Кафедра биофизики

Nowadays, both cancer and infections caused by antibiotic resistant microorganisms are problems that affect the entire planet. Phototherapy (namely photodynamic therapy (PDT) and photodynamic inactivation (PDI) of microorganisms) are an alternative method for the treatment of these diseases. That requires adequate photosensitizers and, in this sense, boron-dipyrromethenes (BODIPYs) have interesting properties to act as phototherapeutic agents. In the present review, first, we describe the different strategies used to increase reactive oxygen species production. Then, we explain different architectures developed aiming to enhance the solubility of BODIPYs in biological media in order to optimize their targeting and delivery into the cells to be treated. Finally, we discuss the design of BODIPYs that are activated by specific stimuli present in the target tissues, allowing increasing the selectivity of the treatment. The data presented and discussed here show that BODIPYs are outstanding photosensitizers for the treatment of tumors and infections in the presence of oxygen and light.

The rapidly expanding field of photoswitchable biomolecules is a major frontier in scientific research and provides unparalleled opportunities for studying biological pathways and disease progression. In particular, the development of photochromic peptides has delivered both scientific tools and candidates for photopharmaceuticals. The action and function of the peptide can be remotely altered using light, allowing detection of its biological role in complex biological settings, while also enabling folding studies that provide greater understanding of protein structure dynamics. In this review we provide a key, comprehensive overview of the different types of photoswitches that have been used to control peptide structure, excluding the already extensively reviewed azobenzene. This will help address the question as to which synthetic photoswitch to use in a given study.

Photocatalytic materials are attracting attention as emerging resources for agricultural applications. This timely review assesses the current developments in the use of biocompatible titanium dioxide (TiO₂)-based photocatalytic nanomaterials (TiO₂-PN) as models to unravel agricultural growth, harvest, and post-harvest problems. Such developments can lead to technological innovations aimed at addressing the pressing global environmental challenges faced by farming. TiO₂-PN have been used as antimicrobial, growth-regulating, and fertilizer-like agents. The promising agricultural research applications of TiO₂-PN are highlighted along with a discussion of the main challenges that will need to be overcome to fully understand the roles of TiO₂-PN in the sustainable and productive exploitation of land and water for agricultural applications under natural conditions. In particular, rhizosphere internalization, translocation, and plant bioaccumulation pathways of photocatalytic materials from environmental exposition are outlined to illustrate the effect of TiO₂ on the agricultural cycle. Nanotoxicology and regulations are also discussed to illustrate the importance of biocompatibility and green synthesis of nanomaterials for safe use in real applications. This overview is focused on motivating and intensifying our understanding of on-site agricultural studies. Complementary biological approaches and structural damage observed by biological transmission electron, scanning electron, and optical microscopies should accelerate the practical contribution of TiO₂-PN to sustainable agriculture in conjunction with plant factories and plasma nitrogen fixation technology. Loadings below 10 μg/L of TiO₂-PN with a size of 40 nm benefit seed germination and root elongation as well as partially suppressing metal root translocation. However, only approximately 5% of current studies were carried out in real agricultural settings.

Accurate measuring of pH is of great significance for various research areas ranging from environmental to chemical and biological sciences. In the past decades, there has been growing interest in the use of nanoparticles (NPs) for pH measurement, especially for intracellular pH sensing and imaging. In this regard, a number of different NP-based fluorescent pH sensors have been developed, which can be classified into three major categories including (I) fluorescent NPs with direct or indirect responses to pH, (II) nonfluorescent NPs that are used only as scaffold and carriers for pH-sensitive fluorescent dyes, and (III) nonfluorescent NPs whose pH-responsive structural change is converted into the fluorescence signal of their conjugated dyes. This review is a complete coverage of all NPs used so far for fluorescence pH sensing. The authors of this review invite readers to find all design strategies for employing semiconductor quantum dot, nanoclusters, carbon-based dots, polymer dots, upconversion NPs, fluorescent metal-organic frameworks, metallic NPs, silica NPs, polymer NPs, micellar NPs, nanogels, and protein NPs for this purpose.

Solar energy-driven semiconductor photocatalysis has gathered increasing interest in the field of energy and environmental applications. However, a vital problem that limits its application is that photocatalysis requires a continuous light source to perform redox reaction. The ability of keeping catalytic activity in the dark has been the ultimate goal for the wide application of photocatalysis. More and more efforts have been paid to develop photocatalysts to perform photocatalytic reactions under both light and dark conditions, which is so called “round-the-clock photocatalytic system” (RTCPS). RTCPS with an ability of energy storage can work well under both daytime and nighttime, which widely used in the removal of heavy metal ion, the degradation of organic pollutant, disinfection and hydrogen generation. The important potential of RTCPS necessitate timely reviews of the recent advances to streamline efforts. Thus, this review aimed to summarize the recent advances in RTCPS, including the mechanism, characterization techniques and applications. Moreover, future challenge and research direction on the mechanistic study, material design and potential applications are also discussed.

Titanium dioxide (TiO₂) is regarded as an important prototype photocatalytic material for several decades. The charge carrier kinetics determines the photocatalytic properties of TiO₂ materials; this is found to be greatly dependent on electronic structures. It has been revealed that the intrinsic intermediate gap states (intrinsic GSs) play a significant role in charge carrier kinetics that drive the photocatalytic processes of TiO₂ materials, which are not well summarized until now. Motivated by this thought, the purpose of this review focuses on physiochemical science of the intrinsic GSs of TiO₂ materials and their important role in charge carrier kinetics. We first give a summary on the chemical resources of the intrinsic GSs in TiO₂ and their physiochemical nature. Their general energy distribution, charge carrier population, and the associated thermodynamic properties are also elaborated from an overall viewpoint. We further carefully summarize and compare the experimental studies on the energy and the density distribution of the intrinsic GSs and discuss the associated chemical resources and charge carrier localizations. Trapping is the dominant function of intrinsic GSs in the charge carrier kinetics of TiO₂ materials. The significant effect of trapping on the transport, recombination, and interfacial transfer of charge carriers are also comprehensive summarized. Furthermore, the effects of charge carrier kinetics on photocatalytic performances are also discussed to some extents. Because of the importance of intrinsic GSs in modulating charge carrier kinetics, it is expected to increase the photocatalytic activity by engineering the intrinsic GSs, not only for TiO₂ materials, but also for the other semiconductor photocatalysts.

Interest in the application of semiconductors toward the photocatalytic generation of solar fuels, including hydrogen from water-splitting and hydrocarbons from the reduction of carbon dioxide, remains strong due to concerns over the continued emission of greenhouse gases as well as other environmental impacts from the use of fossil fuels. While the efficiency and durability of such systems will depend heavily on the types of the semiconductors, co-catalysts, and mediators employed, the dimensionality of the semiconductors employed can also have a significant impact. Recognizing the broad nature of this field and the many recent advances in it, this review focuses on the emerging approaches from 0-dimensional (0D) to 3-dimensional (3D) semiconductor photocatalysts towards efficient solar fuels generation. We place particular emphasis on systems that are “semi-artificial”, that is, hybrid systems that integrate naturally occurring enzymes or whole cells with semiconductor components that harvest light energy. The semiconductors in these systems must have suitable interfacial properties for immobilization of enzymes to be effective photocatalysts. These requirements are particularly sensitive to surface structures and morphology, making the semiconductor dimensionality a critical factor. In addition to providing an overview of advances towards designing 3D architecture in semi-artificial photosynthetic field, we also present recent advances in fabrication strategies for 3D inorganic photocatalysts.

Carbon dioxide (CO₂) is regarded as a main contributor to the greenhouse effect. As a potential strategy to mitigate its negative impacts, the reduction of CO₂ is environmentally critical, economically meaningful and scientifically challenging. Being both thermodynamically and kinetically unfavored, CO₂ reduction requires catalysts as a crucial component irrespective of the reaction modes, be it electrocatalytic, photoelectrocatalytic or photocatalytic. In an effort to systematically review the types of catalysts that have been studied for CO₂ reduction, we categorize them into two major groups: those being activated by external sources and those being photoexcited and activated themselves. Attention is focused on the detailed mechanisms for each group by which the reduction of CO₂ proceeds, yielding a summary of the guiding principles for catalyst designs. This review highlights the importance of mechanistic studies, which permits us to discuss our perspectives on potential directions of catalyst investigation for future catalytic CO₂ reduction research.

Photoelectrocatalysis studies have emerged tremendous knowledge and experience, which has led to discovery of a number of active materials. Due to complexity of the processes involved, however, development of suitable semiconductor and catalyst for the photoelectrocatalysis still requires a try-and-error approach as different parameters are coherently varied to determine overall performance. This contribution provides insight into the key optoelectronic properties of the semiconductors, such as absorption coefficient, dielectric constant, effective masses, exciton binding energy, and band positions. The combined assessment from theoretical and experimental points of view is reviewed, which may help thorough understanding of the semiconductors and the way to reliably characterize them, and in turn to develop improved photoelectrocatalytic materials.