01853nas a2200205 4500008004100000022001400041245017600055210006900231260007100300300001200371490000700383520098900390100002401379700002601403700001901429700002301448700002901471700002001500856012701520 2010 eng d a0022-326300aExperimental and theoretical study on the remarkable influence of protecting groups on the selectivity of addition of amines to vinyl sulfone-modified hex-2-enopyranosides0 aExperimental and theoretical study on the remarkable influence o a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJAN a303-3140 v753 a

Although phenylmethylene-protected vinyl sulfone-modified carbohydrate 2 alpha reacts with both primary and secondary amines in Michael fashion to afford aminated products, only primary amines react with the dibenzyl-protected 3 alpha, 6-O-trityl-protected 4 alpha, and unprotected 5 alpha, highlighting for the first time the remarkable influence of protecting, groups on the reaction patterns of vinyl sulfone-modified carbohydrates. The quantum chemical calculations suggest that the Michael addition of amines and proton transfer to vinyl sulfone-modified carbohydrates 2 alpha and 5 alpha are possible via relay process in a concerted mechanism. These calculations reveal that the addition of primary amines to vinyl sulfone-modified carbohydrate is preferential due to the low activation energy barriers, whereas the addition of secondary amines has relatively higher activation energy barriers. The theoretical conclusions are in line with the experimental observations.

1 aBhattacharya, Rahul1 aKesharwani, Manoj, K.1 aManna, Chinmoy1 aGanguly, Bishwajit1 aSuresh, Cheravakattu, G.1 aPathak, Tanmaya uhttps://library.ncl.res.in/content/experimental-and-theoretical-study-remarkable-influence-protecting-groups-selectivity-001050nas a2200169 4500008004100000245008200041210006900123260000800192300001600200490000700216520046600223100002600689700002000715700001700735700002300752856010500775 2011 eng d00aBorazine as a sensor for fluoride ion: a computational and experimental study0 aBorazine as a sensor for fluoride ion a computational and experi cMAY a3636–36390 v523 a

The computational and experimental studies have revealed that even simple molecule like borazine can act as a sensor for fluoride ions. This study further reported the various binding modes of analytes using quantum chemical calculations and the nature of such interactions have been examined using electron density surface analysis. Total charge transfer analysis (qCT) correlates well with the binding affinities of analytes with the borazine receptor.

1 aKesharwani, Manoj, K.1 aSuresh, Moorthy1 aDas, Amitava1 aGanguly, Bishwajit uhttps://library.ncl.res.in/content/borazine-sensor-fluoride-ion-computational-and-experimental-study02700nas a2200217 4500008004100000245005900041210005700100260000800157300001400165490000700179520203200186100002002218700002402238700002602262700001902288700002302307700002802330700002002358700001702378856008702395 2011 eng d00aFolding and unfolding movements in a [2]pseudorotaxane0 aFolding and unfolding movements in a 2pseudorotaxane cDEC a138–1440 v763 a

A new dibenzo[24]crown-8 derivative (1) was synthesized and functionalized with aromatic moieties such as naphthalene and coumarin units. These two fluorophores are known to form an effective FRET (Forster resonance energy transfer) pair, and this formed the basis for the design of this host crown ether derivative. Results of the steady-state and time-resolved fluorescence studies confirmed the resonance energy transfer between the donor naphthalene moiety and acceptor coumarin fragment, while NMR spectra and computational studies support a folded conformation for the uncomplexed crown ether 1. This was found to form an inclusion complex, a [2]pseudorotaxane type with imidazolium ion derivatives as the guest molecules with varying alkyl chain lengths ([C4mim]+ or [C10mim]+). The host crown ether (1) tends to adopt an open conformation on formation of the interwoven inclusion complex (1·[C4mim]+ or 1·[C10mim]+). This change in conformation, from the folded to a open one, was predicted by computational as well as 1H NMR studies and was confirmed by single crystal X-ray structure for one (1·[C4mim]+) of the two inclusion complexes. The increase in the effective distance between the naphthalene and coumarin moieties in the open conformation of these inclusion complexes was also supported by the decrease in the effective FRET process that was operational between naphthalene and coumarin moieties in the free molecule (1). Importantly, this inclusion complex formation was found to be reversible, and in the presence of a stronger base/polar solvent, such as triethyl amine/DMSO, the deprotonation/effective solvation of the cationic imidizolium ions ([C4mim]+ or [C10mim]+) resulted in decomplexation or dethreading with restoration of the original emission spectra for 1, which signifies the subsequent increase in the FRET process. Thus we could demonstrate that a molecular folding-unfolding type of movement in the crown ether derivative could be induced by chemical input as an imidazolium ion.

1 aSuresh, Moorthy1 aMandal, Amal, Kumar1 aKesharwani, Manoj, K.1 aAdarsh, N., N.1 aGanguly, Bishwajit1 aKanaparthi, Ravi, Kumar1 aSamanta, Anunay1 aDas, Amitava uhttps://library.ncl.res.in/content/folding-and-unfolding-movements-2pseudorotaxane00896nas a2200193 4500008004100000245008100041210006900122260000800191300001400199490000700213520024200220100001800462700002400480700002600504700002400530700002300554700001700577856010800594 2011 eng d00aReceptor design and extraction of inorganic fluoride ion from aqueous medium0 aReceptor design and extraction of inorganic fluoride ion from aq cMAY a7398-74000 v473 a

A receptor with acidic methylene hydrogens is found to act as an efficient binding mode for F−. This reagent could as well be used for selective and quantitative extraction of F− from the aqueous solution of NaF and sea water.

1 aDas, Priyadip1 aMandal, Amal, Kumar1 aKesharwani, Manoj, K.1 aSuresh, Eringathodi1 aGanguly, Bishwajit1 aDas, Amitava uhttps://library.ncl.res.in/content/receptor-design-and-extraction-inorganic-fluoride-ion-aqueous-medium01418nas a2200181 4500008004100000245009400041210006900135260000800204300001600212520077500228100001801003700001801021700002601039700001601065700002301081700001701104856011501121 2011 eng d00aZnII-2,2?:6?,2?-terpyridine-based complex as fluorescent chemosensor for PPi, AMP and ADP0 aZnII2262terpyridinebased complex as fluorescent chemosensor for  cJUL a3050–30583 a

A new ZnII–2,2′:6′,2″-terpyridine complex, derivatized with a coumarin moiety (L1Zn), acts as a fluorescent chemosensor for different biologically important phosphates like PPi, AMP and ADP in mixed aqueous media. Depending on the proportion of the aqueous fraction present in the solvent mixture, L1Zn shows a preference for different phosphate moieties at physiological pH. In an aqueous acetonitrile (2:3, v/v) medium this reagent shows a preference for AMP as compared to ADP, ATP and PPi. The binding affinities of L1Zn with different phosphate ions and associated shifts in the electronic spectra were rationalized by DFT calculations. Such an example of a receptor that is selective for AMP under physiological conditions is rare in the literature.

1 aDas, Priyadip1 aGhosh, Amrita1 aKesharwani, Manoj, K.1 aRamu, Vadde1 aGanguly, Bishwajit1 aDas, Amitava uhttps://library.ncl.res.in/content/znii-2262-terpyridine-based-complex-fluorescent-chemosensor-ppi-amp-and-adp01865nas a2200193 4500008004100000245012300041210006900164260000800233300001400241490000700255520115700262100001801419700002601437700002101463700002401484700002301508700001701531856012301548 2012 eng d00aAlternative approach: a highly selective dual responding fluoride sensor having active methylene group as binding site0 aAlternative approach a highly selective dual responding fluoride cJAN a2263-22710 v103 a

A newly designed phosphonium derivative (L) having active methylene functionality, shows unusual preference towards F− over all other anions. The binding process through C–H⋯F− hydrogen bond formation was probed by monitoring the changes in either electronic or luminescence spectra. Changes in both cases are significant enough to allow visual detection. The loss of molecular flexibility of L on forming L·F− effectively interrupts the non-radiative deactivation pathway and accounts for the observed switch on fluorescence response. The results of the time-resolved emission studies for L and L·F− using a time-correlated single photon counting technique further corroborate this presumption. The excellent preference of L towards F− is attributed to an efficient hydrogen bonding interaction between the strongly polarized methylene protons and F−, which delineates the subtle difference in the affinity among other competing anionic analytes like CN−, H2PO4−, CH3CO2−, etc. The relative affinities of various anions and the preferential binding of F− to reagent L are also rationalized using computational studies.

1 aDas, Priyadip1 aKesharwani, Manoj, K.1 aMandal, Amal, K.1 aSuresh, Eringathodi1 aGanguly, Bishwajit1 aDas, Amitava uhttps://library.ncl.res.in/content/alternative-approach-highly-selective-dual-responding-fluoride-sensor-having-active01765nas a2200229 4500008004100000245009600041210006900137260000800206300001600214490000700230520098300237100002201220700001701242700001501259700001901274700002801293700002701321700002601348700002301374700001701397856012101414 2012 eng d00aRatiometric detection of Cr3+ and Hg2+ by a naphthalimide-rhodamine based fluorescent probe0 aRatiometric detection of Cr3 and Hg2 by a naphthalimiderhodamine cJAN a1769–17770 v513 a

Newly synthesized rhodamine derivatives, L1 and L2, are found to bind specifically to Hg2+ or Cr3+ in presence of large excess of other competing ions with associated changes in their optical and fluorescence spectral behavior. These spectral changes are significant enough in the visible region of the spectrum and thus, allow the visual detection. For L1, the detection limit is even lower than the permissible [Cr3+] or [Hg2+] in drinking water as per standard U.S. EPA norms; while the receptor, L2 could be used as a ratiometric sensor for detection of Cr3+ and Hg2+ based on the resonance energy transfer (RET) process involving the donor naphthalimide and the acceptor Cr3+/Hg2+-bound xanthene fragment. Studies reveal that these two reagents could be used for recognition and sensing of Hg2+/Cr3+. Further, confocal laser microscopic studies confirmed that the reagent L2 could also be used as an imaging probe for detection of uptake of these ions in A431 cells.

1 aMahato, Prasenjit1 aSaha, Sukdeb1 aSuresh, E.1 aDi Liddo, Rosa1 aParnigotto, Pier, Paolo1 aConconi, Maria, Teresa1 aKesharwani, Manoj, K.1 aGanguly, Bishwajit1 aDas, Amitava uhttps://library.ncl.res.in/content/ratiometric-detection-cr3-and-hg2-naphthalimide-rhodamine-based-fluorescent-probe02265nas a2200229 4500008004100000022001400041245013900055210006900194260007100263300001400334490000700348520137500355100002401730700002001754700002601774700002701800700001901827700002301846700002301869700001701892856012601909 2013 eng d a0022-326300aMolecular interactions, proton exchange, and photoinduced processes prompted by an inclusion process and a [2]pseudorotaxane formation0 aMolecular interactions proton exchange and photoinduced processe a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcAUG a9004-90120 v783 a

Appropriate design of the host and guest components allows formation of a novel [2]pseudorotaxane complex with an interrupted photoinduced electron transfer (PET)-coupled fluorescence resonance energy transfer (FRET) response. This is the first example of an inclusion complex with NO6-based azacrown ether as the host unit (H). Different guest molecules (G1, G2, G3, and G4) with varying stopper size are used for the studies. Unlike G1, G2, and G3, G4 with a relatively bulkier stopper fails to form a [2]pseudorotaxane complex. Isothermal titration microcaloiimetry measurements reveal a systematic increase in the association constant for H.G1, H.G2, and H.G3 with a change in the stopper size. Thermodynamic data suggest that the formation of H.G1/H.G2/H.G3 is exclusively driven by a large positive entropic gain (T Delta S = 19.69/26.80/21.81 kJ.mol(-1)), while the enthalpy change is slightly negative for H.G1/H.G3 (-2.61/-1.97 kJ.mol(-1)) and slightly positive for H.G2 (Delta H = 5.98 kJ.mol(-1)). For these three inclusion complexes, an interrupted PET-coupled FRET response is observed with varying efficiency, which is attributed to the subtle differences in acidity of the NH2+ unit of the guest molecules and thus the proton exchange ability between the host and respective guest. This is substantiated by the results of the computational studies.

1 aMandal, Amal, Kumar1 aSuresh, Moorthy1 aKesharwani, Manoj, K.1 aGangopadhyay, Monalisa1 aAgrawal, Manoj1 aBoricha, Vinod, P.1 aGanguly, Bishwajit1 aDas, Amitava uhttps://library.ncl.res.in/content/molecular-interactions-proton-exchange-and-photoinduced-processes-prompted-inclusion-002517nas a2200193 4500008004100000245018100041210006900222260000800291300001600299490000800315520173800323100002302061700002202084700001902106700002602125700002302151700001702174856013202191 2014 eng d00aHydrogen bonding interaction between active methylene hydrogen atoms and an anion as a binding motif for anion recognition: experimental studies and theoretical rationalization0 aHydrogen bonding interaction between active methylene hydrogen a cMAR a2656–26660 v1183 a

Two new reagents, having similar spatial arrangements for hydrogen atoms of the active methylene functionalities, were synthesized and interactions of such reagents with different anionic analytes were studied using electronic spectroscopy as well as by using 1H and 31P NMR spectroscopic methods. Experimental studies revealed that these two reagents showed preference for binding to F– and OAc–. Detailed theoretical studies along with the above-mentioned spectroscopic studies were carried out to understand the contribution of the positively charged phosphonium ion, along with methylene functionality, in achieving the observed preference of these two receptors for binding to F– and OAc–. Observed differences in the binding affinities of these two reagents toward fluoride and acetate ions also reflected the role of acidity of such methylene hydrogen atoms in controlling the efficiencies of the hydrogen bonding in anion–Hmethylene interactions. Hydrogen bonding interactions at lower concentrations of these two anionic analytes and deprotonation equilibrium at higher concentration were observed with associated electronic spectral changes as well as visually detectable change in solution color, an observation that is generally common for other strong hydrogen bond donor functionalities like urea and thiourea. DFT calculations performed with the M06/6-31+G**//M05-2X/6-31G* level of theory showed that F– binds more strongly than OAc– with the reagent molecules. The deprotonation of methylene hydrogen atom of receptors with F– ion was observed computationally. The metal complex as reagent showed even stronger binding energies with these analytes, which corroborated the experimental results.

1 aAgarwalla, Hridesh1 aJana, Kalyanashis1 aMaity, Arunava1 aKesharwani, Manoj, K.1 aGanguly, Bishwajit1 aDas, Amitava uhttps://library.ncl.res.in/content/hydrogen-bonding-interaction-between-active-methylene-hydrogen-atoms-and-anion-binding-motif