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Mycobacterial infectious diseases, including tuberculosis (TB), severely threaten global public health. Nonreplicating

We present the importance of functional group isomerism on intracellular protein delivery using polymers containing different isomeric side chains. While the physical properties of polymer/protein complexes are relatively similar, different planarity of the isomers greatly influences the cellular entry efficiency.

We demonstrate a successful target gene knockdown in ex vivo normal human bronchial epithelium (NHBE) cells covered with mucus layers using the guanylurea functionalization technique modulating the chemical environment at the positive charge of a gene carrier.

Single-entity electrochemistry is of fundamental importance and shows promise for ultrasensitive biosensing applications. Recently, we have demonstrated that various charged nanoparticles can be detected individually based on the non-redox open-circuit potential (OCP) changes induced by their collision events on a floating carbon nanoelectrode (CNE). Unlike the widely used amperometry approach, the potentiometric method provides the label-free detection of individual nanoscale entities without redox mediators in the solution. However, the CNE lacks specificity for molecular recognition during the collision events because of the limited methods of surface functionalization for carbon surfaces. Herein, we used surface-functionalized gold nanoelectrode (GNE) to overcome this limitation of CNE. The GNE modified with Raman reporter molecule also enabled surface-enhanced Raman spectroscopy (SERS) measurements. By using simultaneous time-resolved OCP and SERS measurements, both the OCP and SERS signals induced by the “hit-n-run” type of gold nanoparticle (GNP) collision events can be better understood. Also, by introducing a zwitterionic molecule, we formed near “stealth” surface and demonstrated that the non-specific adsorptions of GNPs to the surface of GNE have been suppressed, allowing continuous detection of hit-n-run events for over 30 min.

Melt viscosity control of polyamides is an important issue concerning polymer processing and quality composites which are directly influenced by the melt viscosity in extrusion and injection molding processes. In this work, a series of linear and cyclic PA6 (nylon6), PA46 (nylon46), and PA66 (nylon66)-based amide oligomers consisting of 30%. This result suggests that proper hydrogen bonding mismatching in the polymer chain network plays an important role for lowering viscosity. A6-L/PA66 composites impregnated with 40 wt% glass fiber show a twofold increase in the melt flow index while maintaining their mechanical strengths.

In-depth understanding of the biophysicochemical interactions at the nano-bio interface is important for basic cell biology and applications in nanomedicine and nanobiosensors. Here, the extracellular surface potential and topography changes of live cell membranes interacting with polymeric nanomaterials using a scanning ion conductance microscopy-based potential imaging technique are investigated. Two structurally similar amphiphilic conjugated polymer nanoparticles (CPNs) containing different functional groups (i.e., primary amine versus guanidine) are used to study incubation time and functional group-dependent extracellular surface potential and topographic changes. Transmembrane pores, which induce significant changes in potential, only appear transiently in the live cell membranes during the initial interactions. The cells are able to self-repair the damaged membrane and become resilient to prolonged CPN exposure. This study provides an important observation on how the cells interact with and respond to extracellular polymeric nanomaterials at the early stage. This study also demonstrates that extracellular surface potential imaging can provide a new insight to help understand the complicated interactions at the nano-bio interface and the following cellular responses.

A series of flexible, highly bright fluorescent poly(p-phenyleneethynylene)s (PPEs) was prepared by employing a disulfide containing nonconjugated monomer at various ratios under Sonogashira reaction conditions. PPEs with flexible linkers exhibited fluorescence properties comparable to those of a fully conjugated PPE when less than 50% of flexible monomers were incorporated into the backbone. To evaluate the self-assembly properties of PPEs, a series of conjugated polymer nanoparticles (CPNs) was fabricated by treating PPEs with organic acids followed by dialysis. CPNs containing linkers exhibited different complexation behavior with polysaccharides, warranting further investigation into how flexibility and biodegradability of CPNs influence their cellular interaction and entry. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1403–1412

Core-shell conjugated polymer nanoparticles (CPNs) were fabricated by complexing a semi-flexible, primary amine-containing conjugated polymer (CP) with hyaluronic acid (HA). Flexibility introduced in the rigid rod conjugated backbone allows backbone reorganization to increase π-π interaction under ionic complexation, resulting in core-shell nanoparticles with a hydrophobic CP core wrapped with a HA shell. The core-shell nanoparticles exhibited no cellular toxicity and high cancer cell specificity with minimal binding to normal cells.

Understanding the cellular entry pathways of synthetic biomaterials is highly important to improve overall labeling and delivery efficiency. Herein, cellular entry mechanisms of conjugated polymer nanoparticles (CPNs) are presented. CPNs are intrinsic fluorescent materials used for various biological applications. While CPNs cause no toxicity, decreased CPN uptake is observed from cancer cells pretreated with genistein, which is an inhibitor of caveolae-mediated endocytosis (CvME). CvME is further confirmed by high co-localization with caveolin-1 proteins found in the caveolae and caveosomes. Excellent photophysical properties, non-toxicity, and non-destructive delivery pathways support that CPNs are promising multifunctional carriers minimizing degradation of contents during delivery.

We developed a new synthetic approach to high molecular weight poly(p-phenylenebutadiynylene) s (PPBs) by increasing backbone flexibility. The introduction of a small amount of flexible units along the backbone improved both the physical and photophysical properties of the polymers. These materials were successfully fabricated into conjugated polymer nanoparticles (CPNs) and used for fluorescent live cell imaging for the first time.

Biodegradable conjugated polymer nanoparticles (CPNs) were prepared for high mitochondrial targeting in live cancer cells. The degradable CPNs are nontoxic and specifically localized to the mitochondria of live tumor cells through macropinocytosis followed by intracellular degradation and trafficking.

Understanding and controlling aggregation structures of conjugated polymers (CPs) in aqueous solutions is critical to improving the physical and photophysical properties of CPs for biological applications. Here, we present spectroscopic evidence, including nuclear magnetic resonance (NMR) spectroscopic results, that different organic acid treatment induces different aggregation structures and photophysical properties of CPs in water. Conjugated polymer nanoparticles (CPNs) were fabricated by treating a non-aqueous soluble, primary amine-containing poly(phenylene ethynylene) (PPE-NH(2)) with organic acids followed by dialysis. CPNs formed by acetic acid (AA) treatment (CPN-AAs) exhibit characteristics of loose aggregation with minimal π-π stacking, while CPNs formed by tartaric acid (TA) treatment (CPN-TAs) exhibit a high degree of π-π stacking among PPE-NH(2) chains. The controlled aggregation for a specific application was demonstrated by comparing the fluorescence quenching abilities of the CPN-AAs and the CPN-TAs. A doubled Stern-Volmer constant was obtained from the densely packed CPN-TAs compared to that of the loosely aggregated CPN-AAs.

Positively charged conjugated polymer nanoparticles (CPNs) are emerging biomaterials exhibiting high levels of cellular entry. High rate of cellular entry efficiency is believed that the amphiphilic CPNs interact efficiently with the negatively charged hydrophobic cellular membranes. For the first time, the cell surface morphological changes of human cervical cancer cells treated with CPNs using a scanning probe microscopy technique, scanning ion conductance microscopy (SICM) are imaged. After 1 h of CPN incubation, distinct changes are observed in cell surface morphology such as interconnected protrusions and pits with sub-micrometer sizes, which are not observed from cells treated with positively charged polyethyleneimine (PEI) under the same treatment conditions. The change on cell surface morphology is quantified by surface roughness ratio, which is increased as CPN concentration increases, while the ratio first increases and then decreases as the incubation time increases. These results suggest that cells respond actively toward CPN with both positive charges on the side chain and the hydrophobicity from rigid aromatic backbone, which leads to subsequent endocytosis. In conclusion, it is demonstrated that SICM is a suitable imaging technique to reveal the dynamic alternations on the cell surface morphology at the early stage of nanoparticles endocytosis with high resolution.

Thin films of Bi2O3-ZnO-Nb2O5 system with cubic pyrochlore structure can be deposited using both cubic and monoclinic (zirconolite) targets. When monoclinic target was used, the as-deposited phase was nonequilibrium cubic monophase. After post-annealing in the 600–800^∘C range, phase decomposition occurred, resulting in more thermodynamically stable cubic pyrochlore and monoclinic zirconolite phases. The dielectric properties, such as dielectric constant and electric field dependent tunability, showed a steep increase along with phase separation. However, dielectric loss had a reverse tendency. The maximum tunability was about 38%, which exceeds that of cubic pyrochlore monophase films deposited from cubic target.

Aminosilylated surface was treated with halide-substituted aromatic aldehydes, and the resulting molecular layers were examined with synchrotron X-ray photoelectron spectroscopy at the 2B1 SGM and 4B1 microscopy beamline in the Pohang Accelerator Laboratory. It was observed that the halide group of the film diminished upon the irradiation, but the other bands were constant in terms of the intensity and the shape. This observation indicates that the functional groups of the organic monolayers are cleaved selectively by soft X-rays. The cleavage rate was measured as a function of photon energy and normalized with photon flux. The cleavage is first-order to the concentration of the functional group. Its rate constant is sensitive to the molecular structure of the organic monolayers and the kind of substituents on the aromatic ring.

Loosely aggregated conjugated polymer nanoparticles (CPNs) were used as nontoxic and efficient small interfering RNA (siRNA) delivery vehicles with delivery visualization. A significant down regulation (94%) of a target gene was achieved by transfection of HeLa cells with the CPNs/siRNA complexes, supporting CPN as a promising siRNA delivery carrier.

Fluorescence quenching of poly(phenylene ethynylene) (PPE) particles by a Cy-5 labeled oligonucleotide is 2 orders of magnitude more sensitive than direct excitation of the Cy-5 fluorophore.

The subcellular localizations and toxicity of conjugated polymer nanoparticles (CPNs) are dependent on the chemical structure of the side chain and backbone structures. Primary amine-containing CPNs exhibit high Golgi localization with no toxicity. Incorporation of short ethylene oxide and tertiary amine side chains contributes to decreased Golgi localization and increased toxicity, respectively.

The ionic attraction was applied to construct nonlinear optical (NLO) chromophoric layers. In order to fully utilize such an interaction, stilbene-type NLO chromophores having an anionic group at one end of the chromophores were designed. Among such type of the chromophores, trans-4′-(4-sulfonic acid sodium salt)butanoxystyrylpyridine ( 1 ) was synthesized. The pyridine moiety of the chromophore can be easily methylated to augment the molecular hyperpolarizability (β). The above anionic chromophore self-assembles on the cationic surface, which is prepared by treating clean fused silica surface with 3-aminopropyltriethoxysilane and subsequently iodomethane. Characteristics of the molecular layer have been examined with contact angle measurement, UV-Vis spectroscopy, grazing-angle FTIR spectroscopy, and NLO property measurement.

Ionic attractions were applied to the construction of non-linear optical (NLO) chromophoric monolayers. In order to fully utilize such an interaction, stilbene-type NLO chromophores having a long alkyl chain and an anionic group at one end of the chain were designed; of this family of chromophores, sodium 11-[4-(trans-4′-pyridylstyryl)oxy] undecan-1-yl sulfate (3) was synthesized. By allowing a few minutes, this anionic chromophore self-assembles successfully on a cationically charged surface, which is prepared by treating clean fused silica with 3-aminopropyltriethoxysilane and then with iodomethane. The pyridine moiety of the self-assembled chromophore can be methylated to augment the molecular hyperpolarizability, β. The characteristics of the monolayer were examined viacontact angle measurements, UV–VIS spectroscopy, grazing-angle FTIR spectroscopy, and NLO property measurements.