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In situ regeneration of the enamel-like structure of hydroxyapatite (HAp) crystals under oral conditions is significant for dental caries treatment. However, it is still a challenge for dentists to duplicate the elegant and well-aligned apatite structure bonding to the surface of demineralized enamel. A biocompatible amelogenin-inspired matrix, a phase-transited lysozyme (PTL) film mimicking an N-terminal amelogenin with central domain (N-Ame) combined with synthetic peptide (C-AMG) based on the functional domains of C-terminal telopeptide (C-Ame) is shown here, which is formed by amyloid-like lysozyme aggregation at the enamel interface through a rapid one-step aqueous coating process. In the PTL/C-AMG matrix, C-AMG facilitated the oriented arrangement of amorphous calcium phosphate (ACP) nanoparticles and their transformation to ordered enamel-like HAp crystals, while PTL served as a strong interfacial anchor to immobilize the C-AMG peptide and PTL/C-AMG matrix on versatile substrate surfaces. PTL/C-AMG film-coated enamel induced both of the in vivo and in vitro synthesis of HAp crystals, facilitated epitaxial growth of HAp crystals and recovered the highly oriented structure and mechanical properties to levels nearly identical to those of natural enamel. This work underlines the importance of amyloid-like protein aggregates in the biomineralization of enamel, providing a promising strategy for treating dental caries., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A three-branch viscoelastic model based on fractional derivatives is proposed for the viscoelastic behaviours of solid propellants. The simulation results show a satisfactory agreement with the stress relaxation modulus and complex modulus of solid propellants. As a comparison, the static modulus is also characterized by traditional viscoelastic model with integer-order derivatives. Results show that the application of the fractional derivatives to the viscoelastic constitutive model can effectively reduce the number of the required parameters while giving an accurate prediction of viscoelastic behaviours of solid propellants. Moreover, a simple and effective direct search method based on simulated annealing and Powell's mothed is proposed for the data fitting. This article is part of the theme issue 'Advanced materials modelling via fractional calculus: challenges and perspectives'.

Mesoporous carbon/graphene composites (MCG) have exhibited good electrochemical performances; however, the fixed mesoporous carbon, the low specific surface area, and porosity are the main obstacles in their application in supercapacitors. In this paper, mesoporous carbon microspheres/graphene composites (MCMG) were synthesized in situ via a soft template method and subsequent thermal reduction by using cetyltrimethylammonium bromide (CTAB) as the structure-directing agent, and aqueous mesophase pitch (AMP) and graphene oxide (GO) as the carbon sources. The strong electrostatic interaction between GO/CTAB and AMP promoted the self-assembly of CTAB and AMP to form the MCMG precursor. The results showed that the CTAB concentration and aging temperature have an important effect on the morphology and pore structure of the synthesized MCMG. The high aging temperature promoted the formation of mesoporous carbon spheres and its diameter increased with the increase in the concentration of CTAB. The as-prepared MCMG at the aging temperature of 140 °C had obvious spherical and layered carbon materials after carbonization at 900 °C. When the concentration of CTAB was 10.6 g L -1 , the formed mesoporous carbon spheres with the diameter of 30-40 nm were uniformly dispersed among the layered graphenes in MCMG-140-0.2 (the aging temperature of 140 °C and the CTAB content of 0.2 g). In addition, its specific surface area was 1150.5 m 2 g -1 and the mesopore size was centered at 4.3 nm, 7.9 nm, and 17.1 nm. Compared with the MCMG precursor, the ordered degree of the mesopores for MCMG was reduced due to the high temperature carbonization. Importantly, the specific capacitance of MCMG-140-0.2 at the current density of 0.1 A g -1 was as high as 356.3 F g -1 . Moreover, the specific capacitance of MCMG-140-0.2 at 1 A g -1 remained at 278.5 F g -1 , the capacitance retention was 92.1% after 6000 cycles, and the coulombic efficiency was over 98% at a high current density of 2 A g -1 . Therefore, the as-prepared MCMG can be an excellent candidate for electrode materials in supercapacitors., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Bifunctional oligomers with both reducing and stabilizing functionalities were prepared and successfully applied to the preparation of silver colloids of around 2 nm size without employing a strong stabilizer such as S and P, which was quite difficult to achieve. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) were performed to determine the morphology and particle size of the Ag colloids. UV-vis spectroscopy and X-ray absorption spectroscopy (XAS) were implemented to investigate the oxidation state of the Ag colloids. Synthesis parameters such as the density control of the ligating functionalities, the propinquity of the reducing and stabilizing groups, the extent of ligand stabilization and the reducing rates were found to have important effects on the formation and stabilization of Ag colloids. The as-synthesized Ag colloids were very stable even after being deposited on silica; then, they were subjected to calcination to get rid of the organics, which afforded Ag NPs (1.9-3.5 nm) on silica with narrow size distribution. These Ag NPs performed excellently in catalytic 4-nitrophenol reduction with conversion of up to 98% within 10 min. Furthermore, the Ag nanoparticles were quite stable and exhibited excellent reusability for seven successive reaction cycles without obvious decay. The straightforward synthesis of the ultra-small and stable Ag NPs has the potential for applications in the synthesis of other supported late transition metals., Competing Interests: There are no conflicts to declare in this paper., (This journal is © The Royal Society of Chemistry.)

New approach to recycle office waste paper was purposed in this paper, i.e., cellulose nanocrystal (CNC) was extracted from waste paper and then used CNC as the organic filler to reinforce polyurethane elastomer (PUE) in thermal properties. A series of CNC/PUE nanocomposites was prepared in situ using a two-step process in solvent N,N-dimethylformamide solution by changing the content of CNC from 0.5, 1, 2, 3, 4 to 5 wt%. The results showed that CNC was covalently bonded to PUE, and specifically concerned with the hard segments of PUE resulting from the strong hydrogen bonding. The interactions between CNC and PUE caused the increased thermal and thermo-mechanical properties, and decreased water absorption of nanocomposites. Importantly, the initial degradation temperature of PUE with 2 wt% content CNC (CNC/PUE2) increased by 21 °C. CNC/PUE2 had the better comprehensive properties with the worse water absorption, which made CNC/PUE2 appealing in load bearing and outdoor applications. Hence, this work not only provided a new recycling method of waste paper but also provided a thermolstable PUE with lower cost., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Hes3 is a basic helix-loop-helix factor gene, which was found to be involved in neural cell differentiation. Expression and clinicopathological significance of Hes3 in non-small cell lung cancer was not clear. In this study, we used immunohistochemistry to examine Hes3 expression in normal human lung and non-small cell lung cancer tissues. Hes3 expression was detected in cytoplasm and nucleus. Hes3 expression in bronchial epithelial cells and epithelial cells of submucosal glands was relatively weak and the positive rate was of 30.3% (10/33). Hes3 expression in non-small cell lung cancer tissues (51.8% (58/112)) was significantly higher than that in normal lung tissues ( p < 0.05). Hes3 expression in cancer tissues was significantly associated with poor differentiation, advanced TNM stages, lymph node metastasis, and a shorter patient survival time ( p < 0.05). In vitro study showed that overexpression of Hes3 in A549 cells significantly promoted cancer cell proliferation and invasion, while inhibition of Hes3 expression significantly downregulated cancer cell proliferation and invasion ( p < 0.05). Western blotting showed that overexpression of Hes3 significantly upregulated expression of Cyclin D1, Cyclin D3, and MMP7 in A549 cells, while inhibition of Hes3 expression in LK2 cells significantly downregulated the expression of these molecules ( p < 0.05). These results indicated that Hes3 may contribute to the malignant phenotype of non-small cell lung cancer, possibly through regulation of Cyclin D1, Cyclin D3, and MMP7, and may be a promising cancer marker., Competing Interests: Competing Interests: The authors have declared that no competing interest exists.

Waste polyethylene terephthalate (PET) has been a core member in plastic polluters due to the great amount consumption in food packaging, soft-drink bottles, fibers and films. It is essential to recycle waste PET and alcoholysis is a significant way to accomplish chemical recycling. In this work, three kinds of dihydric alcohols, including neopentyl glycol (NPG), dipropylene glycol (DPG) and poly(propylene glycol) (PPG), were employed to decompose waste PET with different temperatures, catalysts, and PET. A series of alcoholysis products with different appearance were obtained. The bulk structure and thermal properties of alcoholysis products were investigated by FTIR, 1 H NMR, MALDI-TOF, DSC and TG experiments. It is found that poly(propylene glycol) may react with waste PET to generate copolymer instead of oligomer products, dimers or trimers, etc. This product possesses excellent shelf stability and present transparent appearance, which may hold a great potential application in chemical industry. Moreover, the alcoholysis activity of DPG is the lowest comparing with NPG and EG in degradation of waste PET., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Polyurethane elastomer (PUE) composites were synthesized with a low additive content of waste natural cellulosic fibers from office paper. A new technology combining prepolymer method with physical blending and modification was adopted. The results showed that cellulosic fibers were covalently bonded to polyurethane molecular chains and served as a cross-linking agent making the degree of phase separation decrease. Even so, the lowest additive content of cellulosic fibers (1 wt%) in this work could make polyurethane still hold a certain degree of phase separation. Besides, thermal stability of polyurethane was improved from 288 to around 300 °C even at the low cellulosic fibers content. PUE with 3% cellulosic fibers had the better interfacial compatibility between cellulosic fibers and polyurethane causing the greater thermal reinforcement. PUE with 4% and 5% cellulosic fibers had the worse interfacial compatibility generating the better damping capacity indicating that cellulosic fibers could improve damping performance of polyurethane, especially polyurethane with 5 wt% fibers. It meant that cellulosic fibers had a potential application in damping materials., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Hydrophobic aluminum oxide films (AOFs) are widely used in anti-oxidation and anti-corrosion applications. In preparing AOFs, complex and high temperature conditions are usually necessary. Here, we report aluminum nanowire structures with hydrophobic properties, prepared using a facile sol-gel method by magnetic stirrer and hydrothermal reaction. The electromagnetic force work has great influence on the structure of AOFs. The surface morphology and compositions of the AOFs were analyzed by scanning electron microscope (SEM), energy dispersive X-ray spec-trometers (EDS), X-ray diffraction (XRD), 3M peeling test, and X-ray photoelectron spectroscopy (XPS). With the increase of water content in hydrothermal reaction, the hydrophobicity of AOFs proportional increased. Adding 10 ml deionized water leads to the formation of the upper nanowires and the lower nanohole with 129.3° water contact angle. Meanwhile, the AOF provide a good substrate for electroless deposition (ELD) of copper (Cu) to achieve a simple fabrication of metal conductor.

Functionalized graphene oxide (GO) was successfully modified by grafting 1,3,5-triglycidylisocyanurate (TGIC) onto the surface of GO. The modified GO was then added to a novolac epoxy composite at various volume fractions to improve the interfacial compatibility between the filler and matrix. Samples of the modified GO/novolac epoxy composite were fabricated through the hot-pressing method. Microstructural analysis revealed that the modified GO dispersed well in the matrix and formed thermal conductive pathways across the matrix. The thermal degradation temperature of 50% weight loss of the modified GO/novolac epoxy composite was 166 °C higher than that of the novolac epoxy. The data for loss factor tan  δ demonstrated that when the composite contained 36.8 wt% of modified GO, the glass transition temperature of the modified GO/novolac epoxy composite was 222 °C, which is 90 °C higher than that of the novolac epoxy. The thermal conductivity of the modified GO/novolac epoxy composite improved from 0.044 W m -1 K -1 to 1.091 W m -1 K -1 . Results indicated that the incorporation of surface-modified GO into the novolac epoxy positively affects the thermal conductivity and various properties of the modified GO/novolac epoxy composite., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Thermoplastic polyurethane (TPU) was blended with recycled polyethylene terephthalate (rPET) to prepare rPET/thermoplastic polyurethane (TPU) composites. Meanwhile, multiple-walled carbon nanotubes (MWCNTs) were employed as a reinforcing filler to study the synergistic effect between CNTs and rPET/TPU composites. The effect of CNT content on the morphology and micro-structure of the composites was investigated using a scanning electron microscope (SEM) and X-ray diffraction (XRD). The thermal properties were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The mechanical properties were investigated using tensile tests and hardness measurements. The results showed that TPU was compatible with rPET. The existence of rPET changed the crystalline phase and affected the glass transition and crystallisation temperature of the TPU matrix. The rPET/TPU composites displayed poor thermal stability and tensile properties when compared to pure TPU. The addition of CNTs had no effect on the crystalline phase of the rPET/TPU composites. Due to the occurrence of interfacial adhesion between the CNTs and rPET, the CNTs displayed an offset effect on the reaction of rPET and decreased the rigidity of the molecular chain in the rPET/TPU composites. The thermal stability and tensile strength of the CNTs/rPET/TPU composites improved with an increase in CNT content., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Annually a tremendous amount of office waste paper (OWP) is discarded creating environmental pollution. Therefore, how to make this paper from waste to wealth and use it in new approaches have become a meaningful and challenging work. In this work, OWP being a cellulose rich biomass was employed for the production of cellulose nanocrystals (CNCs) by acid hydrolysis with different acid concentrations but without subjecting OWP to alkali and bleaching treatments. The testing results showed that CNCs prepared using sulfuric acid concentration of 59% with respect to OWP had the highest crystallinity and this concentration was the transition concentration for the production of opaque CNCs film with convoluted nanofibers to transparent one with orientated nanofibers. Besides, CNCs prepared using acid concentration of 65% coated on PET sheet not only had a better water vapor barrier property but also was on a par with the transparency of PET, which was hopeful to be used as coating materials in packaging materials., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Water plays important roles in organic reactions such as polyurethane synthesis, and the aqueous solution environment affects polymer morphology and other properties. This paper focuses on the morphology and surface properties of waterborne polyurethane resulting from the organic reaction in water involving different forms (solid and liquid), temperatures and aqueous solutions. We provide evidence from TEM observations that the appearance of polyurethane nanoparticles in aqueous solutions presents diverse forms, including imperfect spheres, perfect spheres, perfect and homogenous spheres and tubes. Based on the results on FTIR, GPC, AFM and XRD experiments, we suggest that the shape of the nanoparticles may be decided by the crimp degree (i.e., the degree of polyurethane chains intertangling in the water environment) and order degree, which are determined by the molecular weight (M n ) and hydrogen bonds. Meanwhile, solid water and high-temperature water can both reduce hard segments that gather on the polyurethane film surface to reduce hydrophilic groups and produce a soft surface. Our findings show that water may play key roles in aqueous polymer formation and bring order to molecular chains.

The association between the expression of excision repair cross‑complementing gene 1 (ERCC1), thymidylate synthase (TYMS), ribonuleotide reductase M1 (RRM1), βIII‑tubulin (TUBB3), non‑muscle myosin II, myoglobin and MyoD1 in metastatic lung adenocarcinoma, and clinical outcomes with platinum‑based chemotherapy treatment is not well‑established. Recently, increasing attention has been focused on the involvement of ERCC1, TYMS, RRM1 and TUBB3 in the development of drug resistance. There has been less research into the role of muscle myosin II, myoglobin and MyoD1 in the pathogenesis of lung cancer, although these genes are known to have important functions within tumor cells. In the current study, malignant pleural effusion from 116 patients with untreated lung adenocarcinoma diagnosed between 2011 and 2012, were collected. The protein expression levels of ERCC1, TYMS, RRM1 and TUBB3 were evaluated with immunocytochemistry and western blot analysis. The expression levels of non‑muscle myosin II, myoglobin and MyoD1 were measured in a subset of 50 patients, treated with platinum‑based chemotherapy. The association of each of these seven factors with one another, as well as with patient survival were analyzed. Immunohistochemistry demonstrated that the percentage of pleural fluid samples from patients with lung adenocarcinoma expressing ERCC1, TYMS, RRM1 and TUBB3 was 37, 36.2, 82.7 and 69.8%, respectively. In the subset of 50 patients in whom the remaining factors were analyzed, the percentage expressing non‑muscle myosin II was 48%, for myoglobin the figure was 40% and for MyoD1 it was 38%. There was a positive correlation between each pair of the above seven molecules with the exception of TYMS and RRM1. Expression of ERCC1, TYMS, TUBB3, non‑muscle myosin II, myoglobin and MyoD1 genes was associated with decreased survival in patients with metastatic lung adenocarcinoma. Expression of ERCC1, TYMS, TUBB3, non‑muscle myosin II, myoglobin and MyoD1 was also associated with decreased survival rates of patients with lung adenocarcinoma treated with platinum‑based chemotherapy. These factors may be used as clinical biomarkers to predict the biological behavior and chemoresistance of tumor cells, and the survival of patients with lung carcinoma.

Background: To evaluate the expression and differential diagnostic significance of CK19, TG, Ki67 and galectin-3 in papillary thyroid carcinoma (PTC) (metastatic and non metastatic), follicular adenoma and nodular goiter in patients from the northeastern part of China., Methods: 441 PTC specimens and 151 other benign thyroid specimens (97 cases of nodular goiter, 54 cases of nonmalignant follicular adenoma) were collected. Immunohistochemistry for CK19, TG, Ki67 and galectin-3 was performed., Results: CK19, TG, Ki67 and galectin-3 expression was 96.37% (425/441), 82.77% (365/441), and 40.59% (179/441), 96.82% (427/441), respectively, for the PTC group and the expression of these markers in the benign thyroid lesions group was 25.83% (39/151), 79.47% (120/151), and 37.09% (56/151), 50.99% (77/151), respectively. The expression of CK19 and galectin-3 in PTC was much higher than that in the nonmalignant group (p < 0.05). However, the expression of TG, Ki67 did not differ among these two groups (p > 0.05). The diagnostic efficiency of CK19 and galectin-3 for PTC was 96.37% (537/592) and 84.63% (501/592). CK19 and galectin-3 expression rate in PTC was higher than that in benign disease cases., Conclusions: The diagnostic efficiency of CK19 for PTC was slightly better than galectin-3. The utilization of these markers combined with morphologic evaluation may be helpful in the differential diagnosis of papillary thyroid carcinoma in the northeastern region of China.

Background: Different isoforms of p120-catenin (p120(ctn)), the members of catenin family, are variably expressed in different tissues and cells. These isoforms may confer different properties with respect to cell adhesion and migration, but this concept needs experimental evidence., Methods: To more precisely define their biological roles, we stably transfected isoforms 1A and 3A into the lung cancer cell lines A549 and NCI-H460, which had low expression of p120(ctn). Using RT-PCR, Western Blot, and Transwell, we testified their impact on the expression of E-cadherin, beta-catenin, and the invasiveness of lung cancer cells., Results: Expression of isoform 1A of p120(ctn) upregulated E-cadherin and beta-catenin, as well as the ability of cells to invasion. In contrast, overexpression of isoform 3A had a smaller influence on invasion., Conclusions: P120(ctn) isoforms 1A and 3A may differently regulate the invasive, adhesive of lung cancer cells through distinct regulation of the expression of E-cadherin and beta-catenin.

Objective: To determine the clinicopathologic prognostic factors in adult granulosa cell tumors (GCTs) of the ovary., Methods: This retrospective study was carried out over a period of 10 years (1995-2005) in the Gynecology Department of Shengjing Hospital, China Medical University, Shenyang, China. Forty-six patients with GCT were enrolled in this study. Demographic data, pathologic findings, treatments, and survival time were reviewed and analyzed for prognostic significance., Results: It was found that International Federation of Gynecology and Obstetrics (FIGO) stage (p=0.0003), presence of nuclear atypia (p=0.036), and increased mitoses (p=0.002) were the 3 factors that impacted significantly on survival. Age, residual tumor disease, parity, and size of the tumor had no significant effect on survival. The only factor associated with risk of recurrence was rupture of the tumor (p=0.038). Patients who received chemotherapy had a better median disease-free survival than those who did not (105 versus 78 months), however, this did not reach statistical significance (p=0.080)., Conclusion: The FIGO stage, nuclear atypia, and increased mitoses are the statistically significant prognostic factors, and may be used for selecting patients for adjuvant therapy. A prolonged follow-up is necessary due to risk of recurrences, late, and exceptional for the adult ovarian GCT, especially when the tumor ruptured before, or at operation.

Background: The conformation of a subset of phosphorylated serines or threonines preceding proline motifs is regulated by the prolyl isomerase Pin1. Pin1 plays a critical role in oncogenesis. The aim of this study is to explore the relationship between the expression of Pin1 and clinicopathological factors in squamous cell carcinoma and adenocarcinoma of the lung, and to analyze the correlation between Pin1 and β-catenin., Methods: The expression of Pin1 and β-catenin proteins was detected in 69 lung cancer cases by immunohistochemical SP method, and in 30 fresh lung samples by Western blot., Results: Immunohistochemically, the overexpression of Pin1 and β-catenin in lung cancer was 78.3% (54/69) and 63.8% (44/69), respectively. The expression of Pin1 and β-catenin was not related to age, sex, histological classification, differentiation, lymph node metastasis and pTNM stages. There was a positive correlation between overexpression of Pin1 and aberrant β-catenin expression (P < 0.05). Western blot results showed that the expression of Pin1 and β-catenin in lung cancer tissues was significantly higher than that of paracancerous lung tissues (P < 0.05)., Conclusions: Pin1 is overexpressed in squamous cell carcinoma and adenocarcinoma of the lung and may play a critical role in oncogenesis of lung cancer. Overexpression of Pin1 might contribute to the upregulation of β-catenin and it may be one of the pathways for Pin1 to work.

Background: Immunocytochemistry is valuabale in differentiating malignant fluids from benign ones. However, the diagnostic value of a single tumor marker is limited. The aim of this study is to evaluate the clinical value of capture of cancer cells in pleural fluids of patients with lung cancer by cytochip., Methods: A new pattern cytochip was developed to immunize hybridization of cells in pleural fluids of patients with 42 lung cancers and with 20 lung benign lesions. Ten antibodies were fixed on the cytochip, they were epithelial specific antigen (ESA), CD44V6, ND-1, T cell (CD3), CD45RO, B cell (CD20), CD79a, Hodgkin's cell (CD15), CD30 and macrophage (CD68)., Results: The point of positive hybridization showed round distribution with clear border, and the shape of cell displayed well. The positive numbers of ESA, CD44V6, ND-1 were 35, 30, 38 respectively in pleural fluids of 42 patients with luog cancers; lymphocytes and neutrophils were found on the 1 ESA and 1 ND-1 respectively, and only lymphocytes were found on the 3 CD44V6 in 20 ones with lung benign lesions; the other 7 antibodies did not capture cancer cells except for lymphocytes, neutrophils and macrophages from two pleural fluids., Conclusions: The cytochip could be an important practical foreground in clinic for diagnosing cancer cells in pleural fluids of patients with lung cancer.