A density-functional-theory study of bacteriochlorophyll b

Sundholm, Dage

doi:10.1039/b306301a

Cited by 42 publications

(45 citation statements)

References 78 publications

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“…This feature is also reported by Sundholm [21] in his theoretical studies of bacteriochlorophyll b species. It is thus due to the presence of macrocycle substituents and the isocyclic ring.…”

Section: Resultssupporting

confidence: 83%

“…One should mention that the theoretical studies of the spectroscopic properties of the native chlorophylls and bacteriochlorophylls are also published ( e.g ., [18–21]), but they were undertaken rather in order to elucidate the details of the light absorption in photosynthesis, and not in view of their potential applications in PDT. An interested reader should be referred to the extensive reviews [20, 22, 23] and references therein.…”

Section: Introductionmentioning

confidence: 99%

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Metallobacteriochlorophylls as potential dual agents for photodynamic therapy and chemotherapy

Rutkowska‐Zbik

Witko

2013

J Mol Model

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A theoretical analysis of bacteriochlorophyll a containing its non-native divalent metal ions: Co, Ni, Cu, Zn, Ru, Rh, Pd, and Pt, has been carried out by means of density functional theory (DFT) calculations. The main stress was put on the derivatives with metals, which already found applications as coordination compounds in anti-tumor therapy (Ru, Pt, Pd, and Rh). The idea was to combine their cytotoxic properties with the known suitability of bacteriochlorophylls macrocycle for photodynamic therapy. The geometries of the studied systems are compared and reveal a number of similarities. The cores of the modified bacteriochlorophylls are flat, and the introduced metal ions lie in plane of the macrocycle, showing its large ability to accommodate metal ions of different sizes. However, four metal–nitrogen bonds, linking the central ions with the macrocycle ligand, are not equivalent. Metals are the strongest attached to nitrogens, which come from the pyrrole, which is fused with isocyclic ring. Based on the known spectroscopic data, the absorption properties of the proposed systems are predicted. Finally, it is found that all studied metal–macrocycle adducts are stable in aqueous media. The only exceptions are Mg-BChla (the finding is reflected by experimental facts) and Zn-BChla. The predicted high stability of Ru-, Rh-, Pt- and Pd-bacteriochlorophylls might turn out beneficial for therapeutic purposes.Electronic supplementary materialThe online version of this article (doi:10.1007/s00894-012-1747-y) contains supplementary material, which is available to authorized users.

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Section: Resultssupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Metallobacteriochlorophylls as potential dual agents for photodynamic therapy and chemotherapy

Rutkowska‐Zbik

Witko

2013

J Mol Model

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“…3). This underestimation was also reported in other papers 7,8. Regarding the absorption shift from BChl a to b , the Q y band is significantly red-shifted by 0.075(face)/0.074(back) eV, while the Q x band is hardly shifted.…”

Section: Resultssupporting

confidence: 81%

“…All calculations were performed with Gaussian 09 software14. DFT and TD-DFT calculations with the similar functional and basis set were reported to be sufficiently appropriate to study the properties of excited states and molecular orbitals of the BChl dyes 7,8…”

Section: Computational Detailsmentioning

confidence: 99%

Uncovering the mechanism for selective control of the visible and near-IR absorption bands in bacteriochlorophylls a, b and g

Fujisawa

Nagata

2014

BIOPHYSICS

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Bacteriochlorophylls (BChls) play an important role as light harvesters in photosynthetic bacteria. Interestingly, bacteriochlorophylls (BChls) a, b, and g selectively tune their visible (Qx) and near IR (Qy) absorption bands by the substituent changes. In this paper, we theoretically study the mechanism for the selective control of the absorption bands. Density functional theory (DFT) and time-dependent DFT (TD-DFT) and four-orbital model analyses reveal that the selective red-shift of the Qy band with the substituent change from BChl a to b occurs with the lower-energy shift of the (HOMO, LUMO) excited state directly induced by the molecular-orbital energy changes. In contrast, the Qx band hardly shifts by the cancellation between the higher- and lower-energy shifts of the (HOMO-1, LUMO) excited state directly induced by the molecular-orbital energy changes and configuration interaction, respectively. On the other hand, with the substituent changes from BChl a to g, the Qx band selectively blue-shifts by the larger higher-energy shift of the (HOMO-1, LUMO) excited state directly induced by the molecular-orbital energy shifts than the lower-energy shift due to the configuration interaction. In contrast, the Qy band hardly shifts by the cancellation between the higher- and lower-energy shifts of the (HOMO, LUMO) excited state directly induced by the molecular-orbital energy changes and configuration interaction, respectively. Our work provides the important knowledge for understanding how nature controls the light-absorption properties of the BChl dyes, which might be also useful for design of porphyrinoid chromophores.

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“…This can be a major limitation in applications, especially to smaller systems and negative anions, because GGA potentials are too repulsive which results in too few bound states, as explained above. In other cases, one finds spurious intruder states which "steal" intensity from adjacent transitions of the same symmetry [144]. Nevertheless, apart form the technical difficulties associated with continuum states, the overall shape of the computed spectra is often accurate [145].…”

Section: Vertical Excitation and CD Spectramentioning

confidence: 99%

Density Functional Methods for Excited States: Equilibrium Structure and Electronic Spectra

Furche

Rappoport

2005

Theoretical and Computational Chemistry

258

235

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A density-functional-theory study of bacteriochlorophyll b

Cited by 42 publications

References 78 publications

Metallobacteriochlorophylls as potential dual agents for photodynamic therapy and chemotherapy

Metallobacteriochlorophylls as potential dual agents for photodynamic therapy and chemotherapy

Uncovering the mechanism for selective control of the visible and near-IR absorption bands in bacteriochlorophylls <i>a</i>, <i>b</i> and <i>g </i>

Density Functional Methods for Excited States: Equilibrium Structure and Electronic Spectra

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