@article { ISI:000307494500027, title = {Exploring the potential of doped zero-dimensional cages for proton transfer in fuel cells: a computational study}, journal = {Journal of Physical Chemistry B}, volume = {116}, number = {32}, year = {2012}, month = {AUG}, pages = {9803-9811}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Calculations with density functional theory (DFT) and MP2 have been done to investigate the potential of recently synthesized durable zero-dimensional (OD) nitrogen-based cage structures to perform as efficient proton-exchange membranes (PEMs) in fuel cells. Our calculations suggest that the hydrogenated 0-D cages, in combination with hydrogen-bonding 1,2,3- and 1,2,4-triazole molecules, would perform as highly efficient PEMs. The results are important in the context of the need for efficient PEMs for fuel cells, especially at higher temperatures (greater than 120 degrees C) where conventional water-based PEMs such as Nafion have been found to be ineffective.

}, issn = {1520-6106}, doi = {10.1021/jp303884p}, author = {Mane, Manoj V. and Venkatnathan, Arun and Ghatak, Kamalika and Vanka, Kumar} } @article { ISI:000313230200031, title = {Catalytic and DFT study of selective ethylene oligomerization by nickel(II) oxime-based complexes}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {366}, year = {2013}, month = {JAN}, pages = {238-246}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

The reactivity of nickel(II) thiophenealdoxime complex (3) toward oligomerization of ethylene in the presence of an alkylaluminum co-catalyst has been studied. The complex was found to be a selective ethylene dimerization catalyst in the presence of co-catalysts such as methylalumoxane (MAO) and diethylaluminum chloride (DEAC). With DEAC, the productivity was considerably higher than with MAO. Under optimum conditions the productivity reaches 388 kg/mol catalyst/h/bar with DEAC whereas for MAO this value was 119 kg/mol catalyst/h/bar. Complex 3 displays good ethylene conversions of up to a maximum of 90\% with exceptionally high alpha-selectivity for 1-butene (\>99.5\%) amongst C-4 products. Computational studies using density functional theory (DFT) were also carried out to ascertain the decomposition pathway for 3 as well as that for Ni(II) complex of the pyridine ketoxime ligand 2. The results suggest that loss of one of the two bidentate oxime ligands attached to the metal center through reaction with DEAC is likely for both 2 and 3. Further, calculations indicate that the subsequent decomposition step was significantly more probable for 3 than for 2 thus explaining why the pyridine ketoxime ligand bound nickel complex 2 was experimentally found to be more stable than the thiophene aldoxime bound nickel complex 3. Calculations also show that the proton of the -OH group (oxime) plays a major role in the stability of the molecules. This was confirmed experimentally by synthesizing the Ni(II) dichloro complex of Pyridine-2-carbaldehyde O-methyloxime 5 and reacting it with ethylene under similar conditions. 5 was found to be highly active even at low co-catalyst concentrations. (c) 2012 Elsevier B.V. All rights reserved.

}, keywords = {Butene-1, Ethylene dimerization, Ni(II) complex, Thiophene aldoxime}, issn = {1381-1169}, doi = {10.1016/j.molcata.2012.09.029}, author = {Tayade, Kamlesh N. and Mane, Manoj V. and Sen, Suman and Murthy, C. N. and Tembe, Gopal L. and Pillai, S. Muthukumaru and Vanka, Kumar and Mukherjee, Soumen} } @article { ISI:000338486300020, title = {1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU): a highly efficient catalyst in glycerol carbonate synthesis}, journal = {Journal of Molecular Catalysis A-Chemical}, volume = {391}, year = {2014}, month = {SEP}, pages = {144-149}, publisher = {ELSEVIER SCIENCE BV}, type = {Article}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Transesterification of dimethyl carbonate (DMC) with glycerol (GLY) was investigated using various amines as catalysts. Amidines like 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) were found to be the best catalysts for this reaction. Best results: 98\% conversion of GLY with 96\% selectivity to GC (TON: 9408), were obtained with DBU as a catalyst. Effect of various reaction conditions on activity and selectivity were investigated using DBU as catalyst. The mechanism of the reaction was investigated with the help of H-1, C-13 and N-15 NMR analysis and OFT calculations. (C) 2014 Elsevier B.V. All rights reserved.

}, keywords = {DBU, Glycerol, Glycerol carbonate, transesterification}, issn = {1381-1169}, doi = {10.1016/j.molcata.2014.04.016}, author = {Munshi, Mudassir K. and Gade, Swapna M. and Mane, Manoj V. and Mishra, Deepti and Pal, Sourav and Vanka, Kumar and Rane, Vilas H. and Kelkar, Ashutosh A.} } @article { ISI:000330417100005, title = {Proposing efficient new pendant group polymer electrolyte membranes for fuel cells: a computational study}, journal = {Journal of Physical Chemistry C}, volume = {118}, number = {2}, year = {2014}, month = {JAN}, pages = {784-795}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

There is a need to develop new membranes for fuel cells that can conduct protons with high efficiency and at high temperatures. This paper reports a theoretical study of proton transfer barriers in newly proposed polymer electrolyte membranes (PEMs), having pendant nitrogen containing crown ether groups on an alkyl backbone. The proton transfer in the proposed pendant group PEMs would occur without the need of an external agent such as water or phosphoric acid, and without the need for the pendant groups to rotate and reorient themselves after each proton transfer. The current study shows that this would make the proposed PEMs very efficient, with low proton transfer barriers. This has been seen to be true for a range of different PEM cases considered, differing in the number of linker atoms in the alkyl backbone and in the number of nitrogens contained in each pendant group, thus, indicating the potential of the proposed structures as PEMs for fuel cells.

}, issn = {1932-7447}, doi = {10.1021/jp4081349}, author = {Mane, Manoj V. and Vanka, Kumar} } @article { ISI:000349943000006, title = {Computational study of metal free alcohol dehydrogenation employing frustrated lewis pairs}, journal = {Journal of Organic Chemistry}, volume = {80}, number = {4}, year = {2015}, month = {FEB}, pages = {2081-2091}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

The catalysis of acceptorless alcohol dehydrogenation (AAD) is an important area of research. Transition metal-based systems are known to be effective catalysts for this reaction, but developing metal free catalytic systems would lead to highly desirable cheaper and greener alternatives. With this in mind, this computational study investigates design strategies than can lead to metal free frustrated Lewis pairs (FLPs) that can be employed for AAD catalysis. A careful study of 36 different proposed FLP candidates reveals that several new FLPs can be designed from existing, experimentally synthesized FLPs that can rival or be even better than state-of-the-art transition metal-based systems in catalyzing the alcohol dehydrogenation process.

}, issn = {0022-3263}, doi = {10.1021/jo5023052}, author = {Mane, Manoj V. and Rizvi, Masood A. and Vanka, Kumar} } @article {42859, title = {Gold(I)/chiral br{\o}nsted acid catalyzed enantioselective hydroamination-hydroarylation of alkynes: effect of remote hydroxyl group in the reactivity and enantioselectivity}, journal = {Chemistry - A European Journal}, volume = {21}, year = {2015}, month = {JAN}, pages = {975-979}, doi = {10.1002/chem.201405061}, author = {Shinde, Valmik S. and Mane, Manoj V. and Vanka, Kumar and Mallick, Arijit and Patil, Nitin T.} } @article { ISI:000358370700007, title = {Identifying solid luminogens through gold-catalysed intramolecular hydroarylation of alkynes}, journal = {European Journal of Organic Chemistry}, number = {22}, year = {2015}, month = {AUG}, pages = {4860-4867}, publisher = {WILEY-V C H VERLAG GMBH}, address = {POSTFACH 101161, 69451 WEINHEIM, GERMANY}, abstract = {

The identification of a new class of luminogens based on pyrrolo-quinoxaline embedded coumarin (PQC) structures is reported. The reaction relies on the gold-catalyzed hydroarylation reaction of appropriately substituted aryl alkynoates that produces molecules that exhibit solvatochromism and aggregation-induced emission enhancement (AIEE) phenomena. The application of PQCs for live cell imaging has also been demonstrated.

}, keywords = {Cell imaging, Dyes/pigments, fluorescence, Gold, Luminescence, Solvatochromism}, issn = {1434-193X}, doi = {10.1002/ejoc.201500503}, author = {Shaikh, Aslam C. and Shalini, S. and Vaidhyanathan, Ramanathan and Mane, Manoj V. and Barui, Ayan Kumar and Patra, Chitta Ranjan and Venkatesh, Yeduru and Bangal, Prakriti Ranjan and Patil, Nitin T.} } @article { ISI:000373747700077, title = {Additive mediated syn-anti conformational tuning at nucleation to capture elusive polymorphs: remarkable role of extended pi-stacking interactions in driving the self-assembly}, journal = {Crystal Growth \& Design}, volume = {16}, number = {4}, year = {2016}, month = {APR}, pages = {2416-2428}, publisher = {AMER CHEMICAL SOC}, address = {1155 16TH ST, NW, WASHINGTON, DC 20036 USA}, abstract = {

Understanding the process of prenucleation clustering at supersaturating stage is of significant importance to envisage the polymorphism in crystalline materials. Preferential formation of a thermodynamically stable crystal form suggests energetically favored patterns of interactions which control molecular aggregation during nucleation. Introduction of additives during crystallization is sometimes used as a suitable strategy to obtain metastable polymorphs in cases where it is not easy to capture the same by conventional crystallization methods. Comparative analysis of energy relationships and intermolecular interactions between thermodynamically stable and metastable crystal forms provides valuable clues about the nature of growth synthons at prenucleation clustering and preferential crystallization of the thermodynamic form. Conformationally flexible sulfonamide/sulfoester derivatives constituting electron rich and electron deficient aromatic rings were synthesized to study the interplay between pi-stacking and hydrogen bonding synthons. We have identified and characterized the thermodynamically stable and metastable elusive polymorphs of aromatic sulfonamides 1 and 2 and sulfoesters 3 and 4. However, these compounds eluded polymorphism during crystallisation from various common solvents/conditions and only produced thermodynamically stable crystals forms (form I crystals). Surprisingly, exploitation of pyrazinamide as an additive in different stoichiometric ratios during crystallization gave elusive polymorphs [three for 1 (form 1II, form 1III, and form 1IV) and one each for 2 (form 2II), 3 (form 3II), and 4 (form 4II)]. Molecules in stable crystal forms of these compounds are linked via extended chains of parallel displaced pi...pi stacking interactions that seem to play a vital role in driving the self-assembly of molecules and subsequently governing the nucleation process. In contrast, molecules in metastable polymorphs are devoid of such extended pi-stacking assemblies. Interestingly, differential scanning calorimetry, hot stage microscopy, and X-ray crystallographic studies confirmed the thermal crystal-to-crystal transition of all three metastable polymorphs of 1 (form 1II, form 1III, and form 1IV) to its thermodynamically stable crystal form (form 1I). Conformational analysis of molecule 1 using density functional theory calculations also validated higher stability for syn conformation (observed in Form 1I crystals) over anti and midway conformations (seen in metastable polymorphs). Melt crystallization of form 1I crystals of 1 on the larger face (001) of delta-pyrazinamide and lattice matching analysis (GRACE) revealed that the layered arrangement of molecules of delta-pyrazinamide (on 001 face) during heterogeneous nucleation acts as a template (heteroepitaxy) to provide a preferential site for the nucleation of new metastable polymorphs by selectively inhibiting the most preferred crystal form from growing into the nucleus. Solution state one- and two-dimensional (NOESY) H-1 NMR, scanning electron microscopy, and a Cambridge Structural Database survey were conducted to substantiate the role of additives during crystallization.

}, issn = {1528-7483}, doi = {10.1021/acs.cgd.6b00204}, author = {Gawade, Rupesh L. and Chakravarty, Debamitra K. and Kotmale, Amol and Sangtani, Ekta and Joshi, Pranaya V. and Ahmed, Awais and Mane, Manoj V. and Das, Susanta and Vanka, Kumar and Rajamohanan, Pattuparambil R. and Puranik, Vedavati G. and Gonnade, Rajesh G.} } @article {42844, title = {Au(I)/Ag(I) co-operative catalysis: interception of Ag-bound carbocations with α-gold(I) enals in the imino-alkyne cyclizations with N-allenamides}, journal = {Chemical Communications}, volume = {52}, year = {2016}, month = {NOV}, pages = {14462-14465}, doi = {10.1039/C6CC08385D}, author = {Bagle, Pradip N. and Mane, Manoj V. and Vanka, Kumar and Shinde, Dinesh R. and Shaikh, Samir R. and Gonnade, Rajesh G. and Patil, Nitin T.} } @article { ISI:000369572000029, title = {From insertion to multicomponent coupling: temperature dependent reactions of arynes with aliphatic alcohols}, journal = {Chemical Communications}, volume = {52}, number = {8}, year = {2016}, month = {NOV}, pages = {1665-1668}, publisher = {ROYAL SOC CHEMISTRY}, address = {THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND}, abstract = {

The temperature dependent selectivity switch in the reaction of arynes with aliphatic alcohols in THF has been reported. At -20 degrees C, arynes smoothly insert into the O-H bond of alcohols to form alkyl aryl ethers. Interestingly, at 60 degrees C, a highly selective multicomponent coupling occurs with the solvent THF acting as the nucleophilic trigger affording (4-(alkoxy)butoxy)arenes.

}, issn = {1359-7345}, doi = {10.1039/c5cc08307a}, author = {Thangaraj, Manikandan and Bhojgude, Sachin Suresh and Mane, Manoj V. and Biju, Akkattu T.} } @article {43459, title = {Investigation of the biocompatibility and cytotoxicity associated with ROP initiator and its role in bulk polymerization of L-lactide}, journal = {Polymer}, volume = {111}, year = {2017}, month = {FEB}, pages = {244-251}, abstract = {Poly (L-lactide) (PLLA) is one of the most attractive polymers for use in biomedical applications. In such applications it is necessary to reduce the use of toxic chemicals and catalysts used in PLLA synthesis, to minimize any adverse effects. In view of this, we have performed ring opening polymerization (ROP) of Llactide (LA) using biocompatible initiator, namely, Zinc L-Proline (ZnP) in bulk. High molecular weight PLLA (Mw up to 1.45 x 10(5) Da) was obtained using the ZnP complex. The ZnP complex is safe, easy to prepare, store and handle. H-1 and C-13 NMR spectra of PLLA were used to determine the extent of monomer conversion and stereo sequence respectively. Differential Scanning Calorimetry (DSC) and Size Exclusion Chromatography (SEC) were used to determine thermal properties, Mn, Mw and polydispersity index respectively. The mechanism of ROP of LA in the presence of ZnP was studied using Density Functional Theory (DFf) which was in good agreement with results from H-1 NMR and Matrix-Assisted Laser Desorption/Ionization Spectrometry (MALDI-TOF). Biocompatibility/non toxicity of PLLA prepared using ZnP was studied in-vitro using MTT assay by examining the proliferation rate of mouse myoblast C2C12 cell line. Escherichia coli and Staphylococcus aureus were used for the study of antibacterial activity of PLLA. (C) 2017 Elsevier Ltd. All rights reserved.}, doi = {10.1016/j.polymer.2017.01.058}, author = {Parwe, Sharad P. and Warkad, Shrikant D. and Mane, Manoj V. and Shedage, Pranita S. and Garnaik, Baijayantimala} } @article {44453, title = {Dihedral angle control to improve the charge transport properties of conjugated polymers in organic field effect transistors}, journal = {Chemical Physics Letters}, volume = {695}, year = {2018}, month = {MAR}, pages = {51-58}, abstract = {Diketopyrrolopyrrole (DPP) and i-Indigo (i-Ind) are two monomers that are widely explored as active materials in organic field effect transistor and solar cells. These two molecules showed impressive charge carrier mobility due to better packing that are facilitated by quadrupoles. We hypothesized that the copolymers of these monomers would also exhibit high charge carrier mobility. However, we envisioned that the dihedral angle at the connecting point between the monomers will play a crucial role in packing as well as charge transport. To understand the impact of dihedral angle on charge transport, we synthesized three copolymers, wherein the DPP was sandwiched between benzenes, thiophenes and furans. The copolymer of i-Indigo and furan comprising DPP showed a band gap of 1.4 eV with a very high dihedral angle of 179 degrees. The polymer was found to pack better and the coherence length was found to be 112 angstrom. The hole carrier mobility of these polymer was found to be highest among the synthesized polymer i. e. 0.01 cm(2)/vs. The copolymer comprising benzene did not transport hole and electrons. The dihedral angle at the connecting point between i and Indigo and benzene DPP was 143 angstrom, which the packing and consequently charge transport properties. (C) 2018 Elsevier B. V. All rights reserved.}, doi = {10.1016/j.cplett.2018.01.052}, author = {Dharmapurikar, Satej S. and Chithiravel, Sundaresan and Mane, Manoj V. and Deshmukh, Gunvant and Krishnamoorthy, Kothandam} } @article {46282, title = {Gold-catalyzed cycloisomerization of pyridine-bridged 1,8-Diynes: An expedient access to luminescent cycl[3.2.2]azines}, journal = {Organic Letters}, volume = {21}, year = {2019}, month = {SEP}, pages = {7109-7113}, type = {Article}, abstract = {

Gold-catalyzed diyne cycloisomerizations involving carbene/alkyne metathesis have been the focal point of attention for the past few years as it offers great potential to build complex polycyclic architectures. However, the design of novel cycloisomerizations has been mostly limited to 1,5/1,6-diynes and has remained very challenging to apply for higher 1,n-diynes. Herein, we disclose an unprecedented cycloisomerization of pyridine-bridged 1,8-diynes involving carbene/alkyne metathesis to access luminescent cycl[3.2.2]azines.

}, doi = {10.1021/acs.orglett.9b02677}, author = {Chintawar, Chetan C. and Mane, Manoj V. and Tathe, Akash G. and Biswas, Suprakash and Patil, Nitin T.} } @article {45519, title = {Gold(I)-catalyzed hydroxy group assisted C(sp(2))-H alkylation of enaminones with diazo compounds to access 3-alkyl chromones}, journal = {Organic Letters}, volume = {21}, year = {2019}, month = {JAN }, pages = {335-339}, type = {Article}, abstract = {

A strategy for expedient synthesis of 3-substituted chromones from easily available o-hydroxyarylenaminones and diazo compounds has been developed. Carefully conducted experimental and computational studies led us to propose an uncommon mechanistic pathway involving the hydroxyl group assisted alkylation of enaminones with in situ generated gold carbenes.

}, issn = {1523-7060}, doi = {10.1021/acs.orglett.8b03989}, author = {Bagle, Pradip N. and Mane, Manoj V. and Sancheti, Shashank P. and Gade, Amol B. and Shaikh, Samir R. and Baik, Mu-Hyun and Patil, Nitin T.} } @article {46952, title = {Catalyst-free regioselective [3+2] cycloadditions of alpha,beta-unsaturated N-arylnitrones with alkenes to access functionalized isoxazolidines: a DFT study}, journal = {Chemistry-An Asian Journal}, volume = {15}, year = {2020}, month = {MAR}, pages = {899-903}, type = {Article}, abstract = {

The catalyst-free regioselective [3+2]-cycloaddition of alpha,beta-unsaturated N-arylnitrones with alkenes are developed. The series of synthetically important functionalized isoxazolidines are prepared in good to excellent yields by step economic pathway under ligand and transition-metal-free conditions. The regioselective cycloaddition pathway supported by control experiment and computational study.

}, keywords = {DFT study, isoxazolidines, metal and ligand free, nitrone cycloaddition, Regioselective}, issn = {1861-4728}, doi = {10.1002/asia.201901754, Early Access Date = FEB 2020}, author = {Ghosh, Arnab and Mane, Manoj V. and Rode, Haridas B. and Patil, Siddappa A. and Sridhar, Balasubramanian and Dateer, Ramesh B.} } @article {48191, title = {Enantioselective Au(I)/Au(III) redox catalysis enabled by chiral (P,N)-ligands}, journal = {Journal of the American Chemical Society}, volume = {144}, year = {2022}, month = {APR}, pages = {7089-7095}, type = {Article}, abstract = {

Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88\% yield and 99\% ee). DFT studies were carried out to unravel the enantiodetermining step, which revealed that the stronger trans influence of phosphorus allows selective positioning of the substrate in the C-2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity.

}, issn = {0002-7863}, doi = {10.1021/jacs.2c02799}, author = {Chintawar, Chetan C. and Bhoyare, Vivek W. and Mane, Manoj V. and Patil, Nitin T.} }