We describe an improved force field parameter set for the generalized AMBER force field (GAFF) for urea. Quantum chemical computations were used to obtain geometrical and energetic parameters of urea dimers and larger oligomers using AM1 semiempirical MO theory, density functional theory at the B3LYP/6-31G(d,p) level, MP2 and CCSD ab initio calculations with the 6-311++G(d,p), aug-cc-pVDZ, aug-cc-pVTZ, and aug-cc-pVQZ basis sets, and with the CBS-QB3 and CBS-APNO complete basis set methods. Seven different urea dimer structures were optimized at the MP2/aug-cc-pVDZ level to obtain accurate interaction energies. Atomic partial charges were calculated at the MP2/aug-cc-pVDZ level with the restrained electrostatic potential (RESP) fitting approach. The interaction energies computed with these new RESP charges in the force field are consistent with those obtained from CCSD and MP2 calculations. The linear dimer structure calculated using the force field with modified geometrical parameters and the new RESP charge set agrees well with available experimental data.
The NH activation of ammonia by tetramesityldisilene takes place in three steps: formation of the anti-ammonia-disilene adduct, inversion at the β-silicon, and intramolecular syn-transfer of the proton to give the syn-product.
A series of zinc phthalocyanines (ZnPcs) tetra-substituted with 1,3-di[2-(2-ethoxyethoxy)ethoxy]-2-propanol () or 1,3-di[2-(2-ethoxyethoxy)ethoxy]-2-propanethiol () at peripheral (β) () and non-peripheral (α) () positions have been synthesized and characterized. The spectroscopic, photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen generation and photodegradation) properties of these newly synthesized phthalocyanines have been investigated in DMSO. The effects of the position of the substituents on the phthalocyanine skeleton and the nature of the linker heteroatom on their spectroscopic, photophysical and photochemical properties have been determined. The quenching behavior of the zinc phthalocyanines by 1,4-benzoquinone has been studied in DMSO. All of the zinc(ii) Pc complexes ( and ) showed similar electronic absorption spectra in various solvents (chloroform, dichloromethane, DMF, DMSO, THF and toluene). However, complex gave an extra red-shifted band at 742 nm in chloroform and dichloromethane. DFT and TD-DFT computations were performed on the model structures (, and ) to find out the cause of the extra red-shifted Q band (J-type aggregation or protonation of the Pc ring). The computational results showed that monoprotonation of a meso nitrogen atom leads to the formation of this extra band. Photophysical and photochemical measurements indicated that these newly synthesized ZnPc derivatives are promising candidates for use as photosensitizers in the application of PDT.
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