The relative contribution of adsorption to the overall sorption and transport of small molecules in amber

In 1987, Berner and Landis reported that upon vacuum grinding of 80 million year old amber, a gas mixture was released which suggested an oxygen-rich prehistoric environment. Fundamental to their argument was the assumption that amber, an organic glass formed during the fossilization of tree sap, is a perfect sealant. Their assumption was challenged by three technical comments which collectively concluded that gases diffuse readily through amber. In order to defend their key assumption that gases are perfectly trapped in amber, Berner and Landis dismissed the data obtained through gravimetric sorption experiments as only a measure of surface adsorption rather than bulk absorption in and concomitant diffusion through the amber matrix. The validity of interpreting these gravimetric experiments as a measure of bulk diffusion is demonstrated by exploring the physical basis for interpreting gravimetric sorption data. Most importantly, new experimental gravimetric sorption data are presented which demonstrate an explicit separation of adsorption from diffusion-controlled absorption and also reveal that adsorption accounts for a very small fraction of the total sorption in amber.     

Validation and use of a fast sample preparation method and liquid chromatography–tandem mass spectrometry in analysis of ultra-trace levels of 98 organophosphorus pesticide and carbamate residues in a total diet study involving diversified food types

This paper reports a comprehensive sensitive multi-residue liquid chromatography–tandem mass spectrometry (LC–MS/MS) method for detection, identification and quantitation of 73 pesticides and their related products, a total of 98 analytes, belonging to organophosphorus pesticides (OPPs) and carbamates, in foods. The proposed method makes use of a modified QuEChERS (quick, easy, cheap, effective, rigged, and safe) procedure that combines isolation of the pesticides and sample clean-up in a single step. Analysis is performed by liquid chromatography-electrospray ionization–tandem mass spectrometry operated in the multiple reaction monitoring (MRM) mode, acquiring two specific precursor-product ion transitions per target compound. Two main fragment ions for each pesticide were obtained to achieve the identification according to the SANCO guidelines 10684/2009. The method was validated with various food samples, including edible oil, meat, egg, cheese, chocolate, coffee, rice, tree nuts, citric fruits, vegetables, etc. No significant matrix effect was observed for tested pesticides, therefore, matrix-matched calibration was not necessary. Calibration curves were linear and covered from 1 to 20 μg L⁻¹ for all compounds studied. The average recoveries, measured at 10 μg kg⁻¹, were in the range 70–120% for all of the compounds tested with relative standard deviations below 20%, while a value of 10 μg kg⁻¹ has been established as the method limit of quantitation (MLOQ) for all target analytes. Similar trueness and precision results were also obtained for spiking at 200 μg kg⁻¹. Expanded uncertainty values were in the range 21–27% while the HorRat ratios were below 1. The method has been successfully applied to the analysis of 700 food samples in the course of a baseline monitoring study of OPPs and carbamates.     

New Design for Quantum Dots Cellular Automata to obtain Fault Tolerant Logic Gates

In this paper, we analyze fault tolerance properties of the Majority Gate, as the main logic gate for implementation with Quantum dots Cellular Automata (QCA), in terms of fabrication defect. Our results demonstrate the poor fault tolerance properties of the conventional design of Majority Gate and thus the difficulty in its practical application. We propose a new approach to the design of QCA-based Majority Gate by considering two-dimensional arrays of QCA cells rather than a single cell for the design of such a gate. We analyze fault tolerance properties of such Block Majority Gates in terms of inputs misalignment and irregularity and defect (missing cells) in assembly of the array. We present simulation results based on semiconductor implementation of QCA with an intermediate dimensional dot of about 5 nm in size as opposed to magnetic dots of greater than 100 nm or molecular dots of 2–5Å. Our results clearly demonstrate the superior fault tolerance properties of the Block Majority Gate and its greater potential for a practical realization. We also show the possibility of designing fault tolerant QCA circuits by using Block Majority Gates.     

Water purification by membranes: The role of polymer science

Two of the greatest challenges facing the 21st century involve providing sustainable supplies of clean water and energy, two highly interrelated resources, at affordable costs. Membrane technology is expected to continue to dominate the water purification technologies owing to its energy efficiency. However, there is a need for improved membranes that have higher flux, are more selective, are less prone to various types of fouling, and are more resistant to the chemical environment, especially chlorine, of these processes. This article summarizes the nature of the global water problem and reviews the state of the art of membrane technology. Existing deficiencies of current membranes and the opportunities to resolve them with innovative polymer chemistry and physics are identified. Extensive background is provided to help the reader understand the fundamental issues involved. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Discrepancy of random graphs and hypergraphs

Answering in a strong form a question posed by Bollobás and Scott, in this paper we determine the discrepancy between two random k‐uniform hypergraphs, up to a constant factor depending solely on k. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 47, 147–162, 2015     

Density theorems for bipartite graphs and related Ramsey-type results

In this paper, we present several density-type theorems which show how to find a copy of a sparse bipartite graph in a graph of positive density. Our results imply several new bounds for classical problems in graph Ramsey theory and improve and generalize earlier results of various researchers. The proofs combine probabilistic arguments with some combinatorial ideas. In addition, these techniques can be used to study properties of graphs with a forbidden induced subgraph, edge intersection patterns in topological graphs, and to obtain several other Ramsey-type statements. Research supported by an NSF Graduate Research Fellowship and a Princeton Centennial Fellowship. Research supported in part by NSF CAREER award DMS-0812005 and by USA-Israeli BSF grant.     

Photochemistry of 1,2-dihydronaphthalene oxide: concurrent triplet and singlet processes via singlet excitation

The photochemistry of 1,2-dihydronaphthalene oxide (254 nm) was reexamined and indan was found to be a primary photoproduct, as well as the traditionally assumed secondary photoproduct. Quenching studies demonstrated that indan, as a primary photoproduct, is derived from a triplet pathway, competing with a singlet route, back to the ground state surface. CASSCF calculations strongly suggest that the triplet pathway consists of a dissociation of the oxirane moiety to give a triplet carbene and aldehyde, which via hydrogen abstraction-decarbonylation-ISC recloses to give indan. Conical intersections corresponding to the presumed 1,2-hydrogen shift and 1,2-alkyl shift to give 2-tetralone and 1-indancarbaldehyde, respectively, were located computationally.