Theoretical optical properties of poly-L-proline

A non-perturbational technique is used to calculate the circular dichroism and absorption spectra of polypeptide chains having conformations similar to that of poly-L -proline II. The method employs a Bogoliubov exciton formalism, from which the various optical terms associated with parallel and perpendicular components of the exciton band are obtained. A simple model for the peptide unit, consisting of three Gaussian absorption bands, leads to reasonable results for the polymer spectra, provided the lowest energy peptide π → π* transition is taken at 207 mμ and the value of the Ramachandran angle Ψ is taken to be 390°. The calculations suggest that the polymer circular dichroism spectrum is the resultant of strong interference among the two Gaussian exciton terms and the non-Gaussian helix term. Consequently, the CD spectrum is very sensitive to the value of Ψ. It is found that the small positive CD band in the vicinity of 230 mμ arises partly from the effect of the static (crystal) field interactions on the n → π* CD band.     

Spectroscopic Determinants in the Reaction Center of Rhodopseudomonas Viridis

Assignments are proposed for the long wavelength absorption bands observed in the reaction center of Rhodopseudomonas viridis. The assignments are based on a theoretical treatment in which quantum mechanical calculations are first carried out on the individual chromophores of the reaction center. The energies and wave functions that are obtained are then introduced into an exciton-type perturbation treatment in which extensive configuration interaction is carried out between the excited states of the four bacteriochlorophylls and two bacteriopheophytins of the reaction center. Calculated values for absorption maxima, transition moments, linear dichroism, and rotational strength are compared with experiments in an attempt to distinguish among different assignments. The calculations alone do not lead to unambiguous assignments; indeed it is difficult to account for the reaction center spectra without introducing assumptions as to the effects of the protein on the energy levels of the individual molecules. Even if these effects are treated as free parameters, the experimental spectra still provide useful constraints that restrict the models that are possible. The major result of this work is that the weak 850-nm absorption band is due, primarily, to the higher energy exciton state of the bacteriochlorophyll special pair. Accounting for the 960-nm absorption band of the low energy exciton state of the special pair requires either that a large spectroscopic effect of the protein be introduced, or possibly, that charge transfer states play a major spectroscopic role. The difference in spectra seen in the formation of oxidized or triplet state reaction centers can be understood in terms of a combination of electrochromic effects and modified exciton interactions.     

CD spectrum of bacteriorhodopsin: Best evidence against exciton model

We summarize the predictions of the exciton model that was originally proposed to explain the observed biphasic band shape of its CD spectrum in the visible region of bacteriorhodopsin (bR). It is shown that to reconcile these predictions with the observed results on the linear dichroism, the retinal isomerization time and, the retinal-retinal distance, the biphasic nature of the observed CD spectrum of bR becomes itself an evidence against the exciton model because of the uncertainty principle.

Reduced bR (RbR), which retains its hexagonal structure, shows a monophasic CD spectrum with relatively small rotational strength as compared to bR. This is shown to disagree with predictions made by the exciton model. The results could best be explained in terms of retinal-protein heterogeneity leading to two or more types of bR in which their retinals suffer opposite sense of intramolecular rotational distortion along their retinal long axis. Such a retinal-protein heterogeneity disappears in reduced bR which is known to have a planar (nondistorted) retinal conjugated system, resulting in a monophasic CD with reduced rotational strength, as observed.

     

The induced circular dichroism of proflavine intercalated to DNA. Dye-polymer exciton interactions

The circular dichroism induced in the visible absorption band of proflavine cation isolatedly intercalated to DNA was investigated in terms of the dye-DNA base pair exciton interaction. The remarkable ionic strength dependence of the induced CD magnitude was in good accord with the CD magnitude calculated on the basis of the dye-polymer Frenkel exciton interaction model and under the extent of helix deformation required for intercalation. In particular the application of the internal and modified intercalation models coupled with the deep trap approximation implied that the preference of the modified intercalation due to electrostatic interaction between the acridine-nitrogen atom and the DNA phosphate group is combined with relatively high ionic strength compared with the internal intercalation.     

Optical studies on complexes between DNA and pseudoisocyanine.

Linear dichroism (LD) results when pseudoisocyanine=PIC (1,1-diethy1-2,2-cyannine iodide) binds to flow-oriented DNA. LD may be used to follow the complexation both stoichmetrically and structurally, since when specified to unti complex concentration LD provides a measure of the average orientation of the absorbing transition dipole. Two different types of complexes can be distinguished: I. One strong, ionic-strength insensitive complex with monomeric PIC with an orientation indication intercalation. II. Several weaker complexes of electrostatic nature (only observed at I less than 0.2M Na Cl) among which those with dimeric (IIa) and with polymeric (IIb) PIC are concluded both from LD and from circular dichroism (CD). The dimer is probably formed by employing one intercalated PIC as a second site. The polymer complex is characterized by a very sharp absorption band at 553 nm polarized parallel to the DNA-axis (with positive LD and positive CL). The structure, a right-handed helical array of PIC molecules, is discussed in terms of exciton theory in relation to that of polymeric free PIC ("Scheibe polymer") which is also shown to interact with DNA (IIc) yielding a large aggregate which is degraded at a distinct flow force field...     

Optical properties of polypeptides in the β-conformation

The rotational strengths and oscillator strengths of the nπ* band and ππ* exciton bands have been calculated for antiparallel and parallel β-structures of varying length and width. The results are compared with experiment and with previous theoretical treatments of β-structures. The generally good agreement of calculations on the antiparallel β-structure with experimental results on poly-L -lysine and poly-L -serine indicates that these systems are indeed in the antiparallel conformation. It is found that the exciton component strongest in absorption shifts to longer wavelengths as the width of an antiparallel structure increases, and it is suggested that the position of the ππ* absorption band may be a useful criterion of sheet width. The results also reconcile the linear dichroism measurements of Rosenheck and Sommer on poly-L -lysine films with an anti-parallel structure. Calculations on parallel β-structures indicate that the CD spectra of this form will be rather similar to that of the antiparallel form. However, the major absorption band in the antiparallel form is associated with a small positive CD band, while in the parallel form it coincides with a large negative CD band. Finally, it is pointed out that the large positive CD bands predicted for single-stranded parallel and antiparallel β-structures at about 200 mμ render unlikely the suggestion that random-coil polypeptides contain a substantial fraction of extended chain.     

The calculated circular dichroism of polyproline II in the polarizability approximation

The circular dichroism (CD) spectrum of polyproline II (PPII) has heretofore been moderately well calculated from exciton theory only at the expense of assuming unreasonable chain conformations and accepting a conservative spectrum in the 180–250-nm region (which is not observed). We have incorporated far uv transitions in the polarizability approximation and, together with the π₂π* transition, have calculated the resulting correction to the exciton model. This has been accompanied by a modified assignment of the ππ* transition in PPII, and a simultaneous calculation of the absorption and CD spectra of the α-helix, β structure, PPI, and PPII. We obtain good agreement with the observed CD spectrum of PPII in the 180–250-nm region for acceptable chain conformations. In addition, we predict a negative CD into the far uv, in agreement with recent experimental observations. Our calculations also reproduce features of the far uv CD spectrum of the α-helix, and are in agreement with the CD spectra of the β chain and PPI. The calculated CD of the unordered polypeptide chain is not significantly influenced by far uv contributions, indicating that our previous calculation is valid for such a system. These results demonstrate the importance of incorporating far uv transitions in order to achieve an adequate theoretical explanation of the CD spectra of polypeptides.     

Optical effects of sodium dodecyl sulfate treatment of the isolated light harvesting complex of higher plants

The light-harvesting complex (LHC) of higher plants isolated using Triton X-100 has been studied during its transformation into a monomeric form known as CPII. The change was accomplished by gradually increasing the concentration of the detergent, sodium dodecyl sulfate (SDS). Changes in the red spectral region of the absorption, circular dichroism (CD), and linear dichroism spectra occurring during this treatment have been observed at room temperature. According to a current hypothesis the main features of the visible region absorption and CD spectra of CPII can be explained reasonably successfully in terms of an exciton coupling among its chlorophyll (Chl) b molecules. We suggest that the spectral differences between the isolated LHC and the CPII may be understood basically in terms of an exciton coupling between the Chl b core of a given CPII unit and at least one of the Chla's of either the same or the adjacent CPII. We propose that this Chl a-Chl b coupling existing in LHC disappears upon segregation into CPII, probably as a result of a detergent-related overall rotation of the strongly coupled Chl b core which changes the relative orientations of the two types of pigments and thus the nature of their coupling.Abbreviations Chl Chlorophyll - CD Circular dichroism - LD Linear dichroism - LHC Light-harvesting complex - SDS Sodium dodecyl sulfate - CPII A solubilized form of LHC obtained with SDS polyacrylamide gel electrophoresis Dedicated to Prof. L.N.M. Duysens on the occasion of his retirement     

Exciton interaction among chlorophyll molecules in bacteriochlorophyll a proteins and bacteriochlorophyll a reaction center complexes from green bacteria

Absorption and CD spectra of bacteriochlorophyll a proteins and bacteriochlorophyll a reaction center complexes from two strains of Chlorobium limicola were recorded at 77 °K. Visual inspection showed that the Q_y-band of chlorophyll in either protein was split into at least five components. Analysis of the spectra in terms of asymmetric Gaussian component pairs by means of computer program GAMET showed that six components are necessary to fit the spectra from strain 2K. These six components are ascribed to an exciton interaction between the seven bacteriochlorophyll a molecules in each subunit. The clear difference between the exciton splitting in the two bacteriochlorophyll a proteins shows that the arrangement of the chlorophyll molecules in each subunit must be slightly different.

The spectra for the bacteriochlorophyll a reaction center complexes have a component at 834 nm (absorption) and 832 nm (CD) which does not appear in the spectra of the bacteriochlorophyll a proteins. The new component is ascribed to a reaction center complex which is combined with bacteriochlorophyll a proteins to form the bacteriochlorophyll a reaction center complex. The complete absorption (or CD) spectrum for a given bacteriochlorophyll a reaction center complex can be described to a first approximation in terms of the absorption (or CD) spectrum for the corresponding bacteriochlorophyll a protein plus the new component ascribed to the reaction center complex.     

Unusual CD couplet pattern observed for the pi*<--n transition of enantiopure (Z)-8-methoxy-4-cyclooctenone: an experimental and theoretical study by electronic and vibrational circular dichroism spectroscopy and density functional theory calculation

Ultraviolet absorption (UV) and electronic circular dichroism (ECD) spectra of enantiopure (Z)-8-methoxy-4-cyclooctenone (MCO) were measured in hexane to give a normal single UV absorption band at 298 nm, which is assigned to the carbonyl's pi*<--n transition. Unexpectedly, the ECD spectrum exhibited an apparent couplet pattern with vibrational fine structures. Obviously, the conventional CD exciton coupling mechanism cannot be applied to this bisignate CD signal observed for single-chromophoric MCO. Variable temperature-ECD and vibrational circular dichroism (VCD) spectral measurements, simultaneous UV and ECD spectral band resolution, and density functional theory (DFT) calculations of energy and structure revealed that this apparent CD couplet originates from a rather complicated spectral overlap of more than three conformers of MCO, two of which exhibit mirror-imaged ECD spectra at appreciably deviated wavelengths. In the simultaneous band-resolution analysis, the observed UV and ECD spectra were best fitted to four overlapping bands. Two major conformers were identified by comparing the experimental IR and VCD spectra with the simulated ones, and the other two by comparing the observed UV and ECD spectra with the theoretical ones obtained by time-dependent DFT calculations. It was shown that the combined use of experimental ECD and VCD spectra and theoretical DFT calculations can give a reasonable interpretation for the Cotton effects of the conformationally flexible molecule MCO.     

Photoselection and circular dichroism in the purple membrane.

The transient dichroic ratio D = delta A parallel/delta A perpendicular has been measured in the visible absorption region of bacteriorhodopsin in purple membrane by a flash photolysis method. D is found to be wavelength independent throughout the visible absorption band, and reaches a maximum value of 2.75 +/- 0.15 on reduction of the excitation intensity. This value is close to that expected for a single nondegenerate transition dipole moment and is incompatible with the strong exciton coupling model used to explain circular dichroism (CD) spectrum of purple membrane. A time-dependent analysis of the exciton interaction and consideration of the coupling strength suggests an explanation of these observations. It is concluded that excitation interaction between retinals in purple membrane is of the weak or very weak type defined by Förster.     

Heme-heme interactions in tetramers and dimers of hemoglobin subunits: DeVoe theory calculations

Detectable exciton couplets arising from heme-heme interactions in the hemoglobin (Hb) tetramers of HbO(2) and deoxyHb were predicted by DeVoe theory. This prediction was supported by the observation of an exciton couplet in the CD difference spectrum between the Hb tetramer and the alphabeta dimer of HbCO. In this paper, DeVoe theory is used to calculate the heme-heme interactions in the CO complex of the Hb tetramer (alpha(2)beta(2)) and dimer (alphabeta), the systems studied by Goldbeck et al. The couplet strength of the resulting theoretical CD difference spectrum agrees well with experiment, thus confirming that heme-heme interactions contribute significantly to the CD of HbCO. Given that the heme-heme distances in HbCO are 25 A and more, it is highly likely that heme-heme interactions also contribute significantly to the CD of other multi-heme proteins, e.g., cytochrome c(3), cytochrome oxidase, cytochrome bc(1), etc., where the hemes are in closer proximity.     

Fluorescence polarization and low-temperature absorption spectroscopy of a subunit form of light-harvesting complex I from purple photosynthetic bacteria

Measurements of polarized fluorescence and CD were made on light-harvesting complex 1 and a subunit form of this complex from Rhodospirillum rubrum, Rhodobacter sphaeroides, and Rhodobacter capsulatus. The subunit form of LH1, characterized by a near-infrared absorbance band at approximately 820 nm, was obtained by titration of carotenoid-depleted LH1 complexes with the detergent n-octyl beta-D-glucopyranoside as reported by Miller et al. (1987) [Miller J. F., Hinchigeri, S. B., Parkes-Loach, P. S., Callahan, P. M., Sprinkle, J. R., & Loach, P. A. (1987) Biochemistry 26, 5055-5062]. Fluorescence polarization and CD measurements at 77 K suggest that this subunit form must consist of an interacting bacteriochlorophyll a dimer in all three bacterial species. A small, local decrease in the polarization of the fluorescence is observed upon excitation at the blue side of the absorption band of the B820 subunit. This decrease is ascribed to the presence of a high-energy exciton component, perpendicular to the main low-energy exciton component. From the extent of the depolarization, we estimate the oscillator strength of the high-energy component to be at most 3% of the main absorption band. The optical properties of B820 are best explained by a Bchl a dimer that has a parallel or antiparallel configuration with an angle between the Qy transition dipoles not larger than 33 degrees. The importance of this structure is emphasized by the results showing that core antennas from three different purple bacteria have a similar structure.(ABSTRACT TRUNCATED AT 250 WORDS)     

Study of exciton interactions in some pyrimidine dinucleotides in aqueous solution by means of absorption spectroscopy

The near ultraviolet absorption spectra of CpC, TpT and UpU in aqueous solution have been measured and compared with the corresponding spectra of C, T and U. The differences in shapes of the spectral envelopes between the monomeric and dimeric species have been interpreted in terms of exciton coupling between the bases. The largest differences were observed for the pair CpC/C in neutral solution and these were analysed by the use of vibronic coupling theory. Parameters characteristic of the relative conformation of and the rate of energy transfer between the bases in CpC were derived.     

Optical Properties of Organic Semiconductor Blends with Near‐Infrared Quantum‐Dot Sensitizers for Light Harvesting Applications

We report an optical investigation of conjugated polymer (P3HT)/fullerene (PCBM) semiconductor blends sensitized by near‐infrared absorbing quantum dots (PbS QDs). A systematic series of samples that include pristine, binary and ternary blends of the materials are studied using steady‐state absorption, photoluminescence (PL) and ultrafast transient absorption. Measurements show an enhancement of the absorption strength in the near‐infrared upon QD incorporation. PL quenching of the polymer and the QD exciton emission is observed and predominantly attributed to intermaterial photoinduced charge transfer processes. Pump‐probe experiments show photo‐excitations to relax via an initial ultrafast decay while longer‐lived photoinduced absorption is attributed to charge transfer exciton formation and found to depend on the relative ratio of QDs to P3HT:PCBM content. PL experiments and transient absorption measurements indicate that interfacial charge transfer processes occur more efficiently at the fullerene/polymer and fullerene/nanocrystal interfaces compared to polymer/nanocrystal interfaces. Thus the inclusion of the fullerene seems to facilitate exciton dissociation in such blends. The study discusses important and rather unexplored aspects of exciton recombination and charge transfer processes in ternary blend composites of organic semiconductors and near‐infrared quantum dots for applications in solution‐processed photodetectors and solar cells.     

Red Chlorophylls in the Exciton Model of Photosystem I

Structural arrangement of pigment molecules of Photosystem I of photosynthetic cyanobacterium Synechococcus elongatus is used for theoretical modeling of the excitation energy spectrum. It is demonstrated that a straightforward application of the exciton theory with the assumption of the same molecular transition energy does not describe the red side of the absorption spectrum. Since the inhomogeneity in the molecular transition energies caused by a dispersive interaction with the molecular surrounding cannot be identified directly from the structural model, the evolutionary search procedure is used for fitting the low temperature absorption and circular dichroism spectra. As a result, one dimer, three trimers and one tetramer of chlorophyll molecules responsible for the red side of the absorption spectrum with their assignment to the spectroscopically established three bands at 708, 714 and 719 nm are determined. All of them are found to be situated not in the very close vicinity of the reaction center but are encircling it almost at the same distance. In order to explain the unusual broadening on the red side of the spectrum the exciton state mixing with the charge transfer (CT) states is considered. It is shown that two effects can be distinguished as caused by mixing of those states: (i) the oscillator strength borrowing by the CT state from the exciton transition and (ii) the borrowing of the high density of the CT state by the exciton state. The intermolecular vibrations between two counter-charged molecules determine the high density in the CT state. From the broad red absorption wing it is concluded that the CT state should be the lowest state in the complexes under consideration. Such mixing effect enables resolving the diversity in the molecular transition energies as determined by different theoretical approaches.     

Spectral manifestations of conformation heterogeneity of a cytidine dinucleotide. A fraction with strong exciton base-base interaction

The absorption, emission and excitation luminescence spectra of CpCp have been studied in comparison with the same of Cp at 77K in the glass mixture (ethyleneglycol: water, 1:1, v/v). It is shown, that the CpCp fluorescence is of dual nature: eximer and exciton. The exciton absorption spectrum with split band (3000 cm-1) has been calculated by means of the fluorescence exciton spectrum. It corresponds to the "conservative" part of the CD spectrum.     

Spectroscopy on the B850 band of individual light-harvesting 2 complexes of Rhodopseudomonas acidophila. I. Experiments and Monte Carlo simulations

The electronic structure of the circular aggregate of 18 bacteriochlorophyll a (BChl a) molecules responsible for the B850 absorption band of the light-harvesting 2 (LH2) complex of the photosynthetic purple bacterium Rhodopseudomonas acidophila has been studied by measuring fluorescence-excitation spectra of individual complexes at 1.2 K. The spectra reveal several well-resolved bands that are obscured in the single, broad B850 band observed in conventional absorption measurements on bulk samples. They are interpreted consistently in terms of the exciton model for the circular aggregate of BChl a molecules. From the energy separation between the different exciton transitions a reliable value of the intermolecular interaction is obtained. The spectra of the individual complexes allow for a distinction between the intra- and the intercomplex disorder. In addition to the random disorder, a regular modulation of the interaction has to be assumed to account for all the features of the observed spectra. This modulation has a C(2) symmetry, which strongly suggests a structural deformation of the ring into an ellipse.