Correcting the microscopic coefficient of surface tension of associated liquids

A correction to the association of saturation vapor molecules is introduced into the theory of microscopic surface tension proposed by Sinanoglu. It is determined that the calculated solubility of benzene in water coincides with the one measured using this correction.     

Determination of phenolic compounds derived from hydrolysable tannins in biological matrices by RP-HPLC

An RP-HPLC method for the determination of four phenolic compounds: gallic acid (GA), pyrogallol (PY), resorcinol (RE) and ellagic acid (EA), derived from hydrolysable tannins is reported. Separation was achieved on a SunFire C18 (250 x 4.6 mm id, 5 microm) column at 40 degrees C with gradient elution. UV detection at 280 nm was applied. The developed method was validated in terms of linearity, accuracy and precision. Satisfactory repeatability and between day precision were noticed with RSD values lower than 3%. Recoveries from different biological samples ranged from 91.50 to 105.25%. The LODs were estimated as 1.70 mg/L for PY, 1.68 mg/L for GA, 1.52 mg/L for RE and 0.98 mg/L for EA with a 20 microL injection volume. The method was applied for the determination of these compounds in oak leaves and in ruminal fluid and urine samples taken from beef cattle fed with oak leaves. The proposed method could be used in ruminant nutrition studies to verify the effect that a diet rich in tannins have on ruminal fermentation and to determine the toxicity of these compounds.     

Synthesis,Biochemical Characterization,and Genetic Encoding of a 1,2,4-Triazole Amino Acid as an Acetyllysine Mimic for Bromodomains of the BET Family

Lysine acetylation is a charge-neutralizing post-translational modification of proteins bound by bromodomains (Brds). A 1,2,4-triazole amino acid (ApmTri) was established as acetyllysine (Kac) mimic recruiting Brds of the BET family in contrast to glutamine commonly used for simulating this modification. Optimization of triazole substituents and side chain spacing allowed BET Brd recruitment to ApmTri-containing peptides with affinities similar to native substrates. Crystal structures of ApmTri-containing peptides in complex with two BET Brds revealed the binding mode which mirrored that of Kac ligands. ApmTri was genetically encoded and recombinant ApmTri-containing proteins co-enriched BRD3(2) from cellular lysates. This interaction was blocked by BET inhibitor JQ1. With genetically encoded ApmTri, biochemistry is now provided with a stable Kac mimic reflecting charge neutralization and Brd recruitment, allowing new investigations into BET proteins in vitro and in vivo.     

Photopatterned surfaces for site-specific and functional immobilization of proteins

Photosensitive silanes containing nitroveratryl (Nvoc)-caged amine groups and protein repellent tetraethylene glycol units were synthesized and used for modification of silica surfaces. Functional surface layers containing different densities of caged amine groups were prepared and activated by UV-irradiation of the surface. The performance of these layers for functional and site-selective immobilization of proteins was tested. For this purpose, biotin and tris-nitrilotriacetic acid (tris-NTA) were fist coupled to the activated surface, and the interaction of streptavidin and His-tagged proteins with the functionalized surfaces was monitored by real-time label-free detection. After optimizing the coupling protocols, highly selective functionalization of the deprotected amine groups was possible. Furthermore, the degree of functionalization (and therefore the amount of immobilized protein) was controlled by diluting the surface concentration of the amine-functionalized silane with a nonreactive (OMe-terminated) tetraethylene glycol silane. Immobilized proteins were highly functional on these surfaces, as demonstrated by protein-protein interaction assays with the type I interferon receptor. Protein micropatterns were successfully generated after masked irradiation and functionalization of the caged surface following the optimized coupling protocols.     

Photoresponsive surfaces with two independent wavelength-selective functional levels

Two photoremovable protecting groups, namely, nitroveratryloxycarbonyl (NVo) and diethylamino-coumarin-4-yl (DEACM), have been tested for wavelength-selective, independent removal. The chromophores were attached to the amine group of aminopropyltriethoxysilane and used for the modification of silica surfaces. A photolytic experiment on the photosensitive layers allowed us to identify the irradiation conditions for the selective cleavage of the chromophores. UV measurements revealed that the photolabile DEACM group can be cleaved off with UV light at 412 nm without damaging the NVo group. The NVo group could then be removed at 365 nm. Masked irradiation of substrates modified with a 1:1 molar mixture of both silanes allowed the generation of bifunctional patterns after the selective cleavage of DEACM and NVo in a sequential irradiation process. The deprotection reaction was confirmed by coupling two different fluorescent dyes to the liberated amine groups. The expected two-color pattern could be observed by fluorescence microscopy.     

Structural evolution from the sol to the PbZrO<Subscript>3</Subscript> precursor powders prepared by an alkoxide-based sol–gel route

PbZrO₃ powders have been prepared by an alkoxide-based sol–gel route, starting from lead acetate, zirconium n-butoxide, and n-butanol as a solvent, and hydrolysed with different amounts of water in neutral and alkaline medium. The local environment of Zr and Pb atoms was pursued from the sol to the dried (150 °C) and heated (400 °C) powders, by extended x-ray absorption fine structure (EXAFS). The analysis of the sol revealed links between Pb and Zr, and even more links between Zr and Zr. The metal neighbourhoods in the dried powders are not influenced by the hydrolysis conditions. Pb-Zr correlations are gradually lost from the sol to the dried and heated powders, while the loss of Zr–Zr correlations is considerably lower.     

Increasing the structural complexity of chromium(IV) oxides by high-pressure and high-temperature reactions of CrO2

This work presents an overview of a series of increasingly complex oxides synthesized from CrO 2, under high-pressure and high-temperature conditions, having Cr (4+) in octahedral coordination. Although the emphasis is on the structure and microstructure of the compounds as obtained from X-ray diffraction and transmission electron microscopy and diffraction, attention is also given to their interesting electronic and magnetic properties. The study is complemented with an electron energy loss spectroscopic analysis of the different phases. These are the cubic perovskite SrCrO 3, the orthorhombic perovskite CaCrO 3, the solid solution Sr 1-xCa xCrO 3, the Ruddlesden-Popper-type Sr 3Cr 2O 7, the family CrSr 2RECu 2O 8 (RE = rare earth), a compositionally modulated perovskite "PbCrO 3", and the misfit layer oxide SrO 2[CrO 2] 1.85.     

Gelation Kinetics and Mechanical Properties of Thiol-Tetrazole Methylsulfone Hydrogels Designed for Cell Encapsulation

Hydrogel precursors that crosslink within minutes are essential for the development of cell encapsulation matrices and their implementation in automated systems. Such timescales allow sufficient mixing of cells and hydrogel precursors under low shear forces and the achievement of homogeneous networks and cell distributions in the 3D cell culture. The previous work showed that the thiol-tetrazole methylsulfone (TzMS) reaction crosslinks star-poly(ethylene glycol) (PEG) hydrogels within minutes at around physiological pH and can be accelerated or slowed down with small pH changes. The resulting hydrogels are cytocompatible and stable in cell culture conditions. Here, the gelation kinetics and mechanical properties of PEG-based hydrogels formed by thiol-TzMS crosslinking as a function of buffer, crosslinker structure and degree of TzMS functionality are reported. Crosslinkers of different architecture, length and chemical nature (PEG versus peptide) are tested, and degree of TzMS functionality is modified by inclusion of RGD cell-adhesive ligand, all at concentration ranges typically used in cell culture. These studies corroborate that thiol/PEG-4TzMS hydrogels show gelation times and stiffnesses that are suitable for 3D cell encapsulation and tunable through changes in hydrogel composition. The results of this study guide formulation of encapsulating hydrogels for manual and automated 3D cell culture.     

Pre-service Teachers’ Developing Conceptions about the Nature and Pedagogy of Mathematical Modeling in the Context of a Mathematical Modeling Course

Adopting a multitiered design-based research perspective, this study examines pre-service secondary mathematics teachers’ developing conceptions about (a) the nature of mathematical modeling in simulations of “real life” problem solving, and (b) pedagogical principles and strategies needed to teach mathematics through modeling. Unlike other studies that have focused on single-topic and lesson-sized research sites, a course-sized research site was used in this study. Having been through several iterations over three teaching semesters, the 15-week long course was implemented with 25 pre-service secondary mathematics teachers. Findings revealed that pre-service teachers developed ideas about the nature of mathematical modeling involving what mathematical modeling is, the relationship between mathematical modeling and meaningful understanding, and the nature of mathematical modeling tasks. They also realized the changing roles of teachers during modeling implementations and diversity in students’ ways of thinking. The researchers’ conceptual development, on the other hand, involved realizing the critical aspect of the “teacher role” played by the instructor during modeling implementations, and the need for more experience of modeling implementations for pre-service teachers.