Spatiotemporally controllable nitric oxide (NO)-releasers allow us to analyze the physiological effects of NO, a gaseous mediator that modulates many biological signaling networks, and are also candidate chemotherapeutic agents. We designed synthesized blue-light-controllable NO releaser, named NOBL-1, which bears an N-nitrosoaminophenol moiety for release tethered BODIPY dye harvesting blue light. Photoinduced electron transfer from N-nitrosoaniline antenna upon irradiation with relatively...

Nitroxyl (HNO) is a one-electron reduced and protonated derivative of nitric oxide (NO) has characteristic biological pharmacological effects distinct from those NO. However, studies its biosynthesis activities are restricted by the lack versatile HNO detection methods applicable to living cells. Here, we report first metal-free reductant-resistant imaging probe available for use in cells, P-Rhod. It consists rhodol moiety as fluorophore, linked via an ester diphenylphosphinobenzoyl group,...

We report the design, synthesis and application of a directly photocontrollable hydrogen sulfide (H2S) donor, which releases H2S proportionally to intensity duration photoirradiation. Photocontrolled release from this donor was also demonstrated in bovine serum. This should be suitable for use various biological systems.

Abstract Caged compounds are frequently used in life science research. However, the light to activate them is commonly absorbed and scattered by biological materials, limiting their use basic research cells or small animals. In contrast, hard X‐rays exhibit high bio‐permeability due difficulty of interacting with molecules. With main goal developing X‐ray activatable caged compounds, azo designed synthesized a positive charge long π‐conjugated system increase reaction efficiency hydrated...

We investigated the role of hydroxy group in cleavage azo bond with X-rays. From results product analysis, it was suggested that nonspecific degradation is promoted as number groups increases.

Tools to enable spatiotemporally controlled upregulation of supersulfides, which are highly reactive, unstable sulfur species, needed study the pathophysiological roles post-translational protein modification with catenated atoms. Here, we set out design N,N-diethylaminocoumarin (DEAC)-based visible-light-responsive N-acetylcysteine persulfide donors (NAC-SS-DEAC), and serendipitously found that upon visible light irradiation, they donate a sulfane (S0) atom nucleophiles, including thiols...

We designed and synthesized a photocontrollable peroxynitrite (ONOO–) generator, P-NAP, which has N-methyl-N-nitrosoaminophenol structure with four methyl groups introduced onto the benzene ring to block reaction of photodecomposition product ONOO– lower semiquinoneimine's redox potential. The semiquinoneimine intermediate generated by photoinduced release nitric oxide (NO) reduces dissolved molecular oxygen generate superoxide radical anion (O2•–), reacts NO afford under diffusion control...

Nitric oxide (NO) has been known as a gaseous chemical mediator, which modulates several physiological functions. Spatial and temporal control of NO release facilitates further study medical application NO. Herein, we report design synthesis novel donor, NO-Rosa. NO-Rosa rosamine moiety, absorbs yellowish green light. Upon irradiation with light (530-590 nm), is released from NO-Rosa, presumably via photoinduced electron transfer the N-nitrosoaminophenol moiety to moiety. was detected by ESR...

Nitric oxide (NO) is a physiological signaling molecule, whose biological production precisely regulated at the subcellular level. Here, we describe design, synthesis, and evaluation of novel mitochondria-targeted NO releasers, Rol-DNB-mor Rol-DNB-pyr, that are photocontrollable not only in UV wavelength range but also biologically favorable visible (530-590 nm). These caged compounds consist hindered nitrobenzene as NO-releasing moiety rhodamine chromophore. Their NO-release properties were...

We designed and synthesized a novel Si-rhodamine derivative, NORD-1, as red-light-controllable nitric oxide (NO) releaser, on the basis of photoredox parameter analysis. Red-light-responsive NO release from NORD-1 was confirmed by ESR spin trapping quantified with an electrode means Griess assay. The cross section (ε656 nm·ΦNO) calculated to be 3.65 × 102, which is larger than that previously reported yellowish-green-light-controllable NO-Rosa5. photoresponsiveness precise efficient enough...

Hydrogen sulfide (H2S) has multiple physiological roles, for example, in vasodilation and inflammation. It is a highly reactive gas under ambient conditions, so controllable H2S donors are required studying its biological functions. Here, we describe the design, synthesis application of donor (SPD-2) that utilizes xanthone photochemistry to control release. generation from SPD-2 was completely dependent on UVA-irradiation (325-385nm), as confirmed by methylene blue assay use H2S-selective...

Abstract Spatiotemporally controllable nitric oxide (NO) releasers are required for biological studies and as candidate therapeutic agents. Here, we investigate the structure-efficiency relationship of a series photoinduced electron transfer-triggered NO based on our reported yellowish-green light-controllable releaser, NO-Rosa. The distance between NO-releasing N -nitrosoaminophenol moiety rosamine antenna was critical efficient release. Notably, substitution at phenolic hydroxyl group...

Ectonucleotide pyrophosphatase/phosphodiesterase 1 (ENPP1) is a type II transmembrane glycoprotein that involved in bone metabolism and insulin resistance, hydrolyzes 2',3'-cGAMP (a STING ligand promotes innate immunity), associated with cancer stemness breast cancers glioblastoma. Therefore, ENPP1 considered candidate therapeutic target and/or biomarker for early diagnosis of malignant tumors. In this study, we designed synthesized sensitive fluorescence probe, Tokyo Green (TG) mAMP. We...

The development of efficient antibacterial agents is important for public health. To completely damage bacteria in situ, light has been used as an external stimulus, but the wavelength range limited up to visible at which antimicrobial activity incomplete. Here, we report on our investigation bactericidal effect heat and nitric oxide (NO) generated simultaneously by near-infrared (NIR) using vanadyl naphthalocyanine-doped polymer dots (P-dots). P-dots co-doped with naphthalocyanine N-nitroso...

Two-photon-excitation release of nitric oxide (NO) from our recently synthesized photolabile NO donor, Flu-DNB, was confirmed to allow fine spatial and temporal control at the subcellular level in vitro. We then evaluated vivo applications. Femtosecond near-infrared pulse laser irradiation predefined regions interest living mouse brain treated with Flu-DNB induced NO-release-dependent, transient vasodilation specifically irradiated site. Photoirradiation absence had no effect. Further, by...

Photocontrollable ONOO− generation from a nitrobenzene derivative was demonstrated. The designed compound released NO in response to photoirradiation, and the resulting semiquinone reduced molecular oxygen generate O2˙−; reaction of two generated ONOO−, as confirmed with an ONOO−fluorescent probe, HKGreen-3.

Sirtuins (SIRTs) are a family of NAD+ -dependent histone deacetylases. In mammals, dysfunction SIRTs is associated with age-related metabolic diseases and cancers, so SIRT modulators considered attractive therapeutic targets. However, current screening methodologies problematic, no tools for imaging endogenous activity in living cells have been available until now. this work we present series simple highly sensitive new probes. Fluorescence these probes activated by SIRT-mediated hydrolytic...

The STING (stimulator of interferon genes) pathway is one the pathways that regulate innate immunity, and extracellular hydrolytic enzyme ecto-nucleotide pyrophosphatase/phosphodiesterase 1 (ENPP1) has been identified as its dominant negative regulator. Since activation immune system a promising strategy for treatment various infectious diseases cancers, ENPP1 inhibitors have attracted great attention candidate drugs. We previously small-molecule having [1,2,4]triazolo[1,5-a]pyrimidine...

Histone deacetylases (HDACs) are involved in epigenetic control of the expression various genes by catalyzing deacetylation ε-acetylated lysine residues. Here, we report design, synthesis and evaluation (7-diethylaminocoumarin-4-yl)methyl ester suberoylanilide hydroxamic acid (AC-SAHA) as a caged HDAC inhibitor, which releases known pan-HDAC inhibitor SAHA upon cleavage photolabile protecting group response to photoirradiation. A key advantage AC-SAHA is that derivative itself shows...

A combination of labeling techniques enables site-specific installation fluorescent probes for measuring distances within proteins by Förster resonance energy transfer (FRET).

Sirtuins (SIRTs) are a family of nicotinamide adenine dinucleotide-dependent histone deacetylases that serve as epigenetic regulators many physiological processes. Recent studies have shown in addition to their well-known deacetylase activity, sirtuins also exhibit deacylase such demyristoylase activity. Here, we show our previously reported sirtuin fluorescence probe, SFP3, can measure the defatty-acylase activity SIRT1–3, enabling selective assay We further utilized this finding develop...