Active center determinations on MgCl2‐supported fourth‐ and fifth‐generation Ziegler–Natta catalysts for propylene polymerization

Active center determinations on different Ziegler–Natta polypropylene catalysts, comprising MgCl₂, TiCl₄, and either a diether or a phthalate ester as internal donor, have been carried out by quenching propylene polymerization with tritiated ethanol, followed by radiochemical analysis of the resulting polymers. The purpose of this study was to determine the factors contributing to the high activities of the catalyst system MgCl₂/TiCl₄/diether—AlEt₃. Active center contents (C*) in the range 2–8% (of total Ti present) were measured and a strong correlation between catalyst activity and active center content was found, indicating that the high activity of the diether‐containing catalysts is due to an increased proportion of active centers rather than to a difference in propagation rate coefficients. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1635–1647, 2006     

Eu3+掺杂的PMMA-络合物体系的发光特性

研究了聚甲基丙烯酸甲脂PMMA-Eu(DBM)3(phen)和PMMA-辛酸铕体系的发光特性。已有的结果表明，聚甲基丙烯酸甲脂PMMA—Eu(DBM)3(phen)体系具有较高的色纯度，Eu^3 的主发射峰几乎只有613nm(Eu^3 的^5D0→^7F2)被观测到，其发射强度比PMMA-辛酸盐体系的高一个量级，是潜在的高效稀土红光材料。     

Fast approximations for sums of distances, clustering and the Fermat–Weber problem

We describe two data structures that preprocess a set S of n points in (d constant) so that the sum of Euclidean distances of points in S to a query point q can be quickly approximated to within a factor of . This preprocessing technique has several applications in clustering and facility location. Using it, we derive an O(nlogn) time deterministic and O(n) time randomized -approximation algorithm for the so called Fermat–Weber problem in any fixed dimension.     

基于超级碳点的水致荧光“纳米炸弹”

介绍了一种发光性质依赖于水接触的新型纳米发光材料--基于超级碳点的发光"纳米炸弹"。在甲苯溶液中, 这种"纳米炸弹"光致发光很弱;当遇见水后, "纳米炸弹"分解为小的碳点, 光致发光显著增强。将"纳米炸弹"与纸复合可应用在喷水荧光打印和汗孔成像。目前, 大部分智能荧光材料存在光稳定性差, 潜在的生物毒性, 制备成本高, 或与传统喷墨打印不兼容等缺点。本文报道的碳基纳米材料没有(或很少有)这些缺点, 并可实际应用在光信息存储, 司法鉴定和医疗检测等领域。     

Hybrid density functional study of optically active Er3+ centers in GaN

Understanding the luminescence of GaN doped with erbium (Er) requires a detailed knowledge of the interaction between the rare‐earth dopant and the nitride host, including intrinsic defects and other impurities that may be present in the host material. We address this problem through a first‐principles hybrid density functional study of the structure, energetics, and transition levels of the Er impurity and its complexes with N and Ga vacancies, substitutional C and O impurities, and H interstitials in wurtzite GaN. We find that, in the interior of the material, Er_Ga is the dominant Er³⁺ center with a formation energy of 1.55 eV, Er_Ga–V_N possesses a deep donor level at 0.61 eV which can assist in the transfer of energy to the 4f ‐electron core. Multiple optically active Er³⁺ centers are possible in Er‐doped GaN. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

纳米MgBO_2(OH):Eu~(3+)的制备及发光性能研究

利用水热法,制备得到了纳米线组装的绒球状和纳米带聚集的絮状Mg BO2(OH):Eu3+,对它们进行了EDS、XRD、IR、SEM等表征及发光性能研究。研究发现两个产品的最高激发峰和发射峰分别都位于λ=250nm和λ=615nm处,为红色发光材料;且发现绒球状Mg BO2(OH):Eu3+的峰强度明显强于絮状Mg BO2(OH):Eu3+,但絮状Mg BO2(OH):Eu3+的红橙比(R/O)更高。     

几种三维镧系配位聚合物的合成、结构表征及其性质测定

在水热条件下合成了四个氨三乙酸配合物[Ln(NTA)(H2O)]n(Ln=Sm(III)、Gd(III)、Dy(III)和Er(III);NTA=氨三乙酸),分别标记为1、2、3和4;利用元素分析、红外光谱和X射线单晶衍射等对其进行了结构表征.结果表明,配合物1-4同晶同构,中心原子采取N1O7的配位模式形成扭曲的十二面体几何构型.配合物以菱形四面体Ln8C14O28为基本构筑块,通过O—C—O和氢键形成有序的三维结构.此外,四个配合物均存在镧系收缩效应;配合物1显示出反铁磁性,配合物2对Hg2+有良好的荧光选择性.     

Investigation of the distinction between van der Waals interaction and chemical bonding based on the PAEM‐MO diagram

In recent years, the basic problem of understanding chemical bonding, nonbonded, and/or van der Waals interactions has been intensively debated in terms of various theoretical methods. We propose and construct the potential acting on one electron in a molecule‐molecular orbital (PAEM‐MO) diagram, which draws the PAEM inserted the MO energy levels with their major atomic orbital components. PAEM‐MO diagram is able to show clear distinction of chemical bonding from nonbonded and/or vdW interactions. The rule for this is as follows. Along the line connecting two atoms in a molecule or a complex, the existence of chemical bonding between these two atoms needs to satisfy two conditions: (a) a critical point of PAEM exists and (b) PAEM barrier between the two atoms is lower in energy than the occupied major valence‐shell bonding MO which contains in‐phase atomic components (positive overlap) of the two considered atoms. In contrast to the chemical bonding, for a nonbonded interaction or van der Waals interaction between two atoms, both conditions (a) and (b) do not be satisfied at the same time. This is demonstrated and discussed by various typical cases, particularly those related to helium atom and H? H bonding in phenanthrene. There are helium bonds in HHeF and HeBeO molecules, whereas no H? H bonding in phenanthrene. The validity and limitation for this rule is demonstrated through the investigations of the curves of the PAEM barrier top and MO energies versus the internuclear distances for He₂, H₂, and He₂⁺ systems. © 2014 Wiley Periodicals, Inc.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.     

Influence of alkyl length on properties of piezofluorochromic aggregation induced emission compounds derived from 9,10-bis[(N-alkylphenothiazin-3-yl)vinyl]anthracene

Three 9,10-bis[(N-alkylphenothiazin-3-yl)vinyl]anthracene derivatives with different propyl, hexyl, and dodecyl side chains (AnPh₃, AnPh₆, and AnPh₁₂) were synthesized and confirmed by standard spectroscopic methods. All of the compounds exhibited obvious aggregation induced emission (AIE) and piezofluorochromic (PFC) properties. The PFC behaviors were investigated and showed that proportional alkyl-length dependent relationship existed not only in the ground states of the compounds, but also in the melted states compared with the fumed states of the compounds. The PFC mechanism was explored and ascribed to the crystalline–amorphous phase transformation. More importantly, these derivatives showed reversible significant PFC properties and reproducibility in various states including fumed, ground, annealed, and melted states, making them promising stimuli-responsive and smart luminescent materials for pressure-sensors, information-recording, and light-emitting device applications.