Syntheses,Structures, and Photophysical Properties of Two Coordination Polymers Based on 2,3‐Dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic Acid

Two complexes based on the ligand 1,4‐dihydro‐2,3‐quinoxalinedione, namely [Mn(H₂L)₂(H₂O)₂]_n ( 1 ) and {[Zn₂(H₂L)₂(tz)₂] · 5H₂O}_n ( 2 ) (H₃L = 2,3‐dioxo‐1,2,3,4‐tetrahydroquinoxaline‐6‐carboxylic acid, Htz = 1,2,4‐triazole) were hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, as well as single‐crystal and powder X‐ray diffraction. Complex 1 exhibited a 1D comb‐like chain formed by H₂L^– anions linking Mn^II ions, whereas complex 2 was a 2D layer‐like structure with square‐shaped windows and outstretched arms built by combination of H₂L^– and tz^– ligands with Zn^II ions. The adjacent chains or layers connected with each other by intermolecular hydrogen bonding and π–π stacking to further extend to a 3D supermolecular framework. In addition, the thermal stabilities, luminescence properties, and optical energy gap of 1 and 2 were investigated in detail.     

Cucurbit[<Emphasis Type="Italic">n</Emphasis>]uril-based host–guest-metal ion chemistry: an emerging branch in cucurbit[<Emphasis Type="Italic">n</Emphasis>]uril chemistry

The unique pumpkin-shape macrocyclic structure with inherent cavities renders cucurbituril (CB) a type of versatile supramolecular container. On account of their good biocompatibility and low toxicity, the applications of CB to encapsulate drug molecules provide promising candidates and the pharmacological activities have been investigated currently. How to control over the uptake and release of the guest at will is significant for practical applications of drug delivery. The noncovalent nature of supramolecular interactions offers variety of options to control the release of guest molecules from CB under external stimuli, including pH, temperature, metal cations, competing guests, light, redox and so on. Moreover, CB containers are capable of assembling into higher ordered supramolecular structures such as polymers, nanoparticles, hydrogels, and colloids, which greatly enrich the scope of CB-type inclusion materials. Those results provide useful principles and guidelines for controlled release from supramolecular containers.     

Four Mixed 3d-4f 12-Metallacrown-4 Complexes: Syntheses,Structures and Magnetic Properties

The incorporation of Ln^III ions into the 12-metallacrown-4 topology affords the formation of four mixed 3d-4f pentanuclear complexes of compositions [NH(C₂H₅)₃]{[Ln(OAc)₄] [12-MC _Mn ^III _(N)shi-4]}·xH₂O (Ln = Sm (1), Gd (2), Tb (3), Dy (4); x = 0.5 for 1 and 3, x = 0.25 for 2, x = 0 for 4; H₃shi = salicylhydroxamic acid). Compounds 1–4 were obtained from the reactions of H₃shi with Mn(CH₃COO)₂·4H₂O and Ln(NO₃)₃·6H₂O, in the presence of N(C₂H₅)₃. They all contain a crown-like [Mn₄Ln(μ-NO)₄]¹¹⁺ core with four Mn^III atoms being at the rim of the crown and an Ln^III ion occupying the dome of the crown. The peripheral ligation about the core is provided by four η¹:η¹:µ acetate groups. The identity of the Ln^III ions slightly affects the 12-metallacrown-4 frameworks, as demonstrated by the gradual decrease of the distances between the Ln^III ions and the centres of the Mn₄ planes (1.85 Å for 1, 1.81 Å for 2, 1.80 Å for 3, and 1.77 Å for 4). Variable-temperature dc magnetic susceptibility studies were carried out on polycrystalline samples of 1–4. Antiferromagnetic interactions are determined for complexes 1–4.     

双波长分光光度法同时测定浆料中的聚乙烯醇和淀粉

本文报道了用双波长分光光度法同时测定变性聚乙烯醇和淀粉醋酸酯的一种新方法。分别选择670.0～540.0nm以及590.0～730.0nm波长对测定变性聚乙烯醇和淀粉醋酸酯。变性聚乙烯醇)～32μg/ml,淀粉醋酸酯0～130μg/ml浓度范围内,吸光度差值△A遵循比耳定律。当淀粉醋酸酯与变性聚乙烯醇的浓度比在1.3～16范围内,变性聚乙烯醇和淀粉醋酸酯的样品回收率分别为99.5～105%和97～108%。所拟定的方法可测定浆料中变性聚乙烯醇和淀粉醋酸酯。本法与盐酸水解淀粉法测定的聚乙烯醇含量相吻合。本法简便快速。     

关于超高分子量聚丙烯超拉伸膜的结构性能的研究——Ⅰ.拉伸取向过程的表征

 用超高分子量聚丙烯的对二甲苯溶液中冷却析出的结晶沉积压制成的结晶垫,经热拉伸制备了不同拉伸倍数的薄膜.与用低分子量聚丙烯制备的结晶垫或熔融结晶物不同,超高分子量聚丙烯的结晶垫显示出极高的拉伸变形性能,因而制得了高达69倍的拉伸样品.WAXD照片表明在未拉伸的结晶垫中,微晶的c轴沿结晶垫法线方向择优取向,但仅经2-4倍的拉伸,微晶即发生破裂,且产生的较小的折叠链微晶已转向沿拉伸轴方向取向;晶区取向因子在拉伸过程中迅速增加并在较低拉伸倍数下即接近于理想取向.但非晶区取向因子在整个拉伸领域中增加缓慢.随拉伸倍数的增大,晶粒尺寸D₁₁₀及D₀₄₀逐渐减小;而长周期L逐渐增加.这表明在高倍拉伸样品中存在着折叠链被从片晶中拉出并部分形成伸直链结晶的转变.     

关于超高分子量聚丙烯超拉伸膜的结构性能的研究——Ⅱ.形态结构变化对力学性能的影响

 用X-射线衍射、动态力学测定等手段研究了不同拉伸倍数的超高分子量聚丙烯薄膜的力学性能的变化.以X-射线衍射法并基于串联力学模型的假设得到的各样品的表观晶区模量E_c^app约为34-38GPa.样品模量E_b随拉伸倍数增加而逐渐增大,其变化趋势与非晶区取向因子的变化相类似,说明非晶区取向是左右样品模量的重要因素.室温下,69倍拉伸样品的模量为27GPa,约为表观结晶模量的3/4,且其值在-150-160℃的温度范围内没有急剧变化,说明超拉伸明显改善了材料的力学性能及热稳定性.在各拉伸样品中,考虑伸直链结晶生成的可能性,利用并串联力学模型对伸直链结晶的体积分数做了估算,并对X-射线衍射法所得表观结晶模量进行了修正,认为室温下聚丙烯的真正晶区模量约为47GPa.     

关于超高分子量聚丙烯超拉伸膜的结构性能的研究——Ⅱ.形态结构变化对力学性能的影响

用X-射线衍射、动态力学测定等手段研究了不同拉伸倍数的超高分子量聚丙烯薄膜的力学性能的变化.以X-射线衍射法并基于串联力学模型的假设得到的各样品的表观晶区模量E_c~(app)约为34-38GPa.样品模量E_b随拉伸倍数增加而逐渐增大,其变化趋势与非晶区取向因子的变化相类似,说明非晶区取向是左右样品模量的重要因素.室温下,69倍拉伸样品的模量为27GPa,约为表观结晶模量的3/4,且其值在-150-160℃的温度范围内没有急剧变化,说明超拉伸明显改善了材料的力学性能及热稳定性.在各拉伸样品中,考虑伸直链结晶生成的可能性,利用并串联力学模型对伸直链结晶的体积分数做了估算,并对X-射线衍射法所得表观结晶模量进行了修正,认为室温下聚丙烯的真正晶区模量约为47GPa.     

尼龙6,6(PA_(6,6)及其共混物结晶性能的研究

<正> 尼龙6,6(PA_(6,6))是一种典型的结晶性工程塑料,被广泛应用于纺织、机械制造等行业,但其加工温度范围较窄,耐热性差。聚醚砜(PES)具有较高的玻璃化转变温度,是非晶聚合物,可以诱发某些结晶聚合物结晶。PES与PA_(6,6)共混体系的研究报道较少,本文用熔融法将PES与PA_(6,6)制成共混物,企图改善PA_(6,6)的结晶性,以提高其耐热性,取得了较理想的结果。     

Organometallic Compounds of the Lanthanoides. LXVI. Synthesis and X-ray crystal structure of [O(CH2CH2C5H4)2Y(μ-OH]2 and (MeC5H4)3Ho(H2O), two unusual products of the hydrolysis of organolanthanoide compounds

The partial hydrolysis of [O(CH₂CH₂C₅H₄)₂]Y(C₅H₄CH₃) 1 , [O(CH₂CH₂C₅H₄)₂]Y(C₅H₅) 3 , and [O(CH₂CH₂C₅H₄)₂]Ho(C₅H₄CH₃) 5 results in the formation of [O(CH₂CH₂CH₂C₅H₄)₂Y(μ-OH)₂]₂ 2 , (C₅H₅)₃Y(OH₂) 9 and (MeC₅H₄)₃Ho(OH₂) 11 . The new compounds have been characterized by elemental analyses, IR and NMR spectra. The X-ray structural analyses shows 2 to be monoclinic, space group P2₁/n with a = 1146.0(3), b= 1046.6(3), c = 1514.9(3) pm, β = 94.83(2)°. The molecular structure shows bridging hydroxyl groups with a mean distance Y? O = 223.8(3) pm. 11 crystallizes in the cubic space group 14 3d with a = 1847.9(3)pm with Z = 16 molecules per unit cell. The molecules posses symmetry C₃-3, the coordination is trigonal pyramidal with three methylcyclopentadienyl anions and one water molecule as ligands. The distance Ho? O is 231 pm.     

希土烯丙基化合物的研究——Ⅷ.镝、钬、铒、镱和镥的2-甲基烯丙基化合物的合成

用无水希土氯化物与2-甲基烯丙基氯化镁及四甲基乙二胺,0℃下,在四氢呋喃中反应,加乙醚后可得到五个含2-甲基烯丙基的重希土元素的化合物。经元素分析、红外光谱和质谱分析的鉴定,确定该化合物的组成为Ln(C₄H₇)₂Cl₅Mg₂(tmed)₂。