Dissipative operators and additive perturbations in locally convex spaces

Let be a densely defined operator on a Banach space X. Characterizations of when generates a C₀‐semigroup on X are known. The famous result of Lumer and Phillips states that it is so if and only if is dissipative and is dense in X for some . There exists also a rich amount of Banach space results concerning perturbations of dissipative operators. In a recent paper Tyran–Kamińska provides perturbation criteria of dissipative operators in terms of ergodic properties. These results, and others, are shown to remain valid in the setting of general non–normable locally convex spaces. Applications of the results to concrete examples of operators on function spaces are also presented.     

Assessing views of coaching via a video-based tool

Mathematics coaches represent a unique group of didacticians, or individuals who work with practicing teachers. Twenty-eight mathematics coaches participated in this exploratory study, which used video viewing to examine the coach–teacher dynamic. To gather data about participants’ views of effective coaching practices, we developed the Video Assessment of Coaching instrument, which provided coaches with opportunities to express their views of effective practice and implementation. The participants expressed views of effective coaching that often did not align with those of coaching authors. The significance of this research lies in its efforts to document the views that mathematics coaches develop as practitioners, as an early step in the examination of the relationships between the views of coaches and coaches’ effectiveness in improving teacher practice, knowledge, and attitudes.     

Photoactivated Psoralens Elicit Defense Genes and Phytoalexin Production in the Pea Plant

In the pea plant ( Pisum sativum ), compounds that intercalate into DNA induce the production of ∼20 major proteins similar to the pattern induced during nonhost disease resistance to the bean fungal pathogen, Fusarium solani f.sp. phaseoli . The pea phytoalexin, pisatin, as well as RNA homologous to several disease-resistance response (DRR) genes accumulate following treatment with these compounds. Psoralen was chosen to characterize this interaction further because it intercalates into DNA and, following irradiation with 365 nm UV light (UV₃₆₅), forms covalent bonds with pyrimidines on either or both strands of DNA. This produces monoadducts or cross-links, respectively. Dose experiments showed that 60 μg/mL 4'-aminomethyl-4,5',8-trimethylpsoralen followed by 18 J/cm² UV₃₆₅ was sufficient to produce an accumulation of pisatin similar to that produced in response to the fungus. Under these inducing conditions, there was an average of 0.19 adducts per kb of pea genomic DNA. The accumulation of pisatin and the RNA of several DRR genes by psoralen required photoactivation, which suggests that covalent binding to DNA was necessary for induction. As the promoters of several putative fungal-induced pea genes contain long stretches of d(AT)_n, which is the preferred psoralen photobinding site, restriction fragments spanning DRR genes were examined after in vivo psoralen treatment. The rate of crosslinking was compared between fungal-induced and noninduced genes using a modified Southern blot analysis. Implications of the induction of the DRR due to psoralen binding are discussed.     

1-[Hydroxy(sulfonyloxy)iodo]-1H,1H-perfluoroalkanes: Stable, Fluoroalkyl Analogs of Koser's Reagent

1-[Hydroxy(sulfonyloxy)iodo]-1H,1H-perfluoroalkanes 3 [R(f)CH(2)I(OH)OSO(2)R; R = CH(3), CF(3), p-CH(3)C(6)H(4), R(f) = CF(3), C(2)F(5)] can be prepared in two steps from the appropriate iodofluoroalkanes by oxidation with peroxytrifluoroacetic acid and subsequent reaction with TsOH, MsOH, or Me(3)SiOTf. The tosylate derivative 3a reacts with silyl enol ethers under mild conditions to give the respective alpha-(tosyloxy) ketones. A similar reaction of cyclohexene furnishes cis-1,2-bis(tosyloxy)cyclohexane as the major product. Triflates 3c,f react with (trimethylsilyl)arenes under mild conditions to afford the respective (fluoroalkyl) (aryl)iodonium triflates 7, while the analogous reaction with alkynyltrimethylsilanes leads to novel (fluoroalkyl)(alkynyl)iodonium salts 8.     

Thermal behavior of Cu(II)-, Cd(II)-, and Hg(II)-exchanged montmorillonite complexedwith cysteine

The thermal behavior of montmorillonite and organically modified montmorillonite, both treated with heavy metal cations [Cu(II), Cd(II) and Hg(II)], was characterized via thermal analyses (TG, DTG and DTA) combined with evolved species gas mass spectrometry (MS-EGA), and X-ray diffraction at in situ controlled temperature (HTXRD). The reactions involving Cu(II)- and Cd(II)-montmorillonite samples are mostly related to H₂O and OH loss, unlike Hg(II)-montmorillonite, where effects associated to Hg(II) loss are also present. Finally reactions related to dehydration, dehydroxylation and to organic matter decomposition can be observed in montmorillonite samples treated with cysteine.     

Isolation, structure, and antibacterial activity of philipimycin, a thiazolyl peptide discovered from Actinoplanes philippinensis MA7347

Bacterial resistance to antibiotics, particularly to multiple drug resistant antibiotics, is becoming cause for significant concern. The only really viable course of action is to discover new antibiotics with novel mode of actions. Thiazolyl peptides are a class of natural products that are architecturally complex potent antibiotics but generally suffer from poor solubility and pharmaceutical properties. To discover new thiazolyl peptides potentially with better desired properties, we designed a highly specific assay with a pair of thiazomycin sensitive and resistant strains of Staphylococcus aureus, which led to the discovery of philipimycin, a new thiazolyl peptide glycoside. It was isolated along with an acid-catalyzed degradation product by bioassay-guided fractionation. Structure of both compounds was elucidated by extensive application of 2D NMR, 1D TOCSY, and HRESIFT-MS/MS. Both compounds showed strong antibacterial activities against gram-positive bacteria including MRSA and exhibited MIC values ranging from 0.015 to 1 microg/mL. Philipimycin was significantly more potent than the degradation product. Both compounds showed selective inhibition of protein synthesis, indicating that they targeted the ribosome. Philipimycin was effective in vivo in a mouse model of S. aureus infection exhibiting an ED50 value of 8.4 mg/kg. The docking studies of philipimycin suggested that a part of the molecule interacts with the ribosome and another part with Pro23, Pro22, and Pro26 of L11 protein, which helped in explaining the differential of activities between the sensitive and resistant strains. The design and execution of the bioassay, the isolation, structure, in vitro and in vivo antibacterial activity, and docking studies of philipimycin and its degradation product are described.     

Thermally induced mixing of water dominated interstellar ices

Despite considerable attention in the literature being given to the desorption behaviour of smaller volatiles, the thermal properties of complex organics, such as ethanol (C(2)H(5)OH), which are predicted to be formed within interstellar ices, have yet to be characterized. With this in mind, reflection absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD) have been used to probe the adsorption and desorption of C(2)H(5)OH deposited on top of water (H(2)O) films of various thicknesses grown on highly oriented pyrolytic graphite (HOPG) at 98 K. Unlike many other molecules detected within interstellar ices, C(2)H(5)OH has a comparable sublimation temperature to H(2)O and therefore gives rise to a complicated desorption profile. RAIRS and TPD show that C(2)H(5)OH is incorporated into the underlying ASW film during heating, due to a morphology change in both the C(2)H(5)OH and H(2)O ices. Desorption peaks assigned to C(2)H(5)OH co-desorption with amorphous, crystalline (CI) and hexagonal H(2)O-ice phases, in addition to C(2)H(5)OH multilayer desorption are observed in the TPD. When C(2)H(5)OH is deposited beneath ASW films, or is co-deposited as a mixture with H(2)O, complete co-desorption is observed, providing further evidence of thermally induced mixing between the ices. C(2)H(5)OH is also shown to modify the desorption of H(2)O at the ASW-CI phase transition. This behaviour has not been previously reported for more commonly studied volatiles found within astrophysical ices. These results are consistent with astronomical observations, which suggest that gas-phase C(2)H(5)OH is localized in hotter regions of the ISM, such as hot cores.     

Synthesis and structure of iron(iii) diamine-bis(phenolate) complexes

The structures and properties of six new iron(iii) diamine-bis(phenolate) complexes are reported. Reaction of anhydrous FeX(3) salts (where X = Cl or Br) with the diprotonated tripodal tetradentate ligands 2-pyridylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol), H(2)[L(1)], and N,N-dimethyl-N',N'-bis(2-methylene-4-methyl-6-tert-butylphenol)ethylenediamine, H(2)[L(2)], produces the trigonal bipyramidal iron(iii) complexes, [L(1)]FeCl , [L(1)]FeBr , [L(2)]FeCl and [L(2)]FeBr . Reaction of FeX(3) with the related linear tetradentate ligand N,N'-bis(4,6-tert-butyl-2-methylphenol)-N,N'-bismethyl-1,2-diaminoethane, H(2)[L(3)], generates square pyramidal iron(iii) complexes, [L(3)]FeCl and [L(3)]FeBr . Complexes have been characterized using electronic absorption spectroscopy and magnetometry. Single crystal X-ray molecular structures have been determined for complexes 1, 3, 5 and 6.     

Efficient removal of DNA from proteomic samples prior to two-dimensional map analysis

Several methods have been described in the literature for removal of DNA from protein samples prior to proteome analysis. They in general involve protein precipitation techniques. In other protocols, DNAse treatment is suggested prior to precipitation of proteins in excess acetone. All these methods have been evaluated and found to perform poorly in DNA removal, as illustrated by two-dimensional (2D) maps where horizontal and vertical sample streaking are still substantial. Such removal is in general necessary in tissue lysates and especially when analysing sub-cellular organelles, such as nuclei, where the high DNA levels strongly interfere with proteome analysis. Another method is proposed here for efficient DNA removal: two-phase extraction of DNA in chloroform/phenol/isoamyl alcohol, a procedure commonly used to rid DNA samples of protein contaminants, but rarely applied to protein preparation. This extraction is not very efficient if performed at slightly acidic to neutral pH values, but it performs extremely well at pH values of 9.5 or higher. The 2D maps thus obtained of Escherichia coli lysates as well as extracts from purified nuclei of eukaryotic cells are not only devoid of any vertical or horizontal streaking, but exhibit many more spots, especially in the alkaline region of the 2D gels, suggesting that these basic proteins were in general lost to proteome analysis due to co-precipitation in tenacious protein–DNA complexes. It is hypothesized that the alkaline pH values adopted in the two-phase extraction help to fully disrupt any residual DNA–protein complexes, due to strong Coulombic repulsion.