Ruthenium complexes present two states of oxidation that are Ru(II) and Ru(III). Both are assumed to present cytotoxic activity at ground state. On the purpose of highlighting their differences, DFT, TD-DFT and NBO ha...Ruthenium complexes present two states of oxidation that are Ru(II) and Ru(III). Both are assumed to present cytotoxic activity at ground state. On the purpose of highlighting their differences, DFT, TD-DFT and NBO have been performed at both Wb97xd/Lanl2dz and B3lyp/Lanl2dz levels. NBO program shows that both groups of ruthenium complexes present almost the same charge of Ru atom. Moreover, they display nearly the same structure of valence orbitals of the ruthenium. However, when it comes to compare their frontier orbitals HOMO and LUMO, we notice that the chloride atom has a great influence on their energy. The lack of Chloride atoms reduces the energy of frontier orbitals regardless of the functional. And the more the number of chloride atoms, the higher the energy. Also, RuCl<sub>3</sub>Terpy and α-RuCl<sub>2</sub>(Azpy)<sub>2</sub> have been discovered to display the best energy suitable for reaction as cytotoxic agents. Yet, both are from groups different. Thus, at ground state, there is practically no difference between both groups. However, regarding TDDFT prediction with the determination of vertical electronic affinity VEA and vertical ionization potential VIP both at ground state S and at exciting T1 state, we notice that Ru(II) complexes are not active either in the presence or absence of <sup>3</sup>O<sub>2</sub> molecule. Here, only Ru(III) complexes are able to react on Guanine through their radical cations or by generating the superoxide radical anion <img src="Edit_17bbaac1-501f-4de4-bc6b-4f8b513cc344.png" alt="" />. Therefore, the Ru(III) complexes are assumed to be active both at a fundamental state and under the effect of light for photodynamic therapy. We come to conclude that Ru(II) complexes are not active by excitation as their valence electrons are paired thereby making these complexes more stable. Besides, <img src="Edit_30d3bea0-3cbe-4e08-8438-551a2fa7de22.png" alt="" /> , a Ru(II) molecule that is not active at ground state owing certainly to its C<sub>3</sub> symmetry or Azpy ligand展开更多
This work was undertaken to see how Ru II complexes can be suitable for photodynamic therapy through theoretical prediction. For that, four Ru II complexes, α-RuCl<sub>2</sub>(Azpy)<sub>2</sub>...This work was undertaken to see how Ru II complexes can be suitable for photodynamic therapy through theoretical prediction. For that, four Ru II complexes, α-RuCl<sub>2</sub>(Azpy)<sub>2</sub>, , and were used in unrestricted state by providing with no more energy than 2.68 eV. The unrestricted state allows the complex molecule to display each of its electrons in one orbital. All the calculations such as optimization, frequency and TD-DFT calculations were performed at WB97XD/Lanl2dz level. It resulted from this investigation that Ru II complexes are active for both mechanisms suitable for photodynamic therapy in presence or absence of <sup>3</sup>O<sub>2</sub>. Moreover, this reaction was assumed to take place only with Guanine DNA base as demonstrated in literature. Therefore, Guanine is admitted as the base most reacting with ruthenium complexes for photodynamic therapy. This work confirms our prediction regarding metallic complexes that are assumed to be photosensitized in condition that an electron must be isolated to favor the excitation. Nevertheless, Ru II complexes are found suitable for superficial therapy while Ru III must be active for deep therapy.展开更多
Erythroplasia of Queyrat (EQ) is Squamous cell carcinoma in situ of penis usually involving glans and prepuce, commonly found in uncircumcised men with progression into invasive carcinoma in about 30% of cases. We pre...Erythroplasia of Queyrat (EQ) is Squamous cell carcinoma in situ of penis usually involving glans and prepuce, commonly found in uncircumcised men with progression into invasive carcinoma in about 30% of cases. We present a case of 50 yrs, male with reddish, Irritative rash on glans penis;HPE confirms the case of EQ with acanthosis, derangement of stratum spinosum and basement membrane integrity. It successfully treated with two cycle of Photo Dynamic Therapy (PDT). If conservative approach with immquimod, fluorouracil fails then invasive approach should be adopted.展开更多
文摘Ruthenium complexes present two states of oxidation that are Ru(II) and Ru(III). Both are assumed to present cytotoxic activity at ground state. On the purpose of highlighting their differences, DFT, TD-DFT and NBO have been performed at both Wb97xd/Lanl2dz and B3lyp/Lanl2dz levels. NBO program shows that both groups of ruthenium complexes present almost the same charge of Ru atom. Moreover, they display nearly the same structure of valence orbitals of the ruthenium. However, when it comes to compare their frontier orbitals HOMO and LUMO, we notice that the chloride atom has a great influence on their energy. The lack of Chloride atoms reduces the energy of frontier orbitals regardless of the functional. And the more the number of chloride atoms, the higher the energy. Also, RuCl<sub>3</sub>Terpy and α-RuCl<sub>2</sub>(Azpy)<sub>2</sub> have been discovered to display the best energy suitable for reaction as cytotoxic agents. Yet, both are from groups different. Thus, at ground state, there is practically no difference between both groups. However, regarding TDDFT prediction with the determination of vertical electronic affinity VEA and vertical ionization potential VIP both at ground state S and at exciting T1 state, we notice that Ru(II) complexes are not active either in the presence or absence of <sup>3</sup>O<sub>2</sub> molecule. Here, only Ru(III) complexes are able to react on Guanine through their radical cations or by generating the superoxide radical anion <img src="Edit_17bbaac1-501f-4de4-bc6b-4f8b513cc344.png" alt="" />. Therefore, the Ru(III) complexes are assumed to be active both at a fundamental state and under the effect of light for photodynamic therapy. We come to conclude that Ru(II) complexes are not active by excitation as their valence electrons are paired thereby making these complexes more stable. Besides, <img src="Edit_30d3bea0-3cbe-4e08-8438-551a2fa7de22.png" alt="" /> , a Ru(II) molecule that is not active at ground state owing certainly to its C<sub>3</sub> symmetry or Azpy ligand
文摘This work was undertaken to see how Ru II complexes can be suitable for photodynamic therapy through theoretical prediction. For that, four Ru II complexes, α-RuCl<sub>2</sub>(Azpy)<sub>2</sub>, , and were used in unrestricted state by providing with no more energy than 2.68 eV. The unrestricted state allows the complex molecule to display each of its electrons in one orbital. All the calculations such as optimization, frequency and TD-DFT calculations were performed at WB97XD/Lanl2dz level. It resulted from this investigation that Ru II complexes are active for both mechanisms suitable for photodynamic therapy in presence or absence of <sup>3</sup>O<sub>2</sub>. Moreover, this reaction was assumed to take place only with Guanine DNA base as demonstrated in literature. Therefore, Guanine is admitted as the base most reacting with ruthenium complexes for photodynamic therapy. This work confirms our prediction regarding metallic complexes that are assumed to be photosensitized in condition that an electron must be isolated to favor the excitation. Nevertheless, Ru II complexes are found suitable for superficial therapy while Ru III must be active for deep therapy.
文摘Erythroplasia of Queyrat (EQ) is Squamous cell carcinoma in situ of penis usually involving glans and prepuce, commonly found in uncircumcised men with progression into invasive carcinoma in about 30% of cases. We present a case of 50 yrs, male with reddish, Irritative rash on glans penis;HPE confirms the case of EQ with acanthosis, derangement of stratum spinosum and basement membrane integrity. It successfully treated with two cycle of Photo Dynamic Therapy (PDT). If conservative approach with immquimod, fluorouracil fails then invasive approach should be adopted.
