水泥基复合材料集料与浆体界面研究综述(一):实验技术

关于界面研究,概括起来主要可以从以下5个方面考虑：(1)界面研究的相关技术手段;(2)界面微观结构特征的研究;(3)界面微观结构的形成及劣化机理;(4)影响界面微观结构因素的研究;(5)界面过渡区的性能对材料宏观性能(包括：力学性能和耐久性)影响的研究。对这些问题的研究是为了回答以下2个问题：(1)各种层次的界面过渡区到底在多大程度上影响着整个材料的力学性能和耐久性;(2)通过改善界面来达到改善水泥基复合材料的性能这一措施是否可行。由于界面研究的技术手段与方法随着其它相关技术与设备的引入而不断取得新的进展,促进了水泥基复合材料集料与浆体界面相关研究也不断取得新的成果。关于界面研究的新实验技术和方法,从如下4个方面进行了描述：(1)与界面过渡区微观结构表征相关的实验技术;(2)与界面过渡区力学性能(包括：粘结强度、刚度和断裂力学性能)相关的技术和方法;(3)与界面过渡区传输性能相关的技术和方法;(4)与界面过渡区收缩性能相关的技术和方法。     

Periodic reactive flow simulation: Proof of concept for steam cracking coils

Streamwise periodic boundary conditions (SPBCs) have been successful in reducing the computational cost of simulating high aspect ratio processes. Extending beyond the classic assumptions of constant property flows, a novel approach incorporating non‐equilibrium kinetics was developed and implemented for the simulation of an industrial propane steam cracker. Comparison with non‐periodic benchmarks provided validation as relative errors on the main product yields were consistently below 1% for different reactor configurations. A further order‐of‐magnitude reduction of the radial errors on product concentrations was obtained via an intuitive correction method based on the concept of local fluid age. The computational speedup achieved through application of SPBCs was a factor 16–250 compared to the non‐periodic simulations. The presented methodology thus serves as a quick screening tool for the development of novel reactor designs and unlocks the potential for using more elaborate kinetic models or a more fundamental approach toward turbulence modeling. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1715–1726, 2017     

Injectable polyethylene glycol-laponite composite hydrogels as articular cartilage scaffolds with superior mechanical and rheological properties

In this study, injectable PEG-based hydrogels containing Laponite particles with mechanical and structural properties close to the natural articular cartilage are introduced. The nanocomposites are fabricated by imide ring opening reactions utilizing synthesized copolymers containing PEG blocks and nanoclay through a two-step thermal poly-(amic acid) process. Butane diamine is used as nucleophilic reagent and hydrogels with interconnected pores with sizes in the range of 100–250?µm are prepared. Improved viscoelastic properties compared with the conventional PEG hydrogels are shown. Evaluation of cell viability utilizing human mesenchymal stem cells determines cytocompatibility of the nanocomposite hydrogels.     

On shrinkage and structure changes of pure and blended Portland concretes

This research investigates the long‐term shrinkage and Relative Mass Loss (RML) of mature Portland concretes (pure CEMI and blended CEMV/A), at temperatures of 20°C and 80°C. When placed at 80°C and at relative humidities (RH) below 50‐60%, concrete shrinkage increases with very slow stabilization kinetics by several hundreds of μm/m, while RML remains of about 0.2%. The origins of this continued shrinkage, simultaneously with limited RML, are investigated through the changes in (i) the pore structure of the concretes (by Mercury Intrusion Porosimetry and nitrogen adsorption) and in (ii) their solid phases (by TGA/DTA, FTIR spectroscopy coupled to DVS, quantitative X‐Ray Diffraction by Rietveld analysis, and ²⁹Si and ²⁷Al MAS NMR). While the pore structure coarsens during continued shrinkage, several phase transformations occur, namely ettringite decomposition and changes in the silicate chain length of the C–A–S–H. While these structural changes are documented, their relationship with shrinkage/RML and to the pore structure is novel.     

Stability of rare‐earth‐doped spherical yttria‐stabilized zirconia synthesized by ultrasonic spray pyrolysis

Phase stability is one of the crucial requirements for any material that can be used at elevated temperature applications such as thermal barrier coating (TBC). The most traditional TBC material, partially stabilized zirconia, limits the operating temperature due to its phase transformation. Conversely, the low thermal conductivity of fully stabilized zirconia (YSZ) may enable effective reduction in the surface temperature on the coated component, while avoiding deleterious phase transitions, although still being subjected to sintering and grain growth. It has been reported that addition of rare‐earths as dopants to YSZ can significantly increase resistance to grain growth at high temperature. Keeping this under consideration, this work investigates the role of rare‐earths (lanthanum and gadolinium) in increasing thermal stability of YSZ microspheres, the building blocks for high‐temperature photonics for reflective TBC. The spheres were produced by ultrasonic spray pyrolysis, and the doping led to significant improvement of stability by significant inhibition of grain growth. While the individual dopants showed significant growth and sintering inhibition up to 900°C, co‐doping with 4% (in mol) of each (Gd and La) led to coarsening resistance up to 1000°C for 3 hours, when particles retained reasonable spherical features with nanometric crystallite sizes.     

Synthesis and Anti‐herpetic Activity of Phosphoramidate ProTides

Among the many prodrug approaches aimed at delivering nucleoside monophosphates into cells, the phosphoramidate ProTide approach is one that has shown success, which has made it possible for some of the phosphoramidates to enter into clinical trials. Herein, we report the synthesis and antiviral activity of a series of phosphoramidate ProTides designed to bypass the thymidine kinase (TK) dependence of the parent nucleoside analogues. Phosphoramidate derivatives of (E)‐5‐(2‐bromovinyl)‐2′‐deoxyuridine (BVDU) that contain L ‐alanine or pivaloyloxymethyl iminodiacetate (IDA‐POM) exhibit anti‐HSV‐1 and anti‐VZV activity in cell cultures, but they largely lost antiviral potency against TK‐deficient virus strains. Among deazapurine nucleosides and their phosphoramidate derivatives, the 7‐deazaadenine containing nucleosides and their phosphoramidate triester derivatives showed weak antiviral activity against VZV. Apparently, intracellular nucleotide delivery with these phosphoramidates is partly successful. However, none of the compound prodrugs showed superior activity to their parent drugs.     

Discovery of an Acyclic Nucleoside Phosphonate that Inhibits Mycobacterium tuberculosis ThyX Based on the Binding Mode of a 5‐Alkynyl Substrate Analogue

The urgent need for new antibiotics poses a challenge to target un(der)exploited vital cellular processes. Thymidylate biosynthesis is one such process due to its crucial role in DNA replication and repair. Thymidylate synthases (TS) catalyze a crucial step in the biosynthesis of thymidine 5‐triphosphate (TTP), an elementary building block required for DNA synthesis and repair. To date, TS inhibitors have only been successfully applied in anticancer therapy due to their lack of specificity for antimicrobial versus human enzymes. However, the discovery of a new family of TS enzymes (ThyX) in a range of pathogenic bacteria that is structurally and biochemically different from the “classic” TS (ThyA) has opened the possibility to develop selective ThyX inhibitors as potent antimicrobial drugs. Here, the interaction of the known inhibitor 5‐(3‐octanamidoprop‐1yn‐1yl)‐2′‐deoxyuridine‐5′‐monophosphate ( 1 ) with Mycobacterium tuberculosis ThyX enzyme is explored using molecular modeling starting from published crystal structures, with further confirmation through NMR experiments. While the deoxyuridylate (dUMP) moiety of compound 1 occupies the cavity of the natural substrate in ThyX, the rest of the ligand (the “5‐alkynyl tail”) extends to the outside of the enzyme between two of its four subunits. The hydrophobic pocket that accommodates the alkyl part of the tail is formed by displacement of Tyr 44.C, Tyr 108.A and Lys 165.A. Changes to the resonance of the Lys 165 NH₃ group upon ligand binding were monitored in a titration experiment by 2D HISQC NMR. Guided by the results of the modeling and NMR studies, and inspired by the success of acyclic antiviral nucleosides, compounds where a 5‐alkynyl uracyl moiety is coupled to an acyclic nucleoside phosphonate (ANP) were synthesized and evaluated. Of the compounds evaluated, sodium (6‐(5‐(3‐octanamidoprop‐1‐yn‐1‐yl)‐2,4‐dioxo‐3,4‐dihydropyrimidin‐1(2H)‐yl)hexyl)phosphonate ( 3 e ) exhibited 43 % of inhibitory effect on ThyX at 50 μM . While only modest activity was achieved, this is the first example of an ANP inhibiting ThyX, and these results can be used to further guide structural modifications to this class to develop more potent compounds with potential application as antibacterial agents acting through a novel mechanism of action.