Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH₂) and electron-withdrawing (R=NO₂) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L₁)(L₂)]_n ( 1 ) and [Zn(L₁)(L₃)]_n ( 2 ) [L₁=2-(2-pyridyl) benzimidazole (Pbim), L₂=5-aminoisophthalate (Aip), and L₃=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH₂ and NO₂ substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO₂ and NH₂. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.     

Gravitational wave imprint of new symmetry breaking

It is believed that there are more fundamental gauge symmetries beyond those described by the Standard Model of particle physics. The scales of these new gauge symmetries are usually too high to be reachable by particle colliders. Considering that the phase transition (PT) relating to the spontaneous breaking of new gauge symmetries to the electroweak symmetry might be strongly first order, we propose considering the stochastic gravitational waves (GW) arising from this phase transition as an indirect way of detecting these new fundamental gauge symmetries. As an illustration, we explore the possibility of detecting the stochastic GW generated from the PT of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} in the space-based interferometer detectors. Our study demonstrates that the GW energy spectrum is reachable by the LISA, Tianqin, Taiji, BBO, and DECIGO experiments only for the case where the spontaneous breaking of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} is triggered by at least two electroweak singlet scalars.     

不同重力环境下辐射加热材料表面着火特性分析

研究外界辐射加热下，不同重力环境中热薄燃料的着火特性．探讨了重力、环境氧浓度、环境压力及外界辐射强度对着火的影响．结果表明，随着重力的变化，存在不同的着火机制．在微重力和在高的环境氧浓度中，材料的着火延迟时间变短．压力减小，着火延迟时间增大．随着辐射强度的增大，着火延迟时间变小．     

Formation of Interfacial Layers in LaAlO3/Silicon during Film Deposition

We have studied the interracial reactions between amorphous LaAlO3 thin films and Si substrates, using high- resolution transmission electron microscopy and x-ray photoelectron spectroscopy. It has been shown that the interracial layer between LaAlO3 film and Si substrate chemical states show that the ratio of La 4d3/2 to Al 2p is SiLaxAlyOz. The depth distributions of La, Si and Al of the interfacial layer remains unchanged with the depth compared to that of the LaAlO3 film. Moreover, the Si content, in the interracial layer gradually decreases with increasing thickness of the interracial layer. These results strongly suggest that the Al element is not deficient in the interracial layer, as previously believed, and the formation of a SiLaxAlyOz interracial layer is mainly due to the diffusion of Si from the substrate during the LaAlO3 film deposition. With the understanding of the interracial layer formation, ones can control the interface characteristics to ensure the desired performances of devices using high-k oxides as gate dielectrics.     

Effects of the architecture and environment on polymeric molecular assemblies of novel amphiphilic diblock copolynorbornenes with narrow polydispersity via living ring‐opening metathesis polymerization

Diblock copolymers of 5‐(methylphthalimide)bicyclo[2.2.1]hept‐2‐ene (NBMPI) and 1,5‐cyclooctadiene were synthesized by living ring‐opening metathesis polymerization with a well‐defined catalyst {RuCl₂(CHPh)[P(C₆H₁₁)₃]₂}. Unhydrogenated diblock copolymers showed two glass transitions due to poly(NBMPI) and polybutadiene segments, such as two glass‐transition temperatures at ?86.5 and 115.3 °C for poly 1a and ?87.2 and 115.3 °C for poly 1b . However, only one melting temperature could be observed for hydrogenated copolymers, such as 119.8 °C for poly 2a and 121.7 °C for poly 2b . The unhydrogenated diblock copolymer with the longer poly(NBMPI) chain (poly 1a ; temperature at 10% mass loss = 400 °C) exhibited better thermal stability than the one with the shorter poly(NBMPI) chain (poly 1b ; temperature at 10% mass loss = 385 °C). Two kinds of hydrogenated diblock copolymers, poly 2a and poly 2b , exhibited relatively poor solubility but better thermal stability than unhydrogenated diblock copolymers because of the polyethylene segments. Poly[(hydrochloride quaternized 2‐norbornene‐5‐methyleneamine)‐b‐butadiene]‐1 (poly 3a ) was obtained after the hydrolysis and quaternization of poly 1a . Dynamic light scattering measurements indicated that the hydrodynamic diameters of the cationic copolymer (poly 3a ) in water (hydrodynamic diameter = 1580 nm without salt), methanol/water (4/96 v/v; hydrodynamic diameter = 1500 nm without salt), and tetrahydrofuran/water (4/96 v/v; hydrodynamic diameter = 1200 nm without salt) decreased with increasing salt (NaCl) concentration. The effect of temperature on the hydrodynamic diameter of hydrophobically modified poly 3a was also studied. The inflection point of the hydrodynamic diameter of poly 3a was observed at various polymer concentrations around 30 °C. The critical micelle concentration of hydrophobically modified poly 3a was observed at 0.018 g dL^?1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2901–2911, 2006     

Dinuclear iron(II)-cyanocarbonyl complexes linked by two/three bridging ethylthiolates: relevance to the active site of [Fe] hydrogenases

Dinuclear iron(II)-cyanocarbonyl complex [PPN](2)[Fe(CN)(2)(CO)(2)(mu-SEt)](2) (1) was prepared by the reaction of [PPN][FeBr(CN)(2)(CO)(3)] and [Na][SEt] in THF at ambient temperature. Reaction of complex 1 with [PPN][SEt] produced the triply thiolate-bridged dinuclear Fe(II) complex [PPN][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)] (2) with the torsion angle of two CN(-) groups (C(5)N(2) and C(3)N(1)) being 126.9 degrees. The extrusion of two sigma-donor CN(-) ligands from Fe(II)Fe(II) centers of complex 1 as a result of the reaction of complex 1 and [PPN][SEt] reflects the electron-rich character of the dinuclear iron(II) when ligated by the third bridging ethylthiolate. The Fe-S distances (2.338(2) and 2.320(3) A for complexes 1 and 2, respectively) do not change significantly, but the Fe(II)-Fe(II) distance contracts from 3.505 A in complex 1 to 3.073 A in complex 2. The considerably longer Fe(II)-Fe(II) distance of 3.073 A in complex 2, compared to the reported Fe-Fe distances of 2.6/2.62 A in DdHase and CpHase, was attributed to the presence of the third bridging ethylthiolate, instead of pi-accepting CO-bridged ligand as observed in [Fe] hydrogenases. Additionally, in a compound of unusual composition ([Na.(5)/(2)H(2)O][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)])(n)((1)/(2)O(Et)(2))(n) (3), the Na(+) cations and H(2)O molecules combining with dinuclear [(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)](-) anions create a polymeric framework wherein two CN(-) ligands are coordinated via CN(-)-Na(+)/CN(-)-(Na(+))(2) linkages, respectively.     

受限于纳米碳管中的乙醇分子的结构和扩散的分子模拟研究

利用分子模拟研究了常温常压下受限于(8,8) (管径1.081 nm)和(15,15) (管径 2.035 nm)单壁纳米碳管中的乙醇分子. 对受限分子的径向密度分布和氢键等静态性质以及扩散性质进行了分析. 结果显示在管内乙醇分子的平均氢键数目和主体相一致. 乙醇分子在(8,8)碳管内具有高度有序的结构, 而在(15,15)碳管内由于空间的增大导致结构有序度的降低, 其中分子取向已呈随机分布. 进一步对扩散系数的分析发现, 在管内乙醇分子的轴向扩散系数低于主体相, 特别在(8,8)碳管内乙醇分子几乎丧失了轴向扩散能力.     

Paired Electrolysis of Aldoses in a Divided Flow Cell

Simultaneous anodic oxidation and cathodic reduction of aldoses in a divided flow cell were studied. The stream of the anolyte was an aqueous solution containing D-glucose, sodium bromide, and sodium bicarbonate. The stream of the catholyte was also an aqueous solution containing xylose and sodium sulfite. The factors which affected both the anodic and cathodic reactions were studied. The results indicate that the flow rates and temperatures of the anolyte and the catholyte, concentrations of the aldoses, pH values and the material of electrodes significantly affect both anodic and cathodic yields. The selectivities of gluconic acid in the anode and xylitol in the cathode were very high. The power consumption of paired electrolysis in the flow system was less than paired electrolysis in a batch system.     

Synthesis and characterization of sulfone-containing polyesters derived from 4,4′-dicarboxydiphenyl sulfone by direct polycondensation

Several sulfone-containing polyesters having inherent viscosities 0.43-0.19 dL g^?1 were prepared by direct polycondensation of 4,4′-dicarboxydiphenyl sulfone (DCDPS) with various aromatic and aliphatic diols, by p-toluenesulfonyl chloride and N,N′-dimethylformamide in pyridine solution. The polyesters were examined by elementary analysis, IR spectra, inherent viscosity, x-ray diffraction, solubility, DSC, and TGA. The diffraction diagram showed that all polyesters were crystalline except that obtained from bisphenol-A. All polymers were soluble in sulfonic acid (18M), phenol and p-chlorophenol, but not in acetone and toluene. These polymers obtained from aromatic bisphenols lost no mass below 325°C, but 10% loss of mass was recorded above 396°C in nitrogen. DCDPS copolymerized with isophthalic acid (IPA) and bisphenol-A had inherent viscosity up to 0.49 dL g^?1, with relatively narrow distribution of molar mass . © 1995 John Wiley & Sons, Inc.