Fluorescent charge-assisted halogen-bonding macrocyclic halo-imidazolium receptors for anion recognition and sensing in aqueous media

The synthesis and anion binding properties of a new family of fluorescent halogen bonding (XB) macrocyclic halo-imidazolium receptors are described. The receptors contain chloro-, bromo-, and iodo-imidazolium motifs incorporated into a cyclic structure using naphthalene spacer groups. The large size of the iodine atom substituents resulted in the isolation of anti and syn conformers of the iodo-imidazoliophane, whereas the chloro- and bromo-imidazoliophane analogues exhibit solution dynamic conformational behavior. The syn iodo-imidazoliophane isomer forms novel dimeric isostructural XB complexes of 2:2 stoichiometry with bromide and iodide anions in the solid state. Solution phase DOSY NMR experiments indicate iodide recognition takes place via cooperative convergent XB-iodide 1:1 stoichiometric binding in aqueous solvent mixtures. (1)H NMR and fluorescence spectroscopic titration experiments with a variety of anions in the competitive CD(3)OD/D(2)O (9:1) aqueous solvent mixture demonstrated the bromo- and syn iodo-imidazoliophane XB receptors to bind selectively iodide and bromide respectively, and sense these halide anions exclusively via a fluorescence response. The protic-, chloro-, and anti iodo-imidazoliophane receptors proved to be ineffectual anion complexants in this aqueous methanolic solvent mixture. Computational DFT and molecular dynamics simulations corroborate the experimental observations that bromo- and syn iodo-imidazoliophane XB receptors form stable cooperative convergent XB associations with bromide and iodide.     

Q 1 production by hypercharge exchange in π- p interactions at 3.95 GeV/c

Q-meson production is studied in the hypercharge exchange reaction π^- p → (Kππ)Λ at 3.95 GeV/c by selecting events witht(π^- →Kππ)>1.2GeV². An enhancement with a mass of 1294±10 MeV and a width of 66±15 MeV is observed in the (Kππ) mass distribution. A spin-parity analysis of the (Kππ) decay Dalitz plot shows the enhancement to be in theJ ^P=1⁺ S(K?) wave and is therefore attributed toQ ₁-meson production. No evidence is found for the decayQ ₁→K ⁰ω but limited statistics allow only placing an upper limit of 30% for the decay ratioKω/K?⁰. TheQ ₁ production cross section fort(π^- →Kππ)>1.2GeV² is 8±1.3 μb. No evidence is found for the process π^- p→Q ₂Λ withQ ₂→K ^*π for which the partial wave analysis gives an upper cross section limit of 2.5 μb at the 95% confidence level.     

Backward production of a spin-parity 1+ Kϱ resonance at 1.28 GeV

A (K_ππ)⁺ mass enhancement is observed in the reactions K^?p → Ξ ?K^o+π⁺π^o? when events with a small (K^? → Ξ^?) four momentum transfer squared are selected. The signal is also visible in the reaction K^?p → Ξ^?π⁺+ neutrals. The enhancement, centered at 1.28 GeV, is seen to decay preferentially into K? with spin-parity J^P = 1⁺. The cross section for K^?p→ Ξ^?C⁺(1.28) with C⁺ → K? at 4.15 GeV/c incident K^? momentum is (6.2 ± 0.6) μb.     

Total cross sections of charged-current neutrino and antineutrino interactions on isoscalar nuclei

New measurements of the total crosssections of charged-current interactions of muonneutrinos and antineutrinos on isoscalar nuclei have been performed. Data were recorded in an exposure of the CHARM detector in an 160 GeV narrow-band beam. The antineutrino flux was determined from the measurements of the pion and kaon flux, and independently from the muon flux measured in the shield; the two methods are found to agree. The neutrino flux was determined from the muon flux ratio forv _μ and \(\bar v_\mu \) runs which was normalized to the antineutrino flux. The cross-section slopes thus determined are $$\begin{gathered} \sigma _T^{\bar v} /E = (0.335 \pm 0.004(stat) \hfill \\ \pm 0.010(syst)).10^{ - 38} cm^2 /(GeV \cdot nucleon) \hfill \\ \sigma _T^v /E = (0.686 \pm 0.002(stat) \hfill \\ \pm 0.020(syst)).10^{ - 38} cm^2 /(GeV \cdot nucleon) \hfill \\ \end{gathered} $$ The momentum sum of the quarks in the nucleon and the ratio of sea quark to total quark momentum are derived from the measurements.     

UV-photocrosslinking of inulin derivatives to produce hydrogels for drug delivery application

In this work, INU, a natural polysaccharide, has been chemically modified in order to obtain new photocrosslinkable derivatives. To reach this goal, INU has been derivatized with MA thus obtaining four samples (INU-MA derivatives) as a function of the temperature and time of reaction. An aqueous solution of the derivative INU-MA1 was irradiated by using a UV lamp with an emission range from 250 to 364 nm and without using photoinitiators. The obtained hydrogel showed a remarkable water affinity but it underwent a partial degradation in simulated gastric fluid. To overcome this drawback, INU-MA1 was derivatized with SA thus obtaining the INU-MA1-SA derivative designed to produce a hydrogel showing a low swelling and an increased chemical stability in acidic medium. Ibuprofen, as a model drug, was loaded by soaking into INU-MA1 and INU-MA1-SA hydrogels and its release from these matrices was evaluated in simulated gastrointestinal fluids. INU-MA1 hydrogel showed the ability to quickly release the entrapped drug thus indicating its potential as a matrix for an oral formulation. INU-MA1-SA hydrogel showed a pH-responsive drug delivery. Therefore it is a promising candidate for controlled drug release in the intestinal tract.     

Tautomerization of methyldiazene to formaldehyde-hydrazone in ruthenium and osmium complexes

Mixed-ligand hydrazine complexes [M(CO)(RNHNH2)P4](BPh4)2 (1, 2) [M = Ru, Os; R = H, CH3, C6H5; P = P(OEt)3] with carbonyl and triethyl phosphite were prepared by allowing hydride [MH(CO)P4]BPh4 species to react first with HBF4.Et2O and then with hydrazines. Depending on the nature of the hydrazine ligand, the oxidation of [M(CO)(RNHNH2)P4](BPh4)2 derivatives with Pb(OAc)4 at -30 C gives acetate [M(kappa1-OCOCH3)(CO)P4]BPh4 (3a), phenyldiazene [M(CO)(C6H5N=NH)P4](BPh4)2 (3c, 4c), and methyldiazene [M(CO)(CH3N=NH)P4](BPh4)2 (3b, 4b) derivatives. Methyldiazene complexes 3b and 4b undergo base-catalyzed tautomerization of the CH3N=NH ligand to formaldehyde-hydrazone NH2N=CH2, giving the [M(CO)(NH2N=CH2)P4](BPh4)2 (5, 6) derivatives. Complexes 5 and 6 were characterized spectroscopically and by the X-ray crystal structure determination of the [Ru(CO)(NH2N=CH2)[P(OEt)3]4](BPh4)2 (5) derivative. Acetone-hydrazone [M(CO)[NH2N=C(CH3)2]P4](BPh4)2 (7, 8) complexes were also prepared by allowing hydrazine [M(CO)(NH2NH2)P4](BPh4)2 derivatives to react with acetone.     

Efficient cellulose solubilization by a combined cellulosome-β-glucosidase system

The cellulosome, the multienzyme complex of the cellulase system ofClostridium thermocellum, that mediates the solubilization of insoluble cellulose, is strongly inhibited by the major end product, cellobiose. By combining a purified β-glucosidase fromAspergillus niger with the cellulosome, accumulated cellobiose was hydrolyzed thereby resulting in a dramatic enhancement (up to 10-fold) of cellulose degradation. The observed enhancement was expressed both in the rate and degree of solubilization of microcrystalline cellulose, compared with that observed for the unsupplemented cellulosome. Near-complete conversion of cellulose to glucose could be obtained from dense substrate suspensions (up to at least 200 g/L).     

Symplectic small deformations of special instanton bundle on ℙ2n+1

Let be the moduli space of stable symplectic instanton bundles on 2n+1 with second Chern class c₂=k (it is a closed subscheme of the moduli space ).We prove that the dimension of its Zariski tangent space at a special (symplectic) instanton bundle is 2k(5n–1)+4n²–10n+3, k2.     

Selenite Downregulates STAT3 Expression and Provokes Lymphocytosis in the Liver of Chronically Exposed Syrian Golden Hamsters

Arsenic is considered a worldwide pollutant that can be present in drinking water. Arsenic exposure is associated with various diseases, including cancer. Antioxidants as selenite and α-tocopherol-succinate have been shown to modulate arsenic toxic effects. Since changes in STAT3 and PSMD10 gene expression have been associated with carcinogenesis, the aim of this study was to evaluate the effect of arsenic exposure and co-treatments with selenite or α-tocopherol-succinate on the expression of these genes, in the livers of chronically exposed Syrian golden hamsters. Animals were divided into six groups: (i) control, (ii) chronically treated with 100 ppm arsenic, (iii) treated with 6 ppm α-tocopherol-succinate (α-TOS), (iv) treated with 8.5 ppm selenite, (v) treated with arsenic + α-TOS, and (vi) treated with arsenic + selenite. Urine samples and livers were collected after 20 weeks of continuous exposure. The urine samples were analyzed for arsenic species by atomic absorption spectrophotometry, and real-time RT-qPCR analysis was performed for gene expression evaluation. A reduction in STAT3 expression was observed in the selenite-treated group. No differences in PSMD10 expression were found among groups. Histopathological analysis revealed hepatic lymphocytosis in selenite-treated animals. As a conclusion, long-term exposure to arsenic does not significantly alter the expression of STAT3 and PSMD10 oncogenes in the livers of hamsters; however, selenite down-regulates STAT3 expression and provokes lymphocytosis.