Cancer is a very challenging disease to treat, both in terms of treatment efficiency and side-effects. To overcome these problems, there have been extensive studies regarding the possibility improving by employing combination therapy, exploring therapeutic modalities with reduced side-effects (such as photodynamic therapy (PDT)). Herein, this work has two aims: (i) develop self-activating photosensitizers for use light-free which would eliminate light-related restrictions that currently...

Photodynamic therapy (PDT) is an anticancer therapeutic modality with remarkable advantages over more conventional approaches. However, PDT greatly limited by its dependence on external light sources. Given this, would benefit from new systems capable of a light-free and intracellular photodynamic effect. Herein, we evaluated the heavy-atom effect as strategy to provide activity derivatives coelenterazine, chemiluminescent single-molecule widespread in marine organisms. Our results indicate...

The bioluminescent reaction of the "sea firefly" Cypridina hilgendorfii is a prototypical system for marine bioluminescence, as its substrate possesses an imidazopyrazinone core that common link among organisms eight phyla. elucidation mechanism behind bioluminescence essential future applications in bioimaging, biomedicine, and bioanalysis. In this study we have investigated key step chemiexcitation with combined experimental theoretical approach. obtained results indicate neutral...

Imidazopyrazinone dioxetanone is a central molecule in bioluminescence, as it the scaffold responsible for light emission many marine species. Herein, we have theoretically studied thermolysis of its neutral and anionic forms. Our results allowed us to explain imidazopyrazinone bioluminescence with Interstate Crossing-Induced Chemiexcitation (ICIC) mechanism, why forms emit efficiently contrary ones. Both decompose via stepwise-biradical pathway, but biradical formed either an electron...

Cancer is still a challenging disease to treat, both in terms of harmful side effects and therapeutic efficiency the available treatments. Herein, develop new molecules, we have investigated anticancer activity halogenated derivatives different components bioluminescent system marine Coelenterazine: Coelenterazine (Clz) itself, Coelenteramide (Clmd), Coelenteramine (Clm). We found that Clz possess variable toward gastric lung cancer. Interestingly, also brominated Clmd (Br-Clmd) Clm (Br-Clm)...

Backgroung: The rising complexity and associated side effects of cancer treatments highlight the need for safer more effective therapeutic agents. Carbon-based nanomaterials such as CDs have been gaining prominence their unique characteristics, opening avenues diverse applications fluorescence imaging, drug gene transport, controlled delivery, medical diagnosis, biosensing. Despite promising advancements in research, it remains imperative to scrutinize properties potential cytotoxicity newly...

Cypridina bioluminescence has been increasingly used in bioimaging, bioanalysis, and biomedicine, due to high quantum yield signal-to-noise ratio. However, there is still no consensus regarding different aspects of the chemiluminescent mechanism this system, which impairs development new applications. Herein, we have a theoretical DFT TD-DFT approach (i) determine identity dioxetanone species responsible for efficient chemiexcitation (ii) identify bioluminescent emitter if light-emission...

Abstract Despite decades of research, it is still not clear what the mechanism behind efficient chemiexcitation dioxetanones in chemiluminescent and bioluminescent reactions. In fact, long‐standing theories (charge transfer‐initiated luminescence chemically induced electron‐exchange luminescence) have been demonstrated to be able explain this phenomenon. Herein, a theoretical approach using reliable up‐to‐date methodology was used address problem, by focusing on model dioxetanones....

Chemi- and bioluminescence are remarkable light-emitting phenomena, in which thermal energy is converted into excitation due to a (bio)chemical reaction. Among wide variety of chemi-/bioluminescent systems, one the most well-known studied systems that marine imidazopyrazinones, such as Coelenterazine Cypridina luciferin. Due increasing usefulness their reactions terms imaging sensing applications, among others, significant effort has been made over years by researchers develop new...

Cancer is still one of the most challenging diseases to treat, making pursuit for novel molecules with potential anticancer activity an important research topic. Herein, we have performed a comparative investigation into analogs marine coelenterazine and coelenteramine. The former well-known bioluminescent substrate, while latter metabolic product resulting reaction. While both types showed toward lung gastric cancer cell lines, obtained data that highlight relevant differences between these...

Photodynamic therapy (PDT) of cancer possesses advantageous features, such as a minimally invasive nature and few side-effect [1]. However, its use can be restricted to more surface tumors, due dependance on light-irradiation. To overcome this problem, we propose the development single-molecule photosensitizers (PSs), based chemiluminescent (CL) marine Coelenterazine (Clz) [2-6], which self-activated in absence light. Clz analogs were synthesized via routes optimized by our team their...

Replacing the peroxide bond of dioxetanone prevents chemiluminescence by making its thermolysis energetically unfavorable and without a singlet chemiexcitation pathway.

Coelenterazine and other imidazopyrazinones are important bioluminescent substrates widespread in marine species can be found eight phyla of luminescent organisms. Light emission from these systems is caused by the formation subsequent thermolysis a dioxetanone intermediate, whose decomposition allows for efficient chemiexcitation to singlet excited states. Interestingly, some studies have also reported involvement unexpected dioxetane intermediates chemi- reactions Coelenterazine, albeit...

The mode of action toward gastric cancer cells brominated Coelenteramine, an analogue a metabolic product marine bioluminescent reaction, was investigated by synchrotron radiation-based Fourier Transform Infrared spectrocopy (FTIR). This method revealed that the anticancer activity Coelenteramine is closely connected with cellular lipids, affecting their organization and composition. More specifically, there increasing extent oxidative stress, which results in changes membrane polarity,...

The intramolecular chemiexcitation of high-energy peroxide intermediates, such as dioxetanones, is an essential step in different chemi- and bioluminescent reactions. Here, we employed the Time-Dependent Density Functional Theory (TD-DFT) methodology to evaluate if how external stimuli tune model dioxetanones. More specifically, evaluated whether strategic placement ionic species near a neutral dioxetanone could its thermolysis profile. We found that these allow for "dark" catalysis reaction...

Bioluminescence (BL) and chemiluminescence (CL) are remarkable processes in which light is emitted due to (bio)chemical reactions. These reactions have attracted significant attention for various applications, such as biosensing, bioimaging, biomedicine. Some of the most relevant well-studied BL/CL systems that marine imidazopyrazine-based compounds, among Coelenterazine a prime example. Understanding mechanisms behind efficient chemiexcitation essential optimization development practical...

Cancer is a very challenging disease to treat, both in terms of therapeutic efficiency and harmful side effects, which continues motivate the pursuit for novel molecules with potential anticancer activity. Herein, we have designed, synthesized, evaluated cytotoxicity different brominated coelenteramines, are metabolic products synthesis precursors chemi-/bioluminescent system marine coelenterazine. The evaluation these was carried out prostate breast cancer, while also exploring their use...