Photodegradable Polymers for Biotechnological Applications

Photodegradable polymers constitute an emerging class of materials that finds numerous applications in biotechnology, biomedicine, and nanoscience. This article highlights some of the emerging applications of photodegradable polymers in the form of homopolymers, particles and self‐assembled constructs in solution, hydrogels for tissue engineering, and photolabile polymers for biopatterning applications. Novel photochemistries have been combined with controlled polymerization methods, which result in well‐defined photodegradable materials that exhibit light mediated and often controlled fragmentation processes.     

Response surface methodology toward the optimization of high-energy carotenoid extraction from Aristeus antennatus shrimp

High-energy assisted extraction techniques, like ultrasound assisted extraction (UAE) and microwave assisted extraction (MAE), are widely applied over the last years for the recovery of bioactive compounds such as carotenoids, antioxidants and phenols from foods, animals and herbal natural sources. Especially for the case of xanthophylls, the main carotenoid group of crustaceans, they can be extracted in a rapid and quantitative way with the use of UAE and MAE.     

Versatile gold-polymer nanointerfaces probed by GISAXS

An increasing trend toward integration of polymers in microelectronics and organic electronics has recently boosted research focusing in metal-polymer interfaces. These two materials differ vastly, with the former forming dense, crystalline, cohesive structures and the latter forming open structures bound together by weak van der Waals forces. As a result, there is dire need to assess their surface features (e.g., roughness) and correlate them with corresponding growth parameters, as metal-polymer interfaces are mainly determined by the preparation process. Here, we report a laboratory-based grazing-incidence small-angle x-ray scattering (GISAXS) study on distinct gold-polymer interfaces fabricated with different growth mechanisms, utilizing in-plane and oblique sputter geometries. GISAXS provided an improved analytic scheme for the buried surface in free-standing 2D gold-polymer nanosheets (with 19% porosity) revealing their fractal structure (Porod slope: ?1.71). Two quantitative approaches (Height-Height Correlation and Power Spectral Density functions) were used to describe rough surfaces characterized by Atomic Force Microscopy (AFM) in consort with GISAXS data; different correlation length dependencies on growth time were revealed for gold rough surfaces grown on bare and polymerized Si. The results are considered pertinent to interfacial nanoscience and engineering, enabling statistical data collection from large surface areas, in a fast and nondestructive manner.     

Determination of total polyvinylpyrrolidone (PVP) in ophthalmic solutions by size exclusion chromatography with ultraviolet-visible detection

A straightforward size exclusion chromatography (SEC) method was developed and validated for the determination of total polivinylpyrrolidone (PVP) in ophthalmic solutions using the unusual combination of size exclusion chromatography (SEC), ultraviolet-visible detection and quantitation of an analyte peak that elutes in the total exclusion volume of the column. Samples of opthalmic solutions are diluted with water and injected onto a TSKgel G1000PW, 7.5 mm i.d. × 30 cm, 12 μm column at 50°C, with 80:20 0.1M sodium acetate-methanol mobile phase and UV detection at 220 nm. Validation was successful for a stability indicating pharmaceutical method, with parameters including specificity, accuracy, linearity, and precision within typical pharmaceutical acceptance criteria. A stress study with acid, base, peroxide, heat, and light indicates that there is no interference from drug, product, or excipients.     

TiO2-ZrO2 affinity chromatography polymeric microchip for phosphopeptide enrichment and separation

We fabricated a TiO(2)-ZrO(2) affinity chromatography micro-column on 2 mm PMMA plates, and demonstrated the enrichment and separation of (a) a standard mono- and tetra-phosphopeptide, and (b) phosphopeptides contained in a tryptic digest of β-Casein. The chromatography column consisted of 32 parallel microchannels with common input and output ports and was fabricated by lithography directly on the polymeric substrate followed by plasma etching (i.e. standard MEMS processing) and sealed with lamination. The liquid deposited TiO(2)-ZrO(2) stationary phase was characterized by X-ray diffraction and was found to be mostly TiO(2) and ZrO(2) in crystalline phases. Off-chip UV detection and MALDI MS identification of the separated effluents were used. The chip had a capacity of >1.4 μg (0.7 nmol) of a prototype mono-phosphopeptide and a recovery of 94 ± 3%, and can be used with small samples (less than 0.1 μL depending on the syringe pump used). The chip design allows an expansion of its capacity by means of increasing the number of parallel microchannels at a constant sample volume. Our approach provided an alternative to off-line extraction tips (with typical capacities of 1-2 μg and sample volumes of 1-10 μL), and to on-chip efforts based on packed bed and frit formats.     

Photophysical behavior of terpyridine-lanthanide ion complexes incorporated in a poly(N,N-dimethylacrylamide) hydrogel

Poly(N,N-dimethylacrylamide) hydrogel forms complexes with terpyridine and various trivalent ions, like Eu(3+), Tb(3+), Gd(3+), and In(3+). The hydrogel can be obtained in three different phases: swollen with water, lyophilized (i.e., dried by freeze-drying), where it loses the solvent but preserves the swollen configuration, and dried in the air where it shrinks. The three hydrogel phases affect the type of complex formed between terpyridine and the metal ion. Thus, in the swollen and lyophilized phases, metal-centered emission can be obtained by energy transfer from the excited ligand. In the shrunk phase, an intense green fluorescence is emitted, which is ligand-centered and is independent of the complexed ion. In the absence of any ion, the ligand emits blue luminescence, independently of the hydrogel phase. In the presence of europium(III) ions, blue, green, or red emission can be thus produced at appropriate compositions and hydrogel phases. Analysis of the photophysical behavior of the polymer-ligand-metal ion complex is related with the photophysical behavior of the ligand and its complexes in various pure solvents.     

Corresponding-states laws for protein solutions

The solvent around protein molecules in solutions is structured and this structuring introduces a repulsion in the intermolecular interaction potential at intermediate separations. We use Monte Carlo simulations with isotropic, pair-additive systems interacting with such potentials. We test if the liquid-liquid and liquid-solid phase lines in model protein solutions can be predicted from universal curves and a pair of experimentally determined parameters, as done for atomic and colloid materials using several laws of corresponding states. As predictors, we test three properties at the critical point for liquid-liquid separation: temperature, as in the original van der Waals law, the second virial coefficient, and a modified second virial coefficient, all paired with the critical volume fraction. We find that the van der Waals law is best obeyed and appears more general than its original formulation: A single universal curve describes all tested nonconformal isotropic pair-additive systems. Published experimental data for the liquid-liquid equilibrium for several proteins at various conditions follow a single van der Waals curve. For the solid-liquid equilibrium, we find that no single system property serves as its predictor. We go beyond corresponding-states correlations and put forth semiempirical laws, which allow prediction of the critical temperature and volume fraction solely based on the range of attraction of the intermolecular interaction potential.     

A New Approach for the Photosynthetic Antenna–Reaction Center Complex with a Model Organized Around an s‐Triazine Linker

Two new artificial mimics of the photosynthetic antenna‐reaction center complex have been designed and synthesized (BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀). The resulting electron‐donor/acceptor conjugates contain a porphyrin (either in its free‐base form (H₂P) or as Zn‐metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C₆₀‐X‐NH₂ (X=spacer). In both cases, the three different components were connected by s‐triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star‐type arrangement of the three photo‐ and redox‐active components around the central s‐triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy‐ and electron‐transfer properties of the resulting electron‐donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀ with those of BDP‐H₂P, BDP‐ZnP and BDP‐C₆₀, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H₂P or ZnP. This is then followed by an electron transfer to C₆₀, yielding the formation of the singlet charge‐separated states, namely BDP‐H₂P ^.+‐ C₆₀ ^.? and BDP‐ZnP ^.+‐ C₆₀ ^{. ?}. As such, the sequence of energy transfer and electron transfer in the present models mimics the events of natural photosynthesis.