Polymers based on thieno[3,4-c]pyrrole-4,6-dione and pyromellitic diimide by CH-CH arylation reaction for high-performance thin-film transistors.

Three homopolymers were successfully synthesized by direct CH-CH arylation polymerization of thieno[3,4-c]pyrrole-4,6-dione or pyromellitic diimide derivatives affording highly purified polymers with high molecular weights (43.0-174.7 K). Thieno[3,4-c]pyrrole-4,6-dione and pyromellitic diimide derivatives are considered as electron-withdrawing units. The synthesized homopolymers P1, P2, and P3 showed band gaps in the range of 2.13-2.08 eV, respectively. The electron mobilities of the three homopolymers have been investigated. The thin film transistor for P1 prepared by the eutectic-melt-assisted nanoimprinting method achieved an electron mobility of 2.11 × 10-3 cm2 s-1 V-1. Based on the obtained results, the synthesized polymers can be used as potential electron acceptors in solar cell applications.

Synthesis of Alternating Polyisocyanate Copolymers by Anionic Polymerization for Mimicking Amphiphilic Helical Peptides.

The amphiphilic conformation of α-helical peptides has important biological functions, such as ion transport, antifreeze, and innate immunity, which can be mimicked by alternating polyisocyanate copolymers. We synthesized poly(allyl isocyanate-alt-(S)-(-)-α-methylbenzyl isocyanate (P(AIC-alt-SMBIC)) and ammonium-containing P(AIC-alt-SMBIC) (N-P(AIC-alt-SMBIC)), ensuring the amphiphilic helical conformation. The benzyl group of SMBIC plays an important role in alternating copolymerization with its steric and electron-withdrawing effects, while AIC provides an alkene group capable of introducing a customized functional group. The P(AIC-alt-SMBIC) with predominantly alternating sequence was acquired at fSMBIC /fAIC =8 with a controlled molecular weight and narrow dispersity. N-P(AIC-alt-SMBIC)s were synthesized from thiol-ene radical addition with P(AIC-alt-SMBIC).

Intermolecular interactions of an isoindigo-based organic semiconductor with various crosslinkers through hydrogen bonding.

Three crosslinkers (1,4-diaminobutane, 1,8-diaminooctane, and 1,6-hexanediol) were selected to produce hydrogen-bonded networks using a simple and effective method. The effects of these crosslinkers on the arrangement of crystalline structures were successfully studied using X-ray diffraction and high-voltage electron microscopy. The hydrogen-bonded isoindigo-based small molecules with 1,4-diaminobutane showed the best performance, with a crystal structure showing long-range order, due to the more suitable length of the 1,4-diaminobutane chain. The hole mobility estimated from hole-only devices based on isoindigo was enhanced from 1.24 × 10-6 cm2 V-1 s-1 to 7.28 × 10-4 cm2 V-1 s-1 as a result of the inclusion of this crosslinker, due to the formation of stronger interactions between the molecules.

Self-assembly of POSS-Polystyrene Bottlebrush Block Copolymers on an Angle-Robust Selective Absorber for Enhancing the Purity of Reflective Structural Color.

A facile approach for improving color purity is explored by the introduction of an angle-robust selective absorber (ARSA) into bottlebrush block copolymer (BBCP)-based one-dimensional (1D) photonic crystals (PCs). The BBCPs of poly[(3-(12-(cis-5-norbornene-exo-2,3-dicarboximido)dodecanoylamino)propyl POSS)-block-(norbornene-graft-styrene)], Px (x = 1-4), with ultrahigh molecular weights (Mn ∼ 2260 kDa) and low dispersities (D̵ ∼ 1.07) are synthesized by ring-opening metathesis polymerization. The 1D PCs of the lamellar structure are fabricated by self-assembly of the BBCP with different periodicities for full color-generation (blue, green, and red). The optically tailored substrate (i.e., ARSA) is used to modulate the spectral line shape with selective absorption in the near-infrared range. Optical simulation proposes the optimized 1D PC structures on the ARSA, and it provides the reproducibility of the predictable color. The simulated structures are well matched with the experimental results, verifying the enhancement of color saturation even at various incident angles (0-70°).

Synthesis and photophysical properties of N-alkyl dithieno[3,2-b:2',3'-d]pyrrole based donor/acceptor-π-conjugated copolymers for solar-cell application.

Two kinds of donor-acceptor π-conjugated copolymer based on poly{[N-hexyl-dithieno(3,2-b:2',3'-d)pyrrole-2,6-diyl]alt-[isoindigo]} (PDTP-IID) and poly{[N-hexyl-dithieno(3,2-b:2',3'-d)pyrrole-2,6-diyl]alt-[thiazol-2,5-diyl]} (PDTP-Thz) were investigated. These copolymers were synthesized via a Stille coupling reaction. The results showed the structure-property relationships of different donor-acceptor (D-A) combinations. The polymer structures and photophysical properties were characterized by 1H NMR, TGA, DSC, UV-vis absorption spectroscopy, AFM, CV, and XRD measurement. Through UV-vis absorption and cyclic voltammetry (CV) measurements, it showed that the copolymers exhibit not only a low bandgap of 1.29 eV and 1.51 eV but also a deep highest occupied molecular orbital (HOMO) of -5.49 and -5.11 eV. Moreover, photovoltaic properties in combination with the fullerene derivatives were investigated. The device based on the copolymers with PC71BM exhibited higher maximum power conversion efficiency and higher maximum short-circuit current density of 0.23% with 1.64 mA cm-2 of PDTP-IID:PC71BM and 0.13% with 1.11 mA cm-2 of PDTP-Thz:PC71BM than those of the copolymers with PC61BM. Measurements performed for N-hexyl-dithieno(3,2-b:2',3'-d)pyrrole-based copolymers proved the potential of these polymers to be applied in optoelectronic applications.

Clathrate Hydrate Inhibition by Polyisocyanate with Diethylammonium Group.

Polymers containing amide groups have been used as kinetic hydrate inhibitors (KHIs). The amide group has good performance for hydrate nucleus adsorption, resulting in inhibition of hydrate growth. Polyisocyanates composed of an amide backbone can be KHI candidates; however, the use of polyisocyanates as KHIs has not yet been reported. Herein, we prepared water-soluble poly[3-[[2-(diethylamino)ethyl]thio]-1-propyl isocyanate-ran-hexyl isocyanate] (P(DETPIC-ran-HIC)) to investigate the ability of polyisocyanates to inhibit hydrate formation. In the tetrahydrofuran (THF) clathrate hydrate crystal growth inhibition tests, P(DETPIC-ran-HIC) showed better performance than the polyamide, poly(N-vinylpyrrolidone) (PVP).

Preparation of a polymer nanocomposite via the polymerization of pyrrole : biphenyldisulfonic acid : pyrrole as a two-monomer-connected precursor on MoS2 for electrochemical energy storage.

We prepared a poly(pyrrole : biphenyldisulfonic acid : pyrrole (Py:BPDSA:Py)) nanocomposite of molybdenum disulfide (MoS2), P(Py:BPDSA:Py)-MoS2, with high crystallinity. The composite is synthesized by oxidative polymerization of Py:BPDSA:Py as a two-monomer-connected precursor (TMCP) linked by ionic bonding on a molybdenum disulfide (MoS2) monolayer. The chemical, structural and morphological characterization of this composite is confirmed by Raman spectroscopy, FT-IR, X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (EELS), and scanning electron microscopy (SEM). The crystal structure is analysed by X-ray diffraction (XRD) and high-voltage electron microscopy (HVEM), which shows a face-centered cubic (FCC) crystal structure for the composite. Nitrogen adsorption-desorption isotherms show an improved specific surface area (91.3 m2 g-1). The electrochemical properties of the composite with a unique crystal structure and a large specific surface area are analysed through cyclic voltammetry (CV), which shows a specific capacitance of 681 F g-1 demonstrating that the composite can be used as an efficient electrode active material for electrochemical energy storage systems.

Impact of N-Substituent and pKa of Azole Rings on Fuel Cell Performance and Phosphoric Acid Loss.

The influence of N-substituent and pKa of azole rings has been investigated for the performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Imidazole, benzimidazole, and triazole groups were functionalized on the side chains of poly(phenylene oxide), respectively. Each azole group is categorized by their N-substituent into two types: unsubstituted and methyl-substituted azoles. The membranes with methyl-substituted azoles showed higher phosphoric acid (PA) doping levels with an average increase of 20% compared to those with unsubstituted azoles in the full-doped states. However, unsubstituted azoles more effectively improved the proton conductivity and the membrane with unsubstituted imidazole (IMPPO-H) showed a high anhydrous proton conductivity of 153 mS/cm at 150 °C. In contrast, the membranes with methyl-substituted azoles showed a higher PA retention with an average increase of 81% compared to those with unsubstituted azoles. The higher PA retention of methyl-substituted azoles also led to the higher fuel cell performance with the maximum increase of 95% in the power density. It was also revealed that higher pKa of azoles enhanced the PA retention and the fuel cell performance. Based on the experimental results of PA retention and density functional theory calculations, the PA loss mechanism was also proposed.

Electrochemical properties of an activated carbon xerogel monolith from resorcinol-formaldehyde for supercapacitor electrode applications.

Activated carbon xerogel monoliths were prepared from resorcinol and formaldehyde via a catalyst-free and template-free hydrothermal polycondensation reaction, followed by pyrolysis and activation. The ratio of resorcinol (R) to distilled water (W) was varied to afford an interconnected pore structure with controlled pore size, while the pyrolysis temperature was optimized to give high specific surface area. Activation was carried out at 700 °C after soaking the samples in 6 M KOH aqueous solution. The same process, called "heat treatment", was also carried out without soaking in KOH for comparison. The weight loss upon pyrolysis, activation and heat treatment and the weight gain via KOH soaking were measured. Field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and an N2 sorption instrument were utilized for characterization. Additionally, electrochemical properties were evaluated using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) with a 3-electrode system, while a 2-electrode system was also employed for selected samples. The highest specific capacitance of 323 F g-1 via GCD at 1 A g-1 was obtained at the R/W ratio of 45 and with 500 °C pyrolysis. In addition, this sample also exhibited 89.4% retention at 20 A g-1 in the current density variation and 100% retention in 5000 cycling tests.

Solution-State Long-Range Molecular Ordering in Poly(3-hexylthiophene).

A blend of poly(3-hexylthiophene) (P3HT) and poly(n-hexyl isocyanate-block-2-vinylpyridine) (PHIC-b-P2VP) in a common solvent shows the formation of long-range (micrometer-scale) nanowires of P3HT through hydrophobic interactions between the hexyl arms of P3HT and PHIC in a parallel way, which increase the planarity that leads to the generation of vibration bands with a lower free exciton bandwidth (W = 67 meV) in the solution state, which is further decreased to 9 meV after 48 h annealing of the blend film. The resulting nanowires of the P3HT show a 100-fold increase in current in comparison to pristine P3HT.

Changes of ego identity and psychosocial maturity in nursing students: A longitudinal study.

BACKGROUND: Nursing students who have achieved ego identity are able to develop their careers to become professional nurses. To care for patients in a clinical context, nursing students need to be psychologically and socially mature. Attainment of ego identity and maturity is a key developmental task during students' time at university as they prepare to become professional nurses. OBJECTIVES: This study was conducted to examine changes of ego identity and psychosocial maturity in nursing students. DESIGN AND SETTING: A longitudinal study design was employed between June 2016 and June 2019 at a university in a metropolis in South Korea. PARTICIPANTS: The participants were 102 nursing students who responded to surveys on at least two occasions. Seventy-six nursing students completed questionnaires on four occasions (in 2016, 2017, 2018, and 2019). METHODS: Data were collected through self-report questionnaires composed of items assessing ego identity, psychosocial maturity, and demographic characteristics. Participants returned questionnaires every June from 2016 to 2019. The data were analyzed using descriptive statistics, the kappa statistic, repeated-measures analysis of variance, and one-way analysis of variance. RESULTS: In terms of ego identity status, 17.1% of nursing students progressed to a more advanced status, 5.3% of them regressed to a less developed status, 57.9% of students had a fluctuating status, and 19.7% of them had a status that remained stable. Overall, psychosocial maturity in nursing students increased over time. Psychosocial maturity was higher among students in the achievement and moratorium statuses than among those in other statuses. CONCLUSIONS: These findings indicate that ego identity status fluctuated during students' time at nursing school, while psychosocial maturity simultaneously improved. Nursing students who explored their options also became psychologically and socially mature.

Risk Factors of Bacteremia following Multiple Traumas.

BACKGROUND: Bacteremia is a major nosocomial infection that frequently occurs in trauma patients, increasing morbidity and mortality. The aim of this study was to identify risk factors and to describe epidemiological patterns for early onset (EOB) and late onset (LOB) bacteremia after trauma. METHODS: We retrospectively reviewed medical records of all trauma patients admitted to the surgical intensive care unit and general ward between January 2011 and December 2015. The information was collected for each patient and recorded in a computer database: early onset bacteremia (EOB) was defined as when onset occurred within 7 days after trauma, and late onset bacteremia (LOB) was defined as when onset occurred after 7 days from trauma. RESULTS: Thirty-four patients of 859 (4%) developed bacteremia during their hospital stay: 4 (11.8%) developed EOB, 26 (76.4%) LOB, and 4 (11.8%) patients developed both of them. Sixty events of bacteremia happened to these patients: 9 (15.0%) EOB and 51 (85.0%) LOB. Gram-positive cocci were isolated more frequently than Gram-negative bacilli in both groups. Gram-positive cocci were more frequently isolated in EOB than in LOB; otherwise, there was no statistical significance (77.8% vs. 64.7%, p=0.683). Central line-associated blood stream infection (CLABSI) and surgical site infection (SSI) were the most common identified source for LOB. Presence of liver (OR: 2.66, p=0.035) and pelvic injury (OR: 2.25, p=0.038), gastrointestinal tract perforation (OR: 5.48, p=0.002), and massive transfusion (OR: 3.36, p=0.006) represented risk factors for bacteremia. CONCLUSIONS: Presence of pelvic and liver injury on arrival in emergency department, gastrointestinal tract perforation, and massive transfusion within the first 24 hours after trauma appears to be significant risk factors for bacteremia.

The size of pelvic hematoma can be a predictive factor for angioembolization in hemodynamically unstable pelvic trauma.

PURPOSE: Unstable pelvic fracture with bleeding can be fatal, with a mortality rate of up to 40%. Therefore, early detection and treatment are important in unstable pelvic trauma. We investigated the early predictive factors for possible embolization in patients with hemodynamically unstable pelvic trauma. METHODS: From January 2011 to December 2013, 46 patients with shock arrived at a single hospital within 24 hours after injury. Of them, 44 patients underwent CT scan after initial resuscitation, except for 2 who were dead on arrival. Nine patients with other organ injuries were excluded. Seventeen patients underwent embolization. A single radiologist measured the width (longest length in axial view) and length (longest length in coronal view) of pelvic hematoma on CT scans. Demographic, clinical, and radiological data were reviewed retrospectively. RESULTS: Among 35 patients with hemodynamically unstable pelvic fracture, 22 (62.9%) were men. Width (P = 0.002) and length (P = 0.006) of hematoma on CT scans were significantly different between the embolization and nonembolization groups. The predictors of embolization were width of pelvic hematoma (odds ratio [OR], 1.07; P = 0.028) and female sex (OR, 10.83; P = 0.031). The cutoff value was 3.35 cm. More embolization was performed (OR, 12.00; P = 0.003) and higher mortality was observed in patients with hematoma width >3.35 cm (OR, 4.96; P = 0.048). CONCLUSION: Patients with hemodynamically unstable pelvic trauma have a high mortality rate. CT is useful for the initial identification of the need for embolization among these patients. The width of pelvic hematoma can predict possible embolization in patients with unstable pelvic trauma.

Fabrication of a composite anion exchange membrane with aligned ion channels for a high-performance non-aqueous vanadium redox flow battery.

Fabrication of high-conductivity ion exchange membranes (IEMs) is crucial to improve the performance of non-aqueous vanadium redox flow batteries (NAVRFBs). In the present work, anion exchange membranes with high-conductivity were fabricated by aligning ion channels of the polymer electrolyte impregnated in porous polytetrafluoroethylene (PTFE) under electric fields. It was observed that the ion channels of the polymer electrolyte were uniformly orientated in the atomic-force microscopy image. Its morphological change could minimize detouring of the transport of BF4 - ions. The results showed through-plane conductivity was improved from 12.7 to 33.1 mS cm-1. The dimensional properties of the fabricated membranes were also enhanced compared with its cast membrane owing to the reinforcing effect of the substrate. Especially, the NAVRFB assembled with the optimized membrane showed increased capacities, with a 97% coulombic efficiency and 70% energy efficiency at 80 mA cm-2. Furthermore, the optimized membrane made it possible to operate the NAVRFB at 120 mA cm-2. Its operating current density was 120 times higher than that of a frequently used AHA membrane for RFBs.

Electrical and Optical Characteristics of Two-Dimensional MoS2 Film Grown by Metal-Organic Chemical Vapor Deposition.

Atomically thin molybdenum disulfide (MoS2) films were synthesized on a SiO2/Si substrate by metal-organic chemical vapor deposition (MOCVD). Raman spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy studies reveal the double-atomic-layer structure and the surface element composition of the MOCVD-grown MoS2 films. The photoluminescence measurement demonstrates a strong emission peak with a bandgap of 685.1 nm, attributed to highly efficient radiative transition at the double atomic layer. The contact resistance between the doubleatomic-layer MoS2 film and metal electrode was measured using the transmission-line modeling method. A Ti/Au electrode forms an ohmic contact with the double-atomic-layer MOCVD-grown MoS2 film, exhibiting a resistivity of 100 kΩ. The field-effect transistor based on the double-atomiclayer MoS2 film exhibits an electron mobility of 1.3×10-4 cm²/V·s and an on/off ratio of 6.5×10² at room temperature.

Coloration of colloidal polymer particles through selective extraction of Mie backscattering for cation-responsible colorimetric sensors.

Mie backscattering-based coloration of water-dispersed polymer particles is investigated. Diluted colloids and light absorber-added colloids are individually prepared to study the scattering properties. Light absorber-added colloids show ~2.9-fold higher colour saturation than diluted colloids because of the effective elimination of Mie forward scattering. Mechanism of selective extraction of Mie backscattering-based colour in the presence of light absorbers is explained by path length difference of Mie forward and backscattering. Using stimuli-responsive polymer particles, Mie scattering colour-based sensors that respond to pH and heavy metal ions are prepared.

Determination of complex dielectric function of CH3NH3PbBr3 perovskite cubic colloidal quantum dots by modified iterative matrix inversion method.

Recent advances in lead halide perovskite quantum dots appeal with their potential in various optoelectronic devices such as photovoltaics, photodetectors, light-emitting diodes (LEDs) and lasers. However, lack of information on the intrinsic optical properties of lead halide perovskite quantum dots (QDs) lags the progress in device performances and further development in various applications. In this letter, the complex dielectric function of CH3NH3PbBr3 perovskite cubic colloidal QDs was determined from the UV-Vis absorption by using a modified iterative matrix inversion (IMI) method. The modified IMI method takes into account the dilute solution with cubic inclusions, while the conventional method only considers spherical or elliptical inclusions by Maxwell-Garnett (MG) effective medium theory. In addition, singly subtractive Kramer Kronig (SSKK) relations have also been considered to compensate for possible errors arising from the finite wavelength range of the experimental absorption data.

Growth of close-packed crystalline polypyrrole on graphene oxide via in situ polymerization of two-monomer-connected precursors.

Synthesis of a two-dimensional (2D) highly crystalline composite, P(Py:BPDSA:Py)-GO, from the growth of a close-packed polymer crystal, P(Py:BPDSA:Py), on graphene oxide (GO) sheets via in situ polymerization of two-monomer-connected precursors (TMCPs, Py:BPDSA:Py), in which two pyrrole (Py) molecules are linked through a connector (4,4'-biphenyldisulfonic acid) (BPDSA), is reported. When the TMCP is polymerized on GO, it leads to an exceptionally ordered structure determined by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) studies. X-ray crystallography of the composite shows crystalline peaks with d spacings in the [100] direction. Transmission electron microscopy (TEM) analysis indicates that the composite has a face-centered cubic (FCC) crystal structure. Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) show that this composite with a well-defined nanostructure was successfully synthesized. Nitrogen adsorption-desorption isotherms show that this composite, P(Py:BPDSA:Py)-GO, has an improved specific surface area (71 m2 g-1) compared to that of P(Py:BPDSA:Py) (3.1 m2 g-1). The electrochemical properties of the composite studied by cyclic voltammetry indicates a specific capacitance of 480 F g-1 without an additional conducting material such as carbon black, suggesting its use as a pseudocapacitor.

Monolithic carbon xerogel with co-continuous hierarchical porosity via one-step, template- and catalyst-free hydrothermal reaction with resorcinol and formaldehyde.

Monolithic carbon xerogel (MCX) with co-continuous hierarchical porosity was prepared via a one-step, template- and catalyst-free hydrothermal polycondensation reaction with resorcinol (R), formaldehyde (F) and distilled water (W), followed by pyrolysis and CO2 activation. The reaction was carried out in a pressurized Teflon mold at 100 °C for 6 h, while F/R (2.2, 2.4, 2.6, and 2.8) and R/W ratios (40 and 45) were varied to obtain a co-continuous pore structure with interconnected particles. Next, the gels were dried at 60 °C for 36 h and then at 100 °C for 12 h to produce xerogels, which were then subjected to pyrolysis at 900 °C for 2 h and CO2 activation at 1000 °C for 2, 4 or 6 h. A co-continuous pore structure with interconnected particles was observed in gels with F/R = 2.4 and 2.6 at R/W = 40 and with F/R = 2.2 at R/W = 45, but the gel with F/R = 2.4 at R/W = 40 was the only one that showed no crack generation upon 6 h CO2 activation. Thus, this gel was subjected to a N2 sorption study, which resulted in a specific surface area (SSA) of 1418, 2489 and 3418 m2 g-1 at 2, 4 and 6 h activation, respectively. This was attributed to the introduction of micro-pores via activation, which also generated meso- and macro-pores to form hierarchical porosity.

Organic-inorganic hybrid perovskite quantum dots with high PLQY and enhanced carrier mobility through crystallinity control by solvent engineering and solid-state ligand exchange.

The photoluminescence quantum yield (PLQY) and charge carrier mobility of organic-inorganic perovskite QDs were enhanced by the optimization of crystallinity and surface passivation as well as solid-state ligand exchange. The crystallinity of perovskite QDs was determined by the Effective solvent field (Esol) of various solvents for precipitation. The solvent with high Esol could more quickly countervail the localized field generated by the polar solvent, and it causes fast crystallization of the dissolved precursor, which results in poor crystallinity. The post-ligand adding process (PLAP) and post-ligand exchange process (PLEP) increase the PLQY of perovskite QDs by reducing non-radiative recombination and the density of surface defect states through surface passivation. Particularly, the post ligand exchange process (PLEP) in the solid-state improved the charge carrier mobility of perovskite QDs in addition to the PLQY enhancement. The ligand exchange with short alkyl chain length ligands could improve the packing density of perovskite QDs in films by reducing the inter-particle distance between perovskite QDs. The maximum hole mobility of 6.2 × 10-3 cm2 V-1 s-1, one order higher than that of pristine QDs without the PLEP, is obtained at perovskite QDs with hexyl ligands. By using PLEP treatment, compared to the pristine device, a 2.5 times higher current efficiency in perovskite QD-LEDs was achieved due to the improved charge carrier mobility and PLQY.