On the equilibrium of funicular polyhedral frames and convex polyhedral force diagrams

This paper presents a three-dimensional extension of graphic statics using polyhedral form and force diagrams for the design of compression-only and tension-only spatial structures with externally applied loads. It explains the concept of 3D structural reciprocity based on Rankine’s original proposition for the equilibrium of spatial frames. It provides a definition for polyhedral reciprocal form and force diagrams that allows including external forces and discusses their geometrical and topological characteristics. This paper furthermore provides a geometrical procedure for constructing a pair of reciprocal polyhedral diagrams from a given polyhedron representing either the form or force diagram of a structural system. Using this method, this paper furthermore suggests a design strategy for finding complex funicular spatial forms in pure compression (or tension), based on the construction of force diagrams through the aggregation of convex polyhedral cells. Finally, it discusses the effect of changes in the geometry of the force diagram on the geometry of the form diagram and the distribution of forces in it.     

Synthesis of 3,13-diglycidyloxypropyloctaphenyl double-decker polyhedral oligomeric silsesquioxane and the thermal reaction properties with thermosetting phenol-formaldehyde resin

3,13-Diglycidyloxypropyloctaphenyl double-decker silsesquioxane (EP-DDSQ) was synthesized by process of alkaline hydrolysis condensation of phenyltrimethoxysilane and corner capping reaction of methyldichlorosilane, followed by hydrosilylation with allyl glycidyl ether, and the resultant structure was confirmed by fourier transform infrared spectrometer (FTIR) and nuclear magnetic resonance (NMR), respectively. The thermosetting phenol-formaldehyde (PF) resin was then modified by EP-DDSQ, and the reactivity of PF resin with EP-DDSQ and thermal pyrolysis of modified cured resin were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The surface morphologies of modified resins at high temperature were characterized with field emission scanning electron microscope (FESEM), and chemical structure of modified resins was analyzed through X-ray photoelectron spectrometer (XPS). The results showed that the appropriate addition of EP-DDSQ did not affect the curing temperature of the PF resin itself, but could improve the heat resistance of the system. When the amount of EP-DDSQ added was 10%, the initial degradation temperature of PF resin was increased by 49.31°C, and when the amount of EP-DDSQ added was 16%, the char yield of which was reached up to 61.39%, compared with that of pure PF resin (TGA_1,000°C of 57.62%) at Ar atmosphere. More importantly, the modified resin formed a regular and dense layer of SiC and SiO_x ceramic on the surface after ablation in the muffle furnace at 800°C air atmosphere, which is very important for ablative resistant materials.     

多面体低聚倍半硅氧烷的合成研究进展

首先介绍了多面体低聚倍半硅氧烷(POSS)的结构、分类和性质,然后综述了三官能度硅烷或四官能度硅烷在酸、碱和有机盐催化下通过水解缩合反应合成POSS的研究进展,以及以POSS为母体、通过封端关笼法、闭环法和官能团转化法合成POSS的研究进展。     

A Fluorimetric Readout Reporting the Kinetics of Nucleotide‐Induced Human Ribonucleotide Reductase Oligomerization

Human ribonucleotide reductase (hRNR) is a target of nucleotide chemotherapeutics in clinical use. The nucleotide‐induced oligomeric regulation of hRNR subunit α is increasingly being recognized as an innate and drug‐relevant mechanism for enzyme activity modulation. In the presence of negative feedback inhibitor dATP and leukemia drug clofarabine nucleotides, hRNR‐α assembles into catalytically inert hexameric complexes, whereas nucleotide effectors that govern substrate specificity typically trigger α‐dimerization. Currently, both knowledge of and tools to interrogate the oligomeric assembly pathway of RNR in any species in real time are lacking. We therefore developed a fluorimetric assay that reliably reports on oligomeric state changes of α with high sensitivity. The oligomerization‐directed fluorescence quenching of hRNR‐α, covalently labeled with two fluorophores, allows for direct readout of hRNR dimeric and hexameric states. We applied the newly developed platform to reveal the timescales of α self‐assembly, driven by the feedback regulator dATP. This information is currently unavailable, despite the pharmaceutical relevance of hRNR oligomeric regulation.     

笼型倍半硅氧烷（POSS）的功能化改性 及应用研究进展

有机/无机杂化材料的改性及应用是目前材料科学中最富有活力的研究领域之一。其中笼型倍半硅氧烷（Polyhedral oligomeric silsesquioxane，POSS）在分子水平上实现了有机组分与无机组分的结合，结构呈硅氧骨架连接的立体笼型，具有优异的反应活性、耐热阻燃性、多孔性和纳米尺寸效应等特性，通过化学改性可将其应用在多个领域。本文主要从官能团改性、聚合改性和配位改性三个方面阐述了POSS的改性方法，综述了POSS在耐热材料、阻燃材料、增强材料和多孔材料等领域的应用研究进展，并对POSS今后的研究方向提出了展望。可从POSS的构效关系、改性方法以及安全性等方面进行更加深入和系统的研究，以促进POSS材料更广泛的应用。     

Epoxy‐functionalized polyhedral oligomeric silsesquioxane/cyanate ester resin organic–inorganic hybrids with enhanced mechanical and thermal properties

A series of cyanate ester resin (CE) based organic–inorganic hybrids containing different contents (0, 5, 10, 15 and 20 wt%) of epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS‐Ep) were prepared by casting and curing. The hybrid resin systems were studied by the gel time test to evaluate the effect of POSS‐Ep on the curing reactivity of CE. The impact and flexural strengths of the hybrids were investigated. The micromorphological, dynamic mechanical and thermal properties of the hybrids were studied by SEM, dynamic mechanical analysis (DMA) and TGA, respectively. Results showed that POSS‐Ep prolonged the gel time of CE. CE10 containing 10 wt% POSS‐Ep displayed not only the optimum impact strength but the optimum flexural strength. SEM results revealed that the improvement of mechanical properties was attributed to the large amount of tough whirls and fiber‐like pull‐outs observed on the fracture surfaces of CE10. DMA results indicated that POSS‐CE tended to decrease E′ of the hybrids in the glassy state but to increase E′ of the hybrids in the rubbery state. TGA results showed that CE10 also possesses the best thermal stability. The initial temperature of decomposition (T_i) of CE10 is 426 °C, 44 °C higher than that of pristine CE. © 2013 Society of Chemical Industry     

功能化POSS对硅橡胶力学性能的影响及机理研究

研究了八聚笼型倍半硅氧烷(POSS)功能化侧基的种类和用量对硅橡胶力学性能的影响。结果表明,POSS的加入使硅橡胶的拉伸强度和断裂伸长率均下降,硬度均提高。乙烯基POSS的加入显著延长了硅橡胶的正硫化时间。POSS的加入能显著降低硅橡胶的压缩永久变形,乙烯基POSS的效果比甲基POSS好;且乙烯基含量越高,压缩永久变形越小。分析了功能化POSS对硅橡胶力学性能的影响机理。     

POSS改性聚合物复合材料力学性能研究进展

介绍了笼型倍半硅氧烷（POSS）的结构、分类以及POSS改性聚合物力学性能的特点和机理,综述了POSS改性聚合物（包括聚烯烃、环氧树脂、聚丙烯酸酯、聚氨酯等）复合材料力学性能的研究进展,并展望了POSS改性聚合物复合材料的发展前景。     

Synthesis of poly(ε‐caprolactone)/clay nanocomposites using polyhedral oligomeric silsesquioxane surfactants as organic modifier and initiator

Poly(ε‐caprolactone)/clay nanocomposites were synthesized by in situ ring‐opening polymerization of ε‐caprolactone in the presence of montmorillonite modified by hydroxyl functionalized, quaternized polyhedral oligomeric silsesquioxane (POSS) surfactants. The octa(3‐chloropropyl) polyhedral oligomeric silsesquioxane was prepared by hydrolytic condensation of 3‐chloropropyltrimethoxysilane, which was subsequently quaternized with 2‐dimethylaminoethanol. Montmorillonite was modified with the quaternized surfactants by cation exchange reaction. Bulk polymerization of ε‐caprolactone was conducted at 110°C using stannous octoate as an initiator/catalyst. Nanocomposites were analyzed by X‐ray diffraction, transmission electron microscopy, thermo gravimetric analysis, and differential scanning calorimetry. Hydroxyl functionalized POSS was employed as a surface modifier for clay which gives stable clay separation for its 3‐D structure and also facilitates the miscibility of polymer with clay in the nanocomposites due to the star architecture. An improvement in the thermal stability of PCL was observed even at 1 wt % of clay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Methacryl-polyhedral oligomeric silsesquioxane as a crosslinker for expediting photo-crosslinking of Poly(propylene fumarate): Material properties and bone cell behavior

We present photo-crosslinkable hybrid organic-inorganic composites of poly(propylene fumarate) (PPF), an injectable and biodegradable polyester, and methacryl-polyhedral oligomeric silsesquioxane (mPOSS), which has eight methacryl groups tethered with a cage-like hybrid inorganic-organic nanostructure, for bone tissue engineering applications. Two PPF samples, one with a higher molecular weight (HPPF) and one with a lower molecular weight (LPPF), were blended with mPOSS at various mPOSS compositions. We emphasize on the role of mPOSS in modifying the photo-crosslinking kinetics of PPF and the physical properties of crosslinked products, and in regulating mouse pre-osteoblastic MC3T3-E1 cell behavior on the crosslinked substrates. The viscoelastic behavior of uncrosslinked PPF/mPOSS and the mechanical, degradation, and surface characteristics of photo-crosslinked PPF/mPOSS samples have been investigated. The crosslinking kinetics of PPF/mPOSS was characterized using the gel fraction and rheological properties such as storage modulus and viscosity of the samples crosslinked for 0.5-5 min. Blending mPOSS with PPF was found to decrease the viscosity of PPF and expedite the photo-crosslinking process, both of which are important in formation of PPF networks. In addition, tensile modulus was increased by crosslinking PPF with mPOSS up to the mPOSS composition of 15%, above which phase separation occurred. The degradation rate in 1 N NaOH solution could also be regulated by varying the mPOSS composition, while crosslinked PPF/mPOSS samples did not show detectable degradation in one week in phosphate buffered saline (PBS) and mPOSS did not significantly alter surface wettability and serum protein adsorption. MC3T3 cell adhesion, spreading, proliferation, differentiation, and gene expression were examined on crosslinked PPF/mPOSS disks. Addition of mPOSS did not introduce cytotoxicity or influence cell behavior evidently. It is interesting to note that crosslinked HPPF/mPOSS showed distinct physical properties and promoted MC3T3 cell functions compared with their LPPF counterparts possibly because of higher crosslinking densities.