Generation of thiyl radicals in a spatiotemporal controlled manner by light: Applied for the cis to trans isomerization of unsaturated fatty acids/phospholipids.

Thiyl radicals are important reactive sulfur species and can cause cis to trans isomerization on unsaturated fatty acids. However, biocompatible strategies for the controlled generation of thiyl radicals are still lacking. In this work, we report the study of a series of naphthacyl-derived thioethers as photo-triggered thiyl radical precursors.

Phototriggered Hydrogen Persulfide Donors via Hydrosulfide Radical Formation Enhancing the Reactive Sulfur Metabolome in Cells.

Hydrogen persulfide (HS) is an important sulfur-containing signaling molecule that plays a crucial role in the homeostasis of various organ systems, such as the renal, cardiovascular, liver, and gastrointestinal systems. However, research on HS in biological settings is still challenging due to its instability and high reactivity. Compounds that can controllably release HS (also known as donors) are thus crucial research tools.

Metal-Free Visible-Light Catalytic Deoxygenation of Azaaryl N-Oxides: Harnessing Photons for Efficient Greener Synthesis.

Regio- and chemo-selective functionalization of electron deficient azaarenes often required their transformations to corresponding N-oxides and subsequent removal of oxygen after functionalization to get back the desired substituted azaarenes. An efficient metal-free visible-light photo-redox catalytic deoxygenation of N-oxides of azaheterocyclic compounds has been developed using acridinium based organo-photocatalyst in blue LED light. High efficiency and mildness of this methodology has been demonstrated through higher deoxygenation yield of wide variety of azaheterocyclic N-oxides with reactive functional groups.

Single-Component Photo-Responsive Template for the Controlled Release of NO and HS.

Redox signaling molecules include a number of reactive oxygen species (ROS), reactive nitrogen species (RNS), and reactive sulfur species (RSS). These molecules work collectively in the regulation of many physiological processes. Understanding the crosstalk mechanisms in these signaling molecules is important but challenging.

Cu(II)-Based Coordination Polymer as a Pristine Form Usable Electrocatalyst for Oxygen Reduction Reaction: Experimental Evaluation and Theoretical Insights into Biomimetic Mechanistic Aspects.

As the postsynthesis-processed metal-organic material-based catalysts for energy applications add additional cost to the whole process, the importance of developing synthesized usable pristine catalysts is quite evident. The present work reports a new Cu-based coordination polymer (Cu-CP) catalyst to be used in its pristine form for oxygen reduction reaction (ORR) application. The catalyst was characterized using single-crystal X-ray diffraction, field emission scanning electron microscopy, and X-ray photoemission spectroscopy.

NIR-Responsive Lysosomotropic Phototrigger: An "AIE + ESIPT" Active Naphthalene-Based Single-Component Photoresponsive Nanocarrier with Two-Photon Uncaging and Real-Time Monitoring Ability.

In recent times, organelle-targeted drug delivery systems have gained tremendous attention due to the site-specific delivery of active drug molecules, resulting in enhanced bioefficacy. In this context, a phototriggered drug delivery system (DDS) for releasing an active molecule is superior, as it provides spatial and temporal control over the release. So far, a near-infrared (NIR) light-responsive organelle-targeted DDS has not yet been developed.

A Carbohydrate-based Synthetic Approach to Diverse Structurally and Stereochemically Complex Chiral Polyheterocycles.

Chiral polyheterocycles are one of the most frequently encountered scaffolds in natural products and in current drugs repertoire. A carbohydrate-based diversity oriented synthetic (DOS) approach has been employed for gaining access to many structurally diverse and stereochemically complex rigid polyheterocyclic molecules with multiple chiral hydroxyl groups to enhance aqueous solubility. Inexpensive chiral pool of D-Glucose has been judiciously exploited to get access of complex chiral polyheterocyclic structures using inexpensive, common achiral reagents and domino-Knoevenagel hetero-Diels-Alder (DKHDA) reaction as one of the key synthetic tools.

Ground-State Proton-Transfer (GSPT)-Assisted Enhanced Two-Photon Uncaging from a Binol-based AIE-Fluorogenic Phototrigger.

We demonstrated for the first time without any chemical modification the two-photon absorption (TPA) cross-section can be enhanced and red-shifted to the near-infrared (NIR) region by the ground-state proton-transfer (GSPT) process. Using GSPT, we developed a simple binol-based aggregation-induced emission (AIE)-fluorogenic phototrigger having a large two-photon uncaging cross-section in the "phototherapeutic window". As a proof of concept, we showed our phototrigger for the release of two different anticancer drugs in the NIR region.

Targeting the Trypanothione Reductase of Tissue-Residing in Hosts' Reticuloendothelial System: A Flexible Water-Soluble Ferrocenylquinoline-Based Preclinical Drug Candidate.

Since inception, the magic bullets developed against leishmaniasis traveled a certain path and then dropped down due to either toxicity or the emergence of resistance. The route of administration is also an important concern. We developed a series of water-soluble ferrocenylquinoline derivatives, targeting , among which CQFC1 showed the highest efficacy even in comparison to other drugs, in use or used, both in oral and intramuscular routes.

A two-photon responsive naphthyl tagged p-hydroxyphenacyl based drug delivery system: uncaging of anti-cancer drug in the phototherapeutic window with real-time monitoring.

We report a two-photon responsive drug delivery system (DDS), namely, p-hydroxyphenacyl-naphthalene-chlorambucil (pHP-Naph-Cbl), having a two-photon absorption (TPA) cross-section of ≥20 GM in the phototherapeutic window (700 nm). Our DDS exhibited both AIE and ESIPT phenomena, which were utilized for the real-time monitoring of anti-cancer drug release.

Ni(ii)-Catalyzed vinylic C-H functionalization of 2-acetamido-3-arylacrylates to access isotetronic acids.

A ligand-free Ni(ii)-catalyzed cascade annulation reaction for the synthesis of 4-aryl-substituted isotetronic acids from 2-acetamido-3-arylacrylates via vinylic C-H functionalization is reported. The reaction proceeds through heteroatom guided electrophilic insertion of nickel to the vinylic double bond followed by annulation with dibromomethane. This unconventional route features cascade steps, sole product formation, multiple functional group tolerance, low cost of catalysts and reagents, and readily available starting materials.

Stepwise dual stimuli triggered dual drug release by a single naphthalene based two-photon chromophore to reverse MDR for alkylating agents with dual surveillance in uncaging steps.

In this work, we depleted glutathione (GSH) by releasing SO2 with internal stimulus GSH itself, and also selectively marked the cancer cells followed by release of anticancer drug using another orthogonal stimulus i.e., two-photon (TP) NIR light by a single naphthalene based chromophore (TP absorbance 77 GM and uncaging cross-section 21 GM).

Formation or Cleavage of Rings via Sulfide-Mediated Reduction Offers Background-Free Detection of Sulfide.

A set of three highly selective probes for sulfide detection has been developed. Two novel mechanistic strategies for the detection, including (a) transformation of a pro-fluorophore into an active fluorophore and (b) destruction of a fused ring to activate a fluorophore, have been explored. The structural features of the probes including azido groups ("active" and "latent") and leaving groups (with or without being attached to the fluorophore) have been investigated.

Humidity sensing using THz metamaterial with silk protein fibroin.

In this study, we developed hybrid humidity sensing methods by incorporating silk fibroin protein onto metamaterials, operating in the terahertz (THz) frequencies; the resonant frequency shifted but saturated at a specific thickness due to the limited sensing volume of the metamaterial. From the saturated value, we extracted the dielectric constant for the silk films. We also observed additional resonance shifts when we applied humid air to silk-coated metamaterials, due to the increased water molecule numbers on the film.

A Curious Case of Ankylosing Spondylosis and Motor Neuron Disease: A Mere Coincidence or Correlation?

Ankylosing spondylitis (AS) is a chronic (progressive) painful inflammatory rheumatic disease with genetic predisposition. Genetic susceptibility and common expression cause susceptibility to other inflammatory diseases such as psoriasis, ulcerative colitis, and Crohn's disease. However, cases of motor neuron disease (MND) in patients of biologically treated patients of AS have been rarely reported.

A Minimalist Approach for Distinguishing Individual Lanthanide Ions Using Multivariate Pattern Analysis.

To discriminate among the 14 trivalent lanthanide ions, curcumin, a naturally occurring, nontoxic, off-the-shelf, commercially available compound containing a single fluorophore, was chosen as a probe in the water media at pH 6.8 and pH 8.2.

Protein-Based Electronic Skin Akin to Biological Tissues.

Human skin provides an interface that transduces external stimuli into electrical signals for communication with the brain. There has been considerable effort to produce soft, flexible, and stretchable electronic skin (E-skin) devices. However, common polymers cannot imitate human skin perfectly due to their poor biocompatibility, biofunctionality, and permeability to many chemicals and biomolecules.

Hydrazine functionalized probes for chromogenic and fluorescent ratiometric sensing of pH and F: experimental and DFT studies.

Two novel hydrazine based sensors, BPPIH (N,N-bis(perfluorophenyl)isophthalohydrazide) and BPBIH (N,N-bis(perfluorobenzylidene)isophthalohydrazide), are presented here. BPPIH is found to be a highly sensitive pH sensor in the pH range 5.0 to 10.

Highly Selective Sub-ppm Naked-Eye Detection of Hydrazine with Conjugated-1,3-Diketo Probes: Imaging Hydrazine in Drosophila Larvae.

A pair of pyrene- and anthracene-based turn-on fluorescent probes (1 and 2, respectively) reported here can be easily synthesized in a single-step process and also exhibit outstanding sensing behavior toward hydrazine over various competing nucleophilic species and environmentally relevant ions. The probes display dramatic enhancements in the emission intensity with as high as 83- and 173-fold increases in the presence of hydrazine. Nitrogenous bases, thiols, and lanthanides do not interfere in the fluorometric detection.

Ground state charge transfer complex formation of some metalloporphyrins with aromatic solvents: Further theoretical and experimental investigations.

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Potential of small-molecule fungal metabolites in antiviral chemotherapy.

Various viral diseases, such as acquired immunodeficiency syndrome, influenza, and hepatitis, have emerged as leading causes of human death worldwide. Scientific endeavor since invention of DNA-dependent RNA polymerase of pox virus in 1967 resulted in better understanding of virus replication and development of various novel therapeutic strategies. Despite considerable advancement in every facet of drug discovery process, development of commercially viable, safe, and effective drugs for these viruses still remains a big challenge.

Synthesis and in vitro antiviral evaluation of 4-substituted 3,4-dihydropyrimidinones.

A series of 4-substituted 3,4-dihydropyrimidine-2-ones (DHPM) was synthesized, characterized by IR, H NMR, C NMR and HRMS spectra. The compounds were evaluated in vitro for their antiviral activity against a broad range of DNA and RNA viruses, along with assessment for potential cytotoxicity in diverse mammalian cell lines. Compound 4m, which possesses a long lipophilic side chain, was found to be a potent and selective inhibitor of Punta Toro virus, a member of the Bunyaviridae.

Genotype-Phenotype Study of the Middle Gangetic Plain in India Shows Association of rs2470102 with Skin Pigmentation.

Our understanding of the genetics of skin pigmentation has been largely skewed towards populations of European ancestry, imparting less attention to South Asian populations, who behold huge pigmentation diversity. Here, we investigate skin pigmentation variation in a cohort of 1,167 individuals in the Middle Gangetic Plain of the Indian subcontinent. Our data confirm the association of rs1426654 with skin pigmentation among South Asians, consistent with previous studies, and also show association for rs2470102 single nucleotide polymorphism.

Photomodulation of fluoride ion binding through anion-π interactions using a photoswitchable azobenzene system.

The discovery of photoswitchable azobenzene-systems that undergo trans-to-cis photoisomerisation was a milestone in supramolecular chemistry. Such photoswitches have possible applications in data storage, stimuli responsive delivery systems, and molecular machines due to fast and selective switching. However, the light induced cis isomer of azobenzene is rather unstable and reverts thermally and photochemically to the thermodynamically stable trans configuration.