Hydrophilic Silica/Copolymer Nanoparticles and Protein-Resistance Coatings

Hydrophilic silica/copolymer nanoparticles of SiO2-g-P(PEGMA)-b-P(PEG) are prepared by silica surface-initiating atom transfer radical polymerization (SI-ATRP) of poly (ethylene glycol) methyl ether methacrylate (PEGMA) and poly(ethylene glycol) methacrylate (PEG), by using Three molar ratios of SiO2-Br/PEGMA/PEG as 1/42.46/19.44, 1/42.46/38.88 and 1/42.46/77.76. Their temperature sensitive behaviour, pH response and surface properties as protein-resistance coatings are characterized. 220 nm core-shell nanoparticles as P(PEGMA)-b-P(PEG) shell grafted on SiO2 core are formed in water solution, which gained LCST at 60。C - 77。C and good dispersion in water when pH > 5.0. The water-casted films by SiO2-g-P(PEGMA)-b-P(PEG) obtain a little rough surface (Ra = 26.8 - 29.7 nm). While, the introduction of P(PEG) segments could slight increase the protein-repelling adsorption of SiO2-g-P(PEGMA)-b-P(PEG) films (△f = ?6.96 Hz ~ ?7.25 Hz) compared with SiO2-g-P(PEGMA) films (△f = ?9.5 Hz). Therefore, SiO2-g-P(PEGMA)-b-P(PEG) could be used as protein-resistance coatings.

Exploring the effect of cooling rate on non-isothermal crystallization of copolymer polypropylene by fast scanning calorimetry

Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.

Influence ofβ-nucleating Compound Agents on the Mechanical Properties and Crystallization Behavior of Polypropylene Random Copolymer

A novel polypropylene random(PPR)composite materials with optimized properties was developed by addingβ-nucleating compound agents(rare earth complex WBG-2 and aryl amide derivative TMB-5)and ternary compound modifier(TPE/WBG-2/CaCO_(3)).The effects of differentβ-nucleating agents and ternary compound modifier on the mechanical properties and crystallization behavior of PPR were analyzed.The results show that,compared with pure PPR materials,both WBG-2 and TMB-5 could significantly improve the impact strength of PPR.The crystallization temperature of PPR increased with the addition ofβ-nucleating agent.The modified PPR prepared with ternary compound modifier showed the most excellent comprehensive properties.

Fabrication and characterization of epoxylated zwitterionic copolymergrafted silica nanoparticle as a new support for lipase immobilization

Our previous work proved that the thermal stability of Candida rugosa lipase(CRL)immobilized on zwitterionic polymer(poly(carboxybetaine methacrylate))grafted silica nanoparticle(SNP)was much higher than that on poly(glycidyl methecrylate)(pGMA)grafted SNP,while the latter showed significantly increased activity.Inspired by the research,we have herein proposed to synthesize copolymers of zwitterionic sulfobetaine methacrylate(SBMA)and GMA for CRL immobilization.The copolymers were grafted onto SNP surface at three GMA/SBMA(G/S)molar ratios(G100/S0,G50/S50,G10/S90),followed by the covalent coupling of CRL to the surface copolymers.The immobilized CRLs on the corresponding supports were denoted as p(G100-S0)-CRL,p(G50-S50)-CRL and p(G10-S90)-CRL.The enzyme loading increased with the increase of GMA content in the copolymer,while the activity varied with the grafted copolymer composition.Kinetic study proved the improvement of enzyme-substrate affinity after immobilization.In comparison to p(G100-S0)-CRL,p(G50-S50)-CRL and p(G10-S90)-CRL presented remarkably enhanced thermal stability and pH tolerance,and p(G10-S90)-CRL showed the highest stability.These results suggest that the copolymer design is promising for development as a versatile platform for enzyme immobilization.

Research on the Marine Antifouling Ability and Mechanism of Acrylate Copolymers and Marine Coatings Based on a Synergistic Effect

Marine biofouling is an urgent global problem in the process of ocean exploitation and utilization.In our work,a series of zinc-based acrylate copolymers(ACZn-x)were designed and synthesized using benzoic acid,zinc oxide(ZnO)and a random quaternion copolymer consisting of ethyl acrylate(EA),butyl acrylate(BA),acrylic acid(AA)and methacrylic acid(MAA)by free radical polymerization and dehydration condensation.The ACZn-x with a zinc benzoate side chain is able to hydrolyze in natural seawater under static conditions,resulting in the formation of a smooth surface.We investigated and confirmed the antifouling(AF)behavior of ACZn-x in the laboratory and revealed that they have better antibacterial(86%for S.aureus and 72%for E.coli)and anti-algal(≥60.1%for N.closterium and≥67.5%for P.subcordiformis)activities.We also assessed the marine AF properties of ACZn-x and corresponding coatings in Qingdao,China;the ACZn-x exhibited ideal AF properties with little silt and biological mucosa adhered to the ACZn-x surface after 6 months,and corresponding coatings exhibited little biofouling after 16 months in the ocean.Importantly,possible AF mechanisms were further proposed at the cellular level.These results could be helpful for the development and application of effective AF coatings.

Highly efficient organic solar cells with improved stability enabled by ternary copolymers with antioxidant side chains

The stability of organic solar cells(OSCs)remains a major concern for their ultimate industrialization due to the photo,oxygen,and water susceptibility of organic photoactive materials.Usually,antioxidant additives are blended as radical scavengers into the active layer.However,it will induce the intrinsic morphology instability and adversely affect the efficiency and long-term stability.Herein,the antioxidant dibutylhydroxytoluene(BHT)group has been covalently linked onto the side chain of benzothiadiazole(BT)unit,and a series of ternary copolymers D18-Cl-BTBHTx(x=0,0.05,0.1,0.2)with varied ratio of BHT-containing side chains have been synthesized.It was found that the introduction of BHT side chains would have a negligible effect on the photophysical properties and electronic levels,and the D18-Cl-BTBHT0.05:Y6-based OSC achieved the highest power conversion efficiency(PCE)of 17.6%,which is higher than those based active layer blended with BHT additives.More importantly,the unencapsulated device based on D18-Cl-BTBHTx(x=0.05,0.1,0.2)retained approximately 50%of the initial PCE over 30 hours operation under ambient conditions,significantly outperforming the control device based on D18-Cl(90%degradation in PCE after 30 h).This work provides a new structural design strategy of copolymers for OSCs with simultaneously improved efficiency and stability.

Surface Photografting of Novel Sulfobetaine Copolymers on Silica

A couple of novel sulfobetaine copolymer is developed via Michael-type addition reaction. The comonomers, diamines and maleimide react via Michael reaction through UV irradiation using AIBN as photoinitiator producing polyamine chain. Further, sulfobetaine copolymers were obtained on treatment of the polyamine with sulfopropylating agent, 1,3-propane sultone. These novel sulfobetaine polymers were grafted on silica surface to produce responsive biocompatible surface. This easy straightforward, catalyst free facile protocol for synthesis of polymer grafted surface is useful for developing biomedical devices. Additionally, both the copolymers show fluorescence characteristics.

Dual responsive block copolymer coated hollow mesoporous silica nanoparticles for glucose-mediated transcutaneous drug delivery

A self-regulated anti-diabetic drug release device mimicking pancreatic cells is highly desirable for the therapy of diabetes. Herein, a glucose-mediated dual-responsive drug delivery system, which combines pH-and H_(2)O_(2)-responsive block copolymer grafted hollow mesoporous silica nanoparticles(HMSNs)with microneedle(MN) array patch, has been developed to achieve self-regulated administration.The poly[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl acrylate]-b-poly[2-(dimethylamino)ethyl methacrylate](PPBEM-b-PDM) polymer serves as gate keeper to prevent drug release from the cavity of HMSNs at normoglycemic level. In contrast, the drug release rate is significantly enhanced upon H_(2)O_(2)and pH stimuli due to the chemical change of H_(2)O_(2)sensitive PPBEM block and acid responsive PDM block. Therefore, incorporation of anti-diabetic drug and glucose oxidase(GOx, which can oxidize glucose to gluconic acid and in-situ produce H_(2)O_(2)) into stimulus polymer coated HMSNs results in a glucose-mediated MN device after depositing the drug-loaded nanoparticles into MN array patch. Both in vitro and in vivo results show this MN device presents a glucose mediated self-regulated drug release characteristic, which possesses a rapid drug release at hyperglycemic level but retarded drug release at normoglycemic level. The result indicates that the fabricated smart drug delivery system is a good candidate for the therapy of diabetes.

Silica-modified Pt/TiO_(2) catalysts with tunable suppression of strong metal-support interaction for cinnamaldehyde hydrogenation

Tuning Strong Metal-support Interactions(SMSI)is a key strategy to obtain highly active catalysts,but conventional methods usually enable TiO encapsulation of noble metal components to minimize the exposure of noble metals.This study demonstrates a catalyst preparation method to modulate a weak encapsulation of Pt metal nanoparticles(NPs)with the supported TiO_(2),achieving the moderate suppression of SMSI effects.The introduction of silica inhibits this encapsulation,as reflected in the characterization results such as XPS and HRTEM,while the Ti4+to Ti3+conversion due to SMSI can still be found on the support surface.Furthermore,the hydrogenation of cinnamaldehyde(CAL)as a probe reaction revealed that once this encapsulation behavior was suppressed,the adsorption capacity of the catalyst for small molecules like H_(2) and CO was enhanced,which thereby improved the catalytic activity and facilitated the hydrogenation of CAL.Meanwhile,the introduction of SiO_(2) also changed the surface structure of the catalyst,which inhibited the occurrence of the acetal reaction and improved the conversion efficiency of C=O and C=C hydrogenation.Systematic manipulation of SMSI formation and its consequence on the performance in catalytic hydrogenation reactions are discussed.

Silica nanoparticle design for colorectal cancer treatment:Recent progress and clinical potential

Colorectal cancer(CRC)is the third most common cancer worldwide and the second most common cause of cancer death.Nanotherapies are able to selectively target the delivery of cancer therapeutics,thus improving overall antitumor eff-iciency and reducing conventional chemotherapy side effects.Mesoporous silica nanoparticles(MSNs)have attracted the attention of many researchers due to their remarkable advantages and biosafety.We offer insights into the recent advances of MSNs in CRC treatment and their potential clinical application value.

Al-modified yolk-shell silica particle-supported NiMo catalysts for ultradeep hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene:Efficient accessibility of active sites and suitable acidity

Yolk-shell SiO2 particles(YP)with center-radial meso-channels were fabricated through a simple and effective method.Al-containing YP-supported NiMo catalysts with different Al amounts(NiMo/AYP-x,x=Si/Al molar proportion)were prepared and dibenzothiophene(DBT)and 4,6-dimethyl-dibenzothiophene(4,6-DMDBT)were employed as the probes to evaluate the hydrodesulfurization(HDS)catalytic performance.The as-prepared AYP-x carriers and corresponding catalysts were characterized by some advanced characterizations to obtain deeper correlations between physicochemical properties and the HDS performance.The average pore sizes of series AYP-x supports are above 6.0 nm,which favors the mass transfer of organic sulfides.The cavity between the yolk and the shell is beneficial for the enrichment of S-containing compounds and the accessibility between reactants and active metals.Aluminum embedded into the silica framework could facilitate the formation of Lewis(L)and Brønsted(B)acid sites and adjust the metal-support interaction(MSI).Among all the as-synthesized catalysts,NiMo/AYP-20 catalyst shows the highest HDS activities.The improved HDS activity of NiMo/AYP-20 catalyst is attributed to the perfect combination of excellent structural properties of the yolk-shell mesoporous silica,enhanced acidity,moderate MSI,and good accessibility/dispersion of active components.

New Data on Coal, Gypsum, Iron and Silica Sand Deposits and Geochemical Exploration (Pakistan): Revision of 25 Years History of Dinosaur Discoveries from Pakistan

Discoveries of many coal seams at depths by drilling carried by Geological Survey of Pakistan in Sor Range and Harnai Gochina, extended the coal seams at depth which is challenge for mine owners to exploit feasibly. Bed to bed gypsum samplings (and their chemical analyses) of huge gypsum deposits from Sulaiman foldbelt is a base for industrialist and also planers to develop cement and gypsum industries to increase export and foreign exchange for the development of area and Pakistan. Low and high grade sedimentary iron deposits, silica sand and uranium host rocks and their extensions in Sulaiman and Kirthar foldbelts are presented. Anomalies of a few base metals arise as a result of geochemical exploration carried at part of Loralai District of Balochistan. Theropod dinosaurs were frequent in India, while Poripuchian titanosaurs (Sauropoda, Dinosauria) were frequent in Pakistan. Besides some ichnotaxa, many bone taxa such as 1 titanosauriform, 14 titanosaurian sauropod (including one new titanosaur), and 3 theropod dinosaurs are established from Pakistan. Among these 12 titanosaur species and 3 theropod species are named in about 10 km2 area of Vitakri dome and 2 titanosaur species are named in about a few hundred square meter area of Mari Bohri (Kachi Bohri) which is about 10 km westward from Vitakri dome. Pakistan is a unique country which discoverd 14 diversified titanosaurs in a short area and also in a short period (67 - 66 million years ago/Ma). About 400 bones found from a few meter thick upper part of upper shale horizon of latest Maastrichtian Vitakri Formation which is base for titanosaur taxa. Cranial material is in low fraction (but include significant diverse snouts), caudal vertebrae are prominent, the cervicals, dorsals and sacrals have significant numbers, forelimb and hind limb bones have balanced fraction. Humeri, femora and tibiae are most common. To know the position of Pakistani titanosaurs among titanosaurs and sauropods, there is a need to extend list of characters for phylogenetic analyses. This broad feature list should include main characters of titanosaurs from Pakistan and also from global world.

Gypsum-based Silica Gel Humidity-controlling Composite Materials:Preparation,Characterization,and Performance

Gypsum was used as substrate,and silica gel was mixed into substrate at a certain mass ratio to prepare humidity-controlling composites;moreover,the moisture absorption and desorption properties of gypsum-based composites were compared with adding different silica gel particle size and proportion.The morphological characteristics,the isothermal equilibrium moisture content curve,moisture absorption and desorption rate,moisture absorption and desorption stability,and humidity-conditioning performance were tested and analyzed.The experimental results show that,compared with pure-gypsum,the surface structure of the gypsum-based composites is relatively loose,the quantity,density and aperture of the pores in the structure increase.The absorption and desorption capacity increase along with the increase of silica gel particle size and silica gel proportion.When 3 mm silica gel particle size is added with a mass ratio of 40%,the maximum equilibrium moisture content of humidity-controlling composites is 0.161 g/g at 98% relative humidity(RH),3.22 times that of pure-gypsum.The moisture absorption and desorption rates are increased,the equilibrium moisture absorption and desorption rates are 2.68 times and 1.61 times that of pure-gypsum at 58.5% RH,respectively.The gypsum-based composites have a good stability,which has better timely response to dynamic humidity changes and can effectively regulate indoor humidity under natural conditions.

Green synthesis of ZSM-5 using silica fume and catalytic co-cracking of lignin and plastics for production of monocyclic aromatics

ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.

Residual stress modeling of mitigated fused silica damage sites with CO_(2)laser annealing

A numerical model based on measured fictive temperature distributions is explored to evaluate the residual stress fields of CO_(2)laser-annealed mitigated fused silica damage sites.The proposed model extracts the residual strain from the differences in thermoelastic contraction of fused silica with different fictive temperatures from the initial frozen-in temperatures to ambient temperature.The residual stress fields of mitigated damage sites for the CO_(2)laser-annealed case are obtained by a finite element analysis of equilibrium equations and constitutive equations.The simulated results indicate that the proposed model can accurately evaluate the residual stress fields of laser-annealed mitigated damage sites with a complex thermal history.The calculated maximum hoop stress is in good agreement with the reported experimental result.The estimated optical retardance profiles from the calculated radial and hoop stress fields are consistent with the photoelastic measurements.These results provide sufficient evidence to demonstrate the suitability of the proposed model for describing the residual stresses of mitigated fused silica damage sites after CO_(2)laser annealing.

A novel responsive stabilizing Janus nanosilica as a nanoplugging agent in water-based drilling fluids for exploiting hostile shale environments

Thermo-responsive nanocomposites have recently emerged as potential nanoplugging agents for shale stabilization in high-temperature water-based drilling fluids(WBDFs). However, their inhibitory properties have not been very effective in high-temperature drilling operations. Thermo-responsive Janus nanocomposites are expected to strongly interact with clay particles from the inward hemisphere of nanomaterials, which drive the establishment of a tighter hydrophobic membrane over the shale surface at the outward hemisphere under geothermal conditions for shale stabilization. This work combines the synergistic benefits of thermo-responsive and zwitterionic nanomaterials to synchronously enhance the chemical inhibitions and plugging performances in shale under harsh conditions. A novel thermoresponsive Janus nanosilica(TRJS) exhibiting zwitterionic character was synthesized, characterized,and assessed as shale stabilizer for WBDFs at high temperatures. Compared to pristine nanosilica(Si NP)and symmetrical thermo-responsive nanosilica(TRS), TRJS exhibited anti-polyelectrolyte behaviour, in which electrolyte ions screened the electrostatic attraction between the charged particles, potentially stabilizing nanomaterial in hostile shaly environments(i.e., up to saturated brine or API brine). Macroscopically, TRJS exhibited higher chemical inhibition than Si NP and TRS in brine, prompting a better capability to control pressure penetration. TRJS adsorbed onto the clay surface via chemisorption and hydrogen bonding, and the interactions became substantial in brine, according to the results of electrophoretic mobility, surface wettability, and X-ray diffraction. Thus, contributing to the firm trapping of TRJS into the nanopore structure of the shale, triggering the formation of a tight hydrophobic membrane over the shale surface from the outward hemisphere. The addition of TRJS into WBDF had no deleterious effect on fluid properties after hot-treatment at 190℃, implying that TRJS could find potential use as a shale stabilizer in WBDFs in hostile environments.

Theoretical study on the effective thermal conductivity of silica aerogels based on a cross-aligned and cubic pore model

Aerogel nanoporous materials possess high porosity, high specific surface area, and extremely low density due to their unique nanoscale network structure. Moreover, their effective thermal conductivity is very low, making them a new type of lightweight and highly efficient nanoscale super-insulating material. However, prediction of their effective thermal conductivity is challenging due to their uneven pore size distribution. To investigate the internal heat transfer mechanism of aerogel nanoporous materials, this study constructed a cross-aligned and cubic pore model(CACPM) based on the actual pore arrangement of SiO_(2) aerogel. Based on the established CACPM, the effective thermal conductivity expression for the aerogel was derived by simultaneously considering gas-phase heat conduction, solid-phase heat conduction, and radiative heat transfer. The derived expression was then compared with available experimental data and the Wei structure model. The results indicate that, according to the model established in this study for the derived thermal conductivity formula of silica aerogel, for powdery silica aerogel under the conditions of T = 298 K, a_(2)= 0.85, D_(1)= 90 μm, ρ = 128 kg/m^(3), within the pressure range of 0–10^(5)Pa, the average deviation between the calculated values and experimental values is 10.51%. In the pressure range of 10^(3)–10^(4)Pa, the deviation between calculated values and experimental values is within 4%. Under these conditions, the model has certain reference value in engineering verification. This study also makes a certain contribution to the research of aerogel thermal conductivity heat transfer models and calculation formulae.

Preparation of Mesoporous Carbons from Acrylonitrile-methyl Methacrylate Copolymer/Silica Nanocomposites Synthesized by in-situ Emulsion Polymerization

Acrylonitrile-methyl methacrylate (AN-MMA) copolymer/silica nanocomposites were synthesized by in-situ emulsion polymerization initiated by 2,2′-azobis(2-amidinopropane) dihydrochloride absorbed onto colloidal silica particles, and the mesoporous carbon materials were prepared through carbonization of the obtained AN-MMA copolymer/silica nanocomposites, followed by HF etching. Thermogravimetric analysis of AN-MMA copolymer/silica nanocomposites showed that the carbon yield of copolymer was slightly decreased as silica parti-cle incorporated. N2 adsorption-desorption, scan electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the mesoporous carbon materials. Both SEM and TEM results showed that disordered mesopores were formed in the obtained carbon material mainly through tem-plating effect of silica nanoparticles. The diameter of mesopores was mainly distributed in the range from 5 nm to 15 nm. The mean pore diameter and total pore volume of the material increased as the mass fraction of silica in the nanocomposites increased from 0 to 24.93%. The significant increase of the mean pore diameter and the decrease of surface area for the carbon material prepared from the nanocomposite with 24.93% silica were caused by partial aggregation of silica nanoparticles in the polymer matrix.

EFFECT OF AMPHIPHILIC POLY (STYRENE-B-ETHYLENE OXIDE) DIBLOCK COPOLYMER INTERCALATED LAYERED SILICATE AS FILLER ON ACRYLONITRILE-BUTADIENE-STYRENE RESIN

The diblock copolymers intercalated layered silicate was prepared via a melt dispersion technique. Then the effect of intercalated hybrid as filler on acrylonitrile- butadiene-styrene resin was characterized by X-ray diffraction, transmission electron microscopy, stress-strain measurements in elongation.

Copolymer 1保护高眼压大鼠视神经的免疫学机制

目的探讨Copolymer 1(Cop 1)对实验性高眼压性青光眼视神经保护作用的相关免疫学机制。方法对27只大鼠采用烧灼巩膜上静脉制作双眼高眼压模型,在眼压升高的第3周,取12只模型大鼠于后脚皮内注射100μg Cop 1和等体积的完全弗氏佐剂(CFA)混合乳化液(实验组);另取12只模型大鼠作为对照组,后脚皮内注射等体积PBS和CFA的混合乳化液;其余3只模型大鼠作为空白对照组,不做任何处理。1周后取出大鼠脾淋巴细胞,采用流式细胞仪检测T细胞亚群的变化;ELISA法检测T细胞分泌细胞因子的变化;[3H]thymidine标记检测淋巴细胞的增殖。结果实验组大鼠的CD4+CD25+Treg/CD4+比值显著高于对照组和空白对照组(P<0.05)。实验组IL-10分泌量和分泌浓度均显著高于对照组和空白对照组,差异有统计学意义(P<0.05),但三组间INF-γ分泌量和分泌浓度比较差异均无统计学差异(P>0.05)。三组间体外刺激淋巴细胞指数比较差异无统计学意义(P>0.05)。结论 Cop 1能诱导CD4+CD25-向CD4+CD25+Treg转化,促进Th1转化为Th2,并增加IL-10的分泌。