- The flexibility-complementarity dichotomy in receptor-ligand interactions
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Synthetic supramolecular complexes provide an opportunity for quantitative systematic exploration of the relationship between chemical structure and molecular recognition phenomena. A family of closely related zinc porphyrin-pyridine complexes was used to examine the interplay of conformational flexibility and geometric complementarity in determining the selectivity of molecular recognition events. The association constants of 48 zinc porphyrin-pyridine complexes were measured in two different solvents, toluene and 1,1,2,2-tetrachloroethane (TCE). These association constants were used to construct 32 chemical double mutant cycles to dissect the free energy contributions of intramolecular H-bonds between the phenol side arms of the porphyrins and the ester or amide side arms of the pyridine ligands. Effective molarities (EM) for the intramolecular interactions were determined by comparison with the corresponding intermolecular H-bonding interactions. The values of EM do not depend on the solvent and are practically identical for amide and ester H-bond acceptors located at the same site on the ligand framework. However, there are variations of an order of magnitude in EM depending on the flexibility of the linker used to connect the H-bond acceptors to the pyridine ligands. Rigid aromatic linkers give values of EM that are an order of magnitude higher than the values of EM for the corresponding ester linkers, which have one additional torsional degree of freedom. However, the most flexible ether linkers give values of EM that are also higher than the values of EM for the corresponding ester linkers, which have one less torsional degree of freedom. Although the penalty for conformational restriction on binding is higher for the more flexible ether linkers, this flexibility allows optimization of the geometric complementarity of the ligand for the receptor, so there is a trade off between preorganization and fit.
- Sun, Hongmei,Hunter, Christopher A.,Llamas, Eva Marina
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Read Online
- Multi-dimensional copper(I) and silver (I) coordination polymers assembled with a pyridyl bis-urea macrocyclic ligand
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We report the synthesis of a new flexible multimodal macrocyclic ligand, protected pyridyl bis-urea macrocycle 1, and two of its coordination polymers Cu2I2(1)2·(CH3CN)1.63 (2) and [Ag(1)](NO3).(H2O)2.49 (3). The ligand possesses conformational flexibility and adopts different conformations and binding modes depending on the metal ions. The crystal structure of 2 shows a 2D coordination network constructed from rhomboidal Cu2I2 dimer units and 1 as a bridging ligand binding through the pyridyl N atoms. 3 forms a sophisticated 3D structure with 1D chains formed by N-Ag-N links between pyridyl N atoms of two adjacent macrocyclic ligands and Ag(I) ions. These chains form 2D layers through longer Ag-O interactions and the chains are linked together into a 3D network by hydrogen bonding involving interstitial water molecules. These results indicate the potential of ligand 1 in the self-assembly of coordination polymers with diverse topology and functional applications.
- Som, Bozumeh,Smith, Mark D.,Shimizu, Linda S.
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- ANTIBODY-DRUG CONJUGATES COMPRISING ANTI-B7-H3 ANTIBODIES
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The present disclosure relates to antibody-drug conjugates (ADCs) wherein one or more active agents are conjugated to an anti-B7-H3 antibody through a linker. The linker may comprise a unit that covalently links active agents to the antibody. The disclosure further relates to monoclonal antibodies and antigen binding fragments, variants, multimeric versions, or bispecifics thereof that specifically bind B7-H3, as well as methods of making and using these anti-B7-H3 antibodies and antigen-binding fragments thereof in a variety of therapeutic, diagnostic and prophylactic indications
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Page/Page column 149; 190
(2022/01/04)
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- NOVEL BENZODIAZEPINE DERIVATIVES AND USES THEREOF
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The present disclosure provides compounds and compositions capable of extending lifespan, and methods of use thereof.
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Paragraph 0489-0491
(2019/12/24)
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- NOVEL MACROCYCLIC DIACETYLENE COMPOUND AND METHOD FOR MANUFACTURING THEREOF
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The present invention relates to a macrocyclic diacetylene compound, and a production method thereof. More specifically, the present invention relates to a macrocyclic diacetylene compound enabling production of diameter-adjustable polydiacetylene nanotube. The present invention further relates to a production method thereof. According to the present invention, it is possible to produce diacetylene nanotube having various ranges of diameter by undergoing crystallization of the diacetylene compound, and polydiacetylene nanotube can be formed by making the diacetylene nanotube irradiated with ultraviolet light or gamma rays.COPYRIGHT KIPO 2018
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Paragraph 0250; 0253
(2018/04/12)
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- Synthesis of pyridine acrylates and acrylamides and their corresponding pyridinium ions as versatile cross-linkers for tunable hydrogels
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A small library of cross-linkers for hydrogels was synthesized. The cross-linkers consisted of 2,6- and 3,5-diacylpyridine or 2,4,6-triacylpyridine as the core unit, which were tethered via ethylene glycol, amino ethanol, and 1,n-diamine spacers to terminal acrylate or acrylamide moieties. Esterification and amide formation of the terminal acryl units were found to be dependent on the ratio of NH/O in the spacer, the constitution pattern of the pyridine ring, and the total number of acryl groups. Thus, esters generally gave higher yields than amides decreasing with increasing number of NH in the spacer and with increasing number of acryl units. In the case of 3,5-diacylpyridine derivatives, these trends were less prominent as compared to the 2,6-diacylpyridine series, indicating that steric hindrance and unfavorable hydrogen bonding interaction of the spacers might influence the observed reactivity differences. The 3,5-diacylpyridines were converted to the N-methylpyridinium salts and selected members of both neutral and cationic 3,5-diacylpyridinium derivatives were submitted to hydrogelations with synthetic polymer poly(1-glycidylpiperazine) via aza-Michael addition and thiolated natural hyaluronan via thio-Michael reaction, respectively. Rheological properties of the resulting hydrogels were studied, revealing that both spacer type as well as charge affected elastic moduli and degree of swelling. Georg Thieme Verlag Stuttgart New York.
- Mateescu, Markus,Nuss, Isabell,Southan, Alexander,Messenger, Hayley,Wegner, Seraphine V.,Kupka, Julia,Bach, Monika,Tovar, Guenter E. M.,Boehm, Heike,Laschat, Sabine
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p. 1243 - 1253
(2014/05/06)
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- Synthesis and linear and nonlinear absorption properties of dendronised ruthenium(ii) phthalocyanine and naphthalocyanine
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Ruthenium phthalocyanines and naphthalocyanines with axial dendronised pyridine ligands show high solubility in a variety of solvents, and exhibit solid-state absorption spectra that are comparable to those obtained in dilute solution, making them interesting candidates for optical limiting in the visible.
- Dasari, Raghunath R.,Sartin, Matthew M.,Cozzuol, Matteo,Barlow, Stephen,Perry, Joseph W.,Marder, Seth R.
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supporting information; scheme or table
p. 4547 - 4549
(2011/06/21)
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- Synthesis and biological activities of topoisomerase I inhibitors, 6-arylmethylamino analogues of edotecarin
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The replacement of 1,3-dihydroxy-2-propylamino moiety at the N6-position of edotecarin (1) by arylmethylamino groups yielded a number of more potent topoisomerase I inhibitors with better cytotoxic (CTX) activities in vitro than edotecarin. Among them, th
- Sunami, Satoshi,Nishimura, Teruyuki,Nishimura, Ikuko,Ito, Satoru,Arakawa, Hiroharu,Ohkubo, Mitsuru
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supporting information; experimental part
p. 3225 - 3237
(2010/03/25)
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- QUINOLONE ANTIBACTERIAL AGENTS
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Compounds of formula (I, II, III, IV, V, and VI) and methods for their preparation are disclosed. Further disclosed are methods of making biologically active compounds of formula (I) as well as pharmaceutically acceptable compositions comprising compounds of formula (I). Compounds of formula (I) as disclosed herein can be used in a variety of applications including use as antibacterial agents.
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Page/Page column 105
(2010/02/11)
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- A 3D interlocked structure from a 2D template: Structural requirements for the assembly of a square-planar metal-coordinated [2]rotaxane
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One step beyond: The synthesis of a three-dimensional interlocked molecular architecture (a rotaxane) from a two-dimensional square-planar metal template (see scheme) has been achieved. A combination of steric and electronic factors direct the synthesis in the third dimension, either by promoting or preventing interlocking.
- Fuller, Anne-Marie,Leigh, David A.,Lusby, Paul J.,Oswald, Iain D. H.,Parsons, Simon,Walker, D. Barney
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p. 3914 - 3918
(2007/10/03)
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- Appending a tris-imidazole ligand with a Tyr244 mimic on the distal face of bromoacetamidoporphyrin
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(Equation presented) Bromoacetamidoporphyrin is a convenient synthon for the attachment of distal superstructures at room temperature in good yields. New models are presented that contain a tris-imidazole distal ligand set bound to the porphyrin in either a binary or trinary fashion. More importantly, one distal imidazole is cross-linked to a phenol mimicking Tyr244, making this model the closest structural analogue yet reported of the metal free cytochrome c oxidase (CcO) active site.
- Collman, James P.,Decreau, Richard A.,Costanzo, Simona
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p. 1033 - 1036
(2007/10/03)
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- Coordination behaviour of the new multidentate ligand 3,5-bis(dimethyl-aminomethyl)pyridine with palladium(II) and platinum(II) metal centres
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The synthesis of the new potentially tridentate ligand 3,5-bis(dimethylaminomethyl)pyridine (3) is described. Coordination chemistry of this ligand has been investigated with PdII and PtII precursor compounds. Both a bidentate bridging bonding motif and a monodentate bonding mode is observed. The latter compounds incorporate 3 by coordination through the pyridinic N atom only. The former complexes contain ligand 3 bonded to 2 metal centres by bridging through coordination of one trialkyl N donor atom and the pyridinic N atom. The solid-state structure of a ligand bridged Pd dimer has been elucidated by single-crystal X-ray diffraction and corroborates with the solid-state IR data that suggested a trans-PdCl2 unit was present.
- Lagunas, María-Cristina,Gossage, Robert A.,Smeets, Wilberth J. J.,Spek, Anthony L.,Van Koten, Gerard
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p. 163 - 168
(2007/10/03)
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- BOTH-FACES HINDERED PORPHYRINS. PART 2. SYNTHESIS AND CHARACTERIZATION OF INTERNALLY FIVE-CO-ORDINATED IRON(II)BASKET-HANDLE PORPHYRINS DERIVED FROM 5,10,15,20-TETRAKIS(O-HYDROXYPHENYL)PORPHYRIN
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Compounds (9), so-called ether 'hanging base' porphyrins, derived from 5,10,15,20-tetrakis(o-hydroxyohenyl)porphyrin in which one of the faces is hindered by a pyridine-3,5-diylbisalkylene bridge and the other face is protected by an alkylene or an p-arylenebisalkylene chain have been synthesized following the concept of the 'basket handle' porphyrins (BHP).From an analysis of the 1H n.m.r. spectra of the iron(II) derivatives (20) at 34 degC, it has been determined that ca. 85percent were high-spin five-coordinated complexes (s=2).Despite the steric hindrance of the distal face, bimolecular associations typical for this class of compounds have been detected except for the most hindered (20c).An additional bispyridine 'basket handle' porphyrin (21) has been synthesized in order to study the dynamics of the pyridine chain.
- Momenteau, Michel,Mispelter, Joel,Loock, Bernard,Lhoste, Jean-Marc
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