Atomic Oxygen-Resistant Polyimide Composite Films Containing Nanocaged Polyhedral Oligomeric Silsesquioxane Components in Matrix and Fillers.

For the development of spacecraft with long-servicing life in low earth orbit (LEO), high-temperature resistant polymer films with long-term atomic oxygen (AO) resistant features are highly desired. The relatively poor AO resistance of standard polyimide (PI) films greatly limited their applications in LEO spacecraft. In this work, we successfully prepared a series of novel AO resistant PI composite films containing nanocaged polyhedral oligomeric silsesquioxane (POSS) components in both the PI matrix and the fillers. The POSS-containing PI matrix film was prepared from a POSS-substituted aromatic diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) and a common aromatic diamine, 4,4'-oxydianline (ODA) and the aromatic dianhydride, pyromellitic dianhydride (PMDA) by a two-step thermal imidization procedure. The POSS-containing filler, trisilanolphenyl POSS (TSP-POSS) was added with the fixed proportion of 20 wt% in the final films. Incorporation of TSP-POSS additive apparently improved the thermal stability, but decreased the high-temperature dimensional stable nature of the PI composite films. The 5% weight loss temperature (T5%) of POSS-PI-20 with 20 wt% of DABA-POSS is 564 °C, and its coefficient of linear thermal expansion (CTE) is 81.0 × 10-6/K. The former is 16 °C lower and the latter was 20.0 × 10-6/K higher than those of the POSS-PI-10 film (T5% = 580 °C, CTE = 61.0 × 10-6/K), respectively. POSS components endowed the PI composite films excellent AO resistance and self-healing characteristics in AO environments. POSS-PI-30 exhibits the lowest AO erosion yield (Es) of 1.64 × 10-26 cm3/atom under AO exposure with a flux of 2.51 × 1021 atoms/cm2, which is more than two orders of magnitude lower than the referenced PI (PMDA-ODA) film. Inert silica or silicate passivation layers were detected on the surface of the PI composite films exposed to AO.

Clinical implications of mismatch repair deficiency screening in patients with mixed neuroendocrine non-neuroendocrine neoplasms (MiNEN).

INTRODUCTION: Mixed neuroendocrine non-neuroendocrine neoplasms (MiNEN) are rare tumors, mainly encountered in the gastroenteropancreatic tract. Based on the limited available data, MiNEN is usually a highly aggressive neoplasm combining a high-grade neuroendocrine and a non-neuroendocrine component, associated with a poor prognostic outlook. Deficient DNA mismatch repair (MMR) results in microsatellite instability, which is a useful screening marker for identifying patients with Lynch syndrome and a prognostic factor for chemotherapeutic interventions. Little information on MMR status in MiNEN is available in published studies. Therefore, the purpose of this study was to explore the status and putative role of MMR on MiNEN. METHODS: We investigated the MMR status in 44 cases and characterized their clinicopathological features and prognoses. Immunohistochemistry was performed for four mismatch repair proteins (MLH1, MSH2, MSH6, and PMS2). RESULTS: Mean age at diagnosis was 61 years, and 75% of the patients were male. Lymph node metastases were observed in 14 (35.9%) patients. The most common tumor localizations were gastric (28 patients, 63.6%). Lack of immunohistochemical expression of MMR proteins was shown in 38.6% of cases. The common deletion rates of one or more proteins were 29.4% (5/17) for MLH1/PMS2 and 23.5% (4/17) for MLH1. Correlation between clinicopathological parameters showed that MMR deficiency was significantly associated with early TNM stage and better prognoses in patients with MiNEN. CONCLUSION: MiNENs showed frequent losses of MMR protein expression, which contributes to the knowledge of the pathological and clinical aspects of MiNEN tumors.

Y-box binding protein 1 (YB-1) promotes gefitinib resistance in lung adenocarcinoma cells by activating AKT signaling and epithelial-mesenchymal transition through targeting major vault protein (MVP).

PURPOSE: Gefitinib is a first-line treatment option for epidermal growth factor receptor (EGFR)-mutated lung adenocarcinoma. However, most patients inevitably develop gefitinib resistance. The mechanism underlying this resistance is not fully understood. Y-box binding protein 1 (YB-1) has been reported to play a role in modulating drug sensitivity, but its role in gefitinib resistance is currently unknown. Here, we investigated the role of YB-1 in gefitinib resistance of lung adenocarcinoma. METHODS: We determined the expression of YB-1, epithelial-mesenchymal transition (EMT) and AKT signaling markers, as well as the viability of lung adenocarcinoma cell lines bearing mutant (HCC827, PC-9) or wild-type (H1299) EGFR. We also evaluated PC-9 cell migration and invasion using transwell assays. The clinical importance of YB-1 and major vault protein (MVP) was evaluated using primary lung adenocarcinoma patient samples. RESULTS: We found that YB-1 was significantly upregulated in gefitinib-resistant lung adenocarcinoma cells compared to gefitinib-sensitive cells. YB-1 augmented gefitinib resistance by activating the AKT pathway and promoting EMT. Decreased migration and invasion was observed upon MVP silencing in YB-1-overexpressing PC-9 cells, as well as restored gefitinib sensitivity. A retrospective analysis of 85 patients with lung adenocarcinoma revealed that YB-1 levels were significantly increased in tyrosine kinase inhibitor (TKI)-resistant patients compared to those in TKI-sensitive patients, indicating that YB-1 may serve as a biomarker to clinically predict acquired gefitinib resistance. CONCLUSION: YB-1 activates AKT signaling and promotes EMT at least in part by directly activating MVP. Hence, targeting the YB-1/MVP axis may help to overcome gefitinib resistance in lung adenocarcinoma patients.

Fabrication of step-by-step drug release system both sensitive to magnetic field and temperature based on layered double hydroxides and PNIPAM.

Fabrication of environmental sensitive and controllable drug release systems is urgently needed. In this paper, thermosensitive and magnetic response drug release systems were fabricated via layer-by-layer technique using acetylsalicylic acid (AA) intercalated ZnAl-LDH as core, poly (N-isopropylacrylamide) (PNIPAM) and AA micelles as well as small size ZnAl-LDH sheets as building blocks of the shell. By forming anionic micelles, cationic PNIPAM macromolecules were sandwiched in the LDH sheets with cationic charges which provided a novel way of fabrication of drug release systems. The characteristics of the building blocks, the fabrication process and the release behaviors of the as-prepared drug release systems were characterized in detail. Due to the micro-environmental difference of AA in the core and shell of the systems, step-by-step release behaviors were observed. Also the drug release systems showed obvious temperature and magnetic field dependent responsibility. The obtained assembly is a potential drug release system.

Anomalous but massive removal of two organic dye pollutants simultaneously.

A one-pot method to remove two organic dye contaminants and alkali simultaneously from alkaline wastewater was developed by forming Zn-Al layered double hydroxide (ZnAl-LDH). Using this process, not only alkali but also methyl orange (MO), an anionic contaminant was totally removed from wastewater. In addition, cationic contaminant, methylene blue (MB) was also removed effectively while maintaining the high removal efficiency of MO. The removal efficiency of MO was almost 100% and the pH of the treated wastewater decreased from 12 to 7.38. The charge-limited removal process, molecular arrangement of the contaminants in LDHs, and the anomalous removal mechanism were analyzed experimentally and through simulation. After MO accumulated in the interlayers of LDH by electrostatic interaction, MB entered and trapped by hydrophobic interaction.

Layered Double Hydroxide Assemblies with Controllable Drug Loading Capacity and Release Behavior as well as Stabilized Layer-by-Layer Polymer Multilayers.

A stable drug release system with magnetic targeting is essential in a drug delivery system. In the present work, layered double hydroxide assemblies stabilized by layer-by-layer polymer multilayers were prepared by alternative deposition of poly(allylamine hydrochloride) and poly(acrylic acid) species on composite particles of Fe3O4 and ZnAl-LDH and then covalent cross-linkage of the polymer multilayers by photosensitive cross-linker. The successful fabrication was recorded by Zeta potential and Fourier transform infrared spectrum measurements. The formed assemblies were stable in high pH solutions (pH > 7). The drug loading capacity and release behavior of the assemblies could be controlled by treatment with appropriate acidic solution, and were confirmed by loading and release of a simulated drug, methylene blue. The formed assemblies possessed enough saturated magnetic strength and were sensitive to external magnetic field which was essential for targeting drug delivery. The formed assemblies were multifunctional assemblies with great potential as drug delivery system.

Structure, molecular simulation, and release of aspirin from intercalated Zn-Al-layered double hydroxides.

Aspirin or acetylsalicylic acid (AA), a non-steroidal anti-inflammatory drug, is intercalated into Zn-Al-layered double hydroxides (ZnAl-LDHs) by co-precipitation and reconstruction methods. The composition, structure, and morphology of the intercalated products as well as their release behavior are determined experimentally and theoretically by Material Studio 5.5. Experimental results disclose the strong interaction between the LDHs sheets and AA in the intercalated ZnAl-LDHs produced by co-precipitation and slow release of AA from the intercalated ZnAl-LDHs in both phosphate buffered saline (PBS) and borate buffered saline (BBS) solutions. The percentage of AA released from the ZnAl-LDHs prepared by both methods in PBS (96.87% and 98.12%) are much more than those in BBS (68.59% and 81.22%) implying that both H4BO4(-) and H2PO4(-) can exchange with AA in the ZnAl-LDHs. After AA is released to PBS, ZnAl-LDHs break into small pieces. The experimental results are explained theoretically based on the calculation of the bonding energy between the anions and LDHs sheets as well as the AlO bond length change in the LDHs sheets.

Modification of a Na-montmorillonite with quaternary ammonium salts and its application for organics removal from TNT red water.

Na-montmorillonite (Na-Mont) and organic montmorillonite modified by cetyltrimethylammonium bromide (CTAB-Mont) and tetramethylammonium bromide (TMAB-Mont) were prepared as adsorbents to remove organic contaminants from 2,4,6-trinitrotoluene (TNT) red water. The characterizations of the samples were performed with X-ray diffraction and Fourier transform infrared spectroscopy. The adsorption capacity of CTAB-Mont (15.9 mg/g) was much larger than Na-Mont (0.26 mg/g) and TMAB-Mont (1.7 mg/g). Langmuir isotherm and the pseudo-second-order kinetic models fitted the experimental results well. The main factor in the adsorption promotion was the distribution phase in the interlayer of CTAB-Mont. The arrangement of molecules analyzed by molecular simulation corresponded to the experimental data and supported the adsorption mechanism.

Adsorption of polyvinyl alcohol from wastewater by sintered porous red mud.

Several types of red mud-based porous materials (RMPM) and other raw minerals via different processes were prepared and characterized using X-ray diffraction (XRD) analyses and scanning electron microscope (SEM) observations. Using the polymer sponge method, a 72% apparent porosity could be reached compared with 64% by adding a pore-forming agent. These materials were tested for their adsorption of polyvinyl alcohol (PVA) from simulated textile wastewater. The best mass ratio of RMPM to PVA solution was 50:100 with a removal maximum of 25.8% after they were in contact for 50 min. The adsorption rate and kinetics could be better described by Lagergren's pseudo-second-order model in comparison with the pseudo-first-order model.

Cuprous oxide created on sepiolite: preparation, characterization, and photocatalytic activity in treatment of red water from 2,4,6-trinitrotoluene manufacturing.

Cuprous oxide is firstly created on acidized sepiolite (AS) by a simple deposition method for photocatalytic degradation of the red water produced from 2,4,6-trinitrotoluene (TNT) manufacturing. X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), ultraviolet-visible diffuse reflection absorptive spectroscopy (UV-vis/DRS), and Fourier transform infrared (FT-IR) spectroscopy are used to characterize the photocatalyst composites. Gas chromatography/mass spectrometry (GC/MS) is employed to determine the organic constituents in the red water. The results show that the cuprous oxide particles can be immobilized on the surface of the AS fibers and the structure of the AS is altered when cuprous oxide interacts with AS via chemical reactions besides physical adsorption. The AS improves the optical properties of cuprous oxide and red-shifts the band gap thereby enhancing the utilization of visible light. The Cu(2)O/AS composites demonstrate excellent photocatalytic performance in the degradation of red water. 87.0% of red water can be photocatalytically degraded by Cu(2)O/AS after illumined for 5h and a majority of organic components of red water except 1,3,5-trinitrobenzene were degraded according to GC-MS analysis.

Analysis of hazardous organic residues from sodium hydrosulfite industry and utilization as raw materials in a novel solid lubricant production.

The hazardous organic residual wastes produced by the sodium hydrosulfite industry are demonstrated to be convertible into a novel solid lubricant. Identification and isolation of the organic residues are achieved by Fourier transform infrared (FTIR) spectroscopy, gas chromatography-mass spectrometry (GC-MS), and nuclear magnetic resonance (NMR). FTIR and GC-MS provide important information about the residues and the two main components obtained by column chromatography are further analyzed by NMR. The main organic residues are found to be thiodiglycol and 2,2'-dithiodiethanol which have potential applications in petroleum drilling because of their S-S and/or C-S functional groups. The lubricity of the organic residues is subsequently studied and the influence of different adsorbents on the lubricity is investigated and discussed. This homemade lubricant is observed to have good lubricity and by increasing the concentration of the commercial solid lubricant M, the lubricity diminishes. The process is expected to not only have commercial impact but also help to reduce environmental pollution.

Extraction of organic materials from red water by metal-impregnated lignite activated carbon.

Extraction of organic materials from 2,4,6-trinitrotoluene (TNT) red water by lignite activated carbon (LAC) impregnated with Cu(2+), Ba(2+), Sn(2+), Fe(3+), Ca(2+) and Ag(+) was investigated. The affinity to organic materials in red water was found to follow the order: Cu/LAC>Sn/LAC>Ag/LAC>Ba/LAC>Fe/LAC>Ca/LAC, which was explained by the hard and soft acid base (HSAB) theory. Cu(2+) showed the best performance and several parameters were further studied. X-ray photoelectron spectroscopy (XPS) verified effective loading of Cu(2+) on the LAC surface. The water quality before and after treated by Cu/LAC was evaluated using high performance liquid chromatograph, Gas Chromatography/Mass Spectroscopy (GC/MS), UV-vis spectroscopy and other analyses. The extraction performances and mechanism of organic materials on Cu/LAC were investigated through static methods. The experimental results showed that Cu/LAC possessed stronger extraction ability for the sulfonated nitrotoluenes than the non-sulfonated nitrotoluenes, the kinetic data fitted the pseudo-second-order kinetic model well. In addition, the leaching out of Cu(2+) from Cu/LAC was found much lower in the 100 times diluted red water (0.074%) than in the raw water (10.201%). Column adsorptions with more concentrated red water were also studied. Finally, Cu/LAC was observed to possess excellent reusability as well.