Hydroxylamine as an oxygen nucleophile. Structure and reactivity of ammonia oxide

Ammonia oxide is revealed as a stable molecule in a crystal structure and as a likely reactive species in many reactions of hydroxylamine.     

Dissociative ion-pair formation in collisions of fast potassium atoms with benzene and fluorobenzene

Using a crossed molecular-beam technique, electron transfer is studied in collisions of fast potassium atoms with benzene and fluorobenzene molecules. The negative fragment ions formed in the collision region are extracted by a pulsed voltage, and their masses and energy release distributions analyzed by a time-of-flight (TOF) method. The dominant fragment from C6H5F is F-. The phenyl ring fragments CH- and C2H- are also observed but with lower intensities. In the case of C6H6 the dominant anionic specie is C2H-. The kinetic-energy release distributions of the various fragments are derived from the width and shapes of the TOF peaks in the spectrum.     

Pump-probe spectroscopy of molecules driven by infrared field in both ground and excited electronic states

Pump-probe spectra of molecules driven by strong infrared (IR) field in both ground and excited states are studied theoretically. The role of the final state interaction becomes important when pump and probe pulses overlap, and the Rabi frequency is comparable with the lifetime broadening of the excited state and the duration of the pump pulse. Our theoretical approach is applied to x-ray absorption of nitrogen molecule and valence photoionization of carbon monoxide. It is shown that IR-x-ray pump-probe spectroscopy can directly evidence the delocalization of core hole.     

Self-referencing spectral phase interferometry for direct electric-field reconstruction with chirped pulses

We analyze the characterization of strongly chirped pulses by spectral phase interferometry for direct electric-field reconstruction (SPIDER). We show how to extend the working range of this technique for these relevant cases and derive correction factors for typical operating parameters. The results are straightforward to implement in the calculation algorithms. We demonstrate the validity of this technique by characterizing numerically and experimentally pulses with a known spectral phase profile.     

Chemical composition of mate tea leaves (Ilex paraguariensis): a study of extraction methods

The objective of this work was to investigate the extraction of Ilex paraguariensis leaves by means of three extraction techniques: pressurized liquid extraction (PLE, also called accelerated solvent extraction – ASE), maceration, and sonication. Samples of mate tea leaves were collected from an experiment conducted under agronomic control at Indústria e Comércio de Erva‐Mate Bar?o LTDA, Brazil. Six solvents with increasing polarities (n‐hexane, toluene, dichloromethane, ethyl acetate, acetone, and methanol) were used in this investigation. Chemical analysis of the extracts was performed by GC coupled with a mass spectrometer detector. The identification and quantification were accomplished by coinjections of certified standards. The results showed that no significant differences in the qualities of the extracts were noticed regarding the extraction methods. On the other hand, the PLE technique was found to be more effective for the extractions of caffeine, phytol, palmitic, and stearic acid. The use of PLE led to a significant decrease in the total extraction time, amount of solvent consumption, and manipulation of samples compared to maceration and ultrasound‐assisted extraction methods.     

New analytical procedure based on a cellulose bag and ionic exchanger with p-aminobenzoic acid groups for differentiation of labile and inert metal species in aquatic systems

A new procedure was developed for the in situ characterization of the lability of metal species in aquatic systems by using a system equipped with a diffusion membrane and cellulose organomodified with p-aminobenzoic acid groups (DM-Cell-PAB). To this end, the DM-Cell-PAB system was prepared by adding cellulose organomodified with p-aminobenzoic acid groups (Cell-PAB) to pre-purified cellulose bags. After the DM-Cell-PAB system was sealed, it was examined in the laboratory to evaluate the influence of complexation time, mass of exchanger, pH, metal ions (Cu, Cd, Fe, Mn, and Ni), and concentration of organic matter on the relative lability of metal species. It was found that the pH and kinetics strongly influence the process of metal complexation by the DM-Cell-PAB system. At all pH levels, Cd, Mn, and Ni showed lower complexation with Cell-PAB resin than Cu and Fe metals. Note that relative lability of metals complexed to aquatic humic substances (AHS) in the presence of Cell-PAB resin showed the following order: Cu≅Fe≫Ni>Mn=Cd. The results presented here also indicate that increasing the AHS concentration decreases the lability of metal species by shifting the equilibrium to AHS–metal complexes. Our results indicate that the system under study offers an interesting alternative that can be applied to in situ experiments for differentiation of labile and inert metal species in aquatic systems.     

Recent advances in polyhydroxyalkanoate production by mixed aerobic cultures: from the substrate to the final product

Numerous bacteria have been found to exhibit the capacity for intracellular polyhydroxyalkanoates (PHA) accumulation. Current methods for PHA production at the industrial scale are based on their synthesis from microbial isolates in either their wild form or by recombinant strains. High production costs are associated with these methods; thus, attempts have been made to develop more cost-effective processes. Reducing the cost of the carbon substrates (e.g., through feeding renewable wastes) and increasing the efficiency of production technologies (including both fermentation and downstream extraction and recovery) are two such examples of these attempts. PHA production processes based on mixed microbial cultures are being investigated as a possible technology to decrease production costs, since no sterilization is required and bacteria can adapt quite well to the complex substrates that may be present in waste material. PHA accumulation by mixed cultures has been found under various operational conditions and configurations at both bench-scale and full-scale production. The process known as "feast and famine" or as "aerobic dynamic feeding" seems to have a high potential for PHA production by mixed cultures. Enriched cultures submitted to a transient carbon supply can synthesize PHA at levels comparable to those of pure cultures. Indeed, the intracellular PHA content can reach around 70% of the cell dry weight, suggesting that this process could be competitive with pure culture PHA production when fully developed. Basic and applied research of the PHA production process by mixed cultures has been carried out in the past decade, focusing on areas such as microbial characterization, process configuration, reactor operational strategies, process modeling and control, and polymer characterization. This paper presents a review of the PHA production process with mixed cultures, encompassing the findings reported in the literature as well as our own experimental results in relation to each of these areas.     

The central polynomials for the Grassmann algebra

In this paper we describe the central polynomials for the infinite-dimensional unitary Grassmann algebra G over an infinite field F of characteristic ≠ 2. We exhibit a set of polynomials that generates the vector space C(G) of the central polynomials of G as a T-space. Using a deep result of Shchigolev we prove that if charF = p > 2 then the T-space C(G) is not finitely generated. Moreover, over such a field F, C(G) is a limit T-space, that is, C(G) is not a finitely generated T-space but every larger T-space W ≩ C(G) is. We obtain similar results for the infinite-dimensional nonunitary Grassmann algebra H as well.     

On classes of structures axiomatizable by universal d-Horn sentences and universal positive disjunctions

We provide universal algebraic characterizations (in the sense of not involving any “logical notion”) of some elementary classes of structures whose definitions involve universal d-Horn sentences and universally closed disjunctions of atomic formulas. These include, in particular, the classes of fields, of non-trivial rings, and of directed graphs without loops where every two elements are adjacent. The classical example of this kind of characterization result is the HSP theorem, but there are myriad other examples (e.g., the characterization of elementary classes using isomorphic images, ultraproducts and ultrapowers due to Keisler and Shelah).     

Vector spaces of non-extendable holomorphic functions

In this paper, we analyze the linear structure of the family H _e (G) of holomorphic functions on a domain G of the complex plane that are not analytically continuable beyond the boundary of G. We prove that H _e (G) contains, except for zero, a dense algebra; and, under appropriate conditions, the subfamily of H _e (G) consisting of boundary-regular functions contains dense vector spaces with maximal dimension as well as infinite dimensional closed vector spaces and large algebras. We also consider the case in which G is a domain of existence in a complex Banach space. The results obtained complete or extend a number of previous results by several authors.