Crystallographic and Inclusion Properties of some Diacetylated Calix[4]arenes

Three 5,17-diacetylcalix[4]arene derivatives 3–5 have been prepared, evaluated for inclusion properties, and their single crystal X-ray structures determined. The diacetyl calixarenes 3 and 4 were obtained by acetylation of their parent dimethoxy 1 or dipropoxy 2 compounds, respectively, whereas 5,17-diacetyl-25,26,27,28-tetrapropoxycalix[4]arene 5 was prepared by alkylation of 4. Crystallisation of 3 resulted in no inclusion from chloroform, but yielded lattice inclusion compounds from acetonitrile or acetone. The calixarene 3 maintains its cone conformation in these crystals, but displays degrees of distortion depending upon the included solvent. Crystal structures of solvent-free 4 and 5 are also described. A new preparation of the monomethoxy derivative 6 is described, and its X-ray structure with chloroform guest is analysed.     

Effect of lignocellulosic degradation compounds from steam explosion pretreatment on ethanol fermentation by thermotolerant yeast Kluyveromyces marxianus

The filtrate from steam-pretreated poplar was analyzed to identify degradation compounds. The effect of selected compounds on growth and ethanolic fermentation of the thermotolerant yeast strain Kluyveromyces marxianus CECT 10875 was tested. Several fermentations on glucose medium, containing individual inhibitory compounds found in the hydrolysate, were carried out. The degree of inhibition on yeast strain growth and ethanolic fermentation was determined. At concentrations found in the prehy-drolysate, none of the individual compounds significantly affected the fermentation. For all tested compounds, growth was inhibited to a lesser extent than ethanol production. Lower concentrations of catechol (0.96 g/L) and 4-hydroxybenzaldehyde (1.02 g/L) were required to produce the 50% reduction in cell mass in comparison to other tested compounds.     

Synthesis and structural characterization of a molecular plutonium(IV) compound constructed from dimeric building blocks

Single crystals of Na(8)Pu(2)(O(2))(2)(CO(3))(6) x 12H(2)O, exhibiting bridging mu(2),eta(2)-O(2) ligands in unprecedented Pu(IV) dimeric units, were obtained at ambient temperature from an aqueous Pu(IV) peroxide carbonate solution.     

Size separation of sodium dodecyl sulfate–proteins by capillary electrophoresis in dilute and ultra-dilute dextran solutions

SDS capillary gel electrophoresis is a widely used in the biopharma and the biomedical fields for rapid size separation of proteins. However, very limited information is available on the use of dilute and ultra-dilute sieving matrices for SDS–protein analysis. Here, background electrolytes (BGEs) containing 1%–0% dextran were used in borate-based BGE to separate a protein sizing ladder (PSL) ≤225 kDa and the intact and subunit forms of a therapeutic monoclonal antibody (mAb). The separation performance for the PSL and mAb components differed significantly with decreasing dextran concentration. Ferguson and reptation plots were used to elucidate the separation mechanism. Highly diluted dextran solutions resulted in linear Ferguson plots for both solute types (cf. Ogston theory) in spite of this model assumes a rigid pore structure, thus cannot describe the separation mechanism in ultra-dilute polymer solutions with no reticulations. The saddle differences between the resolution of the PSL and the intact/subunit mAb forms in ultra-dilute dextran-borate matrices suggested the importance of shape selectivity, manifested by the adequate separation of the SDS covered intact as well as light and heavy chain subunits of the therapeutic mAb even at zero dextran concentration.     

Imaging G-SIMS: a novel bismuth-manganese source emitter

G-SIMS (gentle-SIMS) is a powerful method that considerably simplifies complex static secondary ion mass spectrometry (SSIMS) analysis of organics at surfaces. G-SIMS uses two primary ion beams that generate high and low fragmentation conditions at the surface. This allows an extrapolation to equivalent experimental conditions with very low fragmentation. Consequently, the spectra are less complex, contain more structural information and are simpler to interpret. In general, G-SIMS spectra more closely resemble electron ionisation mass spectra than SSIMS spectra. A barrier for the wider uptake of G-SIMS is the requirement for two ion beams producing suitably different fragmentation conditions and the need for their spatial registration (spatial alignment) at the surface, which is especially important for heterogeneous samples. The most popular source is the liquid metal ion source (LMIS), which is now sold with almost every new time-of-flight (TOF)-SIMS instrument. Here, we have developed a novel bismuth-manganese emitter (the 'G-tip') for the popular LMISs. This simplifies the alignment and gives excellent G-SIMS imaging and spectroscopy without significantly compromising the bismuth cluster ion beam performance.     

Dendrimers as Non-Viral Vectors in Gene-Directed Enzyme Prodrug Therapy

Gene-directed enzyme prodrug therapy (GDEPT) has been intensively studied as a promising new strategy of prodrug delivery, with its main advantages being represented by an enhanced efficacy and a reduced off-target toxicity of the active drug. In recent years, numerous therapeutic systems based on GDEPT strategy have entered clinical trials. In order to deliver the desired gene at a specific site of action, this therapeutic approach uses vectors divided in two major categories, viral vectors and non-viral vectors, with the latter being represented by chemical delivery agents. There is considerable interest in the development of non-viral vectors due to their decreased immunogenicity, higher specificity, ease of synthesis and greater flexibility for subsequent modulations. Dendrimers used as delivery vehicles offer many advantages, such as: nanoscale size, precise molecular weight, increased solubility, high load capacity, high bioavailability and low immunogenicity. The aim of the present work was to provide a comprehensive overview of the recent advances regarding the use of dendrimers as non-viral carriers in the GDEPT therapy.     

Topical Dosage Formulation of Lyophilized Philadelphus coronarius L. Leaf and Flower: Antimicrobial,Antioxidant and Anti-Inflammatory Assessment of the Plant

Philadelphus coronarius is a versatile plant and its use in folk medicine has a long tradition; however, scientifically, the medical utilization of the herb is a less explored research field. The aim of our study was to identify and determine the quantity of the bioactive compounds of both the leaf and the flower and prepare a lyophilized product of them, from which medical ointments were formulated, since the topical application of P. coronarius has also not been studied. In vitro drug release, texture analysis and biocompatibility experiments were carried out, as well as the investigation of microbiological, antioxidant and anti-inflammatory properties. According to our results the composition and the selected excipients of the ointments have a great impact on the drug release, texture and bioavailability of the preparation. During the microbiological testing, the P. coronarius leaf was effective against Escherichia coli and Staphylococcus aureus, but it did not significantly decrease IL-4 production when it was tested on HaCaT cells. P. coronarius is a promising herb, and its topical application in antimicrobial therapy can be a useful addition to modern medical therapy.     

Ethanol production from lignocellulosic byproducts of olive oil extraction

The recent implementation of a new two-step centrifugation process for extracting olive oil in Spain has substantially reduced water consumption, thereby eliminating oil mill wastewater. However, a new high sugar content residue is still generated. In this work the two fractions present in the residue (olive pulp and fragm ented stones) were assayed as substrate for ethanol production by the simultaneous saccharification and fermentation (SSF) process. Pretreatment of fragmented olive stones by sulfuric acid-catalyzed steam explosion was the most effective treatment for increasing enzymatic digestibility; however, a pretreatment step was not necessary to bioconvert the olive pulp into ethanol. Theolive pulp and fragmented olive stones were tested by the SSF process using a fed-batch procedure. By adding the pulp three times at 24-h intervals, 76% of the theoretical SSF yield was obtained. Experiments with fed-batch pretreated olive stones provided SSF yields significantly lower than those obtained at standard SSF procedure. The preferred SSF conditions to obtain ethanol from olives stones (61% of theoretical yield) were 10% substrate and addition of cellulases at 15 filter paper units/g of substrate.     

Some algebraic aspects of mesoprimary decomposition

Recent results of Kahle and Miller give a method of constructing primary decompositions of binomial ideals by first constructing “mesoprimary decompositions” determined by their underlying monoid congruences. Monoid congruences (and therefore, binomial ideals) can present many subtle behaviors that must be carefully accounted for in order to produce general results, and this makes the theory complicated. In this paper, we examine their results in the presence of a positive A-grading, where certain pathologies are avoided and the theory becomes more accessible. Our approach is algebraic: while key notions for mesoprimary decomposition are developed first from a combinatorial point of view, here we state definitions and results in algebraic terms, which are moreover significantly simplified due to our (slightly) restricted setting. In the case of toral components (which are well-behaved with respect to the A-grading), we are able to obtain further simplifications under additional assumptions. We also provide counterexamples to two open questions, identifying (i) a binomial ideal whose hull is not binomial, answering a question of Eisenbud and Sturmfels, and (ii) a binomial ideal I for which $I_{\mathrm{toral}}$ is not binomial, answering a question of Dickenstein, Miller and the first author.