Microphase Separation of Resilin-like and Elastin-like Diblock Copolypeptides in Concentrated Solutions.

Diblock copolymers are valued for their ability to form thin films with nanoscale features that typically reflect those of their microphase-separated structures in concentrated solution. Here, we show that such self-assembled structures can be easily formed with diblock copolymers composed of thermally responsive polypeptides, such as resilin-like polypeptides (RLP) and elastin-like polypeptides (ELP), by exploiting the inverse temperature transition behavior of ELPs in aqueous media. Specifically, we examine the self-assembly of a series of RLP-b-ELP diblock copolypeptides in concentrated aqueous solution (30 and 50 wt %) by small-angle X-ray scattering (SAXS). By systematically varying RLP block length and temperature (10-45 °C), we observed microphase separation into hexagonally packed cylinders and lamellae. By analyzing the observed order-order transitions (OOT) and order-disorder transitions (ODT), we determined that self-assembly in this system is primarily driven by polymer-solvent interactions. While these thermally responsive polymers showed clear ODTs and OOTs at certain temperatures, temperature only had a weak effect on the spacing of the resulting nanostructures. In contrast, we found that nanostructure spacing was far more sensitive to RLP block length. Finally, we used atomic force microscopy (AFM) to demonstrate that spin casting RLP-b-ELP diblock copolypeptides also produce nanostructured thin films with spacings that correlate with those in concentrated solution.

Grafting To of Bottlebrush Polymers: Conformation and Kinetics.

Specifically adsorbed bottlebrush coatings are found in nature as brush-like glycoproteins that decorate biointerfaces and provide antifouling, lubrication, or wear-protection. Although various synthetic strategies have been developed to mimic glycoprotein structure and function, the use of these mimics is still limited because of the current lack of understanding of their adsorption behavior and surface conformation. In this paper, we examine the adsorption behavior of PEG-based, biotinylated bottlebrushes with different backbone and bristle lengths to streptavidin model surfaces in phosphate-buffered saline. By using quartz crystal microbalance, localized surface plasmon resonance, and atomic force microscopy, we learn how bottlebrush dimensions impact their adsorption kinetics, surface conformation, mechanical properties, and antifouling properties. Our bottlebrushes qualitatively mirror the adsorption behavior of linear polymers and exhibit three kinetic regimes of adsorption: (I) a transport-limited regime, (II) a pause, and (III) a penetration-limited regime. Furthermore, we find that the bristle length more dramatically affects brush properties than the backbone length. Generally, larger bottlebrush dimensions lead to reduced molar adsorption, retarded kinetics, weaker antifouling, and softer brush coatings. Longer bristles also lead to less mass adsorption, while the opposite trend is observed for increasing backbone length. In summary, our findings aid the rational design of new bottlebrush coatings by elucidating how their dimensions impact adsorption, surface conformation, and the properties of the final coating.

Enzymatically Degassed Surface-Initiated Atom Transfer Radical Polymerization with Real-Time Monitoring.

Polymer brush coatings are frequently prepared by radical polymerization, a notoriously oxygen sensitive process. Glucose oxidase (GOx) can inexpensively enable radical polymerization in solution by enzymatically consuming oxygen as it oxidizes glucose. Here, we report the growth of polymeric brushes using GOx-assisted atom transfer radical polymerization (ATRP) from a surface while open to air. Specifically, we grew a set of biomedically relevant polymer brushes, including poly(oligo(ethylene glycol) methacrylate) (POEGMA), poly(2-dimethylaminoethyl methacrylate) (PDMAEMA), poly(sulfobetaine methacrylate) (PSBMA), and poly(2-(methylsulfinyl)ethyl acrylate (PMSEA). For each of these polymers, we monitored GOx-assisted and GOx-free ATRP reaction kinetics in real time using quartz crystal microbalance (QCM) and verified findings with localized surface plasmon resonance (LSPR). We modeled brush growth kinetics considering bimolecular termination. This model fit our data well ( r2 > 0.987 for all samples) and shows the addition of GOx increased effective kinetic chain lengths, propagation rates, and reproducibility. We tested the antifouling properties of the polymer brush coatings against human blood plasma and were surprised to find that coatings prepared with GOx repelled more plasma proteins in all cases than their GOx-free counterparts.

Synthesis of Modular Brush Polymer-Protein Hybrids Using Diazotransfer and Copper Click Chemistry.

Proteoglycans are important brush-like biomacromolecules, which serve a variety of functions in the human body. While protein-bottlebrush hybrids are promising proteoglycan mimics, many challenges still exist to robustly produce such polymers. In this paper, we report the modular synthesis of protein-brush hybrids containing elastin-like polypeptides (ELP) as model proteins by copper-catalyzed azide-alkyne cycloaddition. We exploit the recently discovered imidazole-1-sulfonyl azide (ISA) in a diazotransfer reaction to introduce an N-terminal azide onto an ELP. Next, we use a click reaction to couple the azido-ELP to an alkyne-terminated amine-rich polymer followed by a second diazotransfer step to produce an azide-rich backbone that serves as a scaffold. Finally, we used a second click reaction to graft alkyne-terminated poly(oligoethylene glycol methacrylate) (POEGMA) bristles to the azide-rich backbone to produce the final protein-bottlebrush hybrid. We demonstrate the effectiveness of this synthetic path at each step through careful characterization with 1H NMR, FTIR, GPC, and diagnostic test reactions on SDS-PAGE. Final reaction products could be consistently obtained for a variety of different molecular weight backbones with final total grafting efficiencies around 70%. The high-yielding reactions employed in this highly modular approach allow for the synthesis of protein-bottlebrush hybrids with different proteins and brush polymers. Additionally, the mild reaction conditions used have the potential to avoid damage to proteins during synthesis.

High-Molecular-Weight Polynucleotides by Transferase-Catalyzed Living Chain-Growth Polycondensation.

We present terminal deoxynucleotidyl transferase-catalyzed enzymatic polymerization (TcEP) for the template-free synthesis of high-molecular-weight, single-stranded DNA (ssDNA) and demonstrate that it proceeds by a living chain-growth polycondensation mechanism. We show that the molecular weight of the reaction products is nearly monodisperse, and can be manipulated by the feed ratio of nucleotide (monomer) to oligonucleotide (initiator), as typically observed for living polymerization reactions. Understanding the synthesis mechanism and the reaction kinetics enables the rational, template-free synthesis of ssDNA that can be used for a range of biomedical and nanotechnology applications.

Superhydrophobic SAM Modified Electrodes for Enhanced Current Limiting Properties in Intrinsic Conducting Polymer Surge Protection Devices.

Surface interface engineering using superhydrophobic gold electrodes made with 1-dodecanethiol self-assembled monolayer (SAM) has been used to enhance the current limiting properties of novel surge protection devices based on the intrinsic conducting polymer, polyaniline doped with methanesulfonic acid. The resulting devices show significantly enhanced current limiting characteristics, including current saturation, foldback, and negative differential effects. We show how SAM modification changes the morphology of the polymer film directly adjacent to the electrodes, leading to the formation of an interfacial compact thin film that lowers the contact resistance at the Au-polymer interface. We attribute the enhanced current limiting properties of the devices to a combination of lower contact resistance and increased Joule heating within this interface region which during a current surge produces a current blocking resistive barrier due to a thermally induced dedoping effect caused by the rapid diffusion of moisture away from this region. The effect is exacerbated at higher applied voltages as the higher temperature leads to stronger depletion of charge carriers in this region, resulting in a negative differential resistance effect.

Validation of ICON-MIGHTI Thermospheric Wind Observations: 1. Nighttime Red-Line Ground-Based Fabry-Perot Interferometers.

Observations of the nighttime thermospheric wind from two ground-based Fabry-Perot Interferometers are compared to the level 2.1 and 2.2 data products from the Michelson Interferometer Global High-resolution Thermospheric Imaging (MIGHTI) onboard National Aeronautics and Space Administration's Ionospheric Connection Explorer to assess and validate the methodology used to generate measurements of neutral thermospheric winds observed by MIGHTI. We find generally good agreement between observations approximately coincident in space and time with mean differences less than 11 m/s in magnitude and standard deviations of about 20-35 m/s. These results indicate that the independent calculations of the zero-wind reference used by the different instruments do not contain strong systematic or physical biases, even though the observations were acquired during solar minimum conditions when the measured airglow intensity is weak. We argue that the slight differences in the estimated wind quantities between the two instrument types can be attributed to gradients in the airglow and thermospheric wind fields and the differing viewing geometries used by the instruments.

Group of R&D on biomedical engineering: Its development and results.

Conducting research and development activities generates new knowledge that can then be applied properly. In this sense, the groups of research and development on biomedical engineering (GRDBE) can contribute a lot in various areas such as teaching (theory and laboratory), as well as the development of prototypes, but mainly with the results they can provide. These contributions should response to specific needs of some sector, for example: health, environment, biology, and others. The present paper provides a description of the development of a GRDBE into a private university. Also, it's presented the amount of papers developed by this group and accepted by international congress on biomedical engineering (BE) on the 2007-2009 period. This paper also shows comparative charts with papers produced by other GRDBE that exist in our country, which are matter of analysis and conclusions.

Electronic system for monitoring the frequency and pressure of mastication: study and approach for its design.

The objective of this work is to study and design a portable non invasive prototype which allows us to supervise the mastication frequency and pressure for specific meals, performing an analysis of sounds and pressures generated by facial muscles when they are chewing. These variables have a direct influence on people nutritious and dietary habits; also, a quickly eating makes people ingest a lot of food instead he needs generating overweight on him. On the other hand, there is no so much study for upheaval of temporal-mandible joints (TMJ) in Peru, keeping as reference that unilateral mastication is one of the principal causes on myofacial pains but, as obesity, there are no studies in Peru about how to prevent these pathologies. In consequence, we propose the development of this prototype which, additional to supervise variables such as mastication frequency and pressure, will allow to the patient an self-correction of his habits.

Opto-electronic system for detection of flat foot by using estimation techniques: study and approach of design.

Distribution of Foot Pressure reflects the deformations of body biomechanical design. They are caused by different reasons: degenerative, by trauma, etc., being flat foots a common pathology in Peru with high incidence. However there isn't the properly technology to detect properly this disease because is detected by a non-reliable visual way using pedoscopes. Flat foot is the degree of internal plantar arch lack and is well observed in foot pressure distribution. This distribution can be obtained by optical or electronic systems. The most required, by their accuracy, are the electronic ones but sensor manufacturing process increases its price, meanwhile optics provides an indirect optical solution whose price depends on scanners resolution. Therefore, this paper takes advantage of both systems: a direct pressure value from electronics and no problems calibration from optical systems. In regard of these reasons, prototype will use a webcam and twelve FSR (Force sensing resistor) sensors including estimation techniques, and thus obtain the foot pressure distribution. Accordingly, the present study is looking for providing to the specialist with an efficient tool to generate better diagnostics in Perú.

Validación en español de un instrumento de pre-escrutinio para la detección de masa ósea baja en mujeres posmenopáusicas: índice SCORE / SCORE Index ia pre-screening questionary used in post-menopausal women in risk of low bone mass

El índice SCORE es un cuestionario que se utiliza como pre-escrutinio de mujeres posmenopáusicas en riesgo de masa ósea baja, en las cuales se puede optimiza el recurso de la densitometría ósea, que tiene un costo elevado. Se validó en español el índice SCORE y se aplicó en 1280 mujeres posmenopáusicas mayores de 45 años de edad que fueron evaludas por densitometría dual de rayos "X" (DXA) en columna lumbar y cuello femoral. El análisis del balance entre sensibilidad/especificidad del índice SCORE en la identificación de mujeres con osteopenia y osteoporosis, muestra que las mujeres posmenopáusicas mestizas mexicanas requieren un punto de corte menor que el utilizado en mujeres posmenopáusicas blancas caucásicas, donde se desarrolló originalmente el índice SCORE siendo este punto de corte muy semejante a las mujeres posmenopáusicas de origen asiático. El índice SCORE es capaz de identificar, entre mujeres mexicanas, osteopenia en columna lumbar con 4 puntos y osteopenia en cuello femoral con 5 puntos. Identifica osteoporosis en columna lumbar con 6 puntos y osteoporosis en cuello femoral con 8 puntos