Comment on “Density functional theory study of 1,2‐dioxetanone decomposition in condensed phase”

In the preceding paper results are presented, which are in serious conflict with state‐of‐the‐art ab initio method. Based on these new results the authors propose a new explanation of the reason for the preferential production of a phosphorescent state. Here we show that these controversial results are flawed, since the model use exclude biradical electron structures. © 2012 Wiley Periodicals, Inc.     

Solvent replacement to thermo‐responsive nanoparticles from long‐subchain hyperbranched PSt grafted with PNIPAM for encapsulation

Long‐subchain hyperbranched polystyrene (lsc‐hp PSt) with uniform subchain length was obtained through copper‐catalyzed azide‐alkyne cycloaddition click chemistry from seesaw macromonomer of PSt having one alkynyl group anchored at the chain centre and two azido group attached to both chain ends [alkynyl‐(PSt‐N₃)₂]. After precipitation fraction, different portions of lsc‐hp PSt having narrow overall molecular weight distribution were obtained for further grafting with alkynyl‐capped poly(N‐isopropylacrylamide) (alkynyl‐PNIPAM), which was obtained via single‐electron transfer living radical polymerization of NIPAM with propargyl 2‐bromoisobutyrate as the initiator and grafted onto the peripheral azido groups of lsc‐hp PSt via click chemistry. Thus, amphiphilic lsc‐hp PSt grafted with PNIPAM chains (lsc‐hp PSt‐g‐PNIPAM) was obtained and would have star‐like conformation in tetrahydrofuran (THF). By replacing THF with water, lsc‐hp PSt‐g‐PNIPAM was dissolved at molecular level in aqueous solution due to the hydrophilicity of PNIPAM and exhibited thermal induced shrinkage of PNIPAM arms. The water‐insoluble lsc‐hp PSt would collapse densely and could be served as a reservoir to absorb hydrophobic chemicals in aqueous solution. The influence of overall molecular weight of lsc‐hp PSt on the absorption of pyrene was studied. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and properties of novel soluble poly(amide‐imide)s with different pendant substituents

Two types of novel fluorinated diimide‐diacid monomers—[2,2′‐(4,4′‐(3′‐methylbiphenyl‐2,5‐diyl)bis(oxy)bis(3‐(trifluoromethyl)‐4,1‐phenylene))bis(1,3‐dioxoisoindoline‐5‐carboxylic acid)] (III) and [2,2′‐(4,4′‐(3′‐(trifluoromethyl)biphenyl‐2,5‐diyl)bis(oxy)bis(3‐(trifluoromethyl)‐4,1‐phenylene))bis(1,3‐dioxoisoindoline‐5‐carboxylic acid)] (IV)—were respectively designed and prepared by the condensation of diamines I and II with two molar equivalents of trimellitic anhydride. From both diimide‐diacids, two series of novel poly(amide‐imide)s (PAIs) (IIIa–IIIe and IVa–IVe) bearing different pendant groups were prepared by direct polymerization with various aromatic diamines (a–e). All the PAIs had a high glass transition temperatures (T_gs, 232–265 °C), excellent thermal stability (exhibiting only 5% weight loss at 493–542 °C under nitrogen) and good solubility in various organic solvents due to the introduction of the bulky pendant groups. The cast films of these PAIs (80–90 μm) had good optical transparency (73–81% at 450 nm, 85–88% at 550 nm and 87–89% at 800 nm) and low dielectric constants (2.65–2.98 at 1 MHz). The spin‐coated films of these PAIs presented a minimum birefringence value as low as 0.0077–0.0143 at 650 nm and low optical absorption at the near‐infrared optical communication wavelengths of 1310 and 1550 nm. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3243–3252     

落球法测定液体粘滞系数误差的研究

液体粘滞系数的测定是一项基础物理实验,影响此实验结果的因素较多,在实际操作中往往会存在误差较大的情况。通过改进实验仪器,对各个重要参数进行了多次规范的测量,并研究了各测量参数的相对误差传递,旨在找出减小误差的方法。     

99Tc NMR as a promising technique for structural investigation of biomolecules: theoretical studies on the solvent and thermal effects of phenylbenzothiazole complex

The phenylbenzothiazole compounds show antitumor properties and are highly selective. In this paper, the ⁹⁹Tc chemical shifts based on the (^99mTc)(CO)₃(NNO) complex conjugated to the antitumor agent 2‐(4′‐aminophenyl)benzothiazole are reported. Thermal and solvent effects were studied computationally by quantum‐chemical methods, using the density functional theory (DFT) (DFT level BPW91/aug‐cc‐pVTZ for the Tc and BPW91/IGLO‐II for the other atoms) to compute the NMR parameters for the complex. We have calculated the ⁹⁹Tc NMR chemical shifts of the complex in gas phase and solution using different solvation models (polarizable continuum model and explicit solvation). To evaluate the thermal effect, molecular dynamics simulations were carried, using the atom‐centered density matrix propagation method at the DFT level (BP86/LanL2dz). The results highlight that the ⁹⁹Tc NMR spectroscopy can be a promising technique for structural investigation of biomolecules, at the molecular level, in different environments. Copyright © 2014 John Wiley & Sons, Ltd.     

Toward a universal quantum QSPR operator

This article presents a discussion about the formalism, which might be associated to a general Quantum quantitative structure–properties relations operator, appearing in a Boltzmann‐like exponential form, which is based in turn on the definition of the concept of thermal voltage, applied to thermally scaled electronic density functions. Three practical numerical examples are presented, corresponding to the calculation of the polarization angle in assorted chiral molecules, the estimation of fish toxicity for perchlorobenzene within the set of chlorobenzenes and a typical quantum QSAR study on the popular Cramer steroid set.     

Wave propagation across a finite heterogeneous interphase modeled as an interface with material properties

Mechanical problems involving an interphase between two well-defined, and eventually different, materials are of interest. The aim of this paper is to present a simplified model that, for low frequency regime, is appropriate for this situation: an interface model with elastic and inertial properties. We present, together with the equations of motion, an identification procedure that is valid for any mass density profile along the thickness of the interphase. For evaluating the accuracy of the model, computations of the reflection coefficients in some relevant cases are shown. Besides, a finite element method is used as a benchmark for both the high and low frequency regimes. It is worth to be noted that the numerical test has been inspired by the problem of the interphase that is formed at the bone-implant boundary.     

涠洲岛两种石珊瑚在高温胁迫下共生细菌群落结构变化特征

石珊瑚中的块状珊瑚与枝状珊瑚对全球气候变暖胁迫的耐受能力明显不同,但其机制仍不清楚。本研究选择北部湾涠洲岛的一种属于块状珊瑚的海孔角蜂巢珊瑚(Favites halicora)和一种属于枝状珊瑚的浪花鹿角珊瑚(Acropora cytherea)为研究对象,通过室内模拟实验,分析高温胁迫下(26～34℃) 2种珊瑚共生细菌群落的响应特征。结果表明:共生细菌多样性具有差异性,A.cytherea共生细菌的多样性随着温度上升变化显著,Shannon指数由2.20变为4.05,而F.halicora变化幅度较小,在2.69～3.19波动;主导细菌存在差异,在门水平上,F.halicora占主导地位的共生细菌为Proteobacteria (29%～73%)、Cyanobacteria (7%～63%)和Bacteroidetes(3%～13%),而A. cytherea为Proteobacteria (49%～90%)、Cyanobacteria (1%～16%)、Bacteroidetes (3%～16%)、Firmicutes (1%～6%)和一个未分类的细菌门unclassified_k_norank(0.6%～21.0%);升温胁迫时,主导细菌的丰度变化存在差别,Bacteroidetes在F.halicora中显著降低,而在A.cytherea中显著升高,unclassified_k_norank在A.cytherea中也显著升高;随着温度升高,2种珊瑚共生细菌的变化趋势一致,但珊瑚中出现潜在致病菌Vibrio的温度不同,F.halicora在34℃胁迫时出现,A.cytherea在30℃和34℃胁迫时均出现。根据上述结果推测,珊瑚共生细菌的差异性可能是导致块状珊瑚比枝状珊瑚更耐受高温的重要原因。     

Polymer chain diffusion in polymer blends: A theoretical interpretation based on a memory function formalism

The diffusion of polymer chains in miscible polymer blends with large dynamic asymmetry—those where the two blend components display very different segmental mobility—is not well understood yet. In the extreme case of the blend system of poly(ethylene oxide) (PEO) and poly(methyl methacrylate)(PMMA), the diffusion coefficient of PEO chains in the blend can change by more than five orders of magnitude while the segmental time scale hardly changes with respect to that of pure PEO. This behavior is not observed in blend systems with small or moderate dynamic asymmetry as, for instance, polyisoprene/poly(vinyl ethylene) blends. These two very different behaviors can be understood and quantitatively explained in a unified way in the framework of a memory function formalism, which takes into account the effect of the collective dynamics on the chain dynamics of a tagged chain. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1239–1245