Revalidation and long-term stability of National Institute of Standards and Technology Standard Reference Materials 1566, 1567, 1568, and 1570

Multiple units of Standard Reference Materials (SRMs) 1566 Oyster Tissue, 1567 Wheat Flour, 1568 Rice Flour, and 1570 Trace Elements in Spinach, produced by the National Institute of Standards and Technology (NIST, then the National Bureau of Standards), were analyzed 17-20 years after the original certification dates and 12-15 years after the certificates became invalid. Instrumental neutron activation analysis and thermal neutron prompt gamma-ray activation analysis were used to measure mass fractions for 27 elements in these SRMs to revalidate them for use in quality assurance (QA) programs required for food analysis programs within the U.S. Food and Drug Administration. With the exception of Se in SRM 1567, all element mass fractions were in agreement with certified values and literature data. Some evidence of B loss from SRM 1568 was observed. These materials were judged to be suitable for continued use in QA programs. Findings showed that these matrixes exhibited stability of moisture, mass fraction, and weight basis for far longer (> or =15 years) than was indicated by the 5-year validity statement on the NIST Certificates of Analysis.     

Synthesis of high-performance superabsorbent glycerol acrylate-cross-linked poly (acrylic acid)

Glycerol acrylate (GA) is synthesised by an acryloylation reaction with acryloyl chloride. An ester was used as a cross-linking agent at varying proportions in the synthesis of poly acrylic acid (PAA). The amount of cross-linking density in the product (GA-PAA) and degree of neutralisation determine the absorbency of the polymer samples. A sample of GA-PAA containing 0.8 % GA was discovered to absorb 395 and 66 g/g of water and saline solution, respectively. Different solvent uptakes were tested with the sample showing varying capacity for different solvents. The temperature of the reaction was maintained at 60 °C and a reaction time of 2½ h. FTIR, TGA, SEM and XRD analyses were used to characterise the products.     

An Efficient Steric Controlled Photo-Fries Rearrangement in the Naphthalene Series

For the work on the synthesis of 2-acyl-5-methoxynaphthoquinones as tricyclic analogues of daunomycinone¹, we wanted to develop an efficient regioselective synthesis of 5-methoxy-2-acyl-1-naphthols without using Lewis acids. This requirement precluded the use of the thermal Fries but not the photo-Fries rearrangement. Although the mechanistic aspects of the photo reaction have received much study², the reaction has been little used preparatively³ because it usually gives poor yields of hydroxy ketones even when only one product is possible.     

Development of an information-intensive structure–activity relationship model and its application to human respiratory chemical sensitizers

Structure–activity relationship (SAR) models are recognized as powerful tools to predict the toxicologic potential of new or untested chemicals and also provide insight into possible mechanisms of toxicity. Models have been based on physicochemical attributes and structural features of chemicals. We describe herein the development of a new SAR modeling algorithm called cat-SAR that is capable of analyzing and predicting chemical activity from divergent biological response data. The cat-SAR program develops chemical fragment-based SAR models from categorical biological response data (e.g. toxicologically active and inactive compounds). The database selected for model development was a published set of chemicals documented to cause respiratory hypersensitivity in humans. Two models were generated that differed only in that one model included explicate hydrogen containing fragments. The predictive abilities of the models were tested using leave-one-out cross-validation tests. One model had a sensitivity of 0.94 and specificity of 0.87 yielding an overall correct prediction of 91%. The second model had a sensitivity of 0.89, specificity of 0.95 and overall correct prediction of 92%. The demonstrated predictive capabilities of the cat-SAR approach, together with its modeling flexibility and design transparency, suggest the potential for its widespread applicability to toxicity prediction and for deriving mechanistic insight into toxicologic effects.     

An Efficient Procedure for the Synthesis of p-Anisidine Phenylglyoxal Imine from Acetophenone

An efficient procedure for the oxidation of acetophenone to phenylglyoxal and its subsequent in situ conversion to the title compound is described herein.     

High-Field Asymmetric-Waveform Ion Mobility Spectrometry and Electron Detachment Dissociation of Isobaric Mixtures of Glycosaminoglycans

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of glycosaminoglycans (GAGs). However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4–10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other.

Reversible and Selective CO2 to HCO2− Electrocatalysis near the Thermodynamic Potential

Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO₂/HCO₂^? conversion catalyzed by [Pt(depe)₂]²⁺ (depe=1,2‐bis(diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO₂ reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO₂ reduction, H₂ evolution is negligible and the Faradaic efficiency for HCO₂^? production is nearly quantitative. A free‐energy analysis reveals H₂ evolution is endergonic, providing a thermodynamic basis for highly selective CO₂ reduction.     

Modification of Adhesive and Latex Properties for Starch Nanoparticle‐Based Pressure Sensitive Adhesives

Starch nanoparticle (SNP)‐based pressure sensitive adhesives (PSAs) with core‐shell particle morphology (starch nanoparticle core/acrylic polymer shell) are produced via seeded, semi‐batch emulsion polymerization at 15 wt% SNP loading (relative to total polymer weight) and 40 wt% latex solids. Crosslinker and chain transfer agent (CTA) are introduced to the acrylic shell polymer formulation at a range of concentrations according to a 3² factorial design to tailor the latex and adhesive properties of SNP‐based latexes. The crosslinker and CTA show no significant effect on polymerization kinetics, particle size, and viscosity. Latex gel content is predicted using an empirical model, which is a function of crosslinker and CTA concentration. Both the gel content and glass transition temperature strongly affect the adhesive properties (tack, peel strength, and shear strength) of the SNP‐based latex films. 3D response surfaces for the adhesive properties are constructed to facilitate the design of SNP‐based PSAs with desired properties.     

Recent Development in Ligation Methods for Glycopeptide and Glycoprotein Synthesis

Glycoproteins are produced by the post‐translational modification process of proteins and they play an important role in mediating various biological processes. Our understanding towards biochemical functions of individual glycoproteins has been seriously hampered due to the heterogeneous expression of carbohydrate parts in glycoproteins. Despite the advancement in recombinant expression and chromatographic techniques, the isolation of pure glycoforms remains nearly impossible. To obtain homogenous glycoproteins, tremendous efforts hves been spent in developing various ligation and glycosylation techniques. This minireview discusses selected methods for the preparation and ligation of glycopeptides. The importance of the development of new chemical synthesis method for glycoproteins has also been discussed, which would be one of the next directions in this field.     

Surface reconstruction and the Debye-Waller factor

A recently developed soft-mode theory of surface reconstruction¹ is used to calculate the surface Debye-Waller factor (SDWF) as a function of temperature near a supposed transition temperature (T₀) between two reconstruction patterns. The soft surface mode gives rise to a sharp decrease in the SDWF as T₀ is approached, suggesting that an examination the LEED Bragg intensities may help verify the soft mode theory.