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.     

Native and stearic acid modified ceria-zirconia supports in normal and reversed-phase HPLC

Porous ceria-zirconia composite with narrow particle size distribution and large specific surface area was synthesized by a sol-gel process. Chromatographic properties of the native supports was investigated in normal phase mode for the separation of test mixtures of basic, neutral and acidic compounds. The new packing material exhibited polar and basic properties, which are suitable for the separation of basic compounds. Lypophilic packing has been obtained by the modification of the ceria-zirconia with stearic acid, which exhibited strong hydrophobicity relative to the native packing. Therefore, the modified ceria-zirconia behaves as a reversed-phase packing material. Different selectivity towards basic compounds was observed on the new packing compared to the native ceria-zirconia and conventional ODS stationary phase.     

Determination of buprenorphine by high-performance liquid chromatography with fluorescence detection: application to human and rabbit pharmacokinetic studies.

A rapid, sensitive, precise and accurate high-performance liquid chromatographic assay with fluorescence detection was developed for the determination of buprenorphine in human, rabbit, pig and dog plasma. It is comprised of only a one-step extraction procedure with hexane-isoamyl alcohol at pH 9.25 and reversed-phase chromatography on a muPorasil column. The recoveries of buprenorphine and nalbuphine (internal standard) were greater than 90%. Calibration graphs were linear over the concentration range 3-300 ng/ml with a coefficient of variation, both within-day and between-day, of less than 9% at any level. The limit of detection was 1.0 ng/ml of plasma based on a signal-to-noise ratio of 3. Eight other clinically used narcotics were investigated to check for potential interferences and their analytical conditions. The possible decomposed compounds of buprenorphine were also checked for the specificity of this assay. The method has been successfully applied to the stability and pharmacokinetic studies of buprenorphine. Buprenorphine in plasma did not decompose significantly at -20 degrees C for four weeks. Pharmacokinetic application in six rabbits and a surgical patient revealed that buprenorphine followed a linear three-compartment model with two distribution phases. The two distribution and elimination half-lives and the clearance of buprenorphine were 1.32, 24.8 and 230 min and 224 ml/min in human plasma, and 0.94, 12.5 and 232 min and 30 ml/min in rabbit plasma.     

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.     

Kinetics of zinc and cadmium dissociation of metallothionein in the presence of chelating agents

The dissociation kinetics of metal ions from native metallothionein (Cd₅Zn₂-MT) of rat liver has been studied in the presence of external ligands including amino acids, peptide and polyamino polycarboxylic acids at 25°C. The study shows that the solution pH affects the metal dissociation process. Different ligands present different multiphasic kinetics. The possible mechanism of metal dissociation from metallothionein has been proposed.     

Mass spectrometry-based chemical mapping and profiling toward molecular understanding of diseases in precision medicine

Precision medicine has been strongly promoted in recent years. It is used in clinical management for classifying diseases at the molecular level and for selecting the most appropriate drugs or treatments to maximize efficacy and minimize adverse effects. In precision medicine, an in-depth molecular understanding of diseases is of great importance. Therefore, in the last few years, much attention has been given to translating data generated at the molecular level into clinically relevant information. However, current developments in this field lack orderly implementation. For example, high-quality chemical research is not well integrated into clinical practice, especially in the early phase, leading to a lack of understanding in the clinic of the chemistry underlying diseases. In recent years, mass spectrometry (MS) has enabled significant innovations and advances in chemical research. As reported, this technique has shown promise in chemical mapping and profiling for answering “what”, “where”, “how many” and “whose” chemicals underlie the clinical phenotypes, which are assessed by biochemical profiling, MS imaging, molecular targeting and probing, biomarker grading disease classification, etc. These features can potentially enhance the precision of disease diagnosis, monitoring and treatment and thus further transform medicine. For instance, comprehensive MS-based biochemical profiling of ovarian tumors was performed, and the results revealed a number of molecular insights into the pathways and processes that drive ovarian cancer biology and the ways that these pathways are altered in correspondence with clinical phenotypes. Another study demonstrated that quantitative biomarker mapping can be predictive of responses to immunotherapy and of survival in the supposedly homogeneous group of breast cancer patients, allowing for stratification of patients. In this context, our article attempts to provide an overview of MS-based chemical mapping and profiling, and a perspective on their clinical utility to improve the molecular understanding of diseases for advancing precision medicine.

An overview of MS-based chemical mapping and profiling, indicating its contributions to the molecular understanding of diseases in precision medicine by answering "what", "where", "how many" and "whose” chemicals underlying clinical phenotypes.