共查询到20条相似文献,搜索用时 125 毫秒
1.
用SP-2558型光谱实验系统测得了天然竹红菌素粗品的三维荧光光谱,给出其随样品浓度变化的规律,进而利用软件和理论分析提出,天然竹红菌素粗品荧光光谱主要是竹红菌甲素(HA)和竹红菌乙素(HB)荧光光谱的贡献,HA的荧光光谱受其他成分影响较大,造成了短波峰的蓝移和长波峰的红移;HA与HB之间的辐射能量转移导致其荧光光谱中长波成分增加,从而形成较宽的谱段;由分子间氢键形成的多聚体会导致天然竹红菌素粗品溶液的发射峰随浓度的增加而红移,因而通过对天然竹红菌素粗品的浓度调控,可以在一定的范围内实现对发射光波段的调控,这对指导临床上的应用具有较高的参考价值。 相似文献
2.
3.
4.
应用表面增强拉曼散射方法,首次获得了竹红菌甲素在黄银胶中的拉曼光谱;分析了电磁增强和荧光猝灭效应在银胶一竹红菌甲素体系中的作用。 相似文献
5.
应用表面增强拉曼散射方法,首次获得了竹红菌甲素在黄银胶中的拉曼光谱;分析了电磁增强和荧光猝灭效应在银胶-竹红菌甲素体系中的作用。 相似文献
6.
以一种新型的醌类光敏剂—菌生素 (HMB)为模型化合物 ,利用量子化学从头算HF/ 6 31G和含时密度泛函TD B3LYP/ 6 31G方法计算研究了卤代作用对醌类光敏剂分子性质和光敏活性的影响 .结果发现 ,卤代作用降低了HMB母体的HOMO和LUMO能级 (EHOMO和ELUMO)及其差值△E ,随卤族元素从上到下 ,EHOMO和ELUMO呈增大趋势 ,而△E呈减小趋势 ,使得分子激发光谱有不同程度的红移 ,在增加PQP三重态量子产率的同时降低了分子最低三重激发态的能量 ,两种作用相互抵消 ,使得卤代物的 1O2 量子产率与母体相似 ;增加了分子的绝热电子亲合势 ,使分子产生O2 -的能力下降 ;卤原子的引入 ,降低了HMB母体分子内氢键的强度 ,同时使顺式构型的分子内质子传递势垒增大 ,而使反式构型势垒减小 . 相似文献
7.
超分子组合流体室温磷光现象(Ⅱ)—醇对环糊精/碘代乙基联 … 总被引:8,自引:0,他引:8
在外部重原子微拢剂溴代环己烷存在下,β-CD/碘代乙基联苯体系可发射一定强度的室温磷光信号,若丁醇作为第四组分存在,则能显著提高体系的室温磷光发射强度。研究了该体系室温磷光发射的适宜条件和多种醇、不同环糊精及其衍生物的影响。认为β-CD/碘代乙基联苯/溴代环乙烷/丁醇体系属于一种超分子组合的发光体系,醇的作用属典型的分子调控作用。β-CD/碘代乙基联苯/溴代环乙烷形成主、客三元包结物,可醇则利用其 相似文献
8.
用~(23)Na NMR技术并借助于水溶性位移试剂Dy(PPPi)_2~(7-) 研究了新型光敏剂—竹红菌乙素光敏损伤对鼠腹水肝癌细胞Na~+通透性的影响。实验结果表明:在乙素光敏作用下,细胞内Na~+浓度随曝光时间的延长和乙素浓度增高而增加。同时观察到细胞外~(23)Na_(ovl)NMR峰的化学位移(δ值)随光照时间增加而向低场位移。分析表明:化学位移的改变与细胞膜损伤引起细胞内K~+泄漏和K~+、Na~+竞争位移试剂有关。因此,化学位移的改变也可作为光敏损伤的指标。本文还就Na~+平衡失调与细胞死亡之间的关系进行了讨论。 相似文献
9.
超分子组合流体室温磷光现象(Ⅱ)——醇对环糊精/碘代乙基联苯/溴代环己烷体系室温磷光的影响 总被引:2,自引:0,他引:2
在外部重原子微拢剂溴代环己烷存在下,β-CD/碘代乙基联苯体系可发射一定强度的室温磷光信号,若丁醇作为第四组分存在,则能显著提高体系的室温磷光发射强度。研究了该体系室温磷光发射的适宜条件和多种醇、不同环糊精及其衍生物的影响。认为β-CD/碘代乙基联苯/溴代环己烷/丁醇体系属于一种超分子组合的发光体系,醇的作用属典型的分子调控作用。β-CD/碘代乙基联苯/溴代环己烷形成主、客三元包结物,而醇则利用其羟基与CD端口羟基形成氢键,其烷基键借助于疏水相互作用力,覆盖在CD上、下端口,对外部氧向CD腔内的扩散起着隔离作用,减少了三线态氧对发光体激发三线态的猝灭,从而显著提高了体系室温磷光发射强度 相似文献
10.
用23Na NMR研究竹红菌乙素光敏损伤对鼠腹水肝癌细胞Na+通透性的影响 总被引:1,自引:0,他引:1
用23Na NMR技术并借助于水溶性位移试剂Dy(PPPi)27-研究了新型光敏剂-竹红菌乙素光敏损伤对鼠腹水肝癌细胞Na+通透性的影响。实验结果表明:在乙素光敏作用下,细胞内Na+浓度随曝光时间的延长和乙素浓度增高而增加。同时观察到细胞外23Naout NMR峰的化学位移(δ值)随光照时间增加而向低场位移。分析表明:化学位移的改变与细胞膜损伤引起细胞内K+泄漏和K+、Na+竞争位移试剂有关。因此,化学位移的改变也可作为光敏损伤的指标。本文还就Na+平衡失调与细胞死亡之间的关系进行了讨论。 相似文献
11.
Witton C Simpson MI Henning GB Rees A Green GG 《The Journal of the Acoustical Society of America》2003,113(1):468-477
When the source of a tone moves with respect to a listener's ears, dichotic (or interaural) phase and amplitude modulations (PM and AM) are produced. Two experiments investigated the psychophysical characteristics of dichotic linear ramp modulations in phase and amplitude, and compared them with the psychophysics of diotic PM and AM. In experiment 1, subjects were substantially more sensitive to dichotic PM than diotic PM, but AM sensitivity was equivalent in the dichotic and diotic conditions. Thresholds for discriminating modulation direction were smaller than detection thresholds for dichotic AM, and both diotic AM and PM. Dichotic PM discrimination thresholds were similar to detection thresholds. In experiment 2, the effects of ramp duration were examined. Sensitivity to dichotic AM and PM, and diotic AM increased as duration was increased from 20 ms to 200 ms. The functions relating sensitivity to ramp duration differed across the stimuli; sensitivity to dichotic PM increased more rapidly than sensitivity to dichotic or diotic AM. This was also reflected in shorter time-constants and minimum integration times for dichotic PM detection. These findings support the hypothesis that the analysis of dichotic PM and AM rely on separate mechanisms. 相似文献
12.
Paper deals with quantum chemical modeling of the optical absorption spectra of 6-fluoro, 7-trifluoromethyl, 6-cyano, 6-carboethoxy and 6-tert-butyl derivatives of 1-phenyl-3-methyl-1H-pyrazolo[3,4-b]quinoline. The calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) applied to the equilibrium molecular conformation in vacuo (T = 0 K) or molecular dynamic (MD) trajectories as obtained within fragmental or total MD simulations at T = 300 K. The results of these calculations are compared with the measured spectra of optical absorption. The quantum chemical analysis show that the dynamics of the methyl, trifluoromethyl, carboethoxy and tert-butyl groups practically does not influence the absorption spectra whereas the strongest their modifications are found to be related with dynamics of the aromatic group. The semiempirical method AM1 in combination with MD simulations gives for all dyes the best agreement between the calculated and measured spectral positions of absorption bands. In most cases the quantum chemical calculations describe properly the trends of their changes depending on the lateral substituent. 相似文献
13.
In the present study, the usability of semiempirical quantum mechanical methods for calculating bond dissociation energy (BDE) was investigated systematically. Density functional theory (DFT) methods with the B3LYP and B97-1 functionals were used for comparison. We introduced a new test set for BDE, called BDE200, which covers a wide range of compounds including large aromatic compounds. The use of BDE200 test set revealed that the accuracy of the methods studied was ordered from best to worst as: B97-1 > B3LYP > rPM6 >> PM7 > PM6 > AM1 > PM3. In addition to the improved accuracy of rPM6 for predicting BDE, it was found that rPM6 can provide a quantitative correlation between BDE values and reactivity. The rPM6 calculated activation enthalpies for C–H hydroxylation catalysed by the compound I of cytochrome P450 were proportional to the calculated and experimental C–H BDE values, in line with the results of previous DFT studies. We believe that rPM6 can help develop a database, for instance, for the determination of site of metabolism. 相似文献
14.
The influence of atomic structure of silicon nanoparticles on the distribution of total and partial state densities in the
valence and conductivity bands as well as on the valence band and gap widths is analyzed based on the calculated geometrical
and electron structure of the Si
24 and MeSi
24 (Me = Na or K) clusters. Semi-empirical AM1 and PM3 methods are used for calculations. The adequacy of calculations is confirmed by their
comparison with the available experimental data.
__________
Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 46–51, February, 2006. 相似文献
15.
In this study, the theoretical conformation analysis of free dapsone has been performed by single point energy calculations at both semi-empirical PM3 and DFT/B3LYP-3-21G theory levels and three stable conformers were determined. Both the IR and Raman spectra of the molecule in solid phase have been recorded. The IR intensities and harmonic vibrational wavenumbers of each conformer were calculated by DFT method at B3LYP/6-31++G(d,p) theory level. For the fundamental characterization, the total energy distribution (TED) calculations of the vibrational modes were done using parallel quantum mechanic solution program (SQM) and the fundamental modes were assigned. The theoretical results are in agreement with the experimental ones. 相似文献
16.
In the present study, a novel blue light source from LED was used to activate hypocrellin B in ovarian cancer HO-8910 cells.
Hypporellin B concentration was kept at 2.5 μM and light doses from 0.5–4.0 J/cm2. Photocytotoxicity was investigated using MTT reduction assay and light microscopy after light irradiation. Cellular morphology
was observed using transmission electron microscopy (TEM). MTT assay showed that the cytotoxicity of blue light-activated
hypocrellin B in HO-8910 cells increased along with light dose. The observations from light microscopy reinforced the above
results. TEM showed that microvillin disappearance, vacuole formation, chromatin condensation, and topical apoptotic body
were observed in the cells treated by both light and hypocrellin B. The findings demonstrated that blue light from LED source
could effectively activate hypocrellin B to cause the destruction of HO-8910 cells, indicating that Blue light-activated hypocrellin
B might be potential therapeutic strategy in the management of ovarian cancer. 相似文献
17.
Temperature dependence of ratio between dielectric anisotropy and order parameter in fluorinated nematic liquid crystals 下载免费PDF全文
Temperature dependence of ratio between dielectric anisotropy and order parameter of fluorinated nematic liquid crystal is investigated by using a semi-empirical molecular orbital package that can accurately calculate an angle between molecular dipole moment and long axis. We optimize the molecular conformations with three semi-empirical Hamiltonians AM1, PM3 and PM5, and then make a comparison between computational results and experimental measurements. It is shown that the results obtained from AM1 method are in good agreement with the measurements. The present study offers an applicable method to predict the dielectric properties of liquid crystal material. 相似文献
18.
RAMAIYER VENKATRAMAN JÓZEF S. KWIATKOWSKI GRZEGORZ BAKALARSKI JERZY LESZCZYNSKI 《Molecular physics》2013,111(6):371-386
The molecular parameters (geometries, rotational constants, dipole moments) and vibrational IR spectra (harmonic wavenumbers, absolute intensities) of bromomethanes (CH3Br, CH2Br2, CHBr3, CBr4) are predicted by a density functional theory with the hybrid Becke3-LYP functional (DFT) and post-Hartree-Fock methods (MP2, CCSD(T)) using a 6-311G(2d,2p)-type basis set. The MP2 calculations are carried out with different numbers of frozen core orbitals to find how the number of bromine orbitals used for electron correlation influences the predicted molecular parameters and IR spectra of the species in question. Three options were used: (a) all electrons (full), with both the core and valence orbitals considered; (b) partial frozen core option (pfc), when the orbitals up to 3p of bromine were frozen; and (c) full frozen core option (ffc), when all core orbitals up to 3d were frozen. The CCSD(T) calculations for geometric parameters were carried out with both the pfc and ffc options, while for the prediction of the IR spectra only the ffc option was used. In addition, the calculations at the DFT and MP2(pfc) levels with inclusion of f functions on carbon and bromine atoms in bromomethanes (and also the CCSD(T)(pfc) calculations for CH3Br) were carried out to predict the changes in the geometric parameters and/or vibrational IR spectra of the molecules upon inclusion of f functions The geometries of bromomethanes (particularly the CBr bond lengths) are predicted better by the DFT and CCSD(T) calculations when the f functions (in particular on bromine atom) are included, while the MP2 calculations without f functions are good enough for correct predictions of the molecular geometries. The molecular parameters and vibrational IR spectra of bromomethanes in question and their deuterated species predicted by the DFT, MP2(ffc) and CCSD(T)(ffc) with the 6-311G(2d,2p) basis set agree well with the available experimental data. 相似文献
19.
Temperature dependence of ratio between dielectric anisotropy and order parameter in fluorinated nematic liquid crystals 下载免费PDF全文
Temperature dependence of ratio between dielectric anisotropy and
order parameter of fluorinated nematic liquid crystal is
investigated by using a semi-empirical molecular orbital package
that can accurately calculate an angle between molecular dipole
moment and long axis. We optimize the molecular conformations with
three semi-empirical Hamiltonians AM1, PM3 and PM5, and then make a
comparison between computational results and experimental
measurements. It is shown that the results obtained from AM1 method
are in good agreement with the measurements. The present study
offers an applicable method to predict the dielectric properties of
liquid crystal material. 相似文献
20.
竹红菌素及其衍生物敏化的生物膜和DNA结构的光损伤的Raman光谱研究 总被引:8,自引:0,他引:8
本文综述了具有抗癌和抗艾滋病毒活性的三种光敏剂—竹红菌素及其衍生物敏化的生物大分子—生物膜和DNA结构的光损伤的Raman光谱特征;上述三种光敏剂对DNA和生物膜损伤最强的均为5-Br-HB,其次是HB,然后是HA,即5-Br-HB>HB>HA。说明药物的结构与它的光敏活性密切相关,修饰结构是增进药效的重要途径。 相似文献