Drug–tea polyphenol interaction

Propericiazine (PCZ) is an antipsychotic agent used for the treatment and the prevention of relapse of schizophrenia. We found that when an oral solution containing PCZ was mixed with a green tea drink, the residual content of PCZ was reduced by forming an insoluble complex between PCZ and tea polyphenol. In this study, the mechanism underlying the incompatibility of PCZ with green tea polyphenol (GTP) in the solution was clarified by isothermal titration microcalorimetry (ITC). Both solutions of 27.4 mM PCZ and 2.2 mM (?)-epigallocatechin gallate (EGCg), which is a main ingredient of GTP, were mixed and then PCZ in the filtrate was reduced to approximately 60 %. According to measurement at 298 K by ITC, PCZ formed an insoluble complex with EGCg at an associate constant (K) of 4.75 × 10² M^?1 exothermically, ΔH = ?40.0 kJ mol^?1. When (?)-epicatechin gallate (ECg) was used as the GTP, PCZ interacted with ECg with K and ΔH values of 3.74 × 10² M^?1 and ?22.1 kJ mol^?1, respectively. On the other hand, little heat of the reaction between PCZ and (?)-epigallocatechin or (?)-epicatechin was observed. The results indicated that the main reason for this incompatibility was the formation of an insoluble complex by PCZ and a gallate-type GTP such as EGCg and ECg in the aqueous solution.     

Excess enthalpies of binary mixtures of butylamines + propanols at 298.15 K

The molar excess enthalpies of eight systems of butylamines + propanols were determined at 298.15 K using a twin-microcalorimeter. All excess enthalpies were exothermic and large. An equilibrium constant K ₁ expressed in terms of mole fractions and standard thermodynamic properties of formation (Δ_f H, Δ_f G, Δ_f S) of 1:1 complex were evaluated by ideal mixtures of monomeric molecules and their associated complexes. Concentration dependence of the FT-Raman spectrum showed systematic changes of bands. Spectroscopic considerations based on this and ab initio calculations on molecules were performed at the Mp2/6-311G(d,p) level of theory. Interaction energies between butylamine and propanol were calculated by the supermolecular and NBO methods. The results were discussed with previous results to clarify the steric and positional effect of the amino and hydroxyl group.     

Practical Synthesis of (20S)‐10‐(3‐Aminopropyloxy)‐7‐ethylcamptothecin,a Water‐Soluble Analogue of Camptothecin

A robust, practical synthesis of (20S)‐10‐(3‐aminopropyloxy)‐7‐ethylcamptothecin (T‐2513, 5 ), which is a water‐soluble analogue of camptothecin, has been developed. The key step in this synthesis is a highly diastereoselective ethylation at the C20 position by using N‐arylsulfonyl‐(R)‐1,2,3,4‐tetrahydroisoquinoline‐3‐carboxylic acid ester as a chiral auxiliary, which affords the key intermediate ethyl‐(S)‐2‐acyloxy‐2‐(6‐cyano‐5‐oxo‐1,2,3,5‐tetrahydroindolizin‐7‐yl)butanoate ( 8 k ) in 93 % yield and 87 % de. Optically pure compound 8 k was obtained by a single recrystallization from acetone and its further elaboration through Friedlander condensation afforded compound 5 . This synthesis does not require any chromatographic purification steps and can provide compound 5 on a multi‐gram scale in 6.3 % overall yield (16 steps).     

Polymer-Supported Bases. 10. Synthesis of Phosphatidylcholines Using Polymer-Supported or Free Acylimidazoles

Dipalmitoylphosphatidylcholine was synthesized in a good yield by the reaction of L-α-glycerophosphorylcholine with 1-palmitoylimidazole in the presence of DBU. Polymer-supported 1-palmitoylimidazole moiety also could be used as the acylating reagent, though the yield of the choline was moderate.     

Design and synthesis of 2-(1,3-dialkoxy-2-methylpropan-2-yl)-1,3-diarylpropanes as tethering units for folded H-stacking polymers

1,3-Diarylpropenes 9 having a 1,3-dialkoxy-2-methylpropan-2-yl group were designed as tethering monomers for folded H-stacking polymers, and were readily synthesized from 2-ethoxymethylidene malonate in four- or five-steps, including a facile sequential addition–elimination–addition reaction of benzyl zinc reagents. The preference for the closed (stacked) conformation in the resulting 2-substituted 1,3-diarylpropanes 9 was evaluated using MM2 calculations, ¹H NMR analyses, and fluorescence measurements. Copolymerization of the resulting monomers 9 with compounds containing π-units provided polymers with blue-shifted UV-absorptions both in solution and as films, compared with that of a model compound containing a single π-unit. This optical property is unique to H-aggregated π-units.     

Development of a fluoride-responsive amide bond cleavage device that is potentially applicable to a traceable linker

A fluoride-responsive (FR) amino acid that induces amide bond cleavage upon the addition of a fluoride was developed, and it was applied to an FR traceable linker. By the use of an alkyne-containing peptide as a model of an alkynylated target protein of a bioactive compound, introduction of the FR traceable linker onto the peptide was achieved. Subsequent fluoride-induced cleavage of the linker followed by labeling of the released peptide derivative was also conducted to examine the potential applicability of the FR traceable linker to the enrichment and labeling of alkynylated target molecules.     

Use of neutron activation analysis and LC–ICP-MS in the development of candidate reference materials for As species determination

Arsenic (As) is widely found in marine organisms, mainly as organic arsenical compounds. With the introduction of regulations for As species in foodstuffs and for environmental control, it has become more important to quantify the amount of arsenic species present. To address this concern new reference materials (RMs) for validation and quality assurance of As speciation measurements are being developed, including a tuna fish tissue and a robalo liver tissue. Instrumental neutron activation analysis (INAA) is used in this work as a proven analytical tool for As determinations and for validating the As mass fraction determined by liquid chromatography coupled to inductively coupled mass spectrometry (LC–ICP-MS) in extracts of the candidate RMs and other fish samples including certified RMs. Various methods for the extraction of water-soluble As species were evaluated. The best results were acquired after methanol/acetone/water extraction yielding in 93 % extractable As in the tuna RM. This procedure was used for the LC–ICP-MS studies. The results demonstrate that INAA can account for 100 % of the distribution of As species in analytical processes. It complements LC–ICP-MS for the validation of the characterization of As species in the development of RMs for such species. Excellent agreement of measured results in certified RMs with the reported values confirms the validity of the applied procedures.     

Quantum transport of massless Dirac fermions

Motivated by recent graphene transport experiments, we undertake a numerical study of the conductivity of disordered two-dimensional massless Dirac fermions. Our results reveal distinct differences between the cases of short-range and Coulomb randomly distributed scatterers. We speculate that this behavior is related to the Boltzmann transport theory prediction of dirty-limit behavior for Coulomb scatterers.     

Object recognition by use of polarimetric phase-shifting digital holography

Pattern recognition by use of polarimetric phase-shifting digital holography is presented. Using holography, the amplitude distribution and phase difference distribution between two orthogonal polarizations of three-dimensional (3D) or two-dimensional phase objects are obtained. This information contains both complex amplitude and polarimetric characteristics of the object, and it can be used for improving the discrimination capability of object recognition. Experimental results are presented to demonstrate the idea. To the best of our knowledge, this is the first report on 3D polarimetric recognition of objects using digital holography.