膜系光谱系数对膜层参数的一阶和二阶偏导数的计算模型

为了寻找一种膜系深入分析与设计的有力辅助计算工具,从光学薄膜光谱系数的矩阵计算理论出发,基于对矩阵求迹运算的巧妙运用,从数学上建立了准确计算膜系光谱系数关于膜层几何厚度、实际折射率和消光系数等膜层参数的一阶和二阶偏导数的解析模型。这一偏导数计算模型物理上与矩阵理论具有一致的通用性和普适性,适用于任何各向同性的均匀膜系统。在数学上也严格成立,数值编程计算不存在差分近似,精度达到了计算机浮点运算的极限精度。而且算法运算费时少,计算速度快,取得了高度准确性和便于实时化的双重优越性能,非常有利于应用于膜系设计领域来提高膜层数较大时的设计速度和效率。同时,这一模型能非常便捷和准确地给出膜系许多实用的导数信息,对膜系分析、测量和膜厚监控等领域中的相关应用具有重要的参考意义。     

Extreme compression behaviour of equations of state

The extreme compression (P→∞) behaviour of various equations of state with K′_∞>0 yields (P/K)_∞=1/K′_∞, an algebraic identity found by Stacey. Here P is the pressure, K the bulk modulus, K^′=dK/dP, and K′_∞, the value of K^′ at P→∞. We use this result to demonstrate further that there exists an algebraic identity also between the higher pressure derivatives of bulk modulus which is satisfied at extreme compression by different types of equations of state such as the Birch–Murnaghan equation, Poirier–Tarantola logarithmic equation, generalized Rydberg equation, Keane's equation and the Stacey reciprocal K-primed equation. The identity has been used to find a relationship between λ_∞, the third-order Grüneisen parameter at P→∞, and pressure derivatives of bulk modulus with the help of the free-volume formulation without assuming any specific form of equation of state.     

紫外-可见光谱法研究二茂铁衍生物与血红素的相互作用

采用紫外-可见光谱法(UV-Vis)研究三种二茂铁衍生物[Fc(COOH)₂(λ_max=286 nm), Fc(OBt)₂(λ_max=305 nm), Fc(Cys)(λ_max=289 nm)]与血红素(heme, λ_max=386 nm)的相互作用。实验结果表明：当固定heme浓度时,heme的吸光度随着Fc(COOH)₂和Fc(Cys)浓度的增加而增大,而heme的吸光度随着Fc(OBt)₂的浓度的增加几乎没有增大;当分别固定Fc(COOH)₂, Fc(Cys)和Fc(OBt)₂的浓度时,Fc(COOH)₂和Fc(Cys)的吸光度随着heme浓度的增加而增大,而Fc(OBt)₂的吸光度随着heme浓度的增加没有变化,说明Fc(COOH)₂和Fc(Cys)与heme存在分子间的相互作用,主要是由于Fc(COOH)₂和 Fc(Cys)与heme能形成氢键,分子链增长,吸收的能量增加,导致吸光度增大;而Fc(OBt)₂与heme没有分子间的相互作用,是由于Fc(OBt)₂没有自由的氢,不能与heme形成分子间的氢键。同时考察了三种二茂铁衍生物与heme 的吸光度随时间的变化,Fc(COOH)₂和 Fc(Cys)与heme的吸光度随着时间的增加而减少,而Fc(OBt)₂与heme的吸光度随时间的变化几乎没有变化。Fc(COOH)₂与Fc(Cys)和heme的反应时间为0.5,18和48 h,当固定Fc(COOH)₂浓度时,在λ_max=384 nm处的吸光度由2.64分别变为2.53和2.51;当固定heme的浓度时,在λ_max=384 nm处的吸光度由1.76分别变为1.72和1.68;当固定Fc(Cys)浓度时,在λ_max=397 nm处的吸光度由2.74分别变为2.63和2.55;当固定heme的浓度时,在λ_max=397 nm处的吸光度由1.82分别变为1.58和1.49。     

新型4-氨基安替比林席夫碱的合成及对Cu2+的选择性识别

设计合成了一种新型安替比林-席夫碱衍生物M(4-氨基安替比林缩5-硝基水杨醛席夫碱),用IR、1H NMR及元素分析对其结构进行了表征。通过紫外光谱和荧光光谱研究了M对Cu2+的选择性识别作用。结果表明:M与Cu2+能够以1∶1的化学计量比形成配合物,结合常数为6.5×104L·mol-1;M和Cu2+的结合导致M在496 nm处的荧光猝灭,紫外可见吸收光谱红移,且M对Cu2+有较高的选择性,受常见离子的干扰较小。     

Optical properties of new 5-(4-phenylethynyl)-substituted-1,10-phenanthroline derivatives

The synthesis and optical properties of a novel family of 5-substituted-1,10-phenanthroline derivatives are reported herein. One carbon-carbon triple-bond function was introduced using a Sonogashira cross-coupling reaction. The effects on optical properties, of the substitution with electro-withdrawing or -donating substituents in the 5th position of the 1,10-phenanthroline are investigated. Experimental chemical structure-polarisability relationship is analyzed according to the Lippert-Mataga correlation and compared to a theoretical study carried out with DFT calculations. These compounds are promising candidates for a fine-tuning of the internal charge-transfers but also as potential nonlinear chromophores and ligands within multifunctional coordination complexes.     

Influence of aliphatic spacer group on adsorption mechanisms of phosphonate derivatives of l-phenylalanine: Surface-enhanced Raman, Raman, and infrared studies

The nature of phosphonopeptides containing N-terminal l-phenylalanine (l-Phe), namely l-Phe-dl-NH-CH(CH(CH₃)₂)-PO₃H₂ (A), l-Phe-l-NH-CH(CH₃)-PO₃H₂ (B), and l-Phe-dl-NH-CH(CH₂CH₂COOH)-PO₃H₂ (C) (Fig. 1 presents molecular structure of these molecules), adsorbed on electrochemically roughened and colloidal silver surfaces has been explored by surface-enhanced Raman spectroscopy (SERS). To reveal adsorption mechanism of these species on the basis of their SERS spectra at first Fourier-transform Raman (FT-RS) and absorption infrared (FT-IR) spectra of non-adsorbed molecules were measured. Examination of enhancement, frequency shifts, and changes in relative intensities of SERS bands due to adsorption and surface roughens variation reveals that the tilted compounds adsorb on the electrochemically roughened silver substrate in similar way, while they behave differently on the colloidal silver surface. A stronger enhancement of in-plane ring vibrations of the l-Phe ring, i.e., ν₃ and ν_18b (B₂), over these of the A₂ symmetry in all SERS spectra on the electrochemically roughened silver substrate suggests that the ring interacts with this surface adopting slightly deflect orientation from the perpendicular one. Also, enhancement of PO and -CH₂-/-CH₃ fragments vibrations points out that they are involved in adsorption process on this substrate. This conclusion was drawn on the basis of the enhancement of 1274-1279 and 1138-1152 (ν(PO)), 1393-1400 (δ(CH) + ρ_b(CNH₂) + ν(C-C_O) + δ(CH₃)), ∼1455 (δ(CCH₃/CCH₂) + ρ_b(CH₃/CH₂), and 1505-1512 cm⁻¹ (δ(CH₂) + Phe(ν_19a)) bands. Although a relative intensity ratio of these bands in the presented SERS spectra is different. On the other hand, on the colloidal silver nanoparticles, the aromatic ring of all molecules is lying flat or takes almost parallel orientation to this surface. Besides, A interacts also via P-terminal group (568, 765, 827, 1040, and 1150 cm⁻¹), whereas B mainly through NH₂-C-(CO)-CNH-(712 and 1255 cm⁻¹). In the case of C, it adsorbs on the silver colloidal surface mainly through the aromatic ring of l-Phe, while other fragments of the molecule are in close proximity to this surface as comes off the weak enhancement of bands due to the aliphatic vibrations.     

Observability analysis of navigation system using point-based visual and inertial sensors

A matrix Kalman filter (MKF) has been implemented for a navigation system using point-based visual and inertial sensors. The observability conditions have been proved by the observability rank criterion based on Lie derivatives. The conditions are: (a) at least one degree of rotational freedom is excited and (b) at least three observed points are not collinear where any two points are linearly independent. Experimental results have demonstrated that the proposed algorithm obtains the same accurate as the line-based algorithm.     

Third-order nonlinear optical studies of new anthraquinone derivatives

Four new donor-acceptor-donor anthraquinone derivatives were synthesized and characterized by UV, IR, ¹H NMR and elemental analysis. Their off-resonant third-order nonlinear optical properties were measured using femtosecond laser and degenerate four-wave mixing technique. The third-order nonlinear optical susceptibilities χ⁽³⁾ were 3.36-3.76 × 10⁻¹³ esu. The nonlinear refractive indexes n₂ were 6.19-6.91 × 10⁻¹² esu. The second-order hyperpolarizabilities γ of the molecules were 3.36-3.76 × 10⁻³¹ esu. The response times were 101-115 fs. The results show that these compounds have potential nonlinear optical applications.     

Processing discontinuous displacement fields by a spatio-temporal derivative technique

In this paper, a digital image correlation (DIC) method coupling cross-correlation with spatio-temporal differential techniques was proposed for assessing discontinuous displacement fields. The accuracy and robustness of the algorithm was assessed on a set of numerical tests by processing computer generated speckled-pattern images. Fracture mechanical tests in mode I were considered, in which both in-plane and out-of-plane rigid-body movements were taken into account. The ability for recovering the analytical asymptotic displacement field in mode I was analysed, and stress intensity factor, crack opening displacement and crack tip location were used as quantitative parameters for validation purposes. Throughout these tests, the results obtained with the proposed method were systematically compared to the ones from Aramis DIC-2D commercial code. Globally, the results computed from both methods are in good agreement with reference values. However, due to the high spatial resolution (point-wise characteristic), a better matching of the displacements in the neighbour of discontinuities could be obtained by the proposed method.     

8-羟基喹啉偶氮苯衍生物应用于阴离子及阳离子的识别

研究了系列8-羟基喹啉偶氮苯衍生物与过渡金属离子如Ni2+,Co2+,Zn2+和Cu2+等离子间的相互作用,探讨了主体分子中的不同取代基对其光谱性质的影响及对阳离子识别选择性的影响。结果表明含有强吸电子基团-NO2或-CN的主体分子对阳离子的亲合力大于含有供电子基团-N(CH3)2或-CH3的