- Preparation method and application of albumin-loaded metal porphyrin complex nanoparticles
-
The invention provides albumin-loaded metalloporphyrin complex nano particles preparation method and an application thereof. The albumin-loaded metalloporphyrin complex nano particles take porphyrin,metal salt and albumin as raw materials, a solvent method is employed for preparing the albumin-loaded metalloporphyrin complex nano particles, the method is simple, operation is easy, repeatability is good, and the prepared albumin-loaded metalloporphyrin complex nano particles solve the problem of water solubility and targeting performance of a metal-based complex medicine; under supersonic waveeffect, the albumin-loaded metalloporphyrin complex nano particles have ultrasonic tumor cell killing effect, and a metal-based complex loaded on albumin molecules has a wide antineoplastic application prospect.
- -
-
Paragraph 0099-0103
(2021/05/26)
-
- Linkage Isomers of 4-Methylimidazolate Mn(II) Porphyrinates: Hindered or Unhindered?
-
Three different manganese(II) porphyrins have been exploited to react with 4-methylimidazolate (4-MeIm-), and the five-coordinate products are characterized by ultraviolet-visible, single-crystal X-ray, and electronic paramagnetic resonance spectroscopies. Interestingly, 4-MeIm- is found to bond to the metal center through either of the two N atoms (N1 or N3), which yielded two linkage isomers with either an unhindered or a hindered ligand conformation, respectively. Investigations revealed it is the large metal out-of-plane displacements (Δ24 and Δ4 ≥ 0.59 ?) that have rendered the equivalence of two isomers with a small energy difference (5.2-8.3 kJ/mol). The nonbonded intra- and intermolecular interactions thus become crucial factors in the balance of linkage isomerization. All of the products in both solution and solid states show the same characteristic resonances of high-spin Mn(II) (S = 5/2) with g⊥ ≈ 5.9 and g⊥ ≈ 2.0 at 4 K, consistent with the weak effects of the axial ligand on core conformation and metal electronic configurations. Zero-field splitting parameters obtained through simulations are also reported.
- Zhao, Jianping,Qian, Fei,Guo, Wenping,Li, Jianfeng,Lin, Zeyuan
-
p. 7465 - 7474
(2021/05/26)
-
- Efficient and selective oxidation of tertiary benzylic C[sbnd]H bonds with O2 catalyzed by metalloporphyrins under mild and solvent-free conditions
-
The direct and efficient oxidation of tertiary benzylic C[sbnd]H bonds to alcohols with O2 was accomplished in the presence of metalloporphyrins as catalysts under solvent-free and additive-free conditions. Based on effective inhibition on the unselective autoxidation and deep oxidation, systematical investigation on the effects of porphyrin ligands and metal centers, and apparent kinetics study, the oxidation system employing porphyrin manganese(II) (T(2,3,6-triCl)PPMn) with bulkier substituents as catalyst, was regarded as the most promising and efficient one. For the typical substrate, the conversion of cumene could reach up to 57.6% with the selectivity of 70.5% toward alcohol, both of them being higher than the current documents under similar conditions. The superiority of T(2,3,6-triCl)PPMn was mainly attributed to its bulkier substituent groups preventing metalloporphyrins from oxidative degradation, its planar structure favoring the interaction between central metal with reactants, and the high efficiency of Mn(II) in the catalytic transformation of hydroperoxides to alcohols.
- Hu, Meng-Yun,Liu, Lei,Qi, Bei,She, Yuan-Bin,Shen, Hai-Min,Ye, Hong-Liang
-
-
- Axial Mn-CCN Bonds of Cyano Manganese(II) Porphyrin Complexes: Flexible and Weak?
-
Three five-coordinate high-spin (cyano)manganese(II) complexes, utilized tetraphenylporphyrin (TPP), tetratolylporphyrin (TTP), and tetramesitylporphyrin (TMP) as ligands, are prepared and studied by single-crystal X-ray, FT-IR, UV-vis, and EPR spectrosco
- He, Mingrui,Li, Xiangjun,Liu, Yanhong,Li, Jianfeng
-
p. 5871 - 5879
(2016/07/06)
-
- Investigation by pulse radiolysis of the redox transformations of manganese tetra(n-tolyl)porphyrin and the effect of molecular oxygen on them
-
Pulse radiolysis has been used to investigate the intermediate stages of the radiolytic transformations of Mn(III)TTP in acetonitrile and the effect of oxygen upon them. It is shown that in the initial stages Mn(III)TTP reacts with the anion radicals CH3CN-· and O2-· to give the complexes Mn(III)TTP...CH3CN-· and Mn(III)TTP...O2-· respectively. Mn(II)TTP is formed with a rate constant k = (4.0 ± 0.5) × 104 sec-1 as a result of electron transfer within the complex Mn(III)TTP...CH3CN-·. The electrochemical or radiolytic reduction of Mn(III)TTP in the presence of oxygen gives the complexes Mn(II)TTP...O2, Mn(III)TTP...O2-· and Mn(IV)TTP...O22- in equilibrium with one another.
- Revina,Volod'ko,Radyushkina
-
p. 1156 - 1162
(2008/10/08)
-
- Thermodynamic and kinetic aspects of two- and three-electron redox processes mediated by nitrogen atom transfer
-
Treatment of (meso-tetra-p-tolylporphyrinato)manganese(V) nitride, (TTP)Mn≡N, with (octaethylporphyrinato)manganese(II), Mn(OEP), in toluene leads to the reversible transfer of the nitrido ligand between the two metal complexes to form (OEP)Mn≡N and Mn(TTP). The net result is a formal three-electron reduction of (TTP)MnvN to (TTP)MnII This occurs with a second-order rate constant of (5.6 ± 1.2) × 103 M-1 s-1 to form an equilibrium mixture with Koq 1.2 ± 0.5 at 20°C. The thermodynamic and activation parameters for this process are ΔH° = 2.0 ± 0.2 kcal/mol, ΔS° = 7.1 ± 0.6 cal/mol·K, ΔH? = 9.4 ± 0.7 kcal/mol, and ΔS? = -10 ± 2 cal/mol·K. In THF at 20°C, the equilibrium constant is 1.8 ± 0.2 and the rate constant drops to 2.3 ± 0.3 M-1 s-1. When a manganese(III) porphyrin complex is used as a reductant, reversible nitrogen atom transfer still occurs but mediates a formal two-electron process. At 22°C, the exchange process between (TTP)MnCl and (OEP)Mn≡N produces (TTP)Mn≡N and (OEP)MnCl with a second-order rate constant of 0.010 ± 0.007 M-1 s-1 (ΔH? = 19 ± 2 kcal/mol and ΔS? = -3 ± 6 cal/mol·K) and forms an equilibrium mixture with Keq = 24.3 ± 3.3 (ΔH° = -7.0 ± 0.6 kcal/mol and ΔS° = -17 ± 2 cal/mol-K). Evidence for the formation of a binuclear μ-nitrido intermediate is presented for both processes. For the two-electron redox reaction, kinetic studies and mechanistic probes support a pathway which involves an initial chloride dissociation from the Mn(III) complex. Nitrogen atom transfer subsequently occurs between the Mn≡N complex and the four-coordinate Mn(III) cationic species.
- Keith Woo,Goll, James G.,Czapla, Donald J.,Alan Hays
-
p. 8478 - 8484
(2007/10/02)
-