Pendant Group Modifications Provide Graft Copolymer Silicones with Exceptionally Broad Thermomechanical Properties.

Graft copolymers offer a versatile platform for the design of self-assembling materials; however, simple strategies for precisely and independently controlling the thermomechanical and morphological properties of graft copolymers remain elusive. Here, using a library of 92 polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, we discover a versatile backbone-pendant sequence-control strategy that addresses this challenge. Small structural variations of pendant groups, e.g., cyclohexyl versus n-hexyl, of small-molecule comonomers have dramatic impacts on order-to-disorder transitions, glass transitions, mechanical properties, and morphologies of statistical and block silicone-based graft copolymers, providing an exceptionally broad palette of designable materials properties. For example, statistical graft copolymers with high PDMS volume fractions yielded unbridged body-centered cubic morphologies that behaved as soft plastic crystals. By contrast, lamellae-forming graft copolymers provided robust, yet reprocessable silicone thermoplastics (TPs) with transition temperatures spanning over 160 °C and elastic moduli as high as 150 MPa despite being both unentangled and un-cross-linked. Altogether, this study reveals a new pendant-group-mediated self-assembly strategy that simplifies graft copolymer synthesis and enables access to a diverse family of silicone-based materials, setting the stage for the broader development of self-assembling materials with tailored performance specifications.

Hierarchically engineered nanostructures from compositionally anisotropic molecular building blocks.

The inability to synthesize hierarchical structures with independently tailored nanoscale and mesoscale features limits the discovery of next-generation multifunctional materials. Here we present a predictable molecular self-assembly strategy to craft nanostructured materials with a variety of phase-in-phase hierarchical morphologies. The compositionally anisotropic building blocks employed in the assembly process are formed by multicomponent graft block copolymers containing sequence-defined side chains. The judicious design of various structural parameters in the graft block copolymers enables broadly tunable compositions, morphologies and lattice parameters across the nanoscale and mesoscale in the assembled structures. Our strategy introduces advanced design principles for the efficient creation of complex hierarchical structures and provides a facile synthetic platform to access nanomaterials with multiple precisely integrated functionalities.

Rapid Access to Diverse Multicomponent Hierarchical Nanostructures from Mixed-Graft Block Copolymers.

Multicomponent nanostructured materials assembled from molecular building blocks received wide attention due to their precisely integrated multifunctionalities. However, discovery of these materials with desirable composition and morphology was limited by their low synthetic scalability and narrow structural tuning window with given building blocks. Here, we report a scalable and diversity-oriented synthetic approach to hierarchically structured nanomaterials based on a few readily accessible building blocks. Mixed-graft block copolymers containing sequence-defined side chains were prepared through ring-opening metathesis copolymerization of three or four types of macromonomers. Intramolecularly defined interfaces promoted the formation of ordered hierarchical structures with lattice sizes tunable across multiple length scales. The same set of macromonomers were arranged and combined in different ways, providing access to diverse morphologies in the resultant structures.

Feasibility and Safety of Laparoscopic Radical Colectomy for T4b Colon Cancer at a University Hospital in Vietnam.

BACKGROUND: The choice of optimal treatment strategies for T4b colon cancers has still been discussed, particularly the initiation of neoadjuvant therapy or surgery. We conducted this study to evaluate the safety and feasibility of laparoscopic multivisceral resection for T4b colon cancers. METHODS: We used the retrospective design to include all 43 patients with T4b colon cancer at a university hospital in Vietnam from March 2017 to March 2019. All patients were followed 30 days after the surgery, and information about the day of the first flatus, length of hospital stay, iatrogenic complications, postoperative morbidity, mortality, and adjuvant chemotherapy was collected. RESULTS: The mean operating time was 187 minutes (ranging from 80 to 310), the mean blood loss was 64.3 ml (5-200), and the conversion rate was 2.3%. The mean number of lymph nodes harvested was 15.5 (SD = 8.06), and 33 patients (76.7%) had at least 12 lymph nodes harvested. A total of 21 patients (48.8%) had lymph node metastases with a mean number of lymph node metastases of 1.89 (SD = 3.4). The radial resection margin was R0 in all 43 patients (100%). The median time until the first flatus and hospital stay were 3 days (2-5) and 7.1 (6-11) days, respectively. There was no mortality at 30 days postoperatively, and one patient had iatrogenic complication (2.3%). CONCLUSION: Laparoscopic radical colectomy was feasible and safe for patients with T4b colon cancer except those requiring major and complicated reconstruction.

Synthesis and Self-Assembly of Mixed-Graft Block Copolymers.

Mixed-graft block copolymers (mGBCPs) consist of two or more types of polymeric side chains grafted on a linear backbone in a random, alternating, or pseudo-alternating sequence. They can phase-separate with the backbone serving as the interface of the blocks, and the side chains dominate their self-assembly behavior. mGBCPs are an accessible polymer architecture for exploring the idea of encoding polymer properties through the macromolecular architecture, as there are two distinct structural components that can be tuned: the backbone and the side chains. In this Concept article, the current literature on the synthesis of mGBCPs is reviewed, and the advantages and disadvantages of each synthetic method are noted. The self-assembly of mGBCPs is also discussed where possible. Finally, directions for future research on mGBCP synthesis and self-assembly are suggested.

Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties.

The graft-through synthesis of Janus graft block copolymers (GBCPs) from branched macromonomers composed of various combinations of homopolymers is presented. Self-assembly of GBCPs resulted in ordered nanostructures with ultra-small domain sizes down to 2.8 nm (half-pitch). The grafted architecture introduces an additional parameter, the backbone length, which enables control over the thermomechanical properties and processability of the GBCPs independently of their self-assembled nanostructures. The simple synthetic route to GBCPs and the possibility of using a variety of polymer combinations contribute to the universality of this technique.

Cell-specific adaptation of two flaviviruses following serial passage in mosquito cell culture.

West Nile Virus (WNV) is a mosquito-borne flavivirus that was introduced into the U.S. in the New York City area in 1999. Despite its successful establishment and rapid spread in a naive environment, WNV has undergone limited evolution since its introduction. This evolutionary stability has been attributed to compromises made to permit alternating cycles of viral replication in vertebrate hosts and arthropod vectors. Outbreaks of a close relative of WNV, St. Louis encephalitis virus (SLEV), occur in the U.S. periodically and are also characterized by limited genetic change overtime. We measured both phenotypic and genotypic changes in WNV and SLEV serially passaged in mosquito cell culture in order to clarify the role of an individual host cell type in flavivirus adaptation and evolution. Genetic changes in passaged WNV and SLEV were minimal but led to increased relative fitness and replicative ability of the virus in the homologous cell line C6/36 mosquito cells. Similar increases were not measured in the heterologous cell line DF-1 avian cells. These phenotypic changes are consistent with the concept of cell-specific adaptation in flaviviruses.