00889nas a2200169 4500008004100000245009200041210006900133260000800202300001500210490000700225520027800232100001800510700001900528700003100547700002800578856011300606 2017 eng d00aExploring the gem-dimethyl effect in the formation of imine-based macrocycles and cages0 aExploring the gemdimethyl effect in the formation of iminebased  cJUL a8721-8724 0 v173 aUsing the gem-dimethyl effect as a platform, a variety of organic [2+2] macrocycles and [2+3] cofacial cages was obtained in high yields. Imine-based macrocyclization could be performed even at high concentrations (0.5 to 1.0 M), via instant mixing of aldehydes and amines.1 aMadhu, Suresh1 aRashmi, E., V.1 aGonnade, Rajesh, Ghanshyam1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/exploring-gem-dimethyl-effect-formation-imine-based-macrocycles-and-cages01173nas a2200157 4500008004100000245007700041210006900118260000800187300001600195490000600211520061900217100001800836700002400854700002800878856010900906 2018 eng d00aThree-dimensional metal-organic polymer of multivalent hexaphenylbenzene0 aThreedimensional metalorganic polymer of multivalent hexaphenylb cDEC a13712-137150 v33 a

Metal-Organic Frameworks(MOFs) synthesized from ligands more than ten co-ordinating sites may offer material applications due to their structural architecture. Herein, a synthesis of metal-organic framework is reported from a ligand featuring 12-aryl carboxylic acid groups appended on a hexaphenylbenzene and s-block element potassium. The synthesized MOF was characterized by thermogravimetric analysis, infrared spectroscopy and X-diffraction studies. The X-ray crystal structure of MOF was shown to have a significant number of trapped and coordinated water molecules in its three-dimensional framework.

1 aMadhu, Suresh1 aGonnade, Rajesh, G.1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/three-dimensional-metal-organic-polymer-multivalent-hexaphenylbenzene01965nas a2200193 4500008004100000022001500041245010400056210006900160260000800229300001400237490000700251520128700258100001801545700002401563700001501587700001701602700002801619856012401647 2018 eng d a 2192-650600a Twelve-armed hexaphenylbenzene-based giant supramolecular framework for entrapping guest molecules0 aTwelvearmed hexaphenylbenzenebased giant supramolecular framewor cNOV a1032-10370 v833 a

Host-guest chemistry is a functional model in supramolecular chemistry for understanding specific process occurring in biological systems. Herein, we describe a rationally designed giant multiarmed hexaphenylbenzene (HPB)-based supramolecular frameworks which encapsulate a variety of guest molecules in the voids of their crystal lattice through the cooperative interplay of multivalency, noncovalent forces and backbone rigidity. In this connection, pseudo-axially substituted twelve-armed hexaphenylbenzene was synthesized and its molecular entrapping nature was studied by varying number of H-bond donor-acceptor sites in the arms. The per-methyl esterified HPB acted as a cavitand to include nonpolar and polar aprotic guests in its crystal structure via C-H center dot center dot center dot pi, C-H center dot center dot center dot O and C-H center dot center dot center dot N interactions. The corresponding amidated HPB showed unprecedented inclusion of ammonia and segregation of the guest molecules according to their polarity in the lattice. Furthermore, this molecular entrapping system has been used to obtain the crystal structure of a hitherto unproven 2-azaallenium intermediate, which had been proposed to be involved in aminomethylation of activated arenes.

1 aMadhu, Suresh1 aGonnade, Rajesh, G.1 aDas, Tamal1 aVanka, Kumar1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/twelve-armed-hexaphenylbenzene-based-giant-supramolecular-framework-entrapping-guest01636nas a2200277 4500008004100000022001400041245009300055210006900148260000900217300001600226490000600242520073400248653001300982653001200995653002101007653001301028653001301041100002601054700003001080700001801110700003501128700002001163700002401183700002801207856012301235 2019 eng d a2365-654900aDimedone-based rigid organic scaffold for organizing symmetrical helical peptide chains.0 aDimedonebased rigid organic scaffold for organizing symmetrical  cOCT  a11518-115220 v43 a

We describe herein design, synthesis and conformational investigations of polypeptides attached on a rigid dimedone template. Two identical peptide chains are attached on a single carbon containing dimedone as a scaffold. Dimedone assists in controlling the secondary interactions through strong intramolecular helical C-12 and C-15 membered bifurcated hydrogen bonding on both the peptide chains along with propagating the helical architecture of the peptide chains attached. There exists a C-6 hydrogen bonding for the single stranded peptides attached to dimedone. Extensive structural investigations involving single crystal X-ray diffraction, solution-state NMR and CD studies of oligopeptides have been undertaken.

10adimedone10aHelical10ahydrogen bonding10aPeptides10atemplate1 aMadica, Krishnaprasad1 aLakshmi, Jerripothula, K.1 aMadhu, Suresh1 aNadimpally, Krishna, Chaitanya1 aGonnade, Rajesh1 aJagadeesh, Bharatam1 aSanjayan, Gangadhar, J. uhttps://library.ncl.res.in/content/dimedone-based-rigid-organic-scaffold-organizing-symmetrical-helical-peptide-chains01237nas a2200157 4500008004100000245007900041210006900120260000800189490000700197520067300204100001800877700002600895700002000921700002700941856011100968 2019 eng d00aSynthesis of hexaphenylbenzene-based template assembled synthetic proteins0 aSynthesis of hexaphenylbenzenebased template assembled synthetic cAUG0 v603 a

Template-assembled synthetic proteins (TASPs) synthesized from rigid templates have attracted attention due to their interesting structural architectures and potential biomedical applications. Herein, we report the design, synthesis and characterizations of TASPs based on hexaphenylbenzene template (HPB) having twelve peptide attachable axial-arms in its structure. The peptides were attached to all the axial-arms of the template in a single step using simple solution phase peptide coupling strategy. The reaction conditions were standardized systematically using simple amines from smaller size to larger ones. (C) 2019 Elsevier Ltd. All rights reserved.

1 aMadhu, Suresh1 aMadica, Krishnaprasad1 aGonnade, Rajesh1 aSanjayan, Gangadhar, J uhttps://library.ncl.res.in/content/synthesis-hexaphenylbenzene-based-template-assembled-synthetic-proteins01673nas a2200133 4500008004100000245009900041210006900140260000800209490000600217520114900223100001801372700002101390856012801411 2021 eng d00aStructural and computational investigation of an imine-based propeller-shaped macrocyclic cage0 aStructural and computational investigation of an iminebased prop cFEB0 v33 aIn this study, we present the synthesis, spectroscopic and structural characterization of self-assembling gem-dimethyl imine based molecular cage (IMC). Self-assembling macrocycles and cages have well-defined cavities and have extensive functionalities ranging from energy storage, liquid crystals, and catalysts to water splitting photo absorber. IMC has large voids i.e., 25% of the total crystal volume thus could accommodate wide substrates. The synthesized imine-based molecular cages are stabilized by coaxial π bonded networks and long-range periodic van der Waal and non-bonded contacts as observed from the crystal structure. IMC also has typical properties of soft condensed matter materials, hence theoretical prediction of stress and strain tensor along with thermophysical properties were computed on crystal system and were found to be stable. Molecular dynamics revealed IMC is stabilized by, strong interactions between the interstitial phenyl rings. Density functional theory (DFT) based physicochemical properties were evaluated and has band gap of around 2.38ev (520 nm) similar to various photocatalytic band gap materials.1 aMadhu, Suresh1 aRaghavan, Sriram uhttps://library.ncl.res.in/content/structural-and-computational-investigation-imine-based-propeller-shaped-macrocyclic-cage