Stability and Lifetime of Quadruply Hydrogen Bonded 2-Ureido-4[1<i>H</i>]-pyrimidinone Dimers

Söntjens, Serge H. M.; Sijbesma, Rint P.; Genderen, Marcel H. P. van; Meijer, E. W.

doi:10.1021/ja000435m

Cited by 526 publications

(525 citation statements)

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“…The lifetime of small molecule UPy dimers in solution 40 was previously found to depend strongly on the polarity of the solvent and ranged from 80 ms (chloroform saturated with water) to 1.7 s (toluene). The PnBA environment considered here is relatively polar, and so the bare lifetime should be low; R-10-4.5, which showed a dropoff of the plateau at the highest frequency, provides an upper limit to the UPy dimer lifetime τ b in PnBA at 25°C of 1.2 s, although NMR exchange experiments would be necessary to determine its actual value.…”

Section: Resultsmentioning

confidence: 99%

“…29,30 To broaden the scope and applicability of supramolecular polymer chemistry, many new strongly hydrogen-bonding moieties have been synthesized [31][32][33][34][35][36][37] and incorporated into networkforming materials. [12][13][14][15][38][39][40][41] The strength and specificity of multiple-hydrogen-bonded (MHB) groups vary widely, from weakly complementary pyridine-phenol pairs 42 to extremely strong, self-complementary 6-H-bonded dimers. 31 The 2-ureido-4[1H]-pyrimidinone (UPy) group first reported by Sijbesma et al 12 was developed as a synthetically accessible, exceptionally strong (K dim = 6 Â 10 7 M -1 in CDCl 3 ) quadruple-hydrogenbonded dimer in order to create highly thermally responsive polymeric materials.…”

Section: Introductionmentioning

confidence: 99%

“…39 Alternately, bulky substituents near UPy's prevent such crystallization while linear alkyl chains enhance it. 40 In both cases, the presence of crystalline stacks (rather than simple pairwise UPy-UPy association) was shown to be crucial for network formation and good mechanical properties.…”

Section: Introductionmentioning

confidence: 99%

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Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Feldman¹,

Kade²,

Meijer³

et al. 2010

Macromolecules

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Random copolymers consisting of n-butyl acrylate backbones with quadruple hydrogenbonding side chains based on 2-ureido-4[1H]-pyrimidinone (UPy) have been synthesized via controlled radical polymerization and postpolymerization functionalization. Through this synthetic strategy high UPy monomer content (15 mol %) can be reached while maintaining low polydispersity and excellent control over molecular weight, providing model reversible networks with well-defined molecular architecture. Despite low T g s and a lack of entanglements or crystallinity, these materials behave as thermoplastic elastomers through the strong but reversible association of UPy groups. Bulk properties such as the plateau modulus, tensile modulus, and relaxation time scale are primarily determined by the average distance between UPy's along the chain. Starting from a difunctional initiator, triblock copolymers can also be synthesized containing a homopolymer midblock and random copolymer end blocks, effectively concentrating the hydrogen-bonding groups near the chain ends. By controlling both the average composition and distribution of UPy's along the polymer chain, macroscopic material properties such as stiffness and resistance to creep can be independently tuned.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Feldman¹,

Kade²,

Meijer³

et al. 2010

Macromolecules

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“…2) was synthesized and studied by fluorescence spectroscopy. This method, recently used by Sijbesma and colleagues (21) to measure the strong dimerization of a module similar to 1, takes advantage of the excimer signal of the pyrene dimer that exhibits an emission band at 500-600 nm that is well separated from that of the monomers. In chloroform saturated with water, the K dimer of 4 was 3.0 (Ϯ0.4) ϫ 10 7 M Ϫ1 ; whereas in freshly opened chloroform ([water] Ϸ17 mM) K dimer ϭ 8.5 (Ϯ1.6) ϫ 10 7 M Ϫ1 .…”

Section: Resultsmentioning

confidence: 99%

Discrete and polymeric self-assembled dendrimers: Hydrogen bond-mediated assembly with high stability and high fidelity

Corbin

Lawless

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

170

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Hydrogen bond-mediated self-assembly is a powerful strategy for creating nanoscale structures. However, little is known about the fidelity of assembly processes that must occur when similar and potentially competing hydrogen-bonding motifs are present. Furthermore, there is a continuing need for new modules and strategies that can amplify the relatively weak strength of a hydrogen bond to give more stable assemblies. Herein we report quantitative complexation studies on a ureidodeazapterin-based module revealing an unprecedented stability for dimers of its self-complementary acceptoracceptor-donor-donor (AADD) array. Linking two such units together with a semirigid spacer that carries a first-, second-, or third-generation Fré chet-type dendron affords a ditopic structure programmed to self assemble. The specific structure that is formed depends both on the size of the dendron and the solvent, but all of the assemblies have exceptionally high stability. The largest discrete nanoscale assembly is a hexamer with a molecular mass of about 17.8 kDa. It is stabilized by 30 hydrogen bonds, including six AADD⅐DDAA contacts. The hexamer forms and is indefinitely stable in the presence of a hexamer containing six ADD⅐DAA hydrogen-bonding arrays. A t the most fundamental level, the readout of stored information in biochemical systems requires both a code and the machinery for expressing the code (1). Distinction at the molecular level is critical in such processes and in its simplest form involves a molecular recognition event. The code may be, for example, the primary sequence of a polypeptide, which through a series of recognition events folds into a specific secondary or tertiary structure, or it may be a linear array of recognition sites that are sequentially processed through a distinctive engagement at each site. However, a distinctive chemical process alone (e.g., DNA base pairing) is not sufficient. It must be coupled with a biological process (e.g., replication) to be considered authentic information retrieval.Inspired by nature's ability to create extraordinarily complex systems from comparatively simple information codes, and with an eye toward creating nanoscale devices (2), chemists have sought to develop small molecules capable of self-assembling into larger structures (3-10). Molecular recognition sites within these small molecules carry the code that guide the assembly. Thus, the information retrieval process is expressed through the formation of the self-assembled structure, which can further manifest itself through the bulk properties of the material formed (11,12). Despite the many successful examples that have appeared over the past decade, the power of this biomimetic self-assembly strategy has not been fully realized largely because of the limited number of recognition motifs available, and, in particular, their relatively low stability (4, 13). Moreover, nearly all self-assembling systems reported to date use a single type of distinction. Developing systems where bi-or polyinstructional codes guide ...

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“…These molecules have also received much attention as fundamental synthetic building blocks because of their hydrogen bonding and π-π stacking potential. In particular, Meijer's ureidopyrimidone (UPy) building block [9,10], with its characteristics of a high dimerization constant and synthetic accessibility, has found widespread applications in supramolecular chemistry, materials science, and catalysis [11,12]. Zimmerman's ureidodeazapterin and ureidonaphthyridine modules are also successful examples of heterocyclic building blocks [13][14][15][16].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of N-phenyl-2-(pyridin-4-ylcarbonyl)hydrazinecarboxamide with Z′ = 4, C₁₃H₁₂N₄O₂

Pansuriya

Patel

Friedrich

et al. 2016

Zeitschrift Für Kristallographie - New Crystal Structures

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C 13 H 12 N4O 2 , orthorhombic, Pbca (no. 61), a = 16.2353(11) Å, b = 16.8474(12) Å, c = 36.028(2) Å, V = 9854.5(11) Å 3 , Z = 32, CCDC no.: 1457416In the gure only one out of four crystallographically independent molecules is shown. Tables 1-3 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters. Source of materialIsoniazid (1 g, 7.2 mmol) and phenyl isocyanate (1 g, 8.3 mmol) were mixed in methanol (30 mL) thoroughly and re uxed for 30 min. After the reaction was completed, the resulting mixture was cooled to room temperature. The products were collected by ltration (1.4 g, 80% yield); M.p.:422-424 K. The title compound was recrystallized from a mixture of methanol and dichloromethane (50:50), colourless single crystals were obtained by slow evaporation. Experimental detailsAbsorption correction was performed using SADABS (Bruker, 2006). All hydrogen atoms were placed in idealised positions

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Stability and Lifetime of Quadruply Hydrogen Bonded 2-Ureido-4[1H]-pyrimidinone Dimers

Cited by 526 publications

References 49 publications

Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Discrete and polymeric self-assembled dendrimers: Hydrogen bond-mediated assembly with high stability and high fidelity

Crystal structure of N-phenyl-2-(pyridin-4-ylcarbonyl)hydrazinecarboxamide with Z′ = 4, C₁₃H₁₂N₄O₂

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Stability and Lifetime of Quadruply Hydrogen Bonded 2-Ureido-4[1H]-pyrimidinone Dimers

Cited by 526 publications

References 49 publications

Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Discrete and polymeric self-assembled dendrimers: Hydrogen bond-mediated assembly with high stability and high fidelity

Crystal structure of N-phenyl-2-(pyridin-4-ylcarbonyl)hydrazinecarboxamide with Z′ = 4, C13H12N4O2

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Crystal structure of N-phenyl-2-(pyridin-4-ylcarbonyl)hydrazinecarboxamide with Z′ = 4, C₁₃H₁₂N₄O₂