From Cooperative Self-Assembly to Water-Soluble Supramolecular Polymers Using Coarse-Grained Simulations

Supramolecular polymers, formed via noncovalent self-assembly of elementary monomers, are extremely interesting for their dynamic bioinspired properties. In order to understand their behavior, it is necessary to access their dynamics while maintaining high resolution in the treatment of the monomer structure and monomer-monomer interactions, which is typically a difficult task, especially in aqueous solution. Focusing on 1,3,5-benzenetricarboxamide (BTA) water-soluble supramolecular polymers, we have developed a transferable coarse-grained model that allows studying BTA supramolecular polymerization in water, while preserving remarkable consistency with the atomistic models in the description of the key interactions between the monomers (hydrophobic, H-bonding, etc.), self-assembly cooperativity, and amplification of order into the growing fibers. This permitted us to monitor the amplification of the key interactions between the monomers (including H-bonding) in the BTA fibers during the dynamic polymerization process. Our molecular dynamics simulations provide a picture of a stepwise cooperative polymerization mechanism, where initial fast hydrophobic aggregation of the BTA monomers in water is followed by the slower reorganization of these disordered aggregates into ordered directional oligomers. Supramolecular polymer growth then proceeds on a slower time scale. We challenged our models via comparison with the experimental evidence, capturing the effect of temperature variations and subtle changes in the monomer structure on the polymerization and on the properties of the fibers seen in the real systems. This work provides a multiscale spatiotemporal characterization of BTA self-assembly in water and a useful platform to study a variety of BTA-based supramolecular polymers toward structure-property relationships

Effect of Concentration on the Supramolecular Polymerization Mechanism via Implicit-Solvent Coarse-Grained Simulations of Water-Soluble 1,3,5-Benzenetricarboxamide

We report an implicit-solvent coarse-grained (CG) model for a water-soluble 1,3,5-benzenetricarboxamide (BTA) supramolecular polymer. The technical advances guaranteed by this CG model allow simulation of the self-assembly of 1000 BTA monomers and easy variation of the BTA concentration into the system down to experimental dilute conditions. In this way, we can monitor the mechanism of supramolecular polymerization as a function of the concentration at submolecular resolution exceeding the microsecond time scale. While increasing the concentration produces rapid formation of large disordered clusters that are then converted into BTA fibers, moving to very dilute concentrations favors early ordering of the oligomers in solution even at small sizes. Interestingly, we observe that below a certain concentration the oligomers that dynamically grow in solution during the self-assembly present the same level (and amplification) of order of prestacked equilibrated oligomers of the same size, meaning that concentration-dependent kinetic effects have disappeared from the polymerization mechanism

Communication: Reduced density matrices in molecular systems: Grand-canonical electron states

Grand-canonical like descriptions of many electron atomic and molecular open systems which are characterized by a non-integer number of electrons are presented. Their associated reduced density matrices (RDMs) are obtained by introducing the contracting mapping for this type of distributions. It is shown that there is loss of information when connecting RDMs of different order by partial contractions. The energy convexity property of these systems simplifies the description. Consequently, this formulation opens the possibility to a new look for chemical descriptors such as chemical potential and reactivity among others. Examples are presented to discuss the theoretical aspects of this work. © 2013 AIP Publishing LLC.Fil:Bochicchio, R.C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.Fil:Rial, D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina

Into the dynamics of a supramolecular polymer at submolecular resolution

To rationally design supramolecular polymers capable of self-healing or reconfiguring their structure in a dynamically controlled way, it is imperative to gain access into the intrinsic dynamics of the supramolecular polymer (dynamic exchange of monomers) while maintaining a high-resolution description of the monomer structure. But this is prohibitively difficult at experimental level. Here we show atomistic, coarse-grained modelling combined with advanced simulation approaches to characterize the molecular mechanisms and relative kinetics of monomer exchange in structural variants of a synthetic supramolecular polymer in different conditions. We can capture differences in supramolecular dynamics consistent with the experimental observations, revealing that monomer exchange in and out the fibres originates from the defects present in their supramolecular structure. At the same time, the submolecular resolution of this approach offers a molecular-level insight into the dynamics of these bioinspired materials, and a flexible tool to obtain structure-dynamics relationships for a variety of polymeric assemblies

Selective mobilization of fatty acids in adipose tissue of heavy pigs

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Minority Stress, Resilience, and Mental Health: A Study of Italian Transgender People

Transgender people often experience oppression because of gender nonconformity. They represent an extremely stigmatized population at high risk of developing mental health problems. The minority stress model is a theoretical model used to understand social stigma as a potential cause of mental health disparities faced by the transgender population. In Italy, studies applying this model to the transgender population are limited. The current study applied the minority stress model to a sample of Italian transgender people (n = 149), analyzing effects of prejudice events, expectations of rejection, and internalized transphobia, and their interaction with protective factors (resilience and social support), on mental health. The results suggest that exposure to everyday discrimination and internalized transphobia are associated with increased mental health problems, while perceived social support from family and resilience significantly reduced the strength of association between everyday discrimination and mental health. Findings have important implications for both social issues and policies

Current Renormalisation Constants with an O(a)-improved Fermion Action

Using chiral Ward identities, we determine the renormalisation constants of bilinear quark operators for the Sheikholeslami-Wohlert action lattice at beta=6.2. The results are obtained with a high degree of accuracy. For the vector current renormalisation constant we obtain Z_V=0.817(2)(8), where the first error is statistical and the second is due to mass dependence of Z_V. This is close to the perturbative value of 0.83. For the axial current renormalisation constant we obtain Z_A = 1.045(+10 -14), significantly higher than the value obtained in perturbation theory. This is shown to reduce the difference between lattice estimates and the experimental values for the pseudoscalar meson decay constants, but a significant discrepancy remains. The ratio of pseudoscalar to scalar renormalisation constants, Z_P/Z_S, is less well determined, but seems to be slightly lower than the perturbative value.Comment: 8 pages uuencoded compressed postscript file. Article to be submitted to Phys.Rev.

The Influence of Minority Stress, Gender, and Legalization of Civil Unions on Parenting Desire and Intention in Lesbian Women and Gay Men: Implications for Social Policy and Clinical Practice

Although the rate of lesbian and gay (LG) parents is increasing, lesbian and gay adults are less likely than heterosexual adults to be parents, as desire and intention to become a parent tend to be lower. This study aims at assessing 290 childless LG individuals (120 lesbian women and 170 gay men) to explore the influence of minority stress, gender differences, and legalization of civil unions in Italy on parenting desire and intention. The results indicated that the minority stressors associated with parenting dimensions included prejudice events, outness, and internalized homophobia for lesbian women, but only felt stigma among gay men. Support from family or significant others buffered the effects of minority stressors on parenting dimensions. Thus, the minority stress processes partly explain the intention and desire to become parents in LG childless individuals. Furthermore, lesbian women showed higher levels of parenting desire and intention than gay men and the levels of these parenting dimensions increased after the law on civil unions was enacted. The findings have important implications for both social policies and clinical practice

Controlling Exchange Pathways in Dynamic Supramolecular Polymers by Controlling Defects

Supramolecular fibers composed of monomers that self-assemble directionally via noncovalent interactions are ubiquitous in nature, and of great interest in chemistry. In these structures, the constitutive monomers continuously exchange in-and-out the assembly according to a well-defined supramolecular equilibrium. However, unraveling the exchange pathways and their molecular determinants constitutes a nontrivial challenge. Here, we combine coarse-grained modeling, enhanced sampling, and machine learning to investigate the key factors controlling the monomer exchange pathways in synthetic supramolecular polymers having an intrinsic dynamic behavior. We demonstrate how the competition of directional vs. nondirectional interactions between the monomers controls the creation/annihilation of defects in the supramolecular polymers, from where monomers exchange proceeds. This competition determines the exchange pathway, dictating whether a fiber statistically swaps monomers from the tips or from all along its length. Finally, thanks to their generality, our models allow the investigation of molecular approaches to control the exchange pathways in these dynamic assemblies