Theory of 2D electronic spectroscopy of water soluble chlorophyll-binding protein (WSCP): Signatures of Chl b derivate.

We investigate how electronic excitations and subsequent dissipative dynamics in the water soluble chlorophyll-binding protein (WSCP) are connected to features in two-dimensional (2D) electronic spectra, thereby comparing results from our theoretical approach with experimental data from the literature. Our calculations rely on third-order response functions, which we derived from a second-order cumulant expansion of the dissipative dynamics involving the partial ordering prescription, assuming a fast vibrational relaxation in the potential energy surfaces of excitons. Depending on whether the WSCP complex containing a tetrameric arrangement of pigments composed of two dimers with weak excitonic coupling between them binds the chlorophyll variant Chl a or Chl b, the resulting linear absorption and circular dichroism spectra and particularly the 2D spectra exhibit substantial differences in line shapes. These differences between Chl a WSCP and Chl b WSCP cannot be explained by the slightly modified excitonic couplings within the two variants. In the case of Chl a WSCP, the assumption of equivalent dimer subunits facilitates a reproduction of substantial features from the experiment by the calculations. In contrast, for Chl b WSCP, we have to assume that the sample, in addition to Chl b dimers, contains a small but distinct fraction of chemically modified Chl b pigments. The existence of such Chl b derivates has been proposed by Pieper et al. [J. Phys. Chem. B 115, 4042 (2011)] based on low-temperature absorption and hole-burning spectroscopy. Here, we provide independent evidence.

Impact of Peripheral Hydrogen Bond on Electronic Properties of the Primary Acceptor Chlorophyll in the Reaction Center of Photosystem I.

Photosystem I (PS I) is a photosynthetic pigment-protein complex that absorbs light and uses the absorbed energy to initiate electron transfer. Electron transfer has been shown to occur concurrently along two (A- and B-) branches of reaction center (RC) cofactors. The electron transfer chain originates from a special pair of chlorophyll a molecules (P700), followed by two chlorophylls and one phylloquinone in each branch (denoted as A-1, A0, A1, respectively), converging in a single iron-sulfur complex Fx. While there is a consensus that the ultimate electron donor-acceptor pair is P700+A0-, the involvement of A-1 in electron transfer, as well as the mechanism of the very first step in the charge separation sequence, has been under debate. To resolve this question, multiple groups have targeted electron transfer cofactors by site-directed mutations. In this work, the peripheral hydrogen bonds to keto groups of A0 chlorophylls have been disrupted by mutagenesis. Four mutants were generated: PsaA-Y692F; PsaB-Y667F; PsaB-Y667A; and a double mutant PsaA-Y692F/PsaB-Y667F. Contrary to expectations, but in agreement with density functional theory modeling, the removal of the hydrogen bond by Tyr → Phe substitution was found to have a negligible effect on redox potentials and optical absorption spectra of respective chlorophylls. In contrast, Tyr → Ala substitution was shown to have a fatal effect on the PS I function. It is thus inferred that PsaA-Y692 and PsaB-Y667 residues have primarily structural significance, and their ability to coordinate respective chlorophylls in electron transfer via hydrogen bond plays a minor role.

Photodynamically Tumor Vessel Destruction Amplified Tumor Targeting of Nanoparticles for Efficient Chemotherapy.

Efficient tumor-targeted drug delivery is still a challenging and currently unbreakable bottleneck in chemotherapy for tumors. Nanomedicines based on passive or active targeting strategy have not yet achieved convincing chemotherapeutic benefits in the clinic due to the tumor heterogeneity. Inspired by the efficient inflammatory-cell recruitment to acute clots, we constructed a two-component nanosystem, which is composed of an RGD-modified pyropheophorbide-a (Ppa) micelle (PPRM) that mediates the tumor vascular-targeted photodynamic reaction to activate local coagulation and subsequently transmits the coagulation signals to the circulating clot-targeted CREKA peptide-modified camptothecin (CPT)-loaded nanodiscs (CCNDs) for amplifying tumor targeting. PPRM could effectively bind with the tumor vasculature and induce sufficient local thrombus by a photodynamic reaction. Local photodynamic reaction-induced tumor target amplification greatly increased the tumor accumulation of CCND by 4.2 times, thus significantly enhancing the chemotherapeutic efficacy in the 4T1 breast tumor model. In other words, this study provides a powerful platform to amplify tumor-specific drug delivery by taking advantage of the efficient crosstalk between the PPRM-activated coagulation cascade and clot-targeted CCND.

Inhibitory effects of chlorophyll pigments on the bioaccessibility of ß-carotene: Influence of chlorophyll structure and oil matrix.

Chlorophylls and ß-carotene are fat-soluble phytochemicals in daily diets, while their bioaccessibility interaction remains unknown. Eight dietary chlorophylls and their derivatives (chlorophyll a, chlorophyll b, pheophytin a, pheophytin b, chlorophyllide a, chlorophyllide b, pheophorbide a, pheophorbide b) were combined with ß-carotene in six different oil matrices (corn oil, coconut oil, medium-chain triglycerides, peanut oil, olive oil and fish oil) and were subjected to in vitro digestion. Generally, chlorophylls significantly decreased ß-carotene bioaccessibility by competitive incorporation into micelles. Dephytylated chlorophylls had a greater inhibitory effect on the micellarization and bioaccessibility of ß-carotene compared to phytylated chlorophylls. In their co-digestion system, olive oil group exhibited the smallest particle size and biggest zeta potential in both digesta and micelles. For chlorophylls, the phytol group and their levels are key factors, which was also buttressed by the mice model where additional supplementation of pheophorbide a significantly hindered the accumulation of ß-carotene and retinoids compounds.

EPR Spin-Trapping for Monitoring Temporal Dynamics of Singlet Oxygen during Photoprotection in Photosynthesis.

A central goal of photoprotective energy dissipation processes is the regulation of singlet oxygen (1O2*) and reactive oxygen species in the photosynthetic apparatus. Despite the involvement of 1O2* in photodamage and cell signaling, few studies directly correlate 1O2* formation to nonphotochemical quenching (NPQ) or lack thereof. Here, we combine spin-trapping electron paramagnetic resonance (EPR) and time-resolved fluorescence spectroscopies to track in real time the involvement of 1O2* during photoprotection in plant thylakoid membranes. The EPR spin-trapping method for detection of 1O2* was first optimized for photosensitization in dye-based chemical systems and then used to establish methods for monitoring the temporal dynamics of 1O2* in chlorophyll-containing photosynthetic membranes. We find that the apparent 1O2* concentration in membranes changes throughout a 1 h period of continuous illumination. During an initial response to high light intensity, the concentration of 1O2* decreased in parallel with a decrease in the chlorophyll fluorescence lifetime via NPQ. Treatment of membranes with nigericin, an uncoupler of the transmembrane proton gradient, delayed the activation of NPQ and the associated quenching of 1O2* during high light. Upon saturation of NPQ, the concentration of 1O2* increased in both untreated and nigericin-treated membranes, reflecting the utility of excess energy dissipation in mitigating photooxidative stress in the short term (i.e., the initial ∼10 min of high light).

Effect of the Drying Method and Storage Conditions on the Quality and Content of Selected Bioactive Compounds of Green Legume Vegetables.

This study aimed to determine the effect of the drying method (freeze-drying, air-drying), storage period (12 months), and storage conditions (2-4 °C, 18-22 °C) applied to two legume species: green beans and green peas. The raw and dried materials were determined for selected physical parameters typical of dried vegetables, contents of bioactive components (vitamin C and E, total chlorophyll, total carotenoids, ß-carotene, and total polyphenols), antioxidative activity against the DPPH radical, and sensory attributes (overall quality and profiles of color, texture, and palatability). Green beans had a significantly higher content of bioactive components compared to peas. Freeze-drying and cold storage conditions facilitated better retention of these compounds, i.e., by 9-39% and 3-11%, respectively. After 12 months of storage, higher retention of bioactive components, except for total chlorophyll, was determined in peas regardless of the drying method, i.e., by 38-75% in the freeze-dried product and 30-77% in the air-dried product, compared to the raw material.

Influence of low-cost Thai leucoxene minerals on the growth, bioactive compounds, and antibacterial activities of Chrysanthemum indium L. cuttings in in vitro culture.

The effects of low-cost Thai leucoxene mineral (LM) at different concentrations (10, 20, 30, 40, 50, and 60 mg/L) on the growth and antibacterial properties of Chrysanthemum indium L. cuttings under in vitro were evaluated. The primary chemical composition of LM was approximately 86% titanium dioxide (TiO2), as determined by dispersive X-ray spectroscopy. The crystalline structure, shape, and size were investigated by X-ray diffraction and scanning electron microscopy. LM at 40 and 50 mg/L significantly increased plant height, leaf number, node number, and fresh and dry weight. These growth-promoting properties were accompanied by improved chlorophyll and carotenoid contents and antioxidant enzyme activities and reduced malondialdehyde levels. Additionally, LM treatment at 40 and 50 mg/L had positive effects on antibacterial activity, as indicated by the lowest minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) values. The high levels of phenolic compounds in the plants contributed to the MIC and MBC values. In conclusion, these findings provide evidence for the effectiveness of LM in enhancing the growth of Chrysanthemum plants in in vitro culture and improving their antibacterial abilities.

Photosensitizer-thioglycosides enhance photodynamic therapy by augmenting cellular uptake.

Photodynamic therapy (PDT) uses photosensitizing agents along with light to ablate tissue, including cancers. Such light-driven localized delivery of free-radical oxygen to kill target tissue depends on photosensitizer cell penetration efficacy. While the attachment of monosaccharides and disaccharides to photosensitizers has been shown to potentially provide improved photosensitizer delivery, the range of glycan entities tested thus far is limited. We sought to expand such knowledge by coupling N-acetylglucosamine (GlcNAc) to pyropheophorbides as thioglycosides, and then testing photosensitizer efficacy. To this end, GlcNAc was conjugated to both pyropheophorbide-a and methyl pyropheophorbide-a. Among the entities tested, the conjugation of N-acetylglucosamine to methyl pyropheophorbide-a ('PSe') as thioglycoside enhanced cell uptake both in the presence and absence of human serum proteins, relative to other compounds tested. The enhanced PSe penetrance into cells resulted in higher cell death upon illumination with 665 nm light. While acting as a potent photosensitizer, PSe did not affect cellular carbohydrate profiles. Overall, the study presents a new pyropheophorbide glycoconjugate with strong in vitro PDT efficacy.

Novel Ag3PO4/ZnWO4-modified graphite felt electrode for photoelectrocatalytic removal of harmful algae: Performance and mechanism.

A novel Ag3PO4/ZnWO4-modified graphite felt electrode (AZW@GF) was prepared by drop coating method and applied to photoelectrocatalytic removal of harmful algae. Results showed that approximately 99.21% of chlorophyll a and 91.57% of Microcystin-LR (MCLR) were degraded by the AZW@GF-Pt photoelectrocatalytic system under the optimal operating conditions with a rate constant of 0.02617 min-1 and 0.01416 min-1, respectively. The calculated synergistic coefficient of photoelectrocatalytic algal removal and MC-LR degradation by the AZW@GF-Pt system was both larger than 1.9. In addition, the experiments of quenching experiments and electron spin resonance (ESR) revealed that the photoelectrocatalytic reaction mainly generated •OH and •O2- for algal removal and MC-LR degradation. Furthermore, the potential pathway for photoelectrocatalytic degradation of MC-LR was proposed. Finally, the photoelectrocatalytic cycle algae removal experiments were carried out on AZW@GF electrode, which was found to maintain the algae removal efficiency at about 91% after three cycles of use, indicating that the photoelectrocatalysis of AZW@GF electrode is an effective emergency algae removal technology.

Feeling the Strain: Quantifying Ligand Deformation in Photosynthesis.

Structural distortion of protein-bound ligands can play a critical role in enzyme function by tuning the electronic and chemical properties of the ligand molecule. However, quantifying these effects is difficult due to the limited resolution of protein structures and the difficulty of generating accurate structural restraints for nonprotein ligands. Here, we seek to quantify these effects through a statistical analysis of ligand distortion in chlorophyll proteins (CP), where ring deformation is thought to play a role in energy and electron transfer. To assess the accuracy of ring-deformation estimates from available structural data, we take advantage of the C2 symmetry of photosystem II (PSII), comparing ring-deformation estimates for equivalent sites both within and between 113 distinct X-ray and cryogenic electron microscopy PSII structures. Significantly, we find that several deformation modes exhibit considerable variability in predictions, even for equivalent monomers, down to a 2 Å resolution, to an extent that probably prevents their utilization in optical calculations. We further find that refinement restraints play a critical role in determining deformation values to resolution as low as 2 Å. However, for those modes that are well-resolved in the structural data, ring deformation in PSII is strongly conserved across all species tested from cyanobacteria to algae. These results highlight both the opportunities and limitations inherent in structure-based analyses of the bioenergetic and optical properties of CPs and other protein-ligand complexes.

Access to the Antenna System of Photosystem I via Single-Molecule Excitation-Emission Spectroscopy.

In the development of single-molecule spectroscopy, the simultaneous detection of the excitation and emission spectra has been limited. The fluorescence excitation spectrum based on background-free signals is compatible with the fluorescence-emission-based detection of single molecules and can provide insight into the variations in the input energy of the different terminal emitters. Here, we implement single-molecule excitation-emission spectroscopy (SMEES) for photosystem I (PSI) via a cryogenic optical microscope. To this end, we extended our line-focus-based excitation-spectral microscope system to the cryogenic temperature-compatible version. PSI is one of the two photosystems embedded in the thylakoid membrane in oxygen-free photosynthetic organisms. PSI plays an essential role in electron transfer in the photosynthesis reaction. PSIs of many organisms contain a few red-shifted chlorophylls (Chls) with much lower excitation energies than ordinary antenna Chls. The fluorescence emission spectrum originates primarily from the red-shifted Chls, whereas the excitation spectrum is sensitive to the antenna Chls that are upstream of red-shifted Chls. Using SMEES, we obtained the inclining two-dimensional excitation-emission matrix (2D-EEM) of PSI particles isolated from a cyanobacterium, Thermosynechococcus vestitus (equivalent to elongatus), at about 80 K. Interestingly, by decomposing the inclining 2D-EEMs within time course observation, we found prominent variations in the excitation spectra of the red-shifted Chl pools with different emission wavelengths, strongly indicating the variable excitation energy transfer (EET) pathway from the antenna to the terminal emitting pools. SMEES helps us to directly gain information about the antenna system, which is fundamental to depicting the EET within pigment-protein complexes.

Site-Directed Mutagenesis of the Chlorophyll-Binding Sites Modulates Excited-State Lifetime and Chlorophyll-Xanthophyll Energy Transfer in the Monomeric Light-Harvesting Complex CP29.

We combine site-directed mutagenesis with picosecond time-resolved fluorescence and femtosecond transient absorption (TA) spectroscopies to identify excitation energy transfer (EET) processes between chlorophylls (Chls) and xanthophylls (Xant) in the minor antenna complex CP29 assembled inside nanodiscs, which result in quenching. When compared to WT CP29, a longer lifetime was observed in the A2 mutant, missing Chl a612, which closely interacts with Xant Lutein in site L1. Conversely, a shorter lifetime was obtained in the A5 mutant, in which the interaction between Chl a603 and Chl a609 is strengthened, shifting absorption to lower energy and enhancing Chl-Xant EET. Global analysis of TA data indicated that EET from Chl a Qy to a Car dark state S* is active in both the A2 and A5 mutants and that their rate constants are modulated by mutations. Our study provides experimental evidence that multiple Chl-Xant interactions are involved in the quenching activity of CP29.

Two-Dimensional Electronic Spectroscopy Characterization of Fucoxanthin-Chlorophyll Protein Reveals Excitonic Carotenoid-Chlorophyll Interactions.

Fucoxanthin Chlorophyll Protein (FCP) is a Light Harvesting Complex found in diatoms and brown algae. It is particularly interesting for its efficiency in capturing the blue-green part of the light spectrum due to the presence of specific chromophores (fucoxanthin, chlorophyll a, and chlorophyll c). Recently, the crystallographic structure of FCP was solved, revealing the 3D arrangement of the pigments in the protein scaffold. While this information is helpful for interpreting the spectroscopic features of FCP, it has also raised new questions about the potential interactions between fucoxanthin and chlorophyll c. These interactions were suggested by their spatial closeness but have never been experimentally observed. To investigate this possible interaction mechanism, in this work, two-dimensional electronic spectroscopy (2DES) has been applied to study the ultrafast relaxation dynamics of FCP. The experiments captured an instantaneous delocalization of the excitation among fucoxanthin and chlorophyll c, suggesting the presence of a non-negligible coupling between the chromophores.

Electric Field Susceptibility of Chlorophyll c Leads to Unexpected Excitation Dynamics in the Major Light-Harvesting Complex of Diatoms.

Diatoms are one of the most abundant photosynthetic organisms on earth and contribute largely to atmospheric oxygen production. They contain fucoxanthin and chlorophyll-a/c binding proteins (FCPs) as light-harvesting complexes with a remarkable adaptation to the fluctuating light on ocean surfaces. To understand the basis of the photosynthetic process in diatoms, the excitation energy funneling within FCPs must be probed. A state-of-the-art multiscale analysis within a quantum mechanics/molecular mechanics framework has been employed. To this end, the chlorophyll (Chl) excitation energies within the FCP complex from the diatom Phaeodactylum tricornutum have been determined. The Chl-c excitation energies were found to be 5-fold more susceptible to electric fields than those of Chl-a pigments and thus are significantly lower in FCP than in organic solvents. This finding challenges the general belief that the excitation energy of Chl-c is always higher than that of Chl-a in FCP proteins and reveals that Chl-c molecules are much more sensitive to electric fields within protein scaffolds than in Chl-a pigments. The analysis of the linear absorption spectrum and the two-dimensional electronic spectra of the FCP complex strongly supports these findings and allows us to study the excitation transfer within the FCP complex.

A critical review on the stability of natural food pigments and stabilization techniques.

This comprehensive review article delves into the complex world of natural edible pigments, with a primary focus on their stability and the factors that influence them. The study primarily explores four classes of pigments: anthocyanins, betalains, chlorophylls and carotenoids by investigating both their intrinsic and extrinsic stability factors. The review examines factors affecting the stability of anthocyanins which act as intrinsic factors like their structure, intermolecular and intramolecular interactions, copigmentation, and self-association as well as extrinsic factors such as temperature, light exposure, metal ions, and enzymatic activities. The scrutiny extends to betalains which are nitrogen-based pigments, and delves into intrinsic factors like chemical composition and glycosylation, as well as extrinsic factors like temperature, light exposure, and oxygen levels affecting for their stability. Carotenoids are analyzed concerning their intrinsic and extrinsic stability factors. The article emphasizes the role of chemical structure, isomerization, and copigmentation as intrinsic factors and discusses how light, temperature, oxygen, and moisture levels influence carotenoid stability. The impacts of food processing methods on carotenoid preservation are explored by offering guidance on maximizing retention and nutritional value. Chlorophyll is examined for its sensitivity to external factors like light, temperature, oxygen exposure, pH, metal ions, enzymatic actions, and the food matrix composition. In conclusion, this review article provides a comprehensive exploration of the stability of natural edible pigments, highlighting the intricate interplay of intrinsic and extrinsic factors. In addition, it is important to note that all the references cited in this review article are within the past five years, ensuring the most up-to-date and relevant sources have been considered in the analysis.

The Structure, Functions and Potential Medicinal Effects of Chlorophylls Derived from Microalgae.

Microalgae are considered to be natural producers of bioactive pigments, with the production of pigments from microalgae being a sustainable and economical strategy that promises to alleviate growing demand. Chlorophyll, as the main pigment of photosynthesis, has been widely studied, but its medicinal applications as an antioxidant, antibacterial, and antitumor reagent are still poorly understood. Chlorophyll is the most important pigment in plants and algae, which not only provides food for organisms throughout the biosphere, but also plays an important role in a variety of human and man-made applications. The biological activity of chlorophyll is closely related to its chemical structure; its specific structure offers the possibility for its medicinal applications. This paper reviews the structural and functional roles of microalgal chlorophylls, commonly used extraction methods, and recent advances in medicine, to provide a theoretical basis for the standardization and commercial production and application of chlorophylls.

Identification of Residues Potentially Involved in Optical Shifts in the Water-Soluble Chlorophyll a-Binding Protein through Molecular Dynamics Simulations.

Reversible light and thermally induced spectral shifts are universally observed in a wide variety of pigment-protein complexes at temperatures ranging from cryogenic to ambient. In this paper, we employed large-scale molecular dynamics (MD) simulations of a prototypical pigment-protein complex to better understand these shifts at a molecular scale. Although multiple mechanisms have been proposed over the years, no verification of these proposals via MD simulations has thus far been performed; our work represents the first step in this direction. From simulations of the water-soluble chlorophyll-binding protein complex, we determined that rearrangements of long hydrogen bonds were unlikely to be the origin of the multiwell landscape features necessary to explain observed spectral shifts. We also assessed small motions of amino acid residues and identified side chain rotations of some of these residues as likely candidates for the origin of relevant multiwell landscape features. The protein free-energy landscapes associated with side chain rotations feature energy barriers of around 1100-1600 cm-1, in agreement with optical spectroscopy results, with the most promising residue type associated with experimental signatures being serine, which possesses a symmetric triple-well landscape and moment of inertia of a relevant magnitude.

Photosensitizing effects and physicochemical properties of chlorophyll a derivatives with hydrophilic oligoethylene glycol fragments at the macrocycle periphery.

In this work, screening studies of the cytotoxic effect of chlorins with fragments of di-, tri-, and pentaethylene glycol at the macrocycle periphery in relation to HeLa, A549, and HT29 cells were performed. It is shown that, despite different hydrophobicity, all the compounds studied have a comparable photodynamic effect. The conjugate of chlorin e6 with pentaethylene glycol, which has the lowest tendency to association among the studied compounds with tropism for low density lipoproteins and the best characteristics of the formation of molecular complexes with Tween 80, has a significant difference in dark and photoinduced toxicity (ratio IC50(dark)/IC50(photo) approximately 2 orders of magnitude for all cell lines), which allows to hope for a sufficiently large "therapeutic window". A study of the interaction of this compound with HeLa cells shows that the substance penetrates the cell and, after red light irradiation induces ROS appearance inside the cell, associated, apparently, with the photogeneration of singlet oxygen. These data indicate that photoinduced toxic effects are caused by damage to intracellular structures as a result of oxidative stress. Programmed type of cell death characterized with caspase-3 induction is prevailing. So, the conjugate of chlorin e6 with pentaethylene glycol is a promising antitumor PS that can be successfully solubilized with Tween 80, which makes it suitable for further in vivo studies.

Modulating spectral response of raw photosynthetic pigments via ternary cadmium chalcogenide quantum dots: simultaneous enhancement at green spectrum and inhibition at UV region.

Photosynthesis relies on the absorption of sunlight by photosynthetic pigments (PPs) such as chlorophylls and carotenoids. While these pigments are outstanding at harvesting light, their natural structure restricts their ability to harvest light at specific wavelengths. In this study, Oleic acid-capped CdSeS and CdTeS ternary quantum dots (QDs) were synthesized using a novel two-phase synthesis method. Then, these QDs were used to interact with raw PPs, a mixture of chlorophylls and carotenoids isolated from spinach. Our findings revealed the following: (1) Interacting QDs with raw PPs effectively inhibited the chlorophyll fluorescence of the pigments upon excitation in UV light region (250-400 nm) without causing any damage to their structure. (2) By forming an interaction with QDs, the chlorophyll fluorescence of raw PPs could be induced through excitation with green-light spectrum. (3) The composition of the QDs played a fundamental role in their interaction with PPs. Our study demonstrated that the photophysical properties of isolated PPs could be modified by using cadmium-based QDs by preserving the structure of the pigments themselves.

Exciton interactions of chlorophyll tetramer in water-soluble chlorophyll-binding protein BoWSCP.

The exciton interaction of four chlorophyll a (Chl a) molecules in a symmetrical tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP was analyzed in the pH range of 3-11. Exciton splitting ΔE = 232 ± 2 cm-1 of the Qy band of Chl a into two subcomponents with relative intensities of 78.1 ± 0.7 % and 21.9 ± 0.7 % was determined by a joint decomposition of the absorption and circular dichroism spectra into Gaussian functions. The exciton coupling parameters were calculated based on the BoWSCP atomic structure in three approximations: the point dipole model, the distributed atomic monopoles, and direct ab initio calculations in the TDDFT/PCM approximation. The Coulomb interactions of monomers were calculated within the continuum model using three values of optical permittivity. The models based on the properties of free Chl a in solution suffer from significant errors both in estimating the absolute value of the exciton interaction and in the relative intensity of exciton transitions. Calculations within the TDDFT/PCM approximation reproduce the experimentally determined parameters of the exciton splitting and the relative intensities of the exciton bands. The following factors of pigment-protein and pigment-pigment interactions were examined: deviation of the macrocycle geometry from the planar conformation of free Chl; the formation of hydrogen bonds between the macrocycle and water molecules; the overlap of wave functions of monomers at close distances. The most significant factor is the geometrical deformation of the porphyrin macrocycle, which leads to an increase in the dipole moment of Chl monomer from 5.5 to 6.9 D and to a rotation of the dipole moment by 15° towards the cyclopentane ring. The contributions of resonant charge-transfer states to the wave functions of the Chl dimer were determined and the transition dipole moments of the symmetric and antisymmetric charge-transfer states were estimated.