TD-DFT Study on the Electronic Spectrum Properties of 2,7′-(Ethylene)-bis-8-hydroxyquinoline and Its Derivatives

The structures of 2,7＇-（ethylene）-bis-8-hydroxyquinoline and its derivatives were optimized at the ground states using ab initio HF and B3LYP methods. At the same time, the molecular structures of the first singlet excited state for 2,7＇-（ethylene）-bis-8-hydroxyqulnoline and its derivatives were optimized by CIS/6-31G（d）. The absorption and emission spectra based on the above structures were obtained by the time-dependent density functional theory （TD-DFT） by the B3LYP method with the 6-31G（d） basis set. The calculated results of luminescence originate from the electronic transition from the hydroxphenol ring of 8-hydroxyquinoline A to the pyridine ring of 8-hydroxyquinoline B. Their luminescence wave bands can be tuned by different substituents on the ligand of 8-hydroxyquinoline.

Identification of the unknown shielding parameters with gammaray spectrum using a derivative-free inverse radiation transport model

Identifying the unknown geometric and material information of a multi-shield object by analyzing the radiation signature measurements is always an important problem in national and global security. In order to identify the unknown shielding layer thicknesses of a source/shield system with gamma-ray spectra, we have developed a derivative-free inverse radiation transport model based on a differential evolution algorithm with global and local neighbourhoods(IRT-DEGL). In the present paper, the IRT-DEGL model is further extended for estimating the unknown thicknesses with random initial guesses and material mass densities of multi-shielding layers as well as their combinations. Using the detected gamma-ray spectra,the illustration of inverse studies is implemented and the main influence factors for inverse results are also analyzed.

Application of derivative ratio spectrophotometry for determination of β-carotene and astaxanthin from Phaffia rhodozyma extract

A derivative ratio spectrophotometric method was used for the simultaneous determination of β-carotene and astaxanthin produced from Phaffia rhodozyma. Absorbencies of a series of the standard carotenoids in the range of 441 nm to 490 nm demonstrated that their absorptive spectra accorded with Beer’s law and that the additivity when the concentrations of β-carotene and astaxanthin and their mixture were within the range of 0 to 5 μg/ml, 0 to 6 μg/ml, and 0 to 6 μg/ml, respectively. When the wavelength interval (?λ) at 2 nm was selected to calculate the first derivative ratio spectra values, the first derivative amplitudes at 461 nm and 466 nm were suitable for quantitatively determining β-carotene and astaxanthin, respectively. Effect of divisor on derivative ratio spectra could be neglected; any concentration used as divisor in range of 1.0 to 4.0 μg/ml is ideal for calculating the derivative ratio spectra values of the two carotenoids. Calibration graphs were established for β-carotene within 0?6.0 μg/ml and for astaxanthin within 0?5.0 μg/ml with their corresponding regressive equations in: y=?0.0082x?0.0002 and y=0.0146x?0.0006, respectively. R-square values in excess of 0.999 indicated the good linearity of the calibration graphs. Sample recovery rates were found satisfactory (>99%) with relative standard deviations (RSD) of less than 5%. This method was suc- cessfully applied to simultaneous determination of β-carotene and astaxanthin in the laboratory-prepared mixtures and the extract from the Phaffia rhodozyma culture.

Extension of covariant derivative(Ⅲ): From classical gradient to shape gradient

This paper further extends the generalized covari ant derivative from the first covariant derivative to the sec ond one on curved surfaces. Through the linear transforma tion between the first generalized covariant derivative and the second one, the second covariant differential transformation group is set up. Under this transformation group, the sec ond class of differential invariants and integral invariants on curved surfaces is made clear. Besides, the symmetric struc ture of the tensor analysis on curved surfaces are revealed.

TD-DFT Study on Pyrazoline Derivatives

The molecular structures of ground state and first single excited state for pyrazoline derivatives are optimized with DFT B3LYP method and ab initio “configuration interaction with single excitations”（CIS） method, respectively. The frontier molecular orbital characteristics have been analyzed systematically, and the electronic transition mechanism has been discussed. Electronic spectra are calculated by using TD-DFT method. These results are consistent with those from the experiment.

Theoretical Study on the Electronic Structures and Spectral Properties of 1,8-Naphthalimide Derivatives

The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.

Low-Frequency Vibrations of Indole Derivatives by Terahertz Time-Domain Spectroscopy

Several indole derivatives with different ＇3-＇ substituents have been investigated by terahertz （THz） time-domain spectroscopy. The low-frequency absorption spectra and refractive indices were obtained in the range of 0.2 THz to 2.5 THz （7 cm-1 to 83 cm-1）. These derivatives with different substituents present distinct features, which suggests that THz spectroscopy is sensitive to different structures and components of these chemicals. The density functional theory was employed to calculate the low-frequency vibrational properties of indole-3-carboxylic acid and indole-3-propionic acid based on their crystal structures, and the intermolecular interactions were involved. Meanwhile, the temperature dependence of the spectra agreed with the calculated results. The quantitative analysis of a ternary mixture was studied by taking the THz fingerprints into account, and the results demonstrate THz spectroscopy has great potential for the practical applications in biochemistry and pharmaceutics.

Synthesis,Crystal Structure and Photoluminescence of Ethyl Coumarin-3-carboxylate Derivatives

The ethyl coumarin-3-carboxylate （1） and its two derivatives, ethyl 7-methoxy-2- oxo-2H-chromene-3-carboxylate （2） and ethyl 7-（3-methylbut-2-enyloxy）-2-oxo-2H-chromene-3- carboxylate（3）, were synthesized, characterized and their UV-vis spectra and photoluminescence were investigated. Compound 2 crystallizes in the monoclinic system with space group C2/c, a = 25.884（4）, b = 6.8365（11）, c = 13.816（2） A, β = 104.876（2）°, V= 2362.9（7） A3, Z = 8, Dc= 1.396 g/cm3, Mr. = 248.23, F（000） = 1040 and g = 0.108 mm-1. Compound 3 crystallizes in the monoclinic system with space group P21/c, a = 15.685（6）, b = 8.373（3）, c = i3.063（5） A, β = 111.862（6）°, V= 1592.2（10） A3, Z = 4, Dc = 1.261 g/cm3, M,.= 302.31, F（000） = 640 and p = 0.093 mm^-1. Both the absorption and emission of the two derivatives were stronger than that of ethyl coumarin-3-carboxylate due to the larger conjugation of their electron donor group moiety at the 7-position. Under ultraviolet light excitation, the two derivatives exhibit strong blue-violet emission.

Synthesis and Characterization of Both Enantiomers of a Chiral C_(60) Derivative Bearing the 1, 1'-Binaphthyl Group

Both enantiomers R-1 and S-1 of a chiral C60 derivative were synthesized by the reactions of C60 with 1, 1'-bi-2-naphthol bis(azidoacetates) and characterized by FD-MS, fT-IR,1H NMR, 13C NMR, UV-VIS, CD spectra.

DERIVED SEQUENCES AND THE FACTOR SPECTRUM OF THE PERIOD-DOUBLING SEQUENCE

Factor properties and their structures are important themes in combinatorics on words.Let D be the infinite one-sided sequence over the alphabet{a,b}generated by the period-doubling substitutionσ(a)=ab andσ(b)=aa.In this paper,we determine the derived sequence D_(ω)(D)for any factorω■D,and study some factor spectra using the structures of derived sequences.We also prove the reflexivity property of derived sequences.

UV-Vis Spectrum and the Third-order Nonlinear Optical Properties of the Chiral Camphorderived β-diketonate Platinum Complexes

UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.

盘锦地区不同品种水稻品质及其冠层高光谱反射率特征分析

对2022年盘锦地区8种水稻进行品质特征分析,并探讨不同品种水稻籽粒加工品质、外观品质、蒸煮品质、营养品质与水稻成熟期冠层原始光谱、一阶导数光谱及连续统去除光谱的相关关系。结果表明:盐粳939的加工品质较好,锦稻106(9系)的外观品质较好,锦稻香103的蒸煮品质较好,盘粳968(3系)的营养品质较好。原始光谱反射率与糙米率指标的相关关系较好,在731~1131 nm和1150~1360 nm两个波段内,相关系数高达0.767;糙米率与一阶导数光谱的相关关系最好,在1459 nm处达到极显著相关,相关系数为0.867;垩白度和垩白粒率均在1804 nm处与连续统去除光谱的相关关系较好,并达到极显著负相关,相关系数分别为-0.979和-0.983;长宽比与原始光谱的相关关系较好,相关系数在659 nm处达到最大值,为0.849;蒸煮品质所包含的食味值、直链淀粉含量和营养品质所包含的蛋白质含量均与连续统去除光谱有较好的相关关系。

头穴针刺联合密集训练治疗孤独症谱系障碍患儿疗效观察及对血清5-HT、BDNF的影响

目的:观察头穴针刺联合密集训练对孤独症谱系障碍(ASD)患儿核心症状及血清5-羟色胺(5-HT)、脑源性神经营养因子(BDNF)的影响。方法:将ASD患儿102例按随机数字表法分为对照组和治疗组各51例。对照组采取常规密集训练治疗,治疗组在对照组基础上联合头穴针刺治疗。比较2组治疗前后孤独症行为(ABC)、儿童孤独症评定量表(CARS)、孤独症治疗评估量表(ATEC)和父母育儿压力指数简表(PSI-SF)评分,以及血清5-HT、BDNF水平。结果:治疗后,2组ABC、CARS、ATEC评分均治疗前降低(P<0.05),且治疗组ABC、CARS、ATEC评分均低于对照组(P<0.05)。治疗后,2组感觉能力、交往能力、躯体运动能力、语言能力和自我照顾能力等ABC量表中各因子评分均较治疗前降低(P<0.05),且治疗组上述各项评分均低于对照组(P<0.05)。治疗后,2组PSI-SF总分及育儿愁苦、亲子互动失调、困难儿童3个维度评分均较治疗前降低(P<0.05),且治疗组上述各项评分均低于对照组(P<0.05)。治疗后,2组血清5-HT水平较治疗前降低(P<0.05),BDNF水平较治疗前升高(P<0.05);且治疗组5-HT水平低于对照组(P<0.05),BDNF水平高于对照组(P<0.05)。结论:头穴针刺联合密集训练能有效调节血清5-HT、BDNF水平,改善ASD患儿的核心症状,减轻父母育儿压力,提高整体治疗效果。

模型约束与机器学习下的植物类胡萝卜素和叶绿素含量反演方法

叶绿素和类胡萝卜素含量是评价植物健康状况的一个重要指标。PROSPECT模型与机器学习耦合反演植被生化特性已得到广泛应用。但由于叶片方向半球反射率因子(DHRF)光谱和二向反射率因子(BRF)光谱之间的差异,耦合模型的应用范围受到限制。为此,以北美地区植物叶片光谱数据库(EcoSIS)作为实验数据集,提出PROSPECT模型作为机器学习的附加约束形成混合数据集,对此混合数据集利用连续小波变换(CWT)产生的小波系数谱和一阶导(FD)产生谱,提出三种全光谱域和VNIR光谱子域下的植物叶片叶绿素、类胡萝卜素的光谱特征变量筛选策略,即是:竞争性自适应重加权算法(CARS)、连续投影算法(SPA)和主成分分析法(PCA)。由此,基于上述2×2×3=12种不同光谱处理方法、特征提取方法组合,分别建立了植物叶片叶绿素和类胡萝卜素含量的人工神经网络(ANN)预测模型。进而开展了不同模型下的预测精度对比分析,结果表明:PROSPECT模型约束下的模拟数据一定程度增强了机器学习的训练集质量;经一阶导、小波变换处理的光谱能较好地减少DHRF模拟光谱和BRF实测光谱间的偏差,并在结合特征提取算法CARS后进一步提升了预测表现。在全光谱域下的FD+CARS组合对叶片叶绿素的反演效果最佳,测试集R2为0.8064,RMSE为2.9114;在VNIR光谱子域下的CWT+CARS组合对叶片类胡萝卜素最佳,测试集R2为0.7972,RMSE为0.4141。该方法可为研究人员从叶片BRF光谱及其他近端反射率图像更精确、高效地提取植物叶片生化特征提供参考。

基于BDNF/TrkB/CREB通路研究六味地黄丸对丙戊酸钠诱导的孤独症谱系障碍模型仔鼠的作用机制

目的基于脑源性神经营养因子(brain-derived neurotrophic factor,BDNF)/酪氨酸激酶受体B(tyrosine kinase receptor B,TrkB)/cAMP反应元件结合蛋白(cAMP response element binding protein,CREB)通路,探讨六味地黄丸对丙戊酸钠(sodium valproate,VPA)诱导的孤独症谱系障碍(autism spectrum disorder,ASD)仔鼠的作用机制。方法将13只SD孕鼠随机分为两组,其中10只孕鼠在第12.5天时腹腔注射VPA溶液(600 mg·kg^(-1))为VPA组,另外3只孕鼠注射等体积生理盐水为对照组。第21天对两组雄性仔鼠开展行为学检测,筛选出符合ASD疾病模型的仔鼠30只,随机分为模型组(等体积生理盐水),维生素D组(1480 IU·kg^(-1)),六味地黄丸高(3 g·kg^(-1))、中(1.5 g·kg^(-1))、低(0.75 g·kg^(-1))剂量组,每组6只。正常雄性仔鼠6只,设为空白组(等体积生理盐水)。各组仔鼠连续灌胃14 d,1次/d,给药后再次开展行为学检测。尼氏染色观察各组仔鼠海马组织神经元形态学变化,比色法检测各组仔鼠海马组织中谷氨酸(glutamic acid,GLU)、γ-氨基丁酸(gamma-aminobutyric acid,GABA)含量;qRT-PCR检测各组仔鼠海马组织中BDNF、TrkB、CREB mRNA相对表达。结果与对照组比较,VPA组仔鼠体质量、身长、尾长更小(P<0.05)。与空白组比较,模型组社交障碍症状明显(P<0.01),焦虑障碍症状明显(P<0.01),重复刻板行为增多(P<0.05或P<0.01),海马神经元结构损伤,GLU升高(P<0.01)、GABA下降(P<0.01),BDNF、TrkB、CREB mRNA表达降低(P<0.05或P<0.01);与模型组比较,维生素D组及六味地黄丸中、低剂量组仔鼠社交能力增强(P<0.05或P<0.01),焦虑障碍减轻(P<0.05或P<0.01),重复刻板行为减少(P<0.01或P<0.05),海马神经元结构明显复原,GLU下降(P<0.01),BDNF、TrkB、CREB mRNA表达增加(P<0.05或P<0.01),六味地黄丸中、低剂量组GABA上升(P<0.05或P<0.01)。结论六味地黄丸能显著改善VPA诱导的ASD仔鼠行为表现,增强海马组织神经元的再生与修复,其机制可能与平衡GLU、GABA水平,上调仔鼠海马组织中BDNF/TrkB/CREB的表达有关。

物相定性分析的综合实验设计与实践

物相定性分析主要用来判定物质组成及其存在状态,是材料、化工和地质等学科专业学生必须掌握的综合性实验技能。为培养学生对材料的物相分析测试能力,设计了未知粉末物相定性分析的综合实验。以氧钼矿、黑铜矿、斜锆石和六方软锰矿的混合粉末作为盲样,依据X射线衍射和能谱元素结果,通过实验数据和综合解析推导,撰写实验分析报告,全面提高学生的仪器操作和数据分析能力。

认知功能障碍:运动、孤独症和脑源性神经营养因子的相互作用

综述脑源性神经营养因子(Brain-derived neurotrophic factor,BDNF)在运动改善孤独症谱系障碍(Autism spectrum disorder,ASD)海马认知功能中的潜在作用。从BDNF的生物功能和参与SIRT1-PGC1a/FNDC5/Src/PLC-γ1、Ras/MAPK、PI3K/Akt信号通路,ASD患者认知功能相关的脑区改变以及BDNF在ASD不同病理下的表达调控等方面阐述其在促进神经元突触可塑性,提高学习记忆能力,最终改善海马认知功能方面的作用,进一步探讨BDNF在运动改善ASD海马认知功能中可能扮演的重要调控作用,为理解运动通过诱导BDNF表达,改善ASD海马认知功能间复杂的因果关系提供新的视角。最后展望以BDNF为靶点为孤独症疾病临床诊断提供可能的生物学标志物和药物开发提供广阔前景,为运动改善ASD的临床治疗和运动康复提供理论依据和新思路。

几类保持映射的刻画

本文研究了一类三元组正交保持的线性映射并刻画了保持τ-可测算子谱的线性映射.我们在更弱的条件下利用性质B刻画了保持三元组正交的线性映射,获得了这类映射是广义的Jordan导子的结果.对于保持τ-可测算子谱的线性映射研究,我们将有界算子中保谱的结果推广到无界算子.

噻吩酰亚胺衍生物二阶非线性光学性质的DFT研究

采用密度泛函理论(DFT)CAM-B3LYP方法,计算研究了12个设计的噻吩酰亚胺衍生物的电子光谱和二阶非线性光学性质.结果表明,此类化合物有较大的第一超极化率β_(tot)值和β_(vec)值,且β_(tot)值和β_(vec)值随引入氰基数目的增加而显著增大.给/吸电子基团引起的电荷转移变化对体系β_(tot)值和β_(vec)值的影响大于分子六元杂环中N杂原子位置变化对其影响.

Spectrum of Signals on the Quaternion Fourier Transform Domain

The quaternion Fourier transform plays a vital role in the representation of two-dimensional signals. This paper characterizes spectrum of quaternion-valued signals on the quaternion Fourier transform domain by the partial derivative.