Switching the Conductance of a Molecular Junction using a Proton Transfer Reaction

A novel mechanism for switching a molecular junction based on a proton transfer reaction triggered by an external electrostatic field is proposed. As a specific example to demonstrate the feasibility of the mechanism, the tautomers [2,5-(4-hydroxypyridine)] and {2,5-[4(1H)-pyridone]} are considered. Employing a combination of first-principles electronic structure calculations and Landauer transport theory, we show that both tautomers exhibit very different conductance properties and realize the "on" and "off" states of a molecular switch. Moreover, we provide a proof of principle that both forms can be reversibly converted into each other using an external electrostatic field.Comment: 14 pages, 5 figure

Age-Related Differences in Vertical Jump Power and Muscle Size and Quality of the Vastus Lateralis

Previous studies have reported that decreases in muscle size and quality of the vastus lateralis (VL) may contribute to the lower vertical jump power observed in old compared to young males. However, we are aware of no previous studies that have examined the contribution of VL muscle size and quality to age-related power differences in females, nor have there been any studies that examined these differences between young, middle, and older age groups. PURPOSE: To determine the effects of age on vertical jump power and muscle size (cross-sectional area [CSA]) and quality (echo intensity [EI]) of the VL in young, middle-aged, and old females. METHODS: Twenty-six young (age = 22 ± 2 yr; height = 163 ± 7 cm; mass = 61 ± 8 kg), 30 middle-aged (36 ± 5 yr; 164 ± 7 cm; 62 ± 11 kg), and 23 old (71 ± 5 yr; 161 ± 5 cm; 59 ± 10 kg) females underwent two diagnostic ultrasound assessments followed by three countermovement vertical jumps (CMJs). Peak power output (Pmax; W) was measured during the CMJs using a portable force plate. VL CSA (cm2) and EI (AU) were measured on the right leg using a portable B-mode ultrasound imaging device and linear-array probe. One-way ANOVAs and post-hoc analyses were used to compare Pmax, CSA, and EI between age groups. Pearson product-moment correlation coefficients (r) were used to examine the relationships between Pmax and CSA and EI. RESULTS: Higher Pmax and CSA values were observed for the young (Pmax = 2257.40 ± 438.42 W; CSA = 20.59 ± 4.23 cm2) compared to the old (Pmax = 1098.55 ± 242.10 W; CSA = 10.69 ± 2.47 cm2) and middle-aged (Pmax = 1958.20 ± 341.87 W; CSA = 18.05 ± 4.24 cm2) and the middle-aged compared to the old (P ≤ 0.001-0.039). EI values for the young (104.29 ± 16.86 AU) and middle-aged (107.71 ± 17.30 AU) were lower than the old (128.35 ± 14.99 AU) (P \u3c 0.001), but they were not different from each other (P = 0.720). There was a significant positive relationship between Pmax and CSA (r = 0.830; P \u3c 0.001) and a significant negative relationship between Pmax and EI (r = -0.442; P \u3c 0.001). CONCLUSION: These findings demonstrated that vertical jump power and muscle size and quality decrease with age. The significant relationships observed between Pmax and CSA and EI perhaps suggest that these age-related declines in VL muscle size and quality may play an important role in the lower vertical jump power observed in middle-aged and older adults

Excited States of Proton-bound DNA/RNA Base Homo-dimers: Pyrimidines

We are presenting the electronic photo fragment spectra of the protonated pyrimidine DNA bases homo-dimers. Only the thymine dimer exhibits a well structured vibrational progression, while protonated monomer shows broad vibrational bands. This shows that proton bonding can block some non radiative processes present in the monomer.Comment: We acknowledge the use of the computing facility cluster GMPCS of the LUMAT federation (FR LUMAT 2764

A bronze-tomato enriched diet affects the intestinal microbiome under homeostatic and inflammatory conditions

Inflammatory bowel diseases (IBD) are debilitating chronic inflammatory disorders that develop as a result of a defective immune response toward intestinal bacteria. Intestinal dysbiosis is associated with the onset of IBD and has been reported to persist even in patients in deep remission. We investigated the possibility of a dietary-induced switch to the gut microbiota composition using Winnie mice as a model of spontaneous ulcerative colitis and chow enriched with 1% Bronze tomato. We used the near isogenic tomato line strategy to investigate the effects of a diet enriched in polyphenols administered to mild but established chronic intestinal inflammation. The Bronze-enriched chow administered for two weeks was not able to produce any macroscopic effect on the IBD symptoms, although, at molecular level there was a significant induction of anti-inflammatory genes and intracellular staining of T cells revealed a mild decrease in IL17A and IFNγ production. Analysis of the microbial composition revealed that two weeks of Bronze enriched diet was sufficient to perturb the microbial composition of Winnie and control mice, suggesting that polyphenol-enriched diets may create unfavorable conditions for distinct bacterial species. In conclusion, dietary regimes enriched in polyphenols may efficiently support IBD remission affecting the intestinal dysbiosis

Immunohistochemical and transcriptional expression of Matrix Metalloproteinases in full-term human umbilical cord and Human Umbilical Vein Endothelial Cells

Matrix metalloproteinases (MMPs) are extracellular zinc-dependent endopeptidases involved in the degradation and remodelling of extracellular matrix in physiological and pathological processes. MMPs also have a role on cell proliferation, migration, differentiation, angiogenesis and apoptosis. Umbilical cord is a special organ subjected to many changes during pre-natal life and whose cells can maintain a certain degree of plasticity also in post-natal period; for example recently they have been used as a source of stem cells. In this work we investigated the expression of MMPs in human umbilical cord and Human Umbilical Vein Endothelial Cells (HUVEC) though immunohistochemistry, RT-PCR and gelatin zymography. MMP-2 protein is expressed in the amniotic epithelium of human umbilical cord and in few sub-epithelial fibroblasts, while MMP-3 and MMP-10 only in the umbilical epithelium. MMP-8, MMP-9 and MMP-13 immunoreactivity is localised in the epithelium and in Wharton\u2019s jelly mesenchymal cells. Immunocytochemistry also revealed protein expression for MMP-2, 3, 8, 9 and 10 in cultured HUVEC. In agreement with immunohistochemical data, RT-PCR analysis performed on samples of whole umbilical cord confirmed the transcriptional expression for the genes encoding all the six matrix metalloproteinases investigated, while in HUVEC only the expression of MMP-2, 3, 9, 10 and 13 mRNAs was detected. Gelatin zymograpgy showed a clear MMP-2 and MMP-9 enzymatic activity in the conditioned medium of HUVEC at different culture passages, suggesting that HUVEC secrete gelatinases, that afterwards undergo extracellular activation, and this ability is not affected by passage number

A Field Procedure To Screen Soil for Hazardous Lead

Soils retain lead contamination from possible sources such as mining, smelting, battery recycling, waste incineration, leaded gasoline, and crumbling paint. Such contamination is often concentrated in toxic hot spots that need to be identified locally. To address this need, a simple field procedure was designed to screen soil for hazardous Pb for use by the general public. The procedure is a modification of the in vitro soil Pb extraction described by Drexler and Brattin (Hum. Ecol. Risk Assess. 2007, 13, 383) and EPA Method 1340, and uses a 0.4 M glycine solution at pH 1.5. A higher soil-to-solution ratio of 1:10 allows for classifying soil samples based on extractable Pb concentrations of/ kg (low), 200−400 mg/kg (medium), and \u3e400 mg/kg (high) using sodium rhodizonate as a color indicator. The 1:10 soil-to-solution ratio also makes it possible to measure Pb concentrations in the glycine extract solutions on a continuous scale using a portable X-ray fluorescence analyzer. The procedure rather consistently extracts about one-third of the Pb extracted by the standard method across a wide range of Pb concentrations. Manufacturing the kit in larger quantities could reduce the cost of the materials well below the current $5/test

Time-dependent density functional study of the electronic spectra of oligoacenes in the charge states -1, 0, +1, and +2

We present a systematic theoretical study of the five smallest oligoacenes (naphthalene, anthracene, tetracene, pentacene, and hexacene) in their anionic,neutral, cationic, and dicationic charge states. We used density functional theory (DFT) to obtain the ground-state optimised geometries, and time-dependent DFT (TD-DFT) to evaluate the electronic absorption spectra. Total-energy differences enabled us to evaluate the electron affinities and first and second ionisation energies, the quasiparticle correction to the HOMO-LUMO energy gap and an estimate of the excitonic effects in the neutral molecules. Electronic absorption spectra have been computed by combining two different implementations of TD-DFT: the frequency-space method to study general trends as a function of charge-state and molecular size for the lowest-lying in-plane long-polarised and short-polarised $\pi\to\pi^\star$ electronic transitions, and the real-time propagation scheme to obtain the whole photo-absorption cross-section up to the far-UV. Doubly-ionised PAHs are found to display strong electronic transitions of $\pi\to\pi^\star$ character in the near-IR, visible, and near-UV spectral ranges, like their singly-charged counterparts. While, as expected, the broad plasmon-like structure with its maximum at about 17-18 eV is relatively insensitive to the charge-state of the molecule, a systematic decrease with increasing positive charge of the absorption cross-section between about 6 and about 12 eV is observed for each member of the class.Comment: 38 pages, 11 figures, 7 tables, accepted for publication in Chemical Physic

Tight-binding parameters for charge transfer along DNA

We systematically examine all the tight-binding parameters pertinent to charge transfer along DNA. The $\pi$ molecular structure of the four DNA bases (adenine, thymine, cytosine, and guanine) is investigated by using the linear combination of atomic orbitals method with a recently introduced parametrization. The HOMO and LUMO wavefunctions and energies of DNA bases are discussed and then used for calculating the corresponding wavefunctions of the two B-DNA base-pairs (adenine-thymine and guanine-cytosine). The obtained HOMO and LUMO energies of the bases are in good agreement with available experimental values. Our results are then used for estimating the complete set of charge transfer parameters between neighboring bases and also between successive base-pairs, considering all possible combinations between them, for both electrons and holes. The calculated microscopic quantities can be used in mesoscopic theoretical models of electron or hole transfer along the DNA double helix, as they provide the necessary parameters for a tight-binding phenomenological description based on the $\pi$ molecular overlap. We find that usually the hopping parameters for holes are higher in magnitude compared to the ones for electrons, which probably indicates that hole transport along DNA is more favorable than electron transport. Our findings are also compared with existing calculations from first principles.Comment: 15 pages, 3 figures, 7 table