Thermal Studies on Rare Earth Metal Ion Chelates of 8-Hydroxyquinoline, 8-Hydroxyquinaldine and Their Derivatives

The thermal behaviors of chelates of oxine, 8-hydroxyquinaldine and their derivatives (DCQ, 5, 7-dichloro-8-hydroxyquinoline; DCQ', 5, 7-dichloro-8-hydroxyquinaldine) in an air atmosphere have been studied. The order of heat stability of chelates, decreased with decreasing basicity of the ligand, i.e. oxine<DCQ<DCQ'. The presence of water or proton-containing compounds in the chelates seemed to lower heat stabilities,     

Aging of poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene)/toluene solutions and subsequent effects on luminescence behavior of cast films

Morphological effects in luminescence properties of a representative semiconducting polymer, poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), has recently attracted much attention. Previous studies indicated that short-term heat treatment of solution-cast MEH-PPV films may result in the formation of mesomorphic order that is responsible for the "red" emission around 640 nm, in contrast to the single-chromophore "yellow" emission near 590 nm from the disordered matrix. On the basis of microscopic and spectroscopic evidence for films cast from freshly prepared and aged solutions, here we show that prolonged storage of MEHyellowPPV solutions at room temperature or lower may result in retardation of the thermally induced mesophase formation in the subsequently cast films. According to small-angle neutron scattering and differential scanning calorimetric observations over aged MEH-PPV/toluene solutions, we propose that the suppressed transformation into mesomorphic order is due to further development of nanocrystalline aggregates that serve as physical cross-links among MEH-PPV chains in the solution state upon long-term storage. These solvent-induced nanocrystalline aggregates, however, do not exhibit new spectroscopic features beyond the suppression of "red" emission at 640 nm from the mesomorphic phase.     

Different reaction routes found in acid-catalyzed glycosylation of endo- and exo-glycals: competition between Ferrier rearrangement and protonation

Acid-mediated glycosylations of endo- and exo-glycals have been carried out in good to excellent yields, in which a mixture of two products is often obtained resulting from Ferrier rearrangement and protonation. The former reaction exclusively takes place with the t-butyl carbonate or hydroxyl substituent at the C3 position of endo-glycals, while the latter mainly occurs in the glycosylation of exo-glycals with allyl benzyl ether or acetate. In addition to the substituent effect, protecting groups are critical to determine the activity and favored reaction pathway. Furthermore, the method is applicable to O-, C-, and N-nucleophiles.     

Novel ene trimerization of 1-phenylcyclopropene

1-Phenylcyclopropene (1) was synthesized by treatment of 1,1,2-tribromo-2-phenylcyclopropane (2) with 2.5 equiv of methyllithium followed by protonation. Compound 1 underwent ene dimerization to form ene dimer 5 followed by ene reaction with monomer 1 (enophile) to give an ene trimer 6. Both of these two ene reactions derived endo transition states. In the meantime, the [2+2] adduct, trans-1,2-diphenylbicyclo[3.1.0.0(2,4)]hexane (7), was also formed. When the adduct 7 was heated at THF refluxing temperature, 1,2-diphenylcyclohexa-1,4-diene (8) was obtained. Compound 8 was treated with DDQ to yield o-diphenylbenzene.     

Chemical Studies of Formosan Cobra (Naja Naja Atra) Venom: Part III. N-Terminal Amino Acid Analysis of Some Purified Protein Components by DNP and DNS Methods

N-Terminal amino acid residues of Fractions IX, X, and XII were reinvestigated by DNP and DNS methods with two-dimensional polyamide thin-layer chromatography. It was found that our previous work¹ had been erroneously concluded. By the present work, it was obvious that all three fractions had Leu as their N-terminal amino acid residues.     

Synthesis and Characteristics of a New Fluorogenic Substrate for Horseradish Peroxidase

N,N′-Dicyanomethyl-o-phenylenediamine was synthesized with a 90% yield by a reaction ofo-phenylenediamine with chloroacetonitrile in triethylamine. Our experimental results showed that it was the effective fluorogenic substrate for horseradish peroxidase (HRP) and hemin. TheK_mfor the HRP system was 48 μM,and that for hemin was 1.3 μM.Properties of the substrate were evaluated from the detection limits of enzymes and H₂O₂. The linear ranges for the determination of HRP and hemin were 21–150 pMand 2–20 nM,respectively. The linear range for the determination of H₂O₂using HRP or hemin was 18–140 and 60–1000 nM,respectively. The structural elucidation of the fluorescent product using NMR and mass spectral techniques was proposed to be 1,2-dihydro-2-imido-imidazo[1,2-a] quinoxaline. Based on the product structure and earlier reports, the possible reaction mechanism of HRP and the substrate was also proposed, i.e., two steps for ring closures, one step of isomerization, and a final step of oxidative dehydrogenation.     

Detection of a biomarker for Alzheimer's disease from synthetic and clinical samples using a nanoscale optical biosensor

A nanoscale optical biosensor based on localized surface plasmon resonance (LSPR) spectroscopy has been developed to monitor the interaction between the antigen, amyloid-beta derived diffusible ligands (ADDLs), and specific anti-ADDL antibodies. Using the sandwich assay format, this nanosensor provides quantitative binding information for both antigen and second antibody detection that permits the determination of ADDL concentration and offers the unique analysis of the aggregation mechanisms of this putative Alzheimer's disease pathogen at physiologically relevant monomer concentrations. Monitoring the LSPR-induced shifts from both ADDLs and a second polyclonal anti-ADDL antibody as a function of ADDL concentration reveals two ADDL epitopes that have binding constants to the specific anti-ADDL antibodies of 7.3 x 10(12) M(-1) and 9.5 x 10(8) M(-1). The analysis of human brain extract and cerebrospinal fluid samples from control and Alzheimer's disease patients reveals that the LSPR nanosensor provides new information relevant to the understanding and possible diagnosis of Alzheimer's disease.     

纳米分辨率的三维形貌检测仪

从光干涉方式，瞳窗关系和光源带宽等基本关系出发，利用空间不变系统理论解析了相移显微干涉检测系统中衍射效应的影响。为了减小横向分辨率对纵向分辨率的影响，利用相关信息提取或数字滤波的方法，获得了纳米分辨率的三维形貌。     

On the Mavroyannis–Stephen relativistic long-range interaction energy term between optically active molecules

The relativistic long-range intermolecular interaction energy term of Mavroyannis and Stephen is estimated for some amino acids by using optical rotatory dispersion data and for hexahelicene by using theoretical values of excitation energies and rotational strengths. The result shows that the interaction energy may be significant for the interaction between some essentially dissymmetric chromophores such as hexahelicene, but that it is unimportant for other cases.     

Synthesis, dual fluorescence, and fluoroionophoric behavior of dipyridylaminomethylstilbenes

The synthesis, dual fluorescence, and fluoroionophoric behavior of two donor-sigma spacer-acceptor (D-s-A) compounds, trans-4-(N,N-bis(2-pyridyl)amino)methylstilbene (1H) and trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-cyanostilbene (1CN), are reported and compared to that of trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-(N,N-dimethylamino)stilbene (1DPA). To gain insights into the dual fluorescence properties for 1H and 1CN in polar but not in nonpolar solvents, model compounds resulting from a replacement of the stilbene group by alkyl (2R) or xylyl (2X) groups or from a replacement of the dipyridylamino (dpa) group by dianisoleamino (3AA), diethylamino (3EE), methylanilino (3MP), or diphenylamino (3PP) groups also have been investigated. In addition to 1H and 1CN, all four compounds of 3 display dual fluorescence. The locally excited (LE) fluorescence mainly results from the stilbene group and the ICT fluorescence from the through-bond interactions between the amino donor and the stilbene acceptors. In the presence of transition metal ions such as Zn(II), Ni(II), Cu(II), and Cd(II), the ICT processes are switched from dpa (D) --> stilbene (A) in 1H and 1CN to stilbene (D) --> dpa/metal ion (A) in their complexes. Whereas the ICT states for the complexes are generally nonfluorescent, an exception was found for the case of 1H/Zn(II). As a result, substituent-dependent fluoroionophoric behavior has been demonstrated by 1H, 1CN, and 1DPA in response to Zn(II).