPa).

Characteristics in oxidative degradation by ozone for saturated hydrocarbons in soil contaminated with diesel fuel.

Although alkanes are relatively less reactive to chemical oxidation compared to alkenes, the chemical oxidation of alkanes has not been adequately explored in the context of environmental remediation efforts. Laboratory-scale column experiments were therefore conducted with soil artificially contaminated by diesel fuel as a surrogate for alkanes of environmental relevance. Particular attention was paid to saturated hydrocarbons refractory to volatilization. Reaction conditions involve 1485mgkg(-1) of the initial concentration of diesel range organics (DRO) and a constant ozone concentration of 119+/-6mgl(-1) at the flow rate of 50mlmin(-1). The observed removal of DRO reached 94% over 14h of continuous ozone injection. Ozone oxidation demonstrated effective removal of non-volatile DRO in the range of C(12)-C(24). Each alkane compound displayed comparable degradation kinetics, suggesting virtually no selectivity of ozone reactions with alkanes in soil. A pseudo-first order kinetic model closely simulated the removal kinetics, yielding a reaction rate constant of 0.213 (+/-0.021)h(-1) and a half-life of 3.3 (+/-0.3)h under the experimental conditions used in this study. An estimate of ozone demand was 32mg of O(3) (mgDRO)(-1).

Block Copolymers: Synthesis, Self-Assembly, and Applications.

Research on block copolymers (BCPs) has played a critical role in the development of polymer chemistry, with numerous pivotal contributions that have advanced our ability to prepare, characterize, theoretically model, and technologically exploit this class of materials in a myriad of ways in the fields of chemistry, physics, material sciences, and biological and medical sciences. The breathtaking progress has been driven by the advancement in experimental techniques enabling the synthesis and characterization of a wide range of block copolymers with tailored composition, architectures, and properties. In this review, we briefly discussed the recent progress in BCP synthesis, followed by a discussion of the fundamentals of self-assembly of BCPs along with their applications.

Enhanced Fenton's destruction of non-aqueous phase perchloroethylene in soil systems.

The Fenton's system is applied to the destruction of perchloroethylene (PCE) present as a dense non-aqueous phase liquid (DNAPL) in soil slurry systems; the initial concentration of PCE was 45 times higher than its aqueous solubility. Studies were conducted in two matrices: Ottawa sand and soil from Warsaw, IN. In Ottawa sand, a 60-62% decrease in PCE concentration was observed, and Cl(-) recovery was 47-58%, whereas in Warsaw soil, a 44-49% decrease in PCE concentration and a Cl(-) recovery of 40-42% were observed after the addition of 600 mM H(2)O(2) and 10 mM dissolved iron. Significantly enhanced destruction resulted during application of N-(2-hydroxyethyl) iminodiacetic acid (HEIDA) to Warsaw soil. For example, in the absence of HEIDA in Warsaw soil, 36% PCE loss and 33% Cl(-) release were observed at 600 mM H(2)O(2) and 5 mM Fe(III), while 74% PCE loss and 63% Cl(-) release were achieved at 600 mM H(2)O(2) and 5 mM Fe(III)-HEIDA. For both soils, the catalytic activities of Fe(II) and Fe(III) were nearly equivalent. These findings clearly demonstrate that system design can be optimized with regard to process variables in Fenton's treatment of DNAPL in soils.