The use of polydiacetylene (PDA) vesicles in sensing systems are wide-spread due to the interesting optical properties of this stimuli-responsive material; however, agglutination based sensing with PDA have been relatively underutilized. To demonstrate the means for rapidly generating an agglutination probe based on peptide-displaying polydiacetylene vesicles, we implement here the use of a biotin mimetic peptide functionalized to a diacetylene amphiphile for proof-of-concept detection of a multivalent target, specifically streptavidin. Tuning of the vesicle composition revealed a distinct limit in the surface density of peptide amphiphile that could be displayed for this particular peptide sequence. A wide operational detection range was demonstrated, and the result also revealed an effective agglutination response of the PDA-based probe to streptavidin suggesting possible use of future formulations in profiling other multivalent targets.

Polydiacetylene (PDA) vesicles provide useful stimuli-responsive behavior as well as by the modular structure afford a means for the design of sensing and delivery systems with tunable target specificity. To reduce inherent non-specific interaction with either anionic or cationic formulations of polydiacetylene vesicles, we explored the use of various lengths of poly(ethylene glycol) (PEG) amphiphiles for integration and polymerization within PDA vesicles. Our results established that as little as 1% of polyethylene glycol amphiphile integration into anionic vesicles was sufficient to significantly reduce non-specific association with mammalian cells. Similarly integrating a low percent of PEG amphiphile content within cationic vesicles could also significantly reduce non-specific cell association, and moreover reduced cytotoxicity. These results may be prove useful in augmenting PDA vesicles formulations for reduced non-specific interaction which is of particularly interest to enhancing selectivity in vesicles designed with integrated targeting moieties for sensing and drug delivery applications.

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium (IV) catalysis, to grow poly(-hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles was "seeded" with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, thus surface tethered catalyst provided the sites for -hexyl isocyanate monomer insertion, to "build up" the surface-grown polymer layers from the "bottom-up". A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by FT-IR, 1H-NMR, GC-MS, GPC, and thermogravimetric analyses.

Prostate-specific membrane antigen (PSMA) is an attractive target for the imaging of prostate cancer (PCa) due to the elevated expression on the surface of prostate tumor cells. Most PSMA-targeted low molecular weight imaging agents are inhibitors of PSMA. We have synthesized a series of substrate-based PSMA-targeted imaging agents by mimicking poly--glutamyl folic acid, an endogenous substrate of PSMA. the -linked polyglutamate conjugates proved to be better substrates than the corresponding -linked glutamates. However, imaging studies of -ray-emitting and -linked glutamates did not demonstrate selective uptake in PSMA-pos-itive over PSMA-negative tumors. Subsequent chromatographic studies and molecular dynamics simulations indicated that hydrolysis of the substrates is slow and access to the enzymatic active site is limited. These results inform the design of future substrate-based imaging agents for PSMA.

Highly porous poly(3-hydroxybutyrate) (PHB) scaffolds were fabricated using non-solvent-induced phase separation with chloroform as the solvent and tetrahydrofuran as the non-solvent. The microporosity, nanofiber morphology, and mechanical strength of the scaffolds were adjusted by varying the fabrication parameters, such as the polymer concentration and solvent composition. The influence of these parameters on the structure and morphology of PHB organogels and scaffolds was elucidated using small-angle neutron scattering and scanning electron microscopy. The organogels and scaffolds in this study have a complex hierarchical structure, extending over a wide range of length scales. viability assays were performed using the human keratinocyte cell line (HaCaT), and all PHB scaffolds demonstrated the excellent cell viability. Microporosity had the greatest impact on HaCaT cell proliferation on PHB scaffolds, which was determined after a 3-day incubation period with scaffolds of different morphologies and mechanical properties. The superior cell viability and the controlled scaffold properties and morphologies suggested PHB scaffolds fabricated by non-solvent-induced phase separation using chloroform and tetrahydrofuran as promising biomaterials for the applications of tissue engineering, particularly of epidermal engineering.

Acrylic pressure sensitive adhesives (PSAs) were prepared by UV polymerization under varying curing conditions of both fast and slow curing, employing high- and low-intensity UV radiation, respectively. The influences of curing conditions and isobornyl acrylate (IBOA) content on PSA performance were comprehensively investigated by measurement of their rheological, thermal, and adhesive properties. In particular, rheological characterization was accomplished by several analytical methods, such as UV rheology, frequency sweep, stress relaxation, and temperature ramp tests, to understand the effect of the UV curing process and IBOA content on the viscoelastic behavior of acrylic PSAs. The slow-cured samples were observed to form more tightly crosslinked networks compared to the fast-cured. On the other hand, at high loading levels of IBOA, in the case of slow curing, the sample exhibited a contrasting trend, having the shortest stress relaxation time and the highest energy dissipation; this was due to molecular chain scission occurring in the crosslinked polymer during UV polymerization. Consequently, we successfully demonstrated the influence of monomer composition of acrylic PSAs, and that of curing conditions employed in UV polymerization. This study provides valuable insights for the development of crosslinked polymer networks of acrylic PSAs for flexible display applications.

The potential of oligonucleotides is exceptional in therapeutics because of their high safety, potency, and specificity compared to conventional therapeutic agents. However, many obstacles, such as low stability and poor cellular uptake, have hampered their clinical success. Use of polymeric carriers can be an effective approach for overcoming the biological barriers and thereby maximizing the therapeutic efficacy of the oligonucleotides due to the availability of highly tunable synthesis and functional modification of various polymers. As loaded in the polymeric carriers, the therapeutic oligonucleotides, such as antisense oligonucleotides, small interfering RNAs, microRNAs, and even messenger RNAs, become nuclease-resistant by bypassing renal filtration and can be efficiently internalized into disease cells. In this review, we introduced a variety of systematic combinations between the therapeutic oligonucleotides and the synthetic polymers, including the uses of highly functionalized polymers responding to a wide range of endogenous and exogenous stimuli for spatiotemporal control of oligonucleotide release. We also presented intriguing characteristics of oligonucleotides suitable for targeted therapy and immunotherapy, which can be fully supported by versatile polymeric carriers.

Although biodegradable plastics are gradually emerging as an effective solution to alleviate the burgeoning plastic pollution, their performance is currently trivial for commercialization. A proposed two-pronged strategy to overcome this limitation includes (1) preparation of the nanocomposites from biorenewable nano-fillers to preserve their biodegradability and (2) tailoring their properties to meet the diverse demands in various applications. Herein, we report the preparation of biodegradable nanocomposites composed of poly(butylene succinate) (PBS) and cellulose nanocrystals (CNCs) (loading of 0.2-3.0 wt%) and propose a rheological strategy to tailor their performances. Depending on the shear frequencies, the rheological evaluation revealed two percolation thresholds at approximately 0.8 and 1.5 wt%. At high shear frequencies, the disappearance of the first threshold (0.8 wt%) and the sole persistence of the second one (1.5 wt%) indicated the collapse of the immature network of partially interconnected CNCs. The tensile and hydrolytic properties of the nanocomposites were found to undergo drastic changes at the thresholds. The tensile strength increased by 17% (from 33.3 to 39.2 MPa) up to 0.8 wt% CNC loading. However, the reinforcing efficiency of CNC decreases sharply with further incorporation, reaching nearly zero at 1.5 wt%. On the other hand, hydrolytic degradation of the nanocomposites was rapidly accelerated above 1.5 wt% CNC loading. Therefore, a thorough understanding of the rheological properties of nanocomposites is essential for the design and development of materials with tailored properties.

'New-Gen Vaccines' are grabbing the attention of scientists as they are much suitable for an immune-compromised group of individuals as well as infants. The major drawbacks of these vaccines are lower immunogenicity and instability. The need for a convenient and safe adjuvant is still under exploration. On the other hand, thermal instability leads to the inactivation of the vaccine and becomes detrimental in many cases. Thus, there is a need to incorporate new kinds of excipients into vaccine formulation to enhance the potency/immunogenicity of vaccine antigens and also act as stabilizers. A limited or single excipient in providing the required dual-activity is vital to break the stereotypical usage of the well-entrenched adverse ingredients. In the proposed review, the efficiency of naturally occurring biocompatible carbohydrate polymers and osmolytes and their 'dual-role' is briefed. In addition, the information on the possible mechanisms of action of carbohydrate polymers in vaccines as adjuvants and stabilizers are also discussed.

Biomass-derived isosorbide (ISB) is a promising alternative to petroleum-based monomers in industrial plastics. In this study, ISB-based thermoplastic polyurethanes (ISB-TPUs) were prepared using ISB as a biomass chain extender, and the effects of the preparation route on the structural and physical properties of the resultant polymers were investigated. Prepolymer methods were more suitable for obtaining the desired molecular weights (MWs) and physical properties of ISB-TPUs than the one-shot method. The presence of the solvent and catalyst in the prepolymer step had significant effects on the structural and physical properties of the resultant polymer. Among several prepolymer conditions, the solvent- and catalyst-free methods were the most suitable for preparing commercial-level ISB-TPUs, with number- and weight-average MWs ( and ) of 32,881 and 90,929 g mol, respectively, and a tensile modulus () and ultimate tensile strength (UTS) of 12.0 and 40.2 MPa, respectively. In comparison, the presence of a catalyst in the prepolymer step resulted in lower MWs and mechanical properties (81,033 g mol and 18.3 MPa of and UTS, respectively). The co-existence of the catalyst/solvent led to a further decline in the properties of ISB-TPUs (26,506 and 10.0 MPa of and UTS, respectively). ISB-TPU prepared via the solvent- and catalyst-free methods exhibited remarkable elastic recovery when subjected to up to 1000% strain in mechanical cycling tests. Rheological characterization confirmed the thermo-reversible phase change (thermoplasticity) of the polymer.