几个分子和负离子的QCI势能曲线

用ＱＣＩＳＤ（Ｔ）／６３１１＋Ｇ（３ｄｆ，２ｐ）（简称ＱＣＩ）计算了ＢＨ－（２Π），ＢＦ－（２Π），ＢＨ（１∑），ＢｅＨ－（１∑），ＢｅＦ－（１∑）和ＢＦ（１∑）的较完整的势能曲线，探讨了这些体系的稳定性和解离过程．同时用Ｍｏｒｓｅ函数和ＥＲ函数拟合得到势能曲线，用拟合结果计算谐性频率和非谐性频率，并与已有的实验数据（ＢＨ和ＢＦ分子）进行比较，由此考察了ＱＣＩ理论方法在远离平衡构型时的可靠性．对于因单参考态近似导致的反常势能曲线进行了ＣＡＳＳＣＦ计算．还比较了ＱＣＩ和Ｇ２理论中标准的ＭＰ２（ｆｕｌ）／６３１平衡几何构型及其对ＱＣＩ总能量的影响．     

GaP低阻欧姆接触层的AES和SIMS分析

本文用AES和SIMS分析讨论了p-GaP与三层金属膜Pd/Zn/Pd形成良好欧姆接触层的性质.     

Novel ions of quaternary ammonium halides in FDMS

Field desorption mass spectrometry exhibited novel ions [ Y-n H+n R ]+and [ Y-nH+nX]+as well as cluster ions [nY+(n-1)X-mH+mR]+and [nY+( n-1)X-mH+mX]+(n,m=0-3; X and Y represent the cation and anion moieties of quaternary ammonium halides),whose formation mechanism was discussed.     

乙烯系单体自由基聚合的阻聚效应——ⅩⅣ.4-甲基丙烯酰氧基-2,2,6,6-四甲基哌啶-1-氧自由基低聚物的合成及对丙烯酸阻聚的研究

研究了数均分子量10~3～5×10~3的聚甲基丙烯酸甲酯的制备及其在甲醇镁存在下和2,2,6,6-四甲基-4-羟基哌啶-1-氧自由基(TMHPO·)间的酯交换反应,合成了聚-4-甲基丙烯酰氧基-2,2,6,6-四甲基哌啶-1-氧自由基(PMTMPO·)低聚物。同时观察了4-甲基丙烯酰氧基2,2,6,6-四甲基哌啶的调聚反应,同样制得PMTMPO·低聚物。利用IR、EPR和TGA技术对PMTMPO·进行了表征。评价了PMTMPO·对AIBN引发的丙烯酸(AA)自由基聚合的影响,表明PMTMPO·对AA有良好的阻聚功效。     

A new spirofluorene-based nonplanar PBI-dyad and its utilization in the film-based photo-production of singlet oxygen

Traditional photosensitizers are predominantly based on various types of polypyrrole macrocycles, which are generally used in homogeneous and/or suspension states. In the present study, a new non-polypyrrole-based photosensitizer(LW-PBI) was developed via the introduction of a nonplanar spirofluorene into a derivative of perylene bisimides(PBI) containing two longalkyl chains. Photophysical studies demonstrated that the compound shows good solubility in common organic solvents, great photochemical stability, and high absorption efficiency in the visible light region. Due to containing of two energetically matchable, independent fluorescent units, the compound as prepared displays strong tendency to form non-fluorescent chargeseparated states under light irradiation in polar solvents. Based on the merits, LW-PBI was examined for its catalytic property in the photo-production of singlet oxygen in film state. Luckily, the compound is an effective photosensitizer in the generation of the active oxygen species as verified by its unique reaction with uric acid(UA). Further studies revealed that the effective photoproduction of singlet oxygen can be also realized via the utilization of a tiny and low-price LED lamp as a light source and as a film support. Detailed studies on the application of the conceptual device as a medical instrument for photodynamic therapy(PDT) are in progress.     

Development and full validation of an LC–MS/MS methodology to quantify capmatinib (INC280) following intragastric administration to rats

A highly sensitive, specific and simple LC–MS/MS method for quantification of capmatinib (INC280) in rat plasma was presented. The LC–MS/MS method was validated in terms of specificity and selectivity, linearity, accuracy and precision, matrix effect, extraction recovery, dilution integrity, carryover and stability as per the US Food and Drug Administration's bioanalytical method validation guideline. The validated assay was applied for quantification of capmatinib from a pharmacokinetic study in rats following oral administration at the doses of 1.0, 3.0 and 9.0 mg/kg. The calibration curve ranges from 1 to 2000 ng/ml with desirable linearity and r² > 0.99. The intra- and inter-batch accuracies were within 99.24–103.59 and 97.76–102.83% with coefficients of variation 5.08–7.36 and 3.18–4.99%, respectively. No significant interference was observed by endogenous peak at the retention time of capmatinib and IS. The assay was free from any matrix effect and showed precise recovery across the calibration curve range, and samples were stable under all experimental conditions. The validated assay was successfully applied to analyze plasma samples of pharmacokinetic study in rat to determine the concentration of capmatinib. In summary, a novel method for analyzing capmatinib in rat plasma has been successfully validated and is now being utilized for quantification of capmatinib from pre-clinical studies.     

Perylene Bisimide-Cored Supramolecular Coordination Complexes: Interplay between Ensembles,Excited State Processes,and Aggregation Behaviors

Manipulating the optical properties of fluorescent species is challenging owing to complicated and tedious synthetic works. Herein, the photophysical properties of perylene bisimide (PBI) were effectively tuned by varying the geometrical arrangement of PBI moieties within supramolecular coordination complexes (SCCs), where a PBI-based dicycle ( 2 ) and a trigonal prism ( 3 ) were generated via using a typical 90° Pt(II) reagent, cis-(PEt₃)₂Pt(OTf)₂-based coordination-driven self-assembly approach. The ligand, an ortho-tetrapyridiyl-PBI ( 1 ), exhibits a moderate fluorescence quantum yield (∼13 %) and efficient inter-system crossing (ISC). 2 , however, is much more emissive with a fluorescence quantum yield of ∼41 %, and the relevant ISC process is significantly hindered. The fluorescence quantum yield of 3 is merely ∼6 % due to the observed symmetry-breaking charge separation (SB-CS), which turns to triplet state upon charge recombination. Interestingly, 3 could be fully transformed into 2 by simply adding a suitable amount of a 90° Pt(II)-based neutral triangle. Moreover, 2 tends to form discrete dimers both in crystal and solution states, but 3 does not show the property. Therefore, controlling geometrical arrangement of fluorophores through coordination-driven self-assembly could be taken as another effective way to tune their excited state relaxation pathways and construct high-performance optical molecular materials, which generally have to be prepared via organic synthesis.     

Preparation of Porous Hollow SiO2 Spheres by a Modified St?ber Process Using MF Microspheres as Templates

Using the surface charged and acid dissolvable melamine formaldehyde (MF) microspheres as sacrificial hard templates, silica coated MF core?Cshell composite microspheres, denoted as MF@SiO₂, were synthesized via a surfactant-assisted sol?Cgel process by using tetraethyl orthosilicate (TEOS) as silica source. Hollow SiO₂ spheres with mesoporous shells were then obtained after selective removal of the MF cores and the pore directing surfactant by hydrochloric acid etching or calcinations in air. Interesting shrinkage phenomena were observed in both the hollow products derived from hydrochloric acid etching and calcinations. The influence of the ratio of MF sphere to TEOS and the removal method of the MF core on the size of the hollow spheres, the shell thickness and the shell surface roughness have been studied. The composition, the thermal stability, the morphology, the surface area and pore size distribution, the wall thickness and adsorption properties of the hollow spheres derived from hydrochloric acid etching and calcinations were also investigated and compared based on the FTIR, SEM, TEM, TGA, Nitrogen adsorption?Cdesorption and spectrophotometer techniques or measurements.