Computer-aided design of formulated products

Formulated products represent a particular class of complex chemical products, and their design is typically based on experience and extensive experimentation. Although still at an early stage, and despite that their potential is not fully accessed and not fully used by the industry, computer-aided design (CAD) methods and tools offer many possibilities in the design of formulated products. The CAD methodology based on computerized models enables the formulation chemists to speed up the design process, without completely replacing experiments.In this work, we summarize previous studies in the field and present important elements of the CAD framework, emphasizing estimation methods for key target properties, link to specifications, and finally, some case studies will illustrate how the CAD framework can be used in practice for formulated products.     

La单掺4H-SiC电子结构和光学性质的第一性原理研究

采用基于密度泛函理论的第一性原理计算方法，对未掺杂及La掺杂4H-SiC的电子结构和光学性质进行理论计算。计算结果表明，未掺杂4C-SiC其禁带宽度为2.257 eV。La掺杂后带隙宽度下降为1.1143eV，导带最低点为G点，价带最高点为F点，是P型间接半导体。掺杂La原子在价带的低能区间贡献比较大，而对价带的高能区和导带的贡献比较小。未掺杂4H-SiC在光子能量为6.25 eV时，出现一个介电峰，这是由于价带电子向导带电子跃迁产生。而La掺杂后，出现3个介电峰，分别对应的光子能量为0.47eV、2.67eV、6.21eV，前两个介电峰是由于价带电子向杂质能级跃迁产生，第三个介电峰是由于价带电子向导带电子跃迁产生。La掺杂后4H-SiC变成负介电半导体材料。未掺杂4h-SiC的静态介电常数为2.01，La掺杂的静态常数为12.01。     

Morphology and properties of super-toughened bio-based poly(lactic acid)/poly(ethylene-co-vinyl acetate) blends by peroxide-induced dynamic vulcanization and interfacial compatibilization

Super-toughened poly(lactic acid) (PLA)/poly(ethylene-co-vinyl acetate) (EVA) blends were prepared via 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD) induced dynamic vulcanization and in situ interfacial compatibilization. The effects of AD on the morphology and properties of PLA/EVA blends were studied using a Brabender torque rheometer, gel content test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC) thermogravimetric analysis (TGA) and mechanical properties test. The torque and gel content demonstrated that EVA and PLA was successfully vulcanized in the presence of free radicals obtained by the decomposition of the 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD). Additionally, the gel content results indicated that, compared with PLA, EVA is more aggressive with free radicals. The SEM revealed that a relatively uniform phase morphology and good interfacial compatibilization were achieved in the dynamically vulcanized PLA/EVA/AD blends. The interfacial reaction and compatibilization between the component polymers resulted in the formation of super-toughened PLA/EVA blended materials.     

Ce掺杂6H-SiC电子结构和光学性质的第一性原理研究

采用基于密度泛函理论的第一性原理计算方法,对未掺杂及Ce掺杂6H-SiC的电子结构和光学性质进行理论计算.计算结果表明,未掺杂6H-SiC是间接带隙半导体,其禁带宽度为2.045 eV,掺杂Ce元素,带隙宽度下降为0.812 eV.未掺杂6H-SiC在价带的低能区,Si-3s、C-2s电子轨道对态密度的贡献较大,在价带的高能区,主要是由Si-3p、Si-3s、C-2p态组成.掺杂后Ce原子的4f轨道主要贡献在导带部分,掺杂后电导率提高.未掺杂时,只有一个介电峰,是价带电子跃迁到导带电子所致,掺杂后有两个介电峰,第一个介电峰是由于导带电子跃迁到Ce原子4f轨道上产生,第二个峰是价带电子向导带电子跃迁产生.未掺杂6H-SiC,在能量为10.31 eV处吸收系数达到最大值,掺杂后在能量为6.57 eV处,吸收系数达到最大值.     

Curing behavior and properties of high biosourced epoxy resin blends based on a triepoxy monomer and a tricarboxylic acid hardener from 10-undecenoic acid

Renewable propane-1,2,3-triyl tris(9-(oxiran-2-yl) nonanoate) (EGU, 100 wt% biogenic) and a tricarboxylic acid triglyceride (CGTU) hardener (85.7 wt% biogenic) were synthesized from 10-undecenoic acid (10-UDA) and used to produce epoxy resins with 52–92 wt% biobased carbon. CGTU was prepared by thermally activated thiol-ene coupling of thioglycolic acid onto propane-1,2,3-triyl tris(undec-10-enoate), (GUD) in the absence of solvent. The characterized CGTU was used as a green hardener of blends based on EGU and a conventional bisphenol A-based epoxy pre-polymer (DGEBA) at various mass percentages (0–100 wt%) with an stoichiometric epoxy/acid equivalent ratio. Calorimetric studies revealed higher peak temperature, lower reaction heats, and longer gelation times in resins with high EGU proportion, evidencing the lower reactivity of aliphatic EGU compared with aromatic DGEBA. Cured resins were yellowish transparent rubber-like materials with glass transition temperatures (Tg) varying from −14 °C to −42 °C and tensile strength in the range of 1750 kPa–790 kPa, for 0 and 100 wt % EGU, respectively. The soluble fraction of all resins was less than 4.3%, reflecting a high level of crosslinking. Thermosets with high biobased content showed both UV-light protection and visible light transparency.     

Designing Dimeric Lanthanide(III)-Containing Ionic liquids

Herein, we report on the preparation of liquid dimeric lanthanide(III)-containing compounds. Starting from the design of dimeric solids, we demonstrate that by tuning of anion and cation structures we can lower the melting points below room temperature, whilst maintaining the dimeric structure. Magnetic measurements could establish the spin-spin interactions of the neighboring lanthanide(III) ions in the liquid state at low temperatures, and matched the interactions of the analogous crystalline solid compounds.     

High-Spin and Reactive Fe13 Cluster with Exposed Metal Sites

Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*₄W₄Fe₁₃S₁₂ , displaying a Fe₁₃ core with M−M bonds that has precedent only in main group and late metal chemistry. M₁₃ clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*₄W₄Fe₁₃S₁₂ displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.     

新型低共熔溶剂的制备、表征及物性研究

以氯化1-丁基-3-甲基咪唑鎓([Bmim]Cl)和二元羧酸为原料,由不同摩尔比混合制备了一类新型低共熔溶剂,采用红外光谱对[Bmim]Cl和二元羧酸之间的作用进行了分析。分别测定了其粘度、电导率、密度、折射率等物理性质,并研究了温度、二元羧酸结构和摩尔比对这些物理性质的影响。结果表明,新型低共熔溶剂的粘度随温度的升高而降低,电导率随温度的升高而增加。温度对两者的影响可以采用VTF方程进行精确地拟合。新型低共熔溶剂的密度随温度的升高而呈线性下降。对新型低共熔溶剂的过量摩尔体积进行计算的结果表明,过量摩尔体积均为正值,二元羧酸对过量摩尔体积的贡献远大于[BMIM]Cl,而结构特性的贡献多于物理作用。折射率和密度随二元羧酸碳数的变化趋势基本相似。     

呋喃基聚酯的结构与性能关系研究进展

呋喃基聚酯是指以2,5-呋喃二甲酸(FDCA)为主要单体合成的生物基或部分生物基高分子,其主链含有刚性的呋喃环,因而在结构、性能上与大规模使用的传统石油基芳香族聚酯(如PET、PBT)相似,有望在瓶、片、薄膜、化纤等领域部分替代后者。本文综述了呋喃基聚酯的分子结构、聚集态结构以及力学、气体阻隔、降解等性能方面的最新研究进展,讨论了结构与性能之间的关系。重点关注呋喃基聚酯突出的阻隔性能及其对应的影响因素,主要从分子结构(呋喃环的非对称性和极性)和聚集态结构(结晶等)两方面加以阐明。简介了呋喃基聚酯的发展现状及其在包装、纺织等领域的潜在应用,并展望其主要研究趋势。     

Ultrasound-assisted extraction and properties of polysaccharide from Ginkgo biloba leaves

Response surface methodology (RSM) was used to optimize the ultrasound-assisted extraction conditions of Ginkgo biloba leaves polysaccharide (GBLP). The optimum extraction conditions for the ultrasound-assisted extraction of GBLP were obtained as liquid to material ratio of 30 mL/g, ultrasonic power of 340 W, and extraction time of 50 min. Under these conditions, the yield of GBLP was 5.37 %. Two chemically modified polysaccharides, CM-GBLP and Ac-GBLP, were obtained by carboxymethylation and acetylation of GBLP. The physicochemical properties of these three polysaccharides were comparatively studied and their in vitro antioxidant activities were evaluated comprehensively. The results showed that the solubility of the chemically modified polysaccharides was significantly enhanced and the in vitro antioxidant activity was somewhat improved. This suggests that carboxymethylation and acetylation are effective methods to enhance polysaccharide properties, but the results exhibited some uncontrollability. At the same time, GBLP has also shown high potential for research and application.