Stereoselective UV sensing of 1,2-diaminocyclohexane isomers based on ligand displacement with a diacridylnaphthalene N,N'-dioxide scandium complex

Stereoselective displacement of diacridylnaphthalene N,N'-dioxide ligands, 1, from a scandium(III) complex can be used for quantitative detection of 1,2-diaminocyclohexane isomers. The diastereoselective sensing assay with Sc(syn-1)(2) shows excellent linearity between the sample de and the measured UV absorption change, and sensing of mixtures comprising both low and high de values gave results within 5% accuracy. All three stereoisomers of 1,2-diaminocyclohexane can be differentiated using Sc[anti-(-)-1](2) in the same ligand displacement assay.     

Detection and Quantitation of Afucosylated N-Linked Oligosaccharides in Recombinant Monoclonal Antibodies Using Enzymatic Digestion and LC-MS

The presence of N-linked oligosaccharides in the CH2 domain has a significant impact on the structure, stability, and biological functions of recombinant monoclonal antibodies. The impact is also highly dependent on the specific oligosaccharide structures. The absence of core-fucose has been demonstrated to result in increased binding affinity to Fcγ receptors and, thus, enhanced antibody-dependent cellular cytotoxicity (ADCC). Therefore, a method that can specifically determine the level of oligosaccharides without the core-fucose (afucosylation) is highly desired. In the current study, recombinant monoclonal antibodies and tryptic peptides from the antibodies were digested using endoglycosidases F2 and H, which cleaves the glycosidic bond between the two primary GlcNAc residues. As a result, various oligosaccharides of either complex type or high mannose type that are commonly observed for recombinant monoclonal antibodies are converted to either GlcNAc residue only or GlcNAc with the core-fucose. The level of GlcNAc represents the sum of all afucosylated oligosaccharides, whereas the level of GlcNAc with the core-fucose represents the sum of all fucosylated oligosaccharides. LC-MS analysis of the enzymatically digested antibodies after reduction provided a quick estimate of the levels of afucosylation. An accurate determination of the level of afucosylation was obtained by LC-MS analysis of glycopeptides after trypsin digestion.     

Effect of crown ethers on the ground and excited state reactivity of samarium diiodide in acetonitrile

Electron transfer from the ground and excited states of Sm[15-crown-5](2)I(2) complex to a series of electron acceptors (benzaldehyde, acetophenone, benzophenone, nitrobenzene, benzyl bromide, benzyl chloride, 1-iodohexane, and 1,4-dinitrobenzene) was investigated in acetonitrile. Electron transfer from the ground state of the Sm(II)-crown system to aldehydes and ketones has a significant inner sphere component indicating that the oxophilic nature of Sm(II) prevails in the system even in the presence of bulky ligands such as 15-crown-5 ether. Activation parameters for the ground state electron transfer were determined, and the values were consistent with the proposed mechanistic models. Since crown ethers stabilize the photoexcited states of Sm(II), the photochemistry of Sm[15-crown-5](2)I(2) system in solution state has been investigated in detail. The results suggest that photoinduced electron transfer from Sm(II)-crown systems to a wide variety of substrates is feasible with rate constant values as high as 10(7) M(-1) s(-1). The results described herein imply that the present difficulty of manipulating the extremely reactive excited state of Sm(II) in solution phase can be overcome through stabilizing the excited state of the divalent metal ion by careful design of the ligand systems.     

Curriculum Materials Supporting Problem-Based Teaching

The vision for school mathematics described by the National Council of Teachers of Mathematics (NCTM) suggests a need for new approaches to the teaching and learning of mathematics, as well as new curriculum materials to support such change. This article discusses implications of the NCTM standards for mathematics curriculum and instruction and provides three examples of lessons from problem-based curricula for various grade levels. These examples illustrate how the teaching of important mathematics through student exploration of interesting problems might unfold, and they highlight the differences between a problem-based approach and more traditional approaches. Considerations for teaching through a problem-based approach are raised, as well as reflections on the potential impact on student learning.     

Does botulinum toxin alter laryngeal secretionsand mucociliary transport?

Localized botulinum toxin injection disrupts cholinergic transmissionand has potential to cause focal dysautonomia. Mucociliary transport and laryngeal secretions are thought to be mediated in part by autonomic, cholinergic transmission. We questioned whether patients who receive Botox® injection for adductor spasmodic dysphonia (ADSD) report postinjection symptoms possibly related to altered mucociliary clearance or laryngeal secretions. Medical histories, audiotaped interviews, and symptom ratings were retrospectively examined for 29 patients with ADSD who were followed after one or more Botox injections. Patients had received bilateral, percutaneous Botox injections of 2.5 units using an EMG-guided approach. One or more weeks after injection, four patients reported either burning, tickling, or irritation of the larynx/throat, excessive thick secretions, or dryness. Symptoms recurred with subsequent injections in two patients and were not associated with swallowing difficulty. These symptoms are consistent with, but not diagnostic of, the known effects of botulinum toxin on cholinergic, autonomic transmission.     

An NMR Investigation of the Conformational Effect of Nitroxide Spin Labels on Ala-Rich Helical Peptides

Nitroxide spin labels, in conjunction with electron spin resonance (ESR) experiments, are extensively employed to probe the structure and dynamics of biomolecules. One of the most ubiquitous spin labeling reagents is the methanethiosulfonate spin label which attaches a spin label selectively to Cys residues via a disulfide bond (Cys-SL). However, the actual effect of the nitroxide spin label upon the conformation of the peptide or protein cannot be unambiguously determined by ESR. In this study, a series of 16-residue Ala-rich helical peptides was characterized by nuclear magnetic resonance techniques. The C_αH chemical shift analysis, NOEs, and³J_NHαcoupling constants for peptides with no Cys, free Cys, and Cys-SL (with the N–O group reduced) were compared. These results indicate that while replacement of an Ala with a Cys residue causes a loss of overall helical structure, the Cys-SL residue is helix supporting, as would be expected for a non-β-branched aliphatic amino acid. Thus, the Cys-SL residue does not perturb helical structure and, instead, exhibits helix-stabilizing characteristics similar to that found for Ala, Met, and Leu.     

MEMS implementation of axial and follower end forces

Although it is challenging to implement follower forces in macroscale laboratory experiments, they can be implemented fairly easily in MEMS devices. This paper discusses the implementation of follower and axial end forces in a beam-type MEMS resonator for the application of resonant frequency tuning.     

Rapid synthesis of substituted 5-phenyl-1,3-dioxolan-4-ones under microwave-induced solvent-free conditions

Under microwave irradiation and without solvent, racemic and optically pure mandelic acid readily condenses with aldehydes and ketones to give 2-alkyl substituted 5-phenyl-1,3-dioxolan-4-ones in good yield.     

Isomorphic Embeddings and Strongly Additive Measures

Strongly additive and non-strongly additive vector measures are studied in the context of spaces of operators. Also, order properties and embedding properties of Banach lattices are linked to the notion of strong additivity.