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DNA release dynamics from layer-by-layer (LbL) films is an important aspect to consider with regards to localized gene delivery systems. The rate of DNA release and the condensation state of DNA during release are of particular interest in the field of gene delivery. A hyperbranched poly(amido amine) (RHB) containing bioreducible disulfide bonds is used to form interpolyelectrolyte complexes with DNA during LbL film assembly. During film disassembly, DNA is released in physiologic conditions due to the reducing nature of the RHB. Uncondensed DNA deposited on the surface was compared to DNA condensed by RHB in polyplex form by using two types of LbL films, RHB/DNA/RHB and polyplex terminated films, RHB/DNA/polyplex. LbL films with up to three layers are used in order to facilitate high-resolution atomic force microscopy (AFM) imaging. X-ray reflectivity, ellipsometry, and Fourier transform infrared spectroscopy are also used. The film disassembly, rearrangement, and release of molecules from the surface due to thiol−disulfide exchange is conducted in reducing dithiothreitol (DTT) solutions. Salt is found to accelerate the overall rate of film disassembly. Additionally, it was found that the polyplex layer disassembles faster than the DNA layer. The predominant intermediate structure is the toroid structure for the polyplex layer and the fiber bundle structure for the DNA layer during film disassembly. This study offers a simple means to modulate DNA release from LbL films by utilizing both condensed and uncondensed DNA in different layers. The study highlights nanostructures, toroids, and bundles as dominant intermediate DNA structures during DNA release from LbL films. [ABSTRACT FROM AUTHOR]

Studies the asymmetrical molecular aggregation in spherulitic dye films. Use of spherulitic crystallization for the preparation of highly ordered nm thin films of the dye 1.7-bis(dimethylamino)heptamethinium perchlorate; Kinetics of the spherulitic growth process; Out-of-plane rotation of molecular axis in banded spherulites.

Active droplets play important roles in microfluidics, robotics, and micro-electromechanical systems. As a special class of active droplets that are conductive, reactive, and of high surface tension, liquid metal droplets (LMDs) can be driven by electric-field-induced surface (Marangoni) flows to function as reconfigurable components in actuators, sensors, catalytic reactors, and antennas. Stimulating LMDs using an electric field induces concurrent electro-hydrodynamic flows and electrochemical surface oxidation (passivation). It is however difficult to decouple these two effects which brings complexity in controlling LMD motions. To address this challenge, pulse time modulation (PTM) signals are used. PTM enables controlled LMD displacement by propelling the droplets forward during the voltage-on phases and facilitating surface recovery from oxidation during the voltage-off phases. Counterintuitively, by taking such intermittent "rests", the LMDs effectively inhibit the unfavorable impact of oxidation, granting high motion controllability. Combining high-speed imaging, motion tracking, machine learning, and electrochemical analysis, the study reveals how electro-hydrodynamic flows and surface oxide formation/dissolution interplay to generate well-defined motion regimes. The study further develops a quasi-analytical model to describe droplet motions and designs a rotary LMD motor to showcase the versatility of the approach. This work provides the fundamental framework and viable strategy for designing innovative liquid metal-based systems. [ABSTRACT FROM AUTHOR]

Purpose: Bombarding high-Z material with x-ray radiation releases Auger electrons and Coster-Kronig electrons, along with deeper penetrating fluorescent x-rays and photoelectrons. The Auger and Coster-Kronig electron penetration distance is on the order of nanometers to micrometers in water or tissue, creating a large dose enhancement accompanied by a RBE greater than 1 at the cellular level. The authors' aim is to measure the gold nanofilm dose enhancement factor (DEF) at the cellular level with unlaminated radiochromic film via primary 50 kVp tungsten x-ray spectrum interaction, similar to an electronic brachytherapy spectrum. Methods: Unlaminated Gafchromic® EBT2 film and Monte Carlo modeling were combined to derive DEF models. Gold film of thickness 23.1± 4.3 nm and surface roughness of 1.2±0.2 nm was placed in contact with unlaminated radiochromic film in a downstream orientation and exposed to a 50 kVp tungsten bremsstrahlung, mean energy 19.2 keV. Film response correction factors were derived by Monte Carlo modeling of electron energy deposition in the film's active layer, and by measuring film energy dependence from 4.5 keV to 50 kVp. Results: The measured DEF within a 13.6 µm thick water layer was 0.29 with a mean dose of 94±9.4 cGy from Au emissions and 324±32.4 cGy from the 50 kVp primary beam. Monte Carlo derived correction factors allowed determination of Au contributed dose in shallower depths at 0.25 µm intervals. Maximum DEF of 18.31 was found in the first 0.25 µm water depth. Conclusions: Dose enhancement from Au nanofilm can be measured at the cellular level using unlaminated radiochromic film. Complementing the measured dose value with Monte Carlo calculations allows estimation of dose enhancement at depth increments within the cellular range. [ABSTRACT FROM AUTHOR]

Forces between colloidal particlesdetermine the performances ofmany industrial processes and products. Colloidal force measurementsconducted between a colloidal particle AFM probe and particles immobilizedon a flat substrate are valuable in selecting appropriate surfactantsfor colloidal stabilization. One of the features of inorganic fillersand extenders is the prevalence of rough surfaceseven thepolymer latex particles, often used as model colloidal systems includingthe current study, have rough surfaces albeit at a much smaller scale.Surface roughness is frequently cited as the reason for disparitybetween experimental observations and theoretical treatment but seldomverified by direct evidence. This work reports the effect of nanoscalesurface roughness on colloidal force measurements carried out in thepresence of surfactants. We applied a heating method to reduce themean surface roughness of commercial latex particles from 30 to 1nm. We conducted force measurements using the two types of particlesat various salt and surfactant concentrations. The surfactants usedwere pentaethylene glycol monododecyl ether, Pluronic F108, and astyrene/acrylic copolymer, Joncryl 60. In the absence of the surfactant,nanometer surface roughness affects colloidal forces only in highsalt conditions when the Debye length becomes smaller than the surfaceroughness. The adhesion is stronger between colloids with higher surfaceroughness and requires a higher surfactant concentration to be eliminated.The effect of surface roughness on colloidal forces was also investigatedas a function of the adsorbed surfactant layer structure characterizedby AFM indentation and dynamic light scattering. We found that whenthe layer thickness exceeds the surface roughness, the colloidal adhesionis less influenced by surfactant concentration variation. This studydemonstrates that surface roughness at the nanoscale can influencecolloidal forces significantly and should be taken into account incolloidal dispersion formulations. [ABSTRACT FROM AUTHOR]

The DNA release dynamics of bioreducible poly(amido amine) polyplexes were studied in real time by atomic force microscopy (AFM). DNA release is triggered by a depolymerization of high-molecular-weight polycations into low-molecular-weight oligocations that occurs by means of the thiol and disulfide exchange reaction mechanism. AFM images were captured in a simulated physiological reducing environment that used dithiothreitol. Distinctive stages of disassembly are common among various polyplexes that have different disulfide content, molecular weight, and polymer architecture, while the DNA release rate depends upon the disulfide content. In the first stage, polyplexes evolve from metastable structures into the more stable toroid structure upon the depolymerization. In the second stage, toroids either aggregate or fuse into larger toroids. In the last stage, DNA wormlike chains and loops are held by a central compact core. The results confirm the prospect of bioreducible poly(amido amine)s as controlled DNA delivery vectors. The study offers new physical insights into the DNA release pathway including intermediate structures that have a high degree of structural heterogeneity and disassembly induced particle growth. The study identifies disassembly induced colloidal and morphological instability as an important issue to be addressed. [ABSTRACT FROM AUTHOR]

Controlled intracellular disassembly of polyelectrolyte complexes of polycations and DNA (polyplexes) is a crucial step for the success of nonviral gene delivery. Motivated by our previous observation of different gene delivery performances among multiblock reducible copolypeptide vectors ( Manickam, D. S.; Oupický, D.Bioconjugate Chem.2006, 17, 1395− 1403), atomic force microscopy is used to visualize plasmid DNA in various decondensed states from reducible polypeptide polyplexes under simulated physiological reducing conditions. DNA decondensation is triggered by reductive degradation of disulfide-containing cationic polypeptides. Striking differences in DNA release dynamics between polyplexes based on polypeptides of histidine-rich peptide (HRP, CKHHHKHHHKC) and nuclear localization signal (NLS, CGAGPKKKRKVC) peptide are presented. The HRP and NLS polyplexes are similar to each other in their initial morphology with a majority of them containing only one DNA plasmid. Upon reductive degradation by dithiothreitol, DNA is released from NLS abruptly regardless of the initial polyplex morphology, while DNA release from HRP polyplexes displays a gradual decondensation that is dependent on the size of polyplexes. The release rate is higher for larger HRP polyplexes. The smaller HRP polyplexes become unstable when they are in contact with expanding chains nearby. The results reveal potentially rich DNA release dynamics that can be controlled by subtle variation in multivalent counterion binding to DNA as well as the cellular matrix. [ABSTRACT FROM AUTHOR]

Poor drug encapsulation efficiency and rapid release of the encapsulated drug limit the use of nanoparticles in biomedical applications involving water-soluble drugs. We have developed a novel polymer-surfactant nanoparticle formulation, using the anionic surfactant Aerosol OT™ (AOT) and polysaccharide polymer alginate, for sustained release of water-soluble drugs. Particle size of nanoparticles, as determined by atomic force microscopy and transmission electron microscopy, was in the range of 40–70 nm. Weakly basic molecules like methylene blue, doxorubicin, rhodamine, verapamil, and clonidine could be encapsulated efficiently in AOT-alginate nanoparticles. In vitro release studies with basic drug molecules indicate that nanoparticles released 60–70% of the encapsulated drug over 4 weeks, with near zero-order release during the first 15 days. Studies with anionic drug molecules demonstrate poorer drug encapsulation efficiency and more rapid drug release than those observed with basic drugs. Further studies investigating the effect of sodium concentration in the release medium and the charge of the drug suggest that calcium-sodium exchange between nanoparticle matrix and release medium and electrostatic interaction between drug and nanoparticle matrix are important determinants of drug release. In conclusion, we have formulated a novel surfactant-polymer drug delivery carrier demonstrating sustained release of water-soluble drugs. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 96: 3379–3389, 2007 [ABSTRACT FROM AUTHOR]

This article describes the stability and reversibility of ultrathin films of N-isopropylacrylamide (NIPA)−vinylimidazole (VI)−poly(ethylene glycol) (PEG) graft terpolymer adsorbed at the solid−liquid interface upon temperature cycling from below to above its phase transition temperature. The coil-to-globule and globule-to-coil phase transitions were captured by in situ fluid tapping atomic force microscopy (AFM). The film thickness of 1 nm was determined by AFM, X-ray photoelectron spectroscopy, and X-ray reflectivity. The concentration required to reach full coverage was found to be higher when adsorption occurred below the phase transition temperature. From 23 to 42 °C, the adsorbed NIPA terpolymer film was observed to be molecularly smooth, corresponding to the close-packed structure of flexible polymer coils. Particles containing between one and a few globules appeared abruptly at the interface at 42−43 °C, the same temperature as the solution phase transition temperature, which was determined by dynamic light scattering. The size of the particles did not change with temperature, whereas the number of particles increased with increasing temperature up to 60 °C. The particles correspond to the collapsed and associated state of the globules. The film morphological changes were found to be reversible upon temperature cycling. Subtle differences were observed between dip-coated and spin-coated films that are consistent with a higher degree of molecular freedom for spin-coated films. The study contributes to the fundamental understanding and applications of smart ultrathin films and coatings. [ABSTRACT FROM AUTHOR]

This article focuses on rod hybrids. Organic-inorganic hybrids form the basis of biomineralization and are attractive materials for electronic, optical, and biosensing applications because they combine and sometimes enhance the functionalities of different material groups. The drive toward device miniaturization demands that functional units such as nanoparticles and nanorods be connected in a predefined manner. Therefore, in addition to the synthesis of nanoparticles and nanorods, an emerging focus is on connecting and assembling the various nano-units.