Ksenofontova, Ksenia V.

Lukanov M.M., Ksenofontova K.V., Kerner A.A., Ksenofontov A.A.

Ksenofontova K.V., Ksenofontov A.A., Kerner A.A., Molchanov E.E., Gessel T.V., Galembikova A.R., Krestova A.N., Borisovskaya E.P., Khodov I.A., Boichuk S.V.

Molchanov E.E., Gavrilova A.N., Shushkova A.S., Soshnikova V.A., Ksenofontova K.V., Maizlish V.E., Dmitriev M.V., Abramov I.G., Marfin Y.S.

Ksenofontova K.V., Shagurin A.Y., Molchanov E.E., Ksenofontov A.A., Sbytov D.A., Kalyamanova Y.E., Danilova E.A., Marfin Y.S.

AbstractTwo π‐extended derivatives of boron‐dipyrromethene (BODIPY) – unsymmetrical benzo[b]‐fused BODIPY 1 and symmetrical naptho[b]‐fused BODIPY 2 – were synthesized. Spectroscopic and photophysical properties of the synthesized fluorescent dyes were investigated in various organic media. Both BODIPY 1 and BODIPY 2 distinguished by bathochromically shifted absorption and emission bands compared to their non‐fused derivatives, while possessing green (526–543 nm) and red (664–708 nm) absorbance and fluorescence, respectively. Spectral characteristics of the investigated fluorescent dyes were found to be weakly depended on solvent polarizability in case of BODIPY 1 and greatly influenced by both solvent polarizability and dipolarity in case of BODIPY 2. Quantum chemical calculations were used to clarify the relationships between geometry/electronic structure and spectral properties/solvatochromic behavior of BODIPY 1 and BODIPY 2.

Antina E.V., Gryaznov D.D., Molchanov E.E., Kalinkina V.A., Kalyagin A.A., Kokurina T.V., Antina L.A., Ksenofontova K.V., Marfin Y.S., Usoltsev S.D.

Pogonin A.E., Kurochkin I.Y., Malyasova A.S., Ksenofontova K.V., Koifman O.I.

Vashurin A.S., Boborov A.V., Botnar A.A., Bychkova A.N., Gornukhina O.V., Grechin O.V., Erzunov D.A., Kovanova M.A., Ksenofontova K.V., Kuznetsov V.V., Lefedova O.V., Latypova A.R., Litova N.A., Marfin Y.S., Pukhovskaya S.G., et. al.

The review presents a generalization of research on the chemistry of solutions and materials based on linear and cyclic polypyrrole compounds carried out at the Department of Inorganic Chemistry of the Ivanovo State University of Chemistry and Technology. The review focuses on key areas related to synthetic approaches to the preparation of boron complexes with pyrrole derivatives, as well as complexes of a wide range of metals of the periodic system with substituted derivatives of the phthalocyanine ligand. Spectroscopic, luminescent, acid-base properties of synthesized compounds and their practical application in sensor systems are considered separately. In addition, the possibilities of obtaining hybrid and functional materials, including derivatives of borondipyrrins and tetrapyrrole macroheterocyclic compounds, which have increased catalytic and biological activity in liquid-phase processes are shown. For citation: Vashurin A.S., Bobrov A.V., Botnar A.A., Bychkova A.N., Gornukhina O.V., Grechin O.V., Erzunov D.A., Kovanova M.A., Ksenofontova K.V., Kuznetsov V.V., Lefedova O.V., Latypova A.R., Litova N.A., Marfin Yu.S., Pukhovskaya S.G., Tarasyuk I.A., Tikhomirova T.V., Rumyantsev E.V., Usoltsev S.D., Filippov D.V. Chemistry of liquid systems and functional materials based on coordination compounds of linear and cyclic polypyrroles. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 7. P. 76-97. DOI: 10.6060/ivkkt.20236607. 6840j.

Ksenofontova K.V., Kerner A.A., Ksenofontov A.A., Shagurin A.Y., Bocharov P.S., Lukanov M.M., Kayumov A.R., Zhuravleva D.E., Iskhakova Z.I., Molchanov E.E., Merkushev D.A., Khodov I.A., Marfin Y.S.

A boron-dipyrromethene (BODIPY) derivative reactive towards amino groups of proteins (NHS-Ph-BODIPY) was synthesized. Spectroscopic and photophysical properties of amine-reactive NHS-Ph-BODIPY and its non-reactive precursor (COOH-Ph-BODIPY) in a number of organic solvents were investigated. Both fluorescent dyes were characterized by green absorption (521–532 nm) and fluorescence (538–552 nm) and medium molar absorption coefficients (46,500–118,500 M−1·cm−1) and fluorescence quantum yields (0.32 – 0.73). Solvent polarizability and dipolarity were found to play a crucial role in solvent effects on COOH-Ph-BODIPY and NHS-Ph-BODIPY absorption and emission bands maxima. Quantum-chemical calculations were used to show why solvent polarizability and dipolarity are important as well as to understand how the nature of the substituent affects spectroscopic properties of the fluorescent dyes. NHS-Ph-BODIPY was used for fluorescent labeling of a number of proteins. Conjugation of NHS-Ph-BODIPY with bovine serum albumin (BSA) resulted in bathochromic shifts of absorption and emission bands and noticeable fluorescence quenching (about 1.5 times). It was demonstrated that the sensitivity of BSA detection with NHS-Ph-BODIPY was up to eight times higher than with Coomassie brilliant blue while the sensitivity of PII-like protein PotN (PotN) detection with NHS-Ph-BODIPY and Coomassie brilliant blue was almost the same. On the basis of the molecular docking results, the most probable binding sites of NHS-Ph-BODIPY in BSA and PotN and the corresponding binding free energies were estimated.

Ksenofontov A.A., Bocharov P.S., Ksenofontova K.V., Antina E.V.

• We have developed new BP1 fluorescent probe for selective detection of HSA in urine. • BP1 – SA complexes are formed predominantly due to the specific interactions. • BP1 – SA complex formation is accompanied by a strong BP1 fluorescence quenching. • BP1 fluorescence quenching is realized through FRET. Interaction of 4,4-difluoro-1,3,7,8-tetramethyl-2,6-disulfo-4-bora-3a,4a-diaza- s -indacene sodium salt (BODIPY, BP1 ) with bovine serum albumin (BSA) and human serum albumin (HSA) was investigated using spectral methods and molecular docking. It was shown that BP1 forms stable supramolecular complexes with BSA and HSA predominantly due to the specific interactions. Supramolecular complex formation was accompanied by strong fluorescence quenching of BP1 as a result of FRET. This effect could be used for the qualitative and quantitative detection of HSA in model physiological fluids. The detection limit of BSA and HSA were 0.26 and 0.05 mg·mL −1 , respectively. The selectivity of BP1 fluorescence response to the co-presence of BSA and HSA in solution was demonstrated. The BP1 fluorescent probe was successfully used for the qualitative and quantitative detection of HSA in human urine samples. The obtained results indicated the capability of using BP1 -based fluorescent sensors in clinical medicine for early detection of microalbuminuria and concomitant diseases.

Ksenofontov A.A., Lukanov M.M., Bichan N.G., Khodov I.A., Kudryakova N.O., Ksenofontova K.V., Antina E.V.

In this paper, we continue the study of non-covalent supramolecular systems based on zinc bis(dipyrromethenate)s ([Zn 2 L 2 ]) with fullerene C 60 and present the results of study of [Zn 2 L 2 ]s periphery methylation degree effect on their supramolecular complexation with C 60 . The structural organization and spectral properties of supramolecular systems based on [Zn 2 L 2 ]s and C 60 were studied by means of UV/vis, fluorescence, time-resolved fluorescence, elemental analysis , FT-IR, PXRD , 1 H NMR, DOSY spectroscopy, and computer modeling. The revealed features and the photoelectrochemical characteristics (photocurrent density, IPCE) obtained by the amperometric method give evidence of potential usage of [Zn 2 L 2 ]s-C 60 supramolecular complexes with 1:4 stoichiometry as optoelectronics and photovoltaic devices components. • The [Zn 2 L 2 ]s were used as a molecular electron donor platform to create new non-covalent supramolecular systems with C 60 . • The supramolecular organization and spectral properties of [Zn 2 L 2 (C 60 ) 4 ]s supramolecular systems with C 60 were studied. • The photoinduced electron transfer is characteristic of [Zn 2 L 2 (C 60 ) 4 ]s. • The photoelectrochemical characteristics of [Zn 2 L 2 (C 60 ) 4 ]s were obtained.

Rumyantsev E.V., Khodov I.A., Ksenofontov A.A., Ksenofontova K.V.

The present work describes direct one-pot synthesis of the two novel amino acids – boron-dipyrromethene (BODIPY) conjugates with histidine and tyrosine residues bound to fluorophore via amino group. The synthesized compounds were fully characterized by means of 1H and 11B nuclear magnetic resonance spectroscopy, infrared spectroscopy, time-of-flight mass spectrometry with matrix-activated laser desorption / ionization. All the data are in accordance with the proposed structures. The amino acids – BODIPY conjugates under study were investigated by means of absorbance and fluorescence spectroscopy. Absorption and emission spectra of the compounds in dimethyl sulfoxide (DMSO) – buffer solution (BS) mixture (1:1) were obtained. Moreover, a number of photophysical characteristics of the conjugates, namely: relative fluorescence quantum yield, molar extinction coefficient, relative fluorescence lifetime, radiative and non-radiative rate constants were calulated. 3D fluorescence spectra of the compounds in DMSO – BS mixture (1:1) were obtained. Absorption and emission titration of the compounds was carried out. The results of the titration allowed us to confirm additionally a stoichiometric composition of the conjugates. Quantum chemical analysis of structural and spectral properties of the compounds in a ground state was carried out. The results of quantum chemical calculations gave an insight to a nature of the BODIPY – amino acid interactions in the conjugates. Besides, the synthesized amino acids – BODIPY conjugates are found to be highly soluble in polar solvents. Thus, a range of unique properties of the objects of the present research enables us to use them for visualization of bioactive macromolecules as well as biochemical processes in living cells.

Ksenofontov A.A., Stupikova S.A., Bocharov P.S., Lukanov M.M., Ksenofontova K.V., Khodov I.A., Antina E.V.

In this paper, the sensitivity of new fluorescent sensors based on zinc(II) bis(dipyrromethenate)s ([Zn2L2]s) to the furosemide presence in organic media is described. It has been shown that the instantaneous spectral response of [Zn2L2]s to the furosemide presence is based on the fluorescence quenching effect. Multi-approach analysis (UV–vis and fluorescent titrations, PXRD, FTIR, 1H NMR, DOSY, and DFT calculations) has shown that the [Zn2L2]s fluorescence quenching is associated with the formation of stable [Zn2L2Fur]s supramolecular systems, capable of photoinduced electron transfer. The furosemide detection limit with using [Zn2L2]s was 65–78 μg L−1. The proposed sensors can be used for the forensic, clinical and sports medicine needs.

Ksenofontova K.V., Ksenofontov A.A., Khodov I.A., Rumyantsev E.V.

Three BODIPY-based conjugates with lysine, methionine, and tryptophan bound via amino group were synthesized and characterized. Spectral properties of the compounds were studied and a number of photophysical characteristics were obtained. Bioconjugates investigated are water soluble, which makes them promising markers for various bioobjects.

Marfin Y.S., Shipalova M.V., Kurzin V.O., Ksenofontova K.V., Solomonov A.V., Rumyantsev E.V.

Two boron-dipyrrin (BODIPY) based dyes with dimethylaminophenyl and carboxyphenyl substituents in 8-position of dipyrrin ligand have been synthesized and characterized. Photophysical and spectral properties of the obtained compounds have been investigated in water-ethanol mixture and water-cyclohexane system with variation of pH values. The equilibria constants of the compounds were identified by classical methods of acid-base titration. BODIPY bearing dimethylaminophenyl and carboxyphenyl subunits show deprotonation/protonation dependent fluorescence off/on-switching. The change of the emission could be mechanistically explained by a PET (photoinduced electron transfer) from the 8-substituent to the fluorophore. The present study demonstrates that BODIPY-based fluorescent sensors can be used to measure the pH in the range of 2–13 extending the scope of BODIPY dyes available as pH-indicators. Investigated compounds demonstrate weak dye-dye interaction allowing their cooperative usage as indicators.

Lytkin A.I., Chernikov V.V., Krutova O.N., Damrina K.V., Skvortsov I.A.

The enthalpies of dissolution of crystalline L-methionine in water and aqueous solutions of potasium hydroxide at 298.15 K are measured by means of direct calorimetry. The standard enthalpies of formation are calculated for L-methionine and products of its dissociation in aqueous solution.

Yang X., Li T., Chen X., Zhang H., Liu C., Tao C., Nie H.

Lv X., Huang W., Jiang N., Bao Y., Qu Y., Zou W., Luo Y., Wang L., Shang C.

Segovia-Pérez R., Ibarra-Rodríguez M., Muñoz-Flores B.M., Jiménez-Pérez V.M.

Maneesha M., Preethi P.C., Harisankar A., Sreeja T.G., Kumar R.V., Veedu S.T., Raghunandan R.

Tian L., Zhang Z., Zhang L., Liu H., Yang D.

Lukanov M.M., Ksenofontova K.V., Kerner A.A., Ksenofontov A.A.

Shelkovnikov V.V., Doroshenko D.D., Kargapolova I.Y., Kozlakov P.A., Shestakov N.A., Sotnikova Y.S.

Objective: Studies of the reaction ability of fluorescent dyes to produce labelled proteins and amino acids are important for bioengineering and biomedicine, particularly for cell visualization by bioimaging and the study of the structure of labelled proteins by biophysical methods. Pyrylium dyes can interact with the amino groups of proteins to form luminescent products, which allows them to be used in the field of proteomics. It is interesting to study the pyrylium conjugates that contain both a polyfluorinated fragment responsible for increased lipophilicity of the protein conjugates and a pyrazoline fragment responsible for anticancer activity. Methods: The pyrylium dyes that contain the pyrazoline fragment and dialkylamino substituents (piperidino-, dibutylamino-, and 4-hydroxypiperidino-) in the donor part of the polyfluorinated aromatic ring have been synthesized by the Knoevenagel condensation reaction. The reaction of pyrylium dyes with compounds containing the primary amino group has been performed to obtain the pyridinium dyes by the ANRORC (Addition of Nucleophiles, Ring Opening and Ring Closure) Mechanism. Results and Discussion: The ability of the pyrуlium dyes to react with bovine serum albumin (BSA) and amino acids, such as Lys, Arg, Cys, and Phe to form pyridinium luminophore has been demonstrated. The spectral-luminescent properties of the resulting luminophores have been investigated. The product of the reaction of the pyrуlium dye (Е)-2,6-dimethyl-4-(4-{3-phenyl-5-[2,3,5,6-tetrafluorо-4-(piperidine-1-yl)phenyl]-4,5-dihydro-1Н-pуrazol-1-yl}-styryl)pyrylium tetrafluoroborate with Lys has been isolated, and its structure has been confirmed by NMR spectroscopy. The binding site of the pyrylium dyes with BSA, i.e., the ε-amino group of Lys, has been determined. Together with the pyridinium luminophores, hydrolysis products are formed in aqueous solutions, which are not bound to the protein and absorb in the short wavelength region. The amount of the pyrylium dye bound to BSA has been calculated to be 2 : 1.The synthesized pyrylium dyes react with BSA in the phosphate buffer-methanol mixture (pH 7.4) 3–4 orders of magnitude faster than the well-known julolidine dye Py-1. The relative reaction rates of (Е)-2,6-dimethyl-4-(4-{3-phenyl-5-[2,3,5,6-tetrafluorо-4-(4-hydroxypiperidine-1-yl)phenyl]-4,5-dihydro-1Н-pуrazol-1-yl}styryl) pyrуlium tetrafluoroborate with amino acids have been evaluated to be as follows: Lys > Cys >> Phe ≥ Arg. Conclusions: The synthesized polyfluoro pyrylium-pyrazoline dyes have the application perspective in the field of bioimaging, proteomics, and biomedicine due to the high conjugation rate and efficiency with BSA and amino acids.

Ksenofontov A.A., Berezin M.B., Bocharov P.S., Khodov I.A., Miloshevskaya O.V., Antina E.V.

The search for fluorophores with intense absorption and emission in the red region of the spectrum is an important task, as such compounds can be used in fluorescence imaging, providing high image resolution due to the deep penetration of low energy photons into tissues. In this paper, we present the results of the synthesis and photophysical characterization of a novel ms-benzimidazole-4,4′,5,5′-tetramethyldipyrromethene bis(difluoroborate) (BOIMPY) compound, which exhibits intensive absorption and emission in the long-wavelength region while maintaining high fluorescence quantum yields (up to 60%). Using DFT analysis, we investigated the geometry of BOIMPY in both ground and excited states and described the influence of the molecular structure on its practically relevant photophysical properties.

Ksenofontova K.V., Ksenofontov A.A., Kerner A.A., Molchanov E.E., Gessel T.V., Galembikova A.R., Krestova A.N., Borisovskaya E.P., Khodov I.A., Boichuk S.V.

Guan Y., Shuai X., Ruan X., Wang Y., Wei Y.

Molchanov E.E., Gavrilova A.N., Shushkova A.S., Soshnikova V.A., Ksenofontova K.V., Maizlish V.E., Dmitriev M.V., Abramov I.G., Marfin Y.S.

Kolokytha C., Sinani A., Manouras T., Angelakos E., Argitis P., Lathiotakis N.N., Riziotis C., Tzeli D.

Ding B., Sang R., Li X., Fan J., Tian Y., Ma Y., Xie C., Xu J., Feng Y.

Anjana E., Gupta I., Mishra A.K.

The present work focuses on the photophysical behavior of meso-N-butylcarbazole-substituted BODIPY (CBZ-BDP) in different organized media towards exploring the possible use of the dye as a molecular sensor and imaging agent. The molecule shows an appreciable change in absorption and emission spectra at 75% water–acetonitrile mixture compared to pure acetonitrile. In water–acetonitrile mixture, it displays aggregate-induced emission (AIE) bands. New emission peaks are observed at 560 nm and 630 nm, corresponding to LE (locally excited) and ICT (intramolecular charge transfer) states of CBZ-BDP aggregates. The fluorescence anisotropy studies of CBZ-BDP in glycerol medium show its better sensitivity towards the microenvironment. CBZ-BDP was used to probe various microheterogeneous systems like bile salts, pluronics, and lipid bilayer systems in aqueous medium. The dye displays sensitive variation in emission intensity and fluorescence anisotropy in sodium cholate (NaC) bile salt in aqueous medium as a function of the bile salt concentration. The molecule detects the temperature-induced phase transitions in pluronic P123 and F127, as well as 1,2-dimyristoylphosphatidylcholine (DMPC) and 1,2-dipalmitoylphosphatidylcholine (DPPC) lipid bilayer systems in aqueous medium. These studies strongly suggest that CBZ-BDP can be used as an efficient fluorescent probe in sensing the micro-environmental changes in bile salts, pluronics, and lipid bilayers in aqueous medium. The imaging studies of CBZ-BDP-embedded Giant Unilamellar Vesicles (GUVs) were carried out. The molecule stains the lipid bilayers and displays bright-green fluorescent images, suggesting its potential in lipid bilayer imaging.

Zhao D., Chen H., Yang K., Wang H., Guo X., Ge Y., Dong X., Sang S.

Liu X., Lin Y., Hua F., Fu Y.

Mercury ion (Hg

Guseva G.B., Lapshina E.N., Antina E.V., Eremeeva Y.V., Lisovskaya S.A., Izmailov A.A., Nikitina L.E.

We conducted a comprehensive study of the influence of the molecular structure and solvent nature on the photophysical properties of the halogen-substituted meso-BODIPY ethers. The compounds were found to be stable over a wide range of pH values and exhibited intense chromophoric properties (lgε ∼ 4.60–5.02) at 497–536 nm. The halogenation at the 2,6-positions of the pyrrole rings of dyes causes a noticeable (up to 36 nm and 44 nm) red shift of the maximum of the absorption and fluorescence bands, respectively, and sharp fluorescence quenching up to φfl ∼ 2–32 %. The introduction of a bulky ester substituent into the meso-position of the dipyrromethene core increases the photostability of the dyes up to ∼ 2.7 times due to screening of the methine spacer. Moreover, the halogen-substituted BODIPYs demonstrated a high ability to generate singlet oxygen (up to ФΔ ∼50–78 %) regardless of the nature of the solvent. Among the studied dyes, the diiodo-substituted meso-BODIPY ether has an appreciable inhibitory effect on the vital activity of fungal cells. In summary, the combination of the meso-substitution and halogenation of the BODIPY core is an excellent way to enhance the affinity of dyes to biostructures and to increase the possibilities of the practical application of dyes as effective photosensitizers for antibacterial photodynamic therapy.

Ksenofontova K.V., Shagurin A.Y., Molchanov E.E., Ksenofontov A.A., Sbytov D.A., Kalyamanova Y.E., Danilova E.A., Marfin Y.S.

AbstractTwo π‐extended derivatives of boron‐dipyrromethene (BODIPY) – unsymmetrical benzo[b]‐fused BODIPY 1 and symmetrical naptho[b]‐fused BODIPY 2 – were synthesized. Spectroscopic and photophysical properties of the synthesized fluorescent dyes were investigated in various organic media. Both BODIPY 1 and BODIPY 2 distinguished by bathochromically shifted absorption and emission bands compared to their non‐fused derivatives, while possessing green (526–543 nm) and red (664–708 nm) absorbance and fluorescence, respectively. Spectral characteristics of the investigated fluorescent dyes were found to be weakly depended on solvent polarizability in case of BODIPY 1 and greatly influenced by both solvent polarizability and dipolarity in case of BODIPY 2. Quantum chemical calculations were used to clarify the relationships between geometry/electronic structure and spectral properties/solvatochromic behavior of BODIPY 1 and BODIPY 2.

Shang L., Huang C., Le Guével X.

Li Y., Jiang M., Yan M., Ye J., Li Y., Dehaen W., Yin S.

New integrated cancer therapy and diagnosis strategies, such as fluorescence imaging, photodynamic therapy, and photothermal therapy, have become a major research topic owing to their high selectivity, low toxicity, and non-invasiveness compared to traditional imaging and treatment methods. As a key factor, the development of integrated nanomaterials for treatment is also gaining momentum. Among various biomaterials, boron–dipyrrin (BODIPY) nanomaterials with near-infrared (NIR) absorption and emission capabilities stand out owing to their excellent optical properties, deep tissue penetration, high biocompatibility, and multiple functionalities. In this review, we first discuss strategies for redshifting the absorption and emission bands of BODIPY dyes, including by increasing the length and degree of molecular conjugation (via structural modification, aromatic ring fusion, and polymerization) and by regulating the aggregation of these materials through a supramolecular strategy. The applications of NIR BODIPY nanomaterials in cancer imaging and treatment are then summarized, and methods for enhancing their photosensitivity and the construction of theranostic nanoplatforms are described. Finally, the development of these promising nanomaterials and the challenges for cancer treatment applications are explored.

Boichuk S.V., Ivoilova T.V.

ABC transporters (ATP Binding Cassette (ABC) transporters) are proteins, which play a dual role in the substances transport across the membrane. On the one hand, they transport nutrients and other molecules inside the cell to supply the necessary nutrients, on the other hand, these proteins excrete some endogenous and exogenous substrates from the cell to maintain their homeostasis in the body and prevent from effects of aggressive environment. ABC transporters play a role in the pathogenesis of various metabolic disorders. In addition, a large amount of evidence has been accumulated about the participation of these proteins in oncogenesis because of their involvement into initiation, progression, invasion and metastasis of tumors, as well as development of multidrug resistance phenotype. Currently, these proteins are attractive therapeutic targets, influence on which can significantly increase the effectiveness of anticancer therapy and improve the prognosis of patients with oncological diseases, including recurrent, metastatic and inoperable forms.The review provides information on drugs that affect the functional activity of ABC transporters and the mechanisms of their action, and also presents the results of clinical trials of these inhibitors.

Mahato K.D., Das S.S., Azad C., Kumar U.

Fluorescent organic dyes are widely used in various fields, including science and technology, research and development, medicine, and drug delivery. Multitudinous attempts have been made by experimentalists to develop such fluorescent organic dyes with the desired Stokes shift property at negligible cost and time. For quickly and accurately predicting the Stokes shift property of fluorescent organic dye, we proposed eight hybrid models based on the combination of nine single machine-learning models. To fulfill the objective, we considered a dataset of 3066 fluorescent organic materials and evaluated the performance of each model using three evaluation parameters: mean absolute error (MAE), root mean squared error (RMSE), and the coefficient of determination (R2). The hybrid cascade model of Extreme Gradient Boosting Regression and Light Gradient Boosting Machine Regression (XGBR + LGBMR) performed best for Stokes shift prediction, with MAE of 13.83 nm, RMSE of 19.95 nm, and R2 of 86.18 %. The prediction performance of all the undertaken models was validated by the experimental data of four xanthene dyes (Rh-19, Rh–B, Rh-6G, and Rh-110). In this regard, the XGBR + DTR (Extreme Gradient Boosting Regression + Decision Tree Regression) model was the best performer, with errors ranging from 5 to 13 nm for four dyes. The resultant errors are much smaller than the recently reported synthesized material with an error of 30 nm. The proposed models allow for rapid and cost-effective screening of a wide range of fluorescent organic dyes, which assists the researchers in gaining prior knowledge of materials and accelerates the discovery of new materials.

Mahato K.D., Kumar U.

Applications of organic dyes, ranging from basic research to industry, are functions of their photophysical properties. Two important aspects- (1) knowledge of the photophysical properties of existing dyes long before real applications and (2) discovery of new organic dyes with desired photophysical properties for either upgradation of existing or development of new applications-are needed to be addressed. These two cases are coupled together with the common goal of estimating photophysical properties with high accuracy at the minimum cost of time and money long before the hard-core laboratory experiment. For this purpose, machine learning-based techniques are the most suitable approach. In this study, we used optimized machine-learning techniques to assess a dataset of 3066 organic dyes, which were evaluated using three evaluation parameters: Root Mean Squared Error (RMSE), Mean Absolute Error (MAE), and the coefficient of determination (R2). The Quadratic Support Vector Machine (QSVM) was the best predictive model for RMSE-16.614, MAE-10.837, and R2-0.961 for absorption wavelengths and RMSE-23.636, MAE-16.278, and R2-0.929 for emission wavelengths. These R2 values are 0.7% and 0.4% greater than the Gradient Boost Regression Tree (GBRT) model's recently reported values of 0.954 and 0.925 for absorption and emission wavelengths, respectively. Furthermore, we estimated the quantum yield and found that the Coarse Gaussian Support Vector Machine (CGSVM) outperformed all examined models. For more validation of these models, we compared the predicted results with the experimental results of selective dyes. The proposed automated approach can be used for predicting photophysical properties without much computer programming knowledge.

Belykh D.V., Pylina Y.I., Kustov A.V., Startseva O.M., Belykh E.S., Smirnova N.L., Shukhto O.V., Berezin D.B.

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.

This report is a continuation of the authors' systematic research in the field of synthesis and study of the properties of phthalocyanines and related compounds. It is devoted to the production of substituted phthalocyanines combining substituents of various nature on the periphery, as well as their derivatives. The work describes spectral, catalytic, liquid crystal properties, thermal stability and solubility in organic solvents, in order to establish the influence of the nature of peripheral substituents, as well as the presence and nature of the metal in the coordination cavity on the physicochemical properties of the synthesized compounds. The presence of aryl substituents can impart liquid crystal, catalytic and luminescent properties of phthalocyanines and their metal complexes, and make it possible to obtain sulfonic acids and their derivatives under relatively mild conditions. Sulfonic acids occupy a special place among water-soluble phthalocyanines and have already found practical application as dyes and catalysts, and are also recommended for use in other fields of science and technology. However, information about compounds of this class combining functional groups of different nature in benzene rings, such as nitro groups, nitrogen-containing heterocyclic (especially saturated heterocycles) and oxyaryl fragments, is limited. The review analyzes and summarizes data on the synthesis of bi-functionally substituted phthalocyanines and possible areas of their practical application. Special attention is paid to the consideration of methods for obtaining initial phthalonitriles.

Mahato K.D., Kumar Das S.S., Azad C., Kumar U.

Fluorescent organic dyes are extensively used in the design and discovery of new materials, photovoltaic cells, light sensors, imaging applications, medicinal chemistry, drug design, energy harvesting technologies, dye and pigment industries, and pharmaceutical industries, among other things. However, designing and synthesizing new fluorescent organic dyes with desirable properties for specific applications requires knowledge of the chemical and physical properties of previously studied molecules. It is a difficult task for experimentalists to identify the photophysical properties of the required chemical molecule at negligible time and financial cost. For this purpose, machine learning-based models are a highly demanding technique for estimating photophysical properties and may be an alternative approach to density functional theory. In this study, we used 15 single models and proposed three different hybrid models to assess a dataset of 3066 organic materials for predicting photophysical properties. The performance of these models was evaluated using three evaluation parameters: mean absolute error, root mean squared error, and the coefficient of determination (R2) on the test-size data. All the proposed hybrid models achieved the highest accuracy (R2) of 97.28%, 95.19%, and 74.01% for predicting the absorption wavelengths, emission wavelengths, and quantum yields, respectively. These resultant outcomes of the proposed hybrid models are ∼1.9%, ∼2.7%, and ∼2.4% higher than the recently reported best models’ values in the same dataset for absorption wavelengths, emission wavelengths, and quantum yields, respectively. This research promotes the quick and accurate production of new fluorescent organic dyes with desirable photophysical properties for specific applications.

Zhang W., Li G., Fan Y., Sun X., Wang B., Zhang C., Feng X., Xu W., Liu J.

Photodynamic therapy provides a promising solution for treating various cancer types. In this study, three distinct asymmetric porphyrin-cisplatin complex photosensitizers (ZnPt-P1, ZnPt-P2, and ZnPt-P3) were synthesized, each having unique side...

Wang J., Gong Q., Jiao L., Hao E.

Photodynamic therapy (PDT) is a promising therapeutic approach for anticancer and antibacterial treatment via photoinduced reactive oxygen species (ROS) generation. Photosensitizer, the most important element of PDT, plays a decisive role in PDT treatment. BODIPY dyes, as a class of well-developed fluorescent dyes, have emerged as a new class of PDT agents over the past decade owing to their versatile and remarkable properties including high molar extinction coefficients and singlet-to-triplet intersystem crossing efficiencies, tunable absorption and emission wavelengths, good ROS-generation ability, excellent photo- and chemical- stability, and easy functionalization. Several chemical approaches have been applied to tune BODIPY fluorophores into triplet photosensitizers via converting the typical fluorescence decay into a non-radiative intersystem crossing to the triplet state. However, the poor water solubility, low tumor selectivity and limited biocompatibility still hamper their biological application. Supramolecular assembly strategies have provided a promising avenue to overcome current problems of BODIPY-based molecular photosensitizers in photodynamic anticancer and antibacterial therapy. So far, numerous types of self-assembled nano-platforms have been established for construction of BODIPY-assembled supramolecular photosensitizers. This review presents the main molecular design approaches for constructing BODIPY-based photosensitizers and systematically summarizes the research progress of BODIPY-assembled supramolecular photosensitizers for PDT treatment to provide meaningful guidance for developing highly efficient BODIPY-based photosensitizers suitable for their clinical translation and application.

Zhao Q., Shan Y., Zhou H., Zhang G., Liu W.

Organic solar cells (OSCs) have received considerable attention as a promising photovoltaic technology. However, it is time-consuming and laborious to design and synthesize high-performance material molecules for OSCs by conventional trial-and-error methods. Data-driven machine learning (ML) can leverage abundant amounts of trustworthy materials data to extract meaningful information, mine potential relationships, and construct scientific models to make reasonable predictions. In this work, 2 decision tree-based models were constructed for predicting power conversion efficiency (PCE) of binary all-small-molecule OSCs based on Y6 acceptor, which both exhibited satisfactory performance. And then, 9673 potential small molecular donor molecules were automatically generated by combination of molecular scaffolds and molecular fragments for virtual screening. The donor molecules with the highest predicted PCE were further analyzed by density functional theory (DFT), including UV–Vis absorption and energy level. Quantum chemical calculations analyzed and verified that the virtual screened 15 donor molecules with high PCE. This work provides a systematic framework for the design and discovery of innovative and promising donor molecules, thereby being expected to accelerate the development of OSCs.

Zhao B., Liao L., Zhu Y., Hu Z., Wu F.

Near-infrared dyes have attracted widespread attention due to their intense absorption and emission in the near-infrared region. As an important class of heteroatom-containing BODIPY derivatives, Aza-BODIPY dyes display excellent performances, such as red-shifted spectra, high molar extinction coefficients, and good photostability. In this review, we summarize the latest advances in Aza-BODIPY dyes. The regulation strategies for photophysical properties and their applications in biomedical imaging are highlighted. Furthermore, we discuss the versatile imaging applications of Aza-BODIPY dyes in cancer diagnoses, organ injuries, and surgical navigation. The future challenges and development prospects of Aza-BODIPY dyes in biomedical field are also presented. We aim at providing meaningful inspiration for further development of functional organic dyes with excellent properties. It is believed that this review will illuminate the way for the development of new Aza-BODIPY contrast agents as well as other organic photosensitizer-based contrast agents in future clinical practices.