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).

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).

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.

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.

Dual function of a living polymerization initiator through the formation of a chain-end-protecting cluster: density functional theory calculation.

Sodium benzanilide (Na(+)BA(-)) initiators have opened a new route to living anionic polymerization of n-hexylisocyanate (HIC) with 100% yield and controlled molecular weight. The NaBA initiators not only provide initiation points for polymerization by attacking HIC monomers but also successfully prevent back-biting side reactions without any help from additives. Our hypothesis on this dual function of the NaBA initiators is that they self-assemble to form protection shields around the chain ends. Indeed, our density functional theory calculations performed under experimental conditions on the free energy of formation of (NaBA)n clusters of various sizes and conformations searched by Monte Carlo simulations show that the BA(-) moiety forms a stable complex with Na(+) in a fan-like circular-sector shape owing to its double binding sites (N(-)-C=O ↔ N=C-O(-)) and that the tightly-bound NaBA units spontaneously self-assemble to form small (NaBA)n clusters (n = 2 and 4). The growing end of the polymer chain [(BA)(HIC)n(-)], which resembles BA(-), would also assemble with n - 1 NaBA units to form an n-mer cluster. We expect that the chain end in this cluster would be more available to attack small HIC monomers coming into the cluster (leading to chain growth) rather than folding back to attack the middle of the chain (leading to cyclotrimerization to isocyanurates and depolymerization).

Isoindigo-based small molecules for high-performance solution-processed organic photovoltaic devices: the electron donating effect of the donor group on photo-physical properties and device performance.

Five solution processable isoindigo-based donor-acceptor-donor (D-A-D) small molecules with different electron donating strengths have been designed and synthesized. The variation in the electron donating strength of the donor group strongly affected the optical, thermal, electrochemical and photovoltaic device performances of the isoindigo organic materials. The highest power conversion efficiency of ~3.2% was achieved in the bulk heterojunction photovoltaic device consisting of ID3T as the donor and PC70BM as the acceptor. This work demonstrates the potential of isoindigo moieties as electron-deficient units and presents guidelines for the synthesis of D-A-D small molecules for producing highly efficient, solution-processed organic photovoltaic devices.

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.

Arrangement of C60 via the self-assembly of post-functionalizable polyisocyanate block copolymer.

Poly(furfuryl isocyanate) (PFIC), which includes the reactive furan group, was synthesized by anionic polymerization using a sodium benzhydroxide (Na-BH), self-assembly initiator. We determined the optimum polymerization conditions by varying both the reaction time and the molar ratio of the monomer to the initiator. Block copolymer, poly(furfuryl isocyanate)-b-poly(n-hexyl isocyanate), was synthesized under optimized polymerization conditions. The PFIC was modified by Diels-Alder reactions with C60 for functionalization. Transmission electron microscopy (TEM) was used to study the self-assembly of block copolymers and modified block copolymer with C60. C60 formed highly ordered aggregates on the PFIC domains via self-assembly of the block copolymer.

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.

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.

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.

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 of Well-defined Amphiphilic Block Copolymers by Organotellurium-Mediated Living Radical Polymerization (TERP).

Low-molecular weight amphiphilic diblock copolymers, polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), and (P2VP-b-PS) with different block ratios were synthesized for the first time via organotellurium-mediated living radical polymerization (TERP). For both the homo- and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2 ) is presented using a site-selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP-b-PS in toluene through the sol-gel method.

Patterning of polymer nanocomposite resists containing metal nanoparticles by electron beam lithography.

Poly(vinyl pyrrolidone) (PVP)-stabilized silver nanoparticles (NPs) were used as a new nanocomposite resist for electron beam lithography. A nanocomposite resist prepared by reducing silver nitrate in an alcoholic PVP solution was patterned by using a scanning electron microscope equipped with a nanometer pattern generation system. Well-defined negative tone patterns with a good sensitivity of 200 microC/cm2 and a contrast of 2.83 were obtained using the prepared nanocomposite resist. In addition, the changes in the morphology and structure of the resist patterns with a thermal treatment temperature were investigated by a FE-SEM with an EDX. The results revealed that the patterns of Ag NPs were formed through sintering the formed resist patterns at above 300 degrees C.

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.

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.

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.

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.

Au/CdS Hybrid Nanoparticles in Block Copolymer Micellar Shells.

A polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) micellar structure with a P2VP core containing 5 nm CdS nanoparticles (NPs) and a PS shell formed in toluene that is a good solvent for PS block undergoes the core-shell inversion by excess addition of methanol that is a good solvent for P2VP block. It leads to the formation of micellar shell-embedded CdS NPs in the methanol major phase. The spontaneous crystalline growth of Au NPs on the CdS surfaces positioned at micellar shells without a further reduction process is newly demonstrated. The nanostructure of Au/CdS/PS-b-P2VP hybrid NPs is confirmed by transmission electron microscopy, energy-dispersive X-ray, and UV-Vis absorption.

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.