Preparation and biological evaluation of 99mTc-N4IPA for single photon emission computerized tomography imaging of hypoxia in mouse tumor.

In order to develop technetium-99m labeled nitroimidazole imaging agent for hypoxia in tumor, we have synthesized (99m)Tc-1-(4-nitroimidazole-yl)-propanhydroxyiminoamide, (99m)Tc-N4IPA complex, in high radiochemical purity and radiochemical yield. The biological evaluation of this complex includes the in vitro/vivo stability, cell uptake and Single Photon Emission Computerized Tomography (SPECT) imaging in mouse tumor models, respectively. These results demonstrate that (99m)Tc-N4IPA may have potential as clinical hypoxia imaging agent. The key features of the biological evaluation include the following: (1) the autoradiogram of (99m)Tc-N4IPA complex in tissue samples of hypoxia overlaps with the area stained by hypoxyprobe-1; (2) SPECT imaging of U87-bearing mice clearly identifies tumors 4 h post injection of (99m)Tc-N4IPA, reaching ID% of 8.48 ± 4.51; (3) the main pathways of excretion of (99m)Tc-N4IPA are through kidneys and livers in both A549 or U87-bearing tumor mice.

Reaction mechanism of Cl2 and 1-alkyl-3-methylimidazolium chloride ionic liquids.

Systems containing 1-alkyl-3-methylimidazolium chloride ionic liquid and chlorine gas were investigated. Using relativistic density functional theory, we calculated the formation mechanism of trichloride and hydrogen dichloride anions in an Emim(+)Cl(-) + Cl(2) system. Emim(+)Cl(3)(-) forms without energy barriers. The more stable species ClEmim(+)HCl(2)(-) forms through chlorine substitution. Substitution of a H on the imidazolium ring is much easier than substitution on the alkyl side chains. Infrared, Raman, ESI-MS, and (1)H NMR spectra were measured for EmimCl, BmimCl, and DmimCl with and without Cl(2) gas. The coexistence of Cl(3)(-) and HCl(2)(-), as well as chlorine-substituted cations, was confirmed by detection of their spectroscopic signals in the Cl(2) added ionic liquids. Cl substitution appears less serious for cations with longer side chains.

Theoretical mechanism study of UF6 hydrolysis in the gas phase (II).

In our previous work (J. Phys. Chem. A 2008, 112, 8877.), we found theoretical evidence indicating UF5OH is an intermediate produced in the first step of UF6 hydrolysis. In this work, we explored the probable reaction channels starting from UF5OH + UF6 and UF5OH + UF5OH systems using relativistic density functional theory calculations. Initially, the two uranium containing species associate to form complex UF6.UF5OH or dimer (UF5OH)2 through hydrogen bonding. The energy released is 12-16 kcal/mol, which may promote further reactions. After H2O or HF are eliminated from the complex or dimer, compounds containing U-O-U bond are produced. These compounds are potentially feasible to associate into larger clusters or solidify. Relative to the isolated initial species, the energies of the final products are -6 to -13 kcal/mol lower, indicating that the reactions may spontaneously proceed. The calculated IR spectra features can be used to indicate the formation and interaction type of the intermediates and products.

Theoretical mechanism study of UF6 hydrolysis in the gas phase.

The mechanism of the gas-phase reaction UF 6 + H 2O --> UOF 4 + 2HF is explored using relativistic density functional theory calculations. Initially, H 2O coordinates with UF 6 to form a 1:1 complex UF 6.H 2O. Over an activation energy barrier of about 19 kcal/mol, H 2O transfers a H atom to a nearby ligand F, resulting in UF 5OH + HF. The eliminated HF or another H 2O molecule may form a hydrogen bond with UF 5OH. Starting from UF 5OH, the second HF elimination results in UOF 4. If UF 5OH is in the isolated form, UF 5OH --> UOF 4 + HF takes place over a barrier of 24 kcal/mol. If UF 5OH is hydrogen-bonded with H 2O or HF, the conversion barrier is less than 10 kcal/mol. Once formed, the unstable UOF 4 tends to associate with additional ligands and hydrogen-bonding donors. The calculated binding energies indicate the significance of such interactions, which may have profound impact on further HF eliminating reactions. The IR spectra features can be used to indicate the formation and interaction type of the intermediates and products.

Influence of H2 on the gas-phase decomposition of formic acid: a theoretical study.

Gas-phase decomposition of formic acid results in final products CO + H2O and CO2 + H2. Experimentally, the CO/CO2 ratio tends to be large, in contradiction with mechanism studies, which show almost equal activation energies for dehydration and decarboxylation. In this work, the influence of H2 on the decomposition mechanism of HCOOH was explored using ab initio calculations at the CCSD(T)/6-311++G**//MP2/6-311++G** level. It was found that, in the presence of H2, the reaction channels leading to CO + H2O are more than those leading to CO2 + H2. With competitive energy, H2 addition to HCOOH can reduce the latter into HCHO, which then dissociates into CO + H2 catalyzed by H2O. Compared to trans-HCOOH, cis-HCOOH and cis-C(OH)2, conformers required for decarboxylation, are less populated due to interactions with H2.

[Spectroscopic research on the interaction of 2-(4-dimethylaminophenyl)-5-fluoro-6-(morpholin-4-yl)-1H-benzimidazole and calf thymus DNA].

UV-Vis spectra of the aqueous solutions of 2-(4-dimethylaminophenyl)-5-fluoro-6-(morpholin-4-yl)-1H-benzimidazole (1) at different pH values revealed that compound 1 is a tertiary base, which can combine three protons. Through the non-linear least square method, the logarithm of the three accumulative protonation constants of compound 1, namely, lgbeta1, lgbeta2 and lgbeta3, were determined to be 4.96 +/- 0.03, 5.72 +/- 0.07 and 7.95 +/- 0.10, respectively. UV-Vis and the steady-state fluorescence spectra indicated that a special interaction occurs between compound 1 and calf thymus DNA at the pH value of 3.40, of which thebinding constant, Kb, is (2.30 +/- 0.10) x 10(4) mol(-1) x L. Compound 1 in the concentration range of 10(-8) to 1.2 x 10(-6) mol x L(-1) has a potential application to the quantitative determination of DNA.