Self-sorting is the phenomenon in which there is high fidelity recognition and preference only for self and avoidance of nonself (narcissistic self-sorting). It has been observed in a number of biological systems and chiral synthetic molecules. We found that blends of biscarbamates, which are model compounds for polyurethanes, self-sort during crystallization [ J. Phys. Chem. B 2008 , 112 , 4223 - 4232 ], although these are not chiral molecules. Even if the two components in the blend differ only by a couple of CH2 groups in the side chain length, no intercomponent hydrogen bond forms, and the molecules self-sort. They do not show any cocrystallization despite being part of a homologous series. We believe that it is the first reported example such behavior among synthetic nonchiral molecules. This is similar to the behavior of blends of hydrogen-bonding polymers including polyurethanes. We show that the difference in the growth rates of the individual species is responsible for the self-sorting behavior in these nonchiral synthetic compounds. While self-sorting might be advantageous for separation of blends, it poses a challenge for modifying properties such as the melting temperatures, spherulite size, etc., for various applications. We will discuss methods that were attempted to bridge the self and nonself that would lead to a more homogeneous system. We evaluated the miscibility using differential scanning calorimetry (DSC), since the occurrence of a single or multiple endotherms would indicate molecular level miscibility. This is similar to the behavior of glass transition temperatures in the case of polymer blends. Optical microscopy (OM) and X-ray diffraction (XRD) were also used. It is concluded that irrespective of the protocol followed for preparing the mixtures, mutual plasticization occurred in most cases (i.e., mixing of domains of the two species) and not molecular mixing.
We describe the gelation of two-component immiscible blends consisting of a set of low molecular weight organogelators and a polymer. We studied the blends of poly(3-caprolactone) (PCL) and biscarbamates (model compounds for polyurethanes) with two hydrogen bonding motifs separated by a (CH 2 ) 6 spacer and symmetrically attached alkyl side chains. Neither PCL nor the biscarbamates form gels with chloroform in their neat forms, although the latter form gels with several other solvents. It is known that PCL does not form a gel by itself in any solvent. Being part of a copolymer or an inclusion complex is necessary for a PCL based gel. In the current work, mixtures of biscarbamates and PCL in chloroform led to phase separation and gelation upon cooling the solution. This gelation behavior depends on the alkyl side chain length of the biscarbamates. Those with alky side chain length below C 11 remained soluble and beyond C 13 precipitated within the concentration range studied here. Morphological studies showed immiscibility between the biscarbamate and PCL, similar to the case of polyurethanes with PCL as the soft segment. When biscarbamates are minor components in the solvent cast blend films, they form aggregate crystals in the PCL matrix. Upon melting and recrystallizing, PCL forms droplets in the matrix of biscarbamates, although it is the major component. X-ray diffraction studies of the xerogels confirmed the immiscibility of the PCL and biscarbamates and ATR-FTIR spectra showed no change in the hydrogen bonding of these self-assembling biscarbamate molecules. Microscopic studies revealed fibrous morphology of the composite gels, which consist of biscarbamate fibers dispersed in the matrix of PCL fibers. The biscarbamate fibers impregnated in the polymer matrix show the same eavestrough and hollow tube morphology as seen in our previous work (Khanna et al., Langmuir, 2009, 25, 13183).
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.