An Adsorption Isotherm from a Micro-state Model

The present study is dedicated to the derivation of an alternative adsorption isotherm for liquid-solid interfaces from a micro-state model, where adsorption is predominantly of a chemical nature. We describe adsorption-desorption on a liquid-solid interface starting from a partition function. In the new model the surface site occupation number is controlled by the Pauli principle (monolayer condition) and additional an attractive or repulsive surface potential, which depends on the overall surface coverage (nonlinearity). The effective potential represents adsorbate adsorbent interaction, as well as an influence of adsorbate adsorbate interactions on the surface potential. A Langmuir equivalent isotherm is recovered in the limit of a weak potential. The proposed model and Langmuirs isotherm are compared using data of humic acid (HA) adsorption on Brazilian Oxisol soil samples. Both models parameterize the experimental data well, but only the new model seems to be self-consistent.     

Caged phosphoproteins

We present the chemical and biological synthesis of caged phosphoproteins using the in vitro nonsense codon suppression methodology. Specifically, phosphoamino acid analogues of serine, threonine, and tyrosine with a single photocleavable o-nitrophenylethyl caging group were synthesized as the amino acyl tRNA adducts for insertion into full-length proteins. For this purpose, a novel phosphitylating agent was developed. The successful incorporation of these bulky and charged amino acids into the alpha-subunit of the nicotinic acetyl choline receptor (nAChR) and the vasodilator-stimulated phosphoprotein (VASP) using an in vitro translation system is reported.     

The reductive metalation of 1,2-dihalobenzocyclobutenes by NaFe(CO)2Cp and HFe(CO)2Cp

The reactions between cis- and trans-1,2-dibromo- or 1,2-diidobenzocyclobutene and NaFe(CO)₂Cp (NaFp) were investigated. The mechanism of formation of 1,2-bis(cyclopentadienyldicarbonyliron)benzocyclobutene (I) and 1-(cyclopentadienyldicarbonyliron)benzocyclobutene (II) is thought to involve initial formation of benzocyclobutadiene, addition of a Fp radical to benzocyclobutadiene and subsequent addition of a second Fp radical to form I, or hydrogen abstraction from FpH to form II.     

Development of an on-line automated sample clean-up method and liquid chromatography–tandem mass spectrometry analysis: application in an in vitro proteolytic assay

Fluorescence detection has been a method of choice in industry for screening assays, including identification of enzyme inhibitors, owing to its high-throughput capabilities, excellent reproducibility, and sensitivity. Occasionally, inhibitors are identified that challenge the fluorescence assay limit, necessitating the development of more sensitive detection methods to assess these compounds. For data mining purposes, however, original assay conditions may be required. A direct method transfer to highly sensitive and specific LC-MS-based methods has not always been possible due to the presence of MS-incompatible neutral detergents and non-volatile salts in the assay matrix. Utilizing an in vitro proteolytic screening assay for the serine protease hepatitis C virus (HCV) nonstructural (NS) 3 protease as a test case, we report the development of an automated sample clean-up procedure implemented on-line with liquid chromatography–tandem mass spectrometry (LC-MS/MS) analysis to complement fluorescence detection. Ion exchange and peptide microtraps were employed to remove MS-incompatible assay matrix components. Three protease inhibitors were used to validate the MS/MS method. Comparable potencies were achieved for these compounds when assessed by fluorescence and MS/MS detection. Furthermore, four-fold less enzyme could be utilized when employing the MS/MS method compared to fluorescence detection. The longer analysis time, however, resulted in reduced sample capacity. The potency of our designed HCV NS3 protease inhibitors are thus routinely evaluated using a continuous fluorescence-based assay. Only pertinent inhibitors approaching the fluorescence assay sensitivity limit are subsequently analyzed further by LC-MS/MS. This methodology allows us to maintain a database and to compare results independent of the detection method. Despite the relatively slow sample turnaround time of this LC-MS approach, the versatility of the automated on-line clean-up procedure and sample analysis can be applied to assays containing reagents which were historically considered to be MS incompatible.     

Migratory insertion of [B(C6F5)2] into C-H bonds: CO promoted transfer of the boryl fragment

The reaction of (eta(5)-C5H5)Fe(CO)2B(C6F5)2 with CO has been shown to proceed via ligand substitution at the metal with accompanying transfer of the boryl fragment (via C-H insertion) to the Cp ring, thereby generating the zwitterion [eta(5)-C5H4B(C6F5)2H]Fe(CO)3 in quantitative yield.     

Conceptualizations of slope in Mexican intended curriculum

Slope is a fundamental mathematics concept in middle and high school that transcends to the university level. An understanding of slope is needed at the university level since slope plays an important role in understanding problems involving variation and change. In this study Mexican curricula documents were examined to determine which conceptualizations of slope are addressed in the intended mathematics curriculum. To explain the results, we use conceptualizations of slope identified in previous research. Our findings reveal that, to a certain extent, the conceptualizations proposed in the Mexican intended mathematics curriculum differ slightly in terms of the emphasis and timing of instruction from what others have identified in the U.S., with slope as a geometric ratio receiving less emphasis in the Mexican curriculum. There was also noted discontinuity within the Mexican curriculum in introducing slope in grade 9 and subsequently introducing of linear functions in grade 10 without explicit mention of slope. Suggestions are made for future studies, both to consider the conceptualizations of slope promoted in the Mexican textbooks and the impact they have in classroom instruction and student learning of slope.