00993nas a2200181 4500008004100000022001500041245011200056210006900168260000800237300001600245490000700261520033200268100002300600700002200623700001900645700002100664856012600685 2018 eng d a 1359-734500a A new class of N-doped ionic PAHs via intramolecular [4+2]-cycloaddition between arylpyridines and alkynes0 anew class of Ndoped ionic PAHs via intramolecular 42cycloadditio cOCT a11909-119120 v543 aReported herein, for the first time, is a copper-promoted intramolecular [4+2]-cycloaddition cascade to access ionic N-doped polycyclic aromatic hydrocarbons (PAHs) with tunable emission wavelengths. It is shown that the reaction can be made catalytic with respect to Cu(OTf)(2) when an external oxidant, Selectfluor, was used.1 aMule, Ravindra, D.1 aShaikh, Aslam, C.1 aGade, Amol, B.1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/new-class-n-doped-ionic-pahs-intramolecular-42-cycloaddition-between-arylpyridines-and01514nas a2200193 4500008004100000022001400041245020700055210006900262260000900331300001400340490000700354520072300361100002201084700002301106700002301129700001701152700002101169856013001190 2019 eng d a0022-326300aExternal oxidant-dependent reactivity switch in copper-mediated intramolecular carboamination of alkynes: access to a different class of fluorescent ionic nitrogen-doped polycyclic aromatic hydrocarbons0 aExternal oxidantdependent reactivity switch in coppermediated in cAPR  a4120-41300 v843 a

An interesting case of external oxidant-controlled reactivity switch leading to a divergent set of ionic nitrogen-doped polycyclic aromatic hydrocarbons (N-doped PAHs), is presented here, which is quite unrecognized in copper-mediated reactions. In the current scenario, from the same pyridino-alkyne substrates, the use of the external oxidant Ph1(0Ac)2, in combination with Cu(OTf)(2), gave N-doped spiro-PAHs via a dearomative 1,2-carboamination process; whereas, without the use of oxidant, an alkyne/azadiene [4 + 2]-cycloaddition cascade occurred to exclusively afford ionic N-doped PAHs. These newly synthesized N-doped PAHs further exhibit tunable emissions, as well as excellent quantum efficiencies.

1 aShaikh, Aslam, C.1 aBanerjee, Somsuvra1 aMule, Ravindra, D.1 aBera, Saibal1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/external-oxidant-dependent-reactivity-switch-copper-mediated-intramolecular-carboamination02414nas a2200205 4500008004100000022001400041245009600055210006900151260000900220300001400229490000700243520169500250100002201945700002401967700002301991700002302014700002502037700002102062856012502083 2019 eng d a0022-326300aIonic pyridinium-oxazole dyads: design, synthesis, and application in mitochondrial imaging0 aIonic pyridiniumoxazole dyads design synthesis and application i cFEB  a1766-17770 v843 a

We recently developed an oxidative intramolecular 1,2-amino-oxygenation reaction, combining gold(I)/gold(III) catalysis, for accessing structurally unique ionic pyridinium-oxazole dyads (PODs) with tunable emission wavelengths. On further investigation, these fluorophores turned out to be potential biomarkers; in particular, the one containing -NMe2 functionality (NMe2-POD) was highly selective for mitochondrial imaging. Of note, because of mitochondria's involvement in early-stage apoptosis and degenerative conditions, tracking the dynamics of mitochondrial morphology with such imaging technology has attracted much interest. Along this line, we wanted to build a library of such PODs which are potential mitochondria trackers. However, Au/Selecfluor, our first-generation catalyst system, suffers from undesired fluorination of electronically rich PODs resulting in an inseparable mixture (1:1) of the PODs and their fluorinated derivatives. In our attempt to search for a better alternative to circumvent this issue, we developed a second-generation approach for the synthesis of PODs by employing Cu(II)/PhI(OAC)(2)-mediated oxidative 1,2-amino-oxygenation of alkynes. Thes newly synthesized PODs exhibit tunable emissions as well as excellent quantum efficiency up to 0.96. Further, this powerful process gives rapid access to a library of NMe2-PODs which are potential mitochondrial imaging agents. Out of the library, the randomly chosen POD-3g was studied for cell-imaging experiments which showed high mitochondrial specificity, superior photostability, and appreciable tolerance to microenvironment changes with respect to commercially available MitoTracker green.

1 aShaikh, Aslam, C.1 aVarma, Mokshada, E.1 aMule, Ravindra, D.1 aBanerjee, Somsuvra1 aKulkarni, Prasad, P.1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/ionic-pyridinium-oxazole-dyads-design-synthesis-and-application-mitochondrial-imaging01280nas a2200193 4500008004100000022001400041245006100055210005900116260000800175300001400183490000700197520066800204100002300872700002600895700002300921700002500944700002100969856009600990 2020 eng d a1523-706000aGold-catalyzed alkynylative meyer-schuster rearrangement0 aGoldcatalyzed alkynylative meyerschuster rearrangement cJUN a4792-47960 v223 a

By applying the ``interplay'' mode, which consolidates two key reactivity modes of gold catalysis, namely pi-activation mode and cross-coupling mode, the first alkynylative Meyer-Schuster rearrangement is designed and successfully implemented. The current protocol gives straightforward access to enynones, a highly valuable building block, from easily available propargyl alcohol feedstocks. Control experiments suggest an Au(III) catalyst triggers the Meyer-Schuster rearrangement, whereas monitoring the reaction with ESI-HRMS provided strong evidence in favor of a key alkynylgold(III) intermediate which supports the proposed ``interplay'' scenario.

1 aBanerjee, Somsuvra1 aAmbegave, Shivhar, B.1 aMule, Ravindra, D.1 aSenthilkumar, Beeran1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/gold-catalyzed-alkynylative-meyer-schuster-rearrangement02789nas a2200301 4500008004100000022001400041245015300055210006900208260000800277300000700285490000800292520177100300653002102071653001402092653001302106653001002119653001502129653001802144100002302162700002702185700002302212700002402235700002602259700002902285700002902314700002002343856012402363 2020 eng d a0032-093500aHigh-throughput metabolomic and transcriptomic analyses vet the potential route of cerpegin biosynthesis in two varieties of Ceropegia bulbosa Roxb.0 aHighthroughput metabolomic and transcriptomic analyses vet the p cJAN a280 v2513 a

Ceropegia bulbosa is an important medicinal plant, used in the treatment of various ailments including diarrhea, dysentery, and syphilis. This is primarily attributed to the presence of pharmaceutically active secondary metabolites, especially cerpegin. As this plant belongs to an endemic threatened category, genomic resources are not available hampering exploration on the molecular basis of cerpegin accumulation till now. Therefore, we undertook high-throughput metabolomic and transcriptomic analyses using different tissues from two varieties namely, C. bulbosa var. bulbosa and C. bulbosa var. lushii. Metabolomic analysis revealed spatial and differential accumulation of various metabolites. We chemically synthesized and characterized the cerpegin and its derivatives by liquid chromatography tandem-mass spectrometry (LC-MS/MS). Importantly, these comparisons suggested the presence of cerpegin and 5-allyl cerpegin in all C. bulbosa tissues. Further, de novo transcriptome analysis indicated the presence of significant transcripts for secondary metabolic pathways through the Kyoto encyclopedia of genes and genomes database. Tissue-specific profiling of transcripts and metabolites showed a significant correlation, suggesting the intricate mechanism of cerpegin biosynthesis. The expression of potential candidate genes from the proposed cerpegin biosynthetic pathway was further validated by qRT-PCR and NanoString nCounter. Overall, our findings propose a potential route of cerpegin biosynthesis. Identified transcripts and metabolites have built a foundation as new molecular resources that could facilitate future research on biosynthesis, regulation, and engineering of cerpegin or other important metabolites in such non-model plants.

10a5-Allyl cerpegin10aCeropegia10aCerpegin10aLC-MS10ametabolite10aTranscriptome1 aGharat, Sachin, A.1 aShinde, Balkrishna, A.1 aMule, Ravindra, D.1 aPunekar, Sachin, A.1 aDholakia, Bhushan, B.1 aJayaramaiah, Ramesha, H.1 aRamaswamy, Gopalakrishna1 aGiri, Ashok, P. uhttps://library.ncl.res.in/content/high-throughput-metabolomic-and-transcriptomic-analyses-vet-potential-route-cerpegin01704nas a2200205 4500008004100000022001400041245009100055210006900146260000800215300001600223490000700239520100400246100002301250700002001273700002701293700002101320700002001341700002101361856011601382 2022 eng d a2041-652000aBQ-AurIPr: a redox-active anticancer Au(i) complex that induces immunogenic cell death0 aBQAurIPr a redoxactive anticancer Aui complex that induces immun cSEP a10779-107850 v133 a

Immunogenic Cell Death (ICD) is a unique cell death mechanism that kills cancer cells while rejuvenating the anticancer immunosurveillance, thereby benefiting the clinical outcomes of various immuno-chemotherapeutic regimens. Herein, we report development of a library of benzo[a]quinolizinium-based Au(i) complexes through an intramolecular amino-auration reaction of pyridino-alkynes. We tested 40 candidates and successfully identified BQ-AurIPr as a novel redox-active Au(i) complex with potent anticancer properties. BQ-AurIPr efficiently triggered generation of DAMPs - the hallmarks of ICD - and was superior in terms of efficiency compared to FDA-approved drugs known to induce ICD. BQ-AurIPr significantly increased immunogenicity of cancer cells enhancing their phagocytosis when co-cultured with immune cells. Our investigation reveals that BQ-AurIPr induces oxidative stress inside mitochondria leading to mitophagy, as the mechanism for immunogenic cell death in A549 cells.

1 aMule, Ravindra, D.1 aKumar, Akhilesh1 aSancheti, Shashank, P.1 aSenthilkumar, B.1 aKumar, Himanshu1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/bq-auripr-redox-active-anticancer-aui-complex-induces-immunogenic-cell-death01998nas a2200349 4500008004100000022001400041245022500055210006900280260000900349300001500358490000700373520077700380653002301157653001201180653001601192653002201208653002601230653001301256100002301269700001501292700002001307700001901327700001701346700002701363700002201390700002301412700002301435700001801458700002501476700002101501856012601522 2022 eng d a0947-653900aInterplay of anion-pi(+) and pi(+)-pi(+) interactions in novel pyrido[2,1-a]isoquinolinium-based aiegens - substituent- and counterion-dependent fluorescence modulation and applications in live cell mitochondrial imaging0 aInterplay of anionpi and pipi interactions in novel pyrido21aiso cJUL  ae2022006320 v283 a

Recently, the concept of anion-pi(+) interactions has witnessed unique applications in the field of AIEgen development. In this contribution, we disclose a consolidated study of a library of N-doped ionic AIEgens accessed through silver-mediated cyclization of pyridino-alkynes. A thorough photophysical, computational and crystallographic study has been conducted to rationalize the observed substituent- and counterion-dependent fluorescence properties of these luminogens. We further elucidate the prominent role of anion-pi(+) interactions, pi(+)-pi(+) interactions and other non-covalent interactions, in inhibiting the undesired ACQ effect. Finally, we have also demonstrated the application of selected AIEgens for imaging of mitochondria in live cells.

10a1-a]isoquinolinium10aAIEgens10aanion-pi(+)10acrystal structure10amitochondrial imaging10apyrido[21 aMule, Ravindra, D.1 aRoy, Rupam1 aMandal, Koushik1 aChopra, Deepak1 aDutta, Tanoy1 aSancheti, Shashank, P.1 aShinde, Popat, S.1 aBanerjee, Somsuvra1 aKoner, Apurba, Lal1 aBhowal, Rohit1 aSenthilkumar, Beeran1 aPatil, Nitin, T. uhttps://library.ncl.res.in/content/interplay-anion-pi-and-pi-pi-interactions-novel-pyrido21-aisoquinolinium-based-aiegens