The interaction of monosubstituted benzenes with the stationary liquid in gas liquid chromatography

In gas liquid chromatography (GLC), the relative retention values log gamma was mainly expressed by van der Waals energy (the sum of the dispersion E(dis) and repulsive E(rep) energies) to the interactions between monosubstituted benzene derivatives and the nonpolar stationary liquid as squalane. The single exception was that of anilines, and it was corrected by the electrostatic energy (E(ES)) due to C-H/pi hydrogen bond. When the stationary liquid changed from the nonpolar to polar, log gamma was estimated by the inductive interaction energy (included in E(ES)) in addition to the sum of E(dis) and E(rep). In the benzene solution, the relative equilibrium values log K/K(o) introduced from the interactions between phenol and substituted benzene derivatives were estimated by E(ES). The E(ES) of COCH(3), CO(2)C(2)H(5) groups is especially originated in the excited dipole moments micro(e). The relative frequency values log nu/nu(o) derived from O-H or O-D stretching vibration of phenol or methanol-D gave the correlation to E(ES) as well as log K/K(o). That of anilines-methanol-D however had been out of a linear relation to E(ES). The cause is concluded that the aniline-methanol-D is making the proton transfer structure from the discussion about the proton affinity (PA) of the base.     

Polycyclic N-heterocyclic compounds. XLV. Synthesis of 4-substituted 5,6-dihydrobenzo[h]quinazolines and 6,7-dihydro-5H-benzo[6,7]cyclohepta[1,2-d]pyrimidines and their inhibitory activity on platelet aggregation

The synthesis of 4-substituted 5,6-dihydrobenzo[h]quinazolines and 6,7-dihydro-5H-benzo[6,7]cyclohepta-[1,2-d]pyrimidines with substituents which are an electron-attracting group such as a nitrite, an amide, a thione, or a carboxyl group is described. Their inhibitory activity against collagen-induced platelet aggregation was also investigated.     

Products of the reaction between alpha- or gamma-tocopherol and nitrogen oxides analyzed by high-performance liquid chromatography with UV-visible and atmospheric pressure chemical ionization mass spectrometric detection

The reaction products of alpha- or gamma-tocopherol with nitric oxide in the presence of molecular oxygen were isolated and characterized. The consumption of tocopherols and the formation of the major products were monitored by high-performance liquid chromatography (HPLC) by a gradient elution method. The quantitative analysis of these compounds with UV-Vis detectors, however, was interfered by several minor products having similar UV spectra and retention times as those of the major ones. In order to establish a quantitative analytical method for the products, we investigated other detection methods, and found that atmospheric pressure chemical ionization (APCI), LC-MS was a more selective and better analytical method for these compounds.     

Separation of nucleotides with an aqueous mobile phase using pH- and temperature-responsive polymer modified packing materials.

A new method for the qualitative analysis of adenosine nucleotides (AMP, ADP, and ATP) and synthetic oligonucleotides has been proposed, utilizing a pH- and temperature-responsive polymer of N-isopropylacrylamide (NIPAAm), butyl methacrylate (BMA) and N,N-dimethylaminopropylacrylamide (DMAPAAm) as the stationary phase of HPLC. In the chromatographic system using the copolymer with ionizable groups of modified packing materials, we investigated how to separate adenosine nucleotides and oligonucleotides by temperature. The properties of the surface of the copolymer-grafted stationary phase altered from hydrophilic to hydrophobic and from charged to non-charged due to changes in the temperature and in the pH, respectively. In addition, it is possible to exhibit and hide ion-exchange groups on the polymer chain surface by temperature changes. These phenomena result from changes in the charge and hydrophobicity of the pH- and temperature-responsive polymer on the stationary surface with the controlling temperature. A pH- and temperature-responsive chromatography would be greatly useful for biopolymer and nucleotide separation and purification.     

Formation of eta'(958)-mesic nuclei and axial UA(1) anomaly at finite density

We discuss the possibility of producing the bound states of the eta'(958) meson in nuclei theoretically. We calculate the formation cross sections of the eta' bound states with the Green function method for the (gamma, p) reaction and discuss the experimental feasibility at photon facilities such as SPring-8. We conclude that we can expect to observe resonance peaks in (gamma, p) spectra for the formation of eta' bound states and we can deduce new information on eta' properties at finite density. These observations are believed to be essential to know the possible mass shift of eta' and deduce new information on the effective restoration of the chiral UA(1) anomaly in the nuclear medium.     

Separation of phosphorylated peptides utilizing dual pH- and temperature-responsive chromatography

The phosphorylation of a peptide is considered to be one of the most important post-translational modification reactions that can alter protein function in mammalian cells. To separate and purify, we developed a dual temperature- and pH-responsive chromatography based on terpolymer composed of N-isopropylacrylamide, N,N'-dimethylaminopropylacrylamide and butylmethacrylate. The property of the surface of the terpolymer-grafted stationary phase altered from hydrophilic to hydrophobic, and from changed to non-charged by changes in the temperature and the pH, respectively. In addition, it was possible to appear and hide ion-exchange groups on the polymer chain surface by temperature changes. These phenomena resulted from changes in the charge and the hydrophobicity of the pH- and temperature-responsive polymer on the stationary surface by controlling the temperature. In the developed environmental-responsive chromatographic system, the ionizable dimethylamino group of N,N'-dimethylaminopropylacrylamide in terpolymer played a key role for the separation. We applied the developed chromatographic system to the separation of phosphorylated compounds, such as phospho-tyrosine, phosphopeptide and oligonucleotides. At a low column temperature, the electrostatic interaction plays a predominant role for retain anionic phosphorylated compounds, because of the strong interaction between the cationic dimethylamino group in the stationary phase and the anionic phosphoric group in the analyte. On the contrary, the hydrophobic interaction became predominant upon increasing the temperature. The results showed that both the electrostatic and the hydrophobic interactions became controllable with a temperature change during the chromatographic process. Dual pH- and temperature-responsive chromatography would be very useful for biomacromolecules separation and purification.     

An efficient preparation, crystal structures, and properties of monocarbenium-ion compounds stabilized by 3-guaiazulenyl and anisyl groups

Reaction of guaiazulene (1) with 2-methoxybenzaldehyde (2) in methanol in the presence of hexafluorophosphoric acid at 25 °C for 2 h gives (3-guaiazulenyl)(2-methoxyphenyl)methylium hexafluorophosphate (5a) in 93% yield. Similarly, reaction of 1 with 3-methoxybenzaldehyde (3) or 4-methoxybenzaldehyde (4) under the same reaction conditions as for 2 affords (3-guaiazulenyl)(3-methoxyphenyl)methylium hexafluorophosphate (6) (91% yield) or (3-guaiazulenyl)(4-methoxyphenyl)methylium hexafluorophosphate (7) (97% yield). The crystal structures as well as the spectroscopic, electrochemical, and chemical properties of these monocarbenium-ion compounds, possessing interesting resonance forms, stabilized by the 3-guaiazulenyl and anisyl (i.e., 2-, 3-, or 4-methoxyphenyl) groups are reported.     

Development of a hypoxia-selective near-infrared fluorescent probe for non-invasive tumor imaging

A near-infrared fluorochrome, GPU-311, was designed, synthesized and evaluated for its application in non-invasive imaging of tumor hypoxia. Efficient synthesis was achieved by nucleophilic substitution and click chemistry ring using the bifunctional tetraethylene glycol linker 2 containing thiol and azide groups for the conjugation of the propargylated nitroimidazole 1 and the heptamethine cyanine dye 3 bearing a 2-chloro-1-cyclohexenyl ring. GPU-311 exhibited long excitation and emission wavelength (Ex/Em=785/802?nm) and a decent quantum yield (0.05). The water solubility and hydrophilicity of GPU-311 increased. After in vitro treatment of SUIT-2/HRE-Luc pancreatic cancer cells with GPU-311, a higher level of fluorescence was observed selectively in hypoxia than in normoxia. However, in vivo fluorescence imaging of a mouse xenograft model after GPU-311 administration revealed inadequate accumulation of GPU-311 in tumors due to its rapid elimination through the liver.