Colorless and transparent poly(amide imide) nanocomposites containing organically modified hectorite.

Polyamic acid (PAA) was synthesized using the diamine monomer N,N'-[2,2'-bis(trifluoromethyl)-4,4'-biphenylene]bis(4-aminobenzamide) and dianhydride monomer 4,4'-oxydiphthalic anhydride. Colorless and transparent poly(amide imide) (CPAI) hybrid films were prepared via multi-step thermal imidization of PAA in which various contents of nano-filler were dispersed. The CPAI hybrid films were prepared by dispersing organoclay STN, which was obtained by organically modifying hectorite, in CPAI by solution intercalation with various contents ranging from 1 to 7 wt%. The thermomechanical properties, morphologies, and optical transparencies of the obtained CPAI hybrid films were investigated based on the dispersed STN content, and the results were compared. Some of the clay in the CPAI hybrid film were agglomerated, which was observed using a transmission electron microscope; however, most clays were well-dispersed, with a nano-size of less than 10 nm. The best thermomechanical properties of the CPAI hybrid film were exhibited with an STN content of 3 wt%, but these properties decreased above the critical content. The coefficients of thermal expansion of all the hybrid films were below 20 ppm per °C regardless of the amount of STN, and the yellow index was 1-2 even when the STN content increased to 7 wt%.

Comparison of the properties of polyimide nanocomposite films containing functionalized-graphene and organoclay as nanofillers.

Poly(amic acid) (PAA) is prepared by the reaction of dianhydride 4,4'-biphthalic anhydride and diamine bis[4-(3-aminophenoxy)phenyl]sulfone in N,N'-dimethylacetamide. Two types of fillers were dispersed in the as-synthesized PAA via a solution intercalation method; polyimide (PI) hybrid films were synthesized under various heat treatment conditions. Octylamine (C8) was introduced into graphene sheets (C8-GS) and bentonite (C8-BTN), which were then used as nanofillers in the PI hybrid films. The synthesized nanofillers were used in varying amounts of 0.25-1.00 wt% with respect to the matrix PI. The thermal and morphological properties and optical transparency of the hybrid films were investigated and compared for both C8-GS and C8-BTN at varying nanofiller content. The C8-BTN nanocomposite showed superior thermal properties, and optical transparency, and the filler was well dispersed in the PI matrix compared to the C8-GS nanocomposite. The thermal stability of the hybrid films improved upon the addition of small amounts of the nanofiller. However, beyond a certain critical filler concentration, the thermal stability declined. These results were verified through the dispersion of fillers via transmission electron microscopy.

Oral Nanomedicines for siRNA Delivery to Treat Inflammatory Bowel Disease.

RNA interference (RNAi) therapies have significant potential for the treatment of inflammatory bowel diseases (IBD). Although administering small interfering RNA (siRNA) via an oral route is desirable, various hurdles including physicochemical, mucus, and cellular uptake barriers of the gastrointestinal tract (GIT) impede both the delivery of siRNA to the target site and the action of siRNA drugs at the target site. In this review, we first discuss various physicochemical and biological barriers in the GI tract. Furthermore, we present recent strategies and the progress of oral siRNA delivery strategies to treat IBD. Finally, we consider the challenges faced in the use of these strategies and future directions of oral siRNA delivery strategies.

Phase transition, thermal stability, and molecular dynamics of organic-inorganic hybrid perovskite [NH3(CH2)6NH3]CuCl4 crystals.

Organic-inorganic hybrid perovskites have various potential applications in fuel cells and solar cells. In this regard, the physicochemical properties of an organic-inorganic [NH3(CH2)6NH3]CuCl4 crystal was conducted. The crystals had a monoclinic structure with space group P21/n and lattice constants a = 7.2224 Å, b = 7.6112 Å, c = 23.3315 Å, ß = 91.930°, and Z = 4 at 300 K, and the phase transition temperature (T C) was determined to be 363 K by X-ray diffraction and differential scanning calorimetry experiments. From the nuclear magnetic resonance experimental results, the changes in the 1H chemical shifts in NH3 and the influence of C1 located close to NH3 in the [NH3(CH2)6NH3] cation near T C are determined to be large, which implies that the structural change of CuCl4 linked to N-H⋯Cl is large. The 1H spin-lattice relaxation time (T 1ρ) in NH3 is shorter than that of CH2, and the 13C T 1ρ values for C1 close to NH3 are shorter than those of C2 and C3 due to the influence of the paramagnetic Cu2+ ion in square planar geometry CuCl4. The structural mechanism for the phase transition was the change in the N-H⋯Cl hydrogen bond and was associated with the structural dynamics of the CuCl4 anion.

Comparison of Properties of Colorless and Transparent Polyimide Nanocomposites Containing Chemically Modified Nanofillers: Functionalized-Graphene and Organoclay.

Poly(amic acid) (PAA) was synthesized from dianhydride 4,4-(4,4-isopropylidenediphenoxy)bis(phthalic anhydride) and diamine bis [4-(3-aminophenoxy) phenyl] sulfone. Colorless and transparent polyimide (CPI) hybrid films were synthesized through thermal imidization after dispersing nanofillers using an intercalation method in a PAA solution. C16-GS and C16-MMT, in which hexadecylamine (C16) was substituted on graphene sheet (GS) and montmorillonite (MMT), respectively, were used as nanofillers to reinforce the CPI hybrid films. These two nanofillers were admixed in varying loadings of 0.25 to 1.00 wt%, and the morphology, thermal properties, and optical transparency of the hybrid films were investigated and compared. The results suggest that the thermal properties of the CPI hybrid films can be improved by adding only a small amount of nanofiller. Transmission electron microscopy results of the CPI hybrid film containing two types of fillers suggested that the fillers were well dispersed in the nano-size in the matrix polymer; however, some of the fillers were observed as agglomerated particles above the critical concentration of 0.50 wt%.

Effect of Methylene Chain Length on the Thermodynamic Properties, Ferroelastic Properties, and Molecular Dynamics of the Perovskite-type Layer Crystal [NH3(CH2) n NH3]MnCl4 (n = 2, 3, and 4).

The structures and phase transitions of [NH3(CH2) n NH3]MnCl4 (n = 2, 3, and 4) crystals were confirmed through X-ray diffraction and differential scanning calorimetry (DSC) experiments. Thermodynamic properties, ferroelastic properties, and molecular dynamics of three crystals were studied as a function of the number (n) of CH2 groups in the alkylene chains. The loss in molecular weight due to a decrease in n marked the onset of the partial thermal decomposition. The thermal decomposition temperature, T d, increased with increasing length of the CH2 chain. While the ferroelastic twin domain walls for n = 2 and 4 were in the same direction at all temperatures, the domain walls for n = 3 were rotated by 45°, and the direction of extinction in phase II was rotated by 45° with respect to phases I and III. The 1H and 13C MAS NMR spectra of the three crystals were recorded as a function of temperature. With increasing length of the CH2 chain, the 1H spin relaxation time decreased, indicating that molecular motions were activated. These results provide insights into the thermodynamic properties and structural dynamics of the [NH3(CH2) n NH3]MnCl4 crystals and are expected to facilitate their potential applications.

Colorless and Transparent Polyimide Microporous Film with Excellent Physicochemical Property.

4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) as a dianhydride and bis(3-aminophenyl) sulfone (APS) and bis(3-amino-4-hydroxyphenyl) sulfone (APS-OH) as diamines were used to synthesize two types of poly(amic acid) (PAA). Varying amounts (0-5.0 wt%) of water-soluble poly(vinyl alcohol) (PVA) were mixed with PAA, and the resulting blend was heat-treated at different stages to obtain the colorless and transparent polyimide (CPI) blend films. The synthesized blended film completely removed water-soluble PVA in water. The possibility as a porous membrane according to the pore size varied according to the amount of PVA was investigated. The dispersibility and compatibility of CPI containing APS-OH monomer were higher than those of the APS monomer. This could be attributed to the hydrogen-bonding interactions between the CPI main chains and PVA. Scanning electron microscopy was conducted to characterize the material. The results revealed that the pore size of the CPI blend film increased as the PVA concentration increased. It was confirmed that uniform pores of µm-size were observed in CPI. The thermal stabilities, morphologies, optical properties, and solubilities of two CPIs obtained using APS and APS-OH monomers were investigated and their properties were compared with each other.

Effects of diamine isomers on the properties of colorless and transparent copoly(amide imide)s.

To fully understand the structure-property relationship of aromatic copoly(amide-imide)s (Co-PAIs) and determine which factors lead to chain rigidity, we prepared two series of Co-PAIs. They were synthesized from two types of amine monomers containing m- and p-isomers and different ratios of 4,4'-(hexafluoroiso-propylidene)diphthalic anhydride (6FDA) and 4,4'-biphthalic anhydride (BPA). m-Substituted and p-substituted N,N'-[2,2'-bis(trifluoromethyl)-4,4'-biphenylene]bis(aminobenzamide) (MPAB) diamine isomers were synthesized from 3- and 4-nitrobenzoyl chloride and 2,2'-bis(trifluoromethyl) benzidine (TFB), respectively. The Co-PAI films were synthesized from poly(amic acid) (PAA), via solution-casting, followed by thermal imidizations. The thermal- and mechanical-properties and optical transparency of the Co-PAI films with different BPA monomer contents were investigated. We also investigated the effects of the different MPAB isomers on the Co-PAI structures. Compared with the m-substituted MPAB Co-PAI films, the p-substituted MPAB Co-PAI films have superior thermo-mechanical properties at the same monomer content. However, the optical transparencies of the m-MPAB Co-PAIs are slightly better than those of the p-MPAB Co-PAIs.

Distinct genetic profile with recurrent population-specific missense variants in Korean adult atypical hemolytic uremic syndrome.

INTRODUCTION: Atypical hemolytic uremic syndrome (aHUS) is a rare thrombotic microangiopathy (TMA), characterized by micro-angiopathic hemolytic anemia, thrombocytopenia, and renal failure. In more than half of cases, genetic defects leading to overactivation of the alternative complement system have been identified. In this study, we investigated genetic defects in Korean adult patients with aHUS. MATERIALS AND METHODS: Sixty-six Korean adult patients with aHUS were ascertained from the Korean TMA Registry. Genetic variants of 15 aHUS-related genes (eight core genes [CFH, CFB, CFI, CD46, C3, THBD, PLG, and DGKE] and seven candidate genes [CFP, C4BPA, and CHFR1-5]) were analyzed from exome sequencing data. Multiplex ligation-dependent probe amplification of CFH and related genes was performed to detect hybrid genes or large deletions. RESULTS: Thirty patients (45%) had at least one aHUS-related variant (s) in eight core genes (total 40 variant alleles). The most frequently affected gene was CFH (13/40, 32%), followed by THBD (8/40, 20%) and CD46 (7/40, 18%). The two most common variants were Asp486Tyr of THBD (N = 7) and Tyr1058His-Val1060Leu of CFH (N = 5, linked on the same allele), accounting for 30% (12/40). In seven candidate genes, 19 variants were detected. When combined, 40 patients (61%) had at least one variant in 15 core or candidate genes. No patients had anti-CFH Ab or hybrid gene/CFHR1 homozygous deletions. CONCLUSIONS: The genetic profile of Korean adult aHUS was unique with recurrent missense variants, demonstrating ethnicity- and age-dependent differences in the genetic background of aHUS.

Prognostic utility of ADAMTS13 activity for the atypical hemolytic uremic syndrome (aHUS) and comparison of complement serology between aHUS and thrombotic thrombocytopenic purpura.

BACKGROUND: Atypical hemolytic uremic syndrome (aHUS) involves dysregulation of the complement system, but whether this also occurs in thrombotic thrombocytopenic purpura (TTP) remains unclear. Although these conditions are difficult to differentiate clinically, TTP can be distinguished by low (<10%) ADAMTS13 activity. The aim was to identify the differences in complement activation products between TTP and aHUS and investigate ADAMTS13 activity as a prognostic factor in aHUS. METHODS: We analyzed patients with thrombotic microangiopathy diagnosed as TTP (N=48) or aHUS (N=50), selected from a Korean registry (N=551). Complement activation products in the plasma samples collected from the patients prior to treatment and in 40 healthy controls were measured by ELISA. RESULTS: The levels of generalized (C3a), alternate (factor Bb), and terminal (C5a and C5b-9) markers were significantly higher (all P<0.01) in the patients than in the healthy controls. Only the factor Bb levels significantly differed (P=0.008) between the two disease groups. In aHUS patients, high normal ADAMTS13 activity (≥77%) was associated with improved treatment response (OR, 6.769; 95% CI, 1.605-28.542; P=0.005), remission (OR, 6.000; 95% CI, 1.693-21.262; P=0.004), exacerbation (OR, 0.242; 95% CI, 0.064-0.916; P=0.031), and disease-associated mortality rates (OR, 0.155; 95% CI, 0.029-0.813; P=0.017). CONCLUSION: These data suggest that complement biomarkers, except factor Bb, are similarly activated in TTP and aHUS patients, and ADAMTS13 activity can predict the treatment response and outcome in aHUS patients.

P3HT-based visible-light organic photodetectors using PEI/PAA multilayers as a p-type buffer layer.

A low leakage current is critical for achieving organic photodetectors (OPDs) with high detectivity. The insertion of buffer layers is an effective approach for reducing the reverse-biased leakage current. In this study, polyelectrolyte multilayers comprising polyethyleneimine (PEI) and polyacrylic acid (PAA) were introduced by a spin-assisted layer-by-layer technique into an OPD as a p-type buffer layer. Although PEI/PAA multilayers are insulators, when used as a buffer layer in our device, they suppressed the leakage current and also provided a high photocurrent due to the light-assisted tunneling effect. The prepared device configuration was ITO/(PEI/PAA)2/P3HT:PC60BM/Yb/Al. The performances of the OPDs were investigated by measuring the current-voltage characteristics, external quantum efficiency, and transient photocurrent. In addition, the operating mechanism of the OPDs was confirmed by impedance analysis. The device comprising (PEI/PAA)2 showed a specific detectivity of 3.11 × 1012 Jones and a bandwidth of 103.2 kHz at -1 V and 525 nm. This performance is a numerical value that can be used in devices such as a line scan camera. In addition, because this device is fabricated by a low-temperature solution process, flexible and large-area substrates can be used.

Oxygen and Acrylic Acid Plasma Treatment on Titanium Mesh for Improving the Hydroxyapatite Formation.

Customized titanium (Ti) meshes were treated with O2 plasma and acrylic acid plasmapolymerization (PPAAc). The optimum conditions for PPAAc were as follows: 20 W, 15 mTorr, and 5 min. Hydroxyapatite formation increased in Ti meshes treated with O2 and PPAAc compared with that in untreated Ti meshes. Moreover, MC3T3-E1 cells exhibited improved cell spreading, attachment, proliferation in PPAAc treated Ti mesh than in untreated Ti mesh. This result revealed that O2 and PPAAc surface treatment on Ti mesh was potential tool for improving the bone formation on the Ti mesh clinically application.

Impaired colony-forming capacity of circulating endothelial progenitor cells in patients with emphysema.

Chronic obstructive pulmonary disease (COPD) is classified into emphysema and chronic bronchitis, which are thought to result from different pathophysiological pathways. Smoking-induced lung parenchymal destruction and inadequate repair are involved in the pathogenesis of emphysema. In addition, decreased expression of vascular endothelial growth factor and increased endothelial cell apoptosis in the lung may participate in emphysema pathogenesis. As stem cells, circulating endothelial progenitor cells (EPCs) may play a key role in the maintenance of vascular integrity by replacing and repairing the damaged endothelial cells in the tissues. To determine whether the lack of appropriate repair by circulating EPCs in cases of smoking-induced endothelial cell injury participates in emphysema pathogenesis, we determined the association between the colony-forming or migratory capacity of circulating EPCs and the presence of emphysema in 51 patients with COPD. The patients were divided into emphysema (n = 23) and non-emphysema groups (n = 28) based on high-resolution computed tomography. Twenty-two smokers with normal lung function and 14 normal non-smokers served as controls. Circulating EPCs isolated from patients with emphysema showed significantly lower colony-forming units (CFUs) than those from patients with non-emphysema group, smokers with normal lung function, and normal non-smokers. EPCs from patients with emphysema showed significantly lower migratory capacity than those from normal non-smoking controls (p < 0.05). On multivariate analysis, the EPC-CFU was independently associated with emphysema (OR 0.944, 95% CI = 0.903-0.987, p = 0.011). Thus, impaired functions of circulating EPCs may contribute to the development of emphysema.

Frequency of Pro475Ser polymorphism of ADAMTS13 gene and its association with ADAMTS-13 activity in the Korean population.

PURPOSE: The in vitro study suggested that proline to serine polymorphism in codon 475 (C1423T) of the A Disintegrin and Metalloprotease with ThromboSpondin type 1 repeats-13 (ADAMTS-13) gene is related to reduced activity of ADAMTS-13. In this study, the frequency of the Pro475Ser polymorphism in Koreans was studied and plasma ADAMTS-13 activity was measured to find out whether this polymorphism contributes to decreased ADAMTS-13 activity in Koreans. PATIENTS AND METHODS: The frequency of the C1423T allele of the ADAMTS13 gene was studied along with measuring plasma ADAMTS-13 activity in 250 healthy Korean individuals. RESULTS: The allele frequency of C1423T polymorphism was 4%, and the median activity of CT type was 107 (69-143)%, which was lower than in controls with the CC genotype [118 (48-197)%, (p=0.021)]. CONCLUSION: Therefore, the Pro475Ser polymorphism seems to be popular in the Korean population, and attenuates ADAMTS-13 plasma activity.