Synthesis and Characterization of Soluble Cardo Poly(ester-imide)s Derived from 9,9-Bis[4-(3,4-dicarboxybenzoyloxy)phenyl]fluorene

A novel fluorenyl cardo dianhydride-9,9-bis[4-(3,4-dicarboxybenzoyloxy)phenyl]fluorene (BDPF) was synthesized and characterized. A series of fluorenyl cardo poly(ester-imide)s (FCPEIs) were prepared by the polycondensation of BDPF with m-phenylene diamine, 4,4′-oxydianiline (4,4′-ODA), 3,4′-oxydianiline (3,4′-ODA), 2,2-bis[4-(4-amino -phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 1,6-hexamethylenediamine. Most of the FCPEIs exhibited excellent solubility in common organic solvents such as 1,2-dichlorobenzene (o-DCB), chloroform, tetrahydrofuran, N,N-dimethylacetamide (DMAc), dimethyl sulfoxide, N-methyl-2-pyrrolidinone, etc. Intrinsic viscosities of FCPEIs in DMAc, for instance, ranged from 0.29–0.52 dL/g. The glass transition temperature of these polymers was between 199°C and 283°C by differential scanning calorimentry, and the 5% weight loss temperature of all polymers exceeded 400°C in air.     

1H and 13C NMR Spectra of Alditolyl Derivatives of 3-Hydrazino-5-Methyl[1,2,4]triazino[5,6-b]indole and Their Cyclized Products.

The ¹H and ¹³C NMR spectra of sugar (5-methyl [1, 2, 4]-triazino [5, 6-b] indol-3-yl) hydrazones (1), per-0-acetyl aldehydo sugar 1-acetyl-1-(5-methyl [1, 2, 4] triazino [5, 6-b]-indol-3-yl) hydrazones (2), l- (penta-0-acetyl-pentitol-1-yl)-10-methyl [l, 2, 4] triazolo [3′, 4′:3, 4] [l, 2, 4] triazino [5, 6-b]-indoles (3) have been investigated. The 2 D NMR (H, C COSY) spectrum of 2a has been studied.     

1H- and 13C-NMR Study of Some 6,7-Dihaloquinolone Nucleosides and Their Derivatives

The ¹H- and ¹³C-NMR spectra of 6,7-dihalo-1,4-dihydro-4-oxo-1-(2,3,5-tri-0-benzoyl-pβ-D-ribofuranosyl)quinoline-3-carboxylic acids (3), (4), the ester (3a), 6-chloro-1-(2-deoxy-3,5-di-O-tolouyl-α- and β-D-erythropentofuranosyl)-7-fluoro-1,4-dihydro-4-oxo-quinoline-3-carboxylic acid (5), and its free a-nucleoside (5a) have been investigated. Resonance signals were assigned by homo- and heteronuclear two dimensional NMR methods (DQF-COSY, HMQC, and HMBC) for (3), (4), (5), and (5a). Ribosylation sites and anomeric configurations were identified from ROESY spectra.     

2,2′-联苯醚二甲酸和邻菲啰啉构筑的单核铽(Ⅲ)配合物:荧光性质及对Fe~(3+)的发光传感

采用水热法合成了一种新的配合物[Tb(2,2′-oba)_2(phen)_2]~-(H_3~+O)(2,2′-oba=2,2′-联苯醚二甲酸,phen=1,10-邻菲啰啉),并用X-ray单晶衍射仪测定了晶体结构。配合物是由两个邻菲啰啉和两个2,2′-联苯醚二甲酸铽离子构成的单核分子。配合物的荧光光谱在489,546,584和622nm处出现发射峰,归属为中心Tb~(3+5)D_4→7 FJ(J=6-3)跃迁产生的特征荧光。在546nm处的发射最强,对应于~5D_4→~7F_5跃迁,为绿光。探讨了不同金属阳离子对配合物的荧光效应影响。实验结果表明Fe3+对配合物具有显著的荧光猝灭作用,在生理环境pH 4.0~8.0范围内仍然适用,因此配合物可用于生命体系中的Fe~(3+)作荧光探针。     

三波段白光有机电致发光器件及其色稳定性的控制

制备并研究了基于3种小分子荧光材料的白光有机电致发光器件。发光层采用红色发光材料DCJTB掺杂绿光材料Alq3构成混合发光层,与OXD-7构成的蓝色发光层形成异质结的结构,并以NPB为空穴注入层。通过改变结构参数详细研究了发射光谱及其色坐标的电场依赖性。通过分析载流子注入/传输特性,控制激子的复合区域等措施得到了色坐标稳定性好、光谱丰富的高性能白光电致发光器件。经过优化的器件结构可以覆盖更大的可见光区域,当电压从9 V增加到13 V时,色坐标仅从CIE(x,y)=(0.364,0.314)偏移到CIE(x,y)=(0.332,0.291),具有较好的色稳定性。     

Preparation and Characterization of New 99Tc and Re-Complexes in Colloidal State

New ⁹⁹Tc and Re-complexes in colloidal state were prepared by the direct reduction of TcO₄- and ReO₄- with NaBH₄ in presence of a new synthezied ligand: 2,2‘(ethan diylidene dinitrilo) diphenol. The two complexes were precipitated in colloidal forms and characterized by spectroscopy and HPL chromatography. The complexes are H₂O soluble.     

NMR Studies of Drugs. Applications of Achiral and Chiral Lanthanide Shift Reagents to a 5-Substituted-4-thiazolidinone

The 60 MHz ¹H NMR spectra of racemic 5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-4-thiazolidinone, 1, have been studied in CDCl₃ solution at 28° with the achiral lanthanide shift reagent (LSR), tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium (III), 2, and the chiral LSRs, tris[3-(heptafluoropropylhydroxymethylene)- (+)-camphoratojeuropium(III), 3, and tris[3-(trifluoromethylhydroxymethylene-(+) -camphorato]europium (III), 4, Significant enantiomeric shift differences were observed in the presence of added 3, for the aryl protons of 1 that should permit direct determination of enantiomeric excess. Relative magnitudes of lanthanide-induced shift for the different nuclei of 1 with the three LSRs are compared and discussed in terms of preferred LSR binding sites. A favored conformation of 1 with respect to rotation about the C(5)-CH₂ bond is suggested.     

Vibrational Spectra of 2,2′-Pyridil and 2,2′-Pyridil-18O and Assignment of Infrared and Raman Bands

Abstract

Vibrational spectra of 2,2′-pyridil and 2,2′-pyridil-¹⁸O in the solid state and in solutions have been measured in the Raman (4000–50 cm^?1) and infrared (4000–100 cm^?1). The assignment of the bands observed is performed using the group vibrational concept and isotopic shifts data of the normal modes. The presence of synand anti-phase vibrations of both pyridyl rings is discussed. The results are compared to the corresponding data for some similar molecules.     

一种新型高效Eu3+选择性化学传感器

合成了一种新型化合物1-(N-甲基-吡咯)-2-(4,4′-二甲基-2,2′-联吡啶)-乙醇,并用紫外、红外、荧光、1H NMR、13C NMR对其表征,测试了其对不同金属离子的紫外和荧光响应,加入Eu3+对该化合物的紫外有明显的增色效应和红移现象,对其荧光有很强的猝灭作用,并从能量传递和电子传递的原理分析了可能的机理,实验结果表明,该化合物是一种新型高效Eu3+选择性化学感应器,可望用于Eu3+的环境和医学检测。     

Adsorption of Bipyridine Compounds on Gold Nanoparticle Surfaces Investigated by UV‐Vis Absorbance Spectroscopy and Surface Enhanced Raman Scattering

Adsorption behaviors of 2,2′‐bipyridine (2,2′‐BiPy), 2,4′‐bipyridine (2,4′‐BiPy), and 4,4′‐bipyridine (4,4′‐BiPy) on gold nanoparticle surfaces have been comparatively investigated by means of UV‐vis absorbance spectroscopy and surface‐enhanced Raman scattering (SERS). The three bipyridine compounds are assumed to have a standing geometry on Au surfaces as indicated from several spectral features and relative vibrational intensity factors on the basis of the electromagnetic (EM) selection rule. 2,4′‐BiPy appears to adsorb on Au surfaces via the 4‐pyridyl nitrogen atom as suggested from the stronger enhancement of the vibrational bands ascribed to the 4‐pyridyl ring. The SERS intensities for the three bipyridine compounds on Au could be ascribed to both the electromagnetic (EM) and charge transfer (CT) enhancement mechanism. The charge transfer is assumed to be dissimilar for 2,2′‐BiPy, 2,4′‐BiPy, and 4,4′‐BiPy due to their different positions of the nitrogen atoms as indicated from the disparate ν_8a band enhancements upon adsorption on surfaces.     

Remarkable emissions in diprotonated 2,2′:6′,2″‐terpyridine derivatives

A series of new metal‐free blue emission compounds, i.e., diprotonated terpyH₂ClPF₆ ( 1 ), tterpyH₂ClPF₆ ( 2 ), ClterpyH₂ClPF₆ ( 3 ), and BterpyH₂(PF₆)₂ ( 4 ), were prepared and characterized by electrospray ionization mass spectrometry, UV–vis spectroscopy, and cyclic voltammetry (CV). Abbreviations used are terpy = 2,2′:6′,2″‐terpyridine, tterpy = 4′‐(4‐tolyl)‐2,2′:6′,2″‐terpyridine, Clterpy = 4′‐chloro‐2,2′:6′,2″‐terpyridine, and Bterpy = 4,4′,4″‐tert‐butyl‐2,2′:6′,2″‐terpyridine. The X‐ray crystal structures of the three new compounds 1, 2, and 4 were determined. Both protonated pyridine rings of the terpyridine derivatives are hydrogen bonded intermolecularly to the adjacent Cl^? ion in compounds 1 , 2, and 3 . The π–π* absorption bands in the UV region for 1, 2, 3, and 4 in acetonitrile were red‐shifted relative to those of the corresponding neutral compounds. All the compounds exhibited stronger emissions (around 400 nm) than their neutral counterparts. All the CVs for the diprotonated species, terpyH, tterpyH, ClterpyH, and BterpyH, showed the first reduction waves around ?0.6 V, which were more positive than those of the neutral ones. Density functional theory was applied to interpret the remarkable differences in the interaction of the Cl^? ion. The attachment of two protons to the two terminal Bterpy nitrogens in 4 elicits remarkable characteristics. Both positive charges on the nitrogens are delocalized over the conjugated pyridine systems and the tertiary carbonium ions are stabilized to lead to stronger emission (Φ = 0.35) than the corresponding neutral Bterpy (Φ = 0.045). CCDC 732045–732047 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif Copyright © 2010 John Wiley & Sons, Ltd.     

Spectral Data of Chemical Modification Products of Costunolide

Epoxidation of costunolide (1) yielded parthenolide (3), 1, 10-epoxycostunolide (4), and the cyclization products of 4, santamarin (5), reynosin (6), magnolialide (7) and a 1, 4-epoxyeudesmanolide (8). Reduction of santamarin (5) with sodium borohydride afforded 11, 13-dihydrosantamarin (9) and an eudesmen-triol (10). Reduction of reynosin (6) provided 11, 13-dihydroreynosin (11) and the two eudesman-triols 12 and 13. The structures of the new compounds were elucidated by ID and 2D ¹H and ¹³C NMR spectral methods.     

一种新型有机蓝光材料的合成及光物理性质研究

利用Witting反应合成了一种含吡啶和吡唑基团的π共轭结构刚性有机分子6-苯基-4'-(4-[4-(1H-吡唑)乙烯]苯基)-2,2'-联吡啶,采用元素分析、红外光谱、核磁共振氢谱、质谱等方法对其进行了表征。通过理论计算研究了化合物的吸收光谱特点,实验研究了化合物在几种不同溶剂中的紫外吸收光谱及荧光发射光谱。研究结果表明,所合成的化合物具有优良的蓝色荧光性能,作为发光材料具有潜在的应用价值。     

诃子与川楝子配伍后挥发油化学成分分析

采用水蒸气蒸馏法将诃子与川楝子按1∶1的质量比配伍后提取挥发油,并用GC-M S联机技术对其化学成分进行研究,分离出249个组分,鉴定了其中的13个,主要成分有单[2-乙基己基]邻苯二甲酸、2,2′-亚甲基叔丁基对甲酚,乙基（2E）-3-[4-甲氧基苯基]-2-丙烯、7-甲基-Z-十四烯-1-醇酯。     

Synthesis and Spectral Studies of Novel Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) Metal Complexes with N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL)

Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) complexes with Schiff base derived from 2-amino-5-(2-amino-1,3,4-thiadiazolyl)-1,3,4-thiadiazole (1) and salicylaldehyde have been prepared. The ligand and its complexes have been characterized by IR, ¹H NMR spectra, elemental analyses, magnetic susceptibility, UV-Vis. and thermogravimetry–differential thermal analysis (TGA-DTA). The analytical data show 1:2 metal-to-ligand ratio for Co(II), Ni(II), Cd(II), and Fe(II) and 2:2 metal-to-ligand ratio for Cu(II) complexes. The suggested structures for the N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL) complexes of Fe(II), Co(II), and Cd(II) are octahedral, for the Ni(II) complex is tetrahedral, and for the Cu(II) complex is square-planar     

13C NMR Chemical Shifts of Heterocycles: Empirical Substituent Effects in 5-Halomethylisoxazoles

Evaluation by empirically derived equations for the Substituent effect (α, β, γ, δ) on the ¹³C NMR chemical shifts for C-3, C-4. C-5 and halomethyl-substituent carbon (C-6) in isoxazoles 1-5 [where C-3 substituent (R¹) = H, alkyl or phenyl, C-4 Substituent (R²) = H, alkyl, and C-5 substituent (R³) = di-or trihalomethyl, methyl and H], taking as reference the compound la, is reported. From the calculated values for the α, β, γ, δ effects for each substituent it was possible to estimate the chemical shift of each carbon of the compounds 1–5. The ¹³ C chemical shifts of the C-3, C-4, C-5, C-6 of these compounds, can be estimated with good precision: 94% of the calculated chemical shifts are found to be within ±1.0ppm, and 100% are found to be within ±1.5ppm.     

Assignments of the 13C NMR Spectra of Enhydrin and 2′,3′-Dehydromelnerin A and the Molecular Structure of Enhydrin

Abstract

Two melampolide-type sesquiterpene lactones, enhydrin and 2,′ 3′-dehydromelnerin A, were isolated from a Louisiana population of Polymnia uvedalia. Their ¹³C NMR spectra were assigned using ¹³C-¹H correlation, DEPT and COLOC experiments. The molecular structure of enhydrin was established by single crystal X-ray diffraction.     

1H NMR Spectral Simplification with Achiral and Chiral Lanthanide Shift Reagents. Methastyridone, 2,2-Dimethyl-5-(2-Phenylethenyl)-4-Oxazolidinone

Abstract

The 60 MHz ¹H NMR spectra of methastyridone, 2,2-dimethyl-5-(2-phenylethenyl)-4-oxazolidinone, 1, have been studied at 28° in CDCl₃ solution with the achiral reagent tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium(III), 2, Eu(FOD)₃, and the chiral reagent tris[3-(heptafluoropropylhydroxy-methylene)-d?camphorato]europium(III), 3, Eu(HFC)₃.     

13C NMR Chemical Shifts of Heterocycles: 3∗. Empirical Substituent Effects in 2-Halomethyl-2-hydroxy-tetrahydrofurans and -5,6-tetrahydro-4H-pyrans

Abstract

Evaluation by empirically derived equations for the Substituent effect (α, β, γ, δ) on the ¹³C NMR chemical shifts for C-2, C-3, C-4, C-5, C-6, the halomethyl-substituted carbon (C-7) and the cyano or oxymic carbon (C-8) in 2-halomethyl-2-hydroxy-tetrahydrofurans 1a-c, 2, 3a, b, 4a and -5,6-tetrahydro-4H-pyrans 5a-c, 6a [with C-2-substituents (R²): CF₃, CCl₃ or CHCl₂, C-3-substituents (R³): CN, C(Me)=NOH, CH=NOMe, C(Me)=NOMe or CH=NOH], taking as reference the 2-trifluoromethyl-2-hydroxy-tetrahydrofuran (la), is reported. From the additivity properties of the α-, β-, γ-, δ-and ?-effects for each Substituent it is possible to predict the chemical shift of each carbon of the compounds 1–6.

     

Two Dimensional 1HNMR Studies on 2′5′-Dideoxyadenosylcobalamin

The ¹HNMR spectrum of 2′,5′-dideoxyadenosylcobalamin, a Coenzyme B₁₂(5′-deoxyadenosylcobalamin) analogue, has been assigned by 2D COSY. Its proton coupling constants have also been measured by J-resolved experiment. The comparison between the analogue and Coenzyme B¹² was made.