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The structures, vibrational spectra, and electronic properties of copper hydroxide hydrates CuOH + (H 2 O) 3-7 were investigated with quantum chemistry computations. As a follow-up to a previous analysis of CuOH + (H 2 O) 0-2 , this investigation examined the progression as the square-planar metal coordination environment was filled and as solvation shells expanded. Four-, five-, and six-coordinate structures were found to be low-energy isomers. The delocalized radical character, which was discovered in the small clusters, was found to persist upon continued hydration, although the hydrogen-bonded water network in the larger clusters was found to play a more significant role in accommodating this spin. Partial charges indicated that the electronic structure includes more Cu 2+ ···OH - character than was observed in smaller clusters, but this structure remains decidedly mixed with Cu + ···OH · configurations and yields roughly half-oxidation of the water network in the absence of any electrochemical potential. Computed vibrational spectra for n = 3 showed congruence with spectra from recent predissociation spectroscopy experiments, provided that the role of the D 2 tag was taken into account. Spectra for n = 4-7 were predicted to exhibit features that are reflective of both the mixed electronic character and proton-/hydrogen-shuttling motifs within the hydrogen-bonded water network.

Gas-phase clusters of the hydrated Cu(II) cation with 2-8 water molecules were investigated using ab initio quantum chemistry. Isomer structures, energies, and vibrational spectra were computed across this size range, yielding a qualitative picture of this ion as an intact Cu 2+ hydrate that also partially oxidizes the surrounding water network at equilibrium. At sufficient cluster sizes, these ion hydrates also become thermodynamically preferred over competitive Cu(II) hydroxide hydrates. Competitive coordination environments were found to exist at some cluster sizes, due to both hydrogen-bonding and d-orbital chemical effects, and the dominant coordination number was found in some cases to be temperature-dependent. Clear spectral signatures of the ion's coordination environment were computed to exist at each cluster size, which should make experimental verification of these computational predictions straightforward. Through comparison to recent studies of hydrated CuOH + , the effective charge on the metal center was shown to converge to approximately +1.5 in both cases, despite qualitatively different behavior of their radical spin densities. Therefore, nominally Cu(II) ions exhibit considerable electronic, chemical, and structural flexibility. The electronic origins of this flexibility─including key roles played by the water network itself─are investigated in this work and should provide a conceptual foundation for future studies of copper-based, water-oxidation catalysts.

Guided ion beam tandem mass spectrometry (GIBMS) was used to measure the kinetic energy dependent product ion cross sections for reactions of the lanthanide metal dysprosium cation (Dy + ) with O 2 , SO 2 , and CO and reactions of DyO + with CO, O 2 , and Xe. DyO + is formed through an exothermic process when Dy + reacts with O 2 , whereas all other processes observed are found to be endothermic. The kinetic energy dependences of these cross sections were analyzed to yield 0 K bond dissociation energies (BDEs) for DyO + , DyC + , DyS + , DyO 2 + , and DySO + . The 0 K BDE for DyO + is determined to be 5.60 ± 0.02 eV from the weighted average of six independent thresholds, which are dominated by the slightly endothermic reaction of Dy + with SO 2 . Combined with the well-established Dy ionization energy (IE), this value indicates that the chemi-ionization reaction, Dy + O → DyO + + e - , is endothermic by 0.33 ± 0.02 eV. Theoretical BDEs for Dy + -O, Dy + -C, Dy + -S, ODy + -O, and Dy + -SO were calculated at several levels of theory and basis sets for comparison with experiment with reasonable agreement achieved.

The copper hydroxide ion, CuOH + , serves as the catalytic core in several recently developed water-splitting catalysts, and an understanding of its chemistry is critical to determining viable catalytic mechanisms. In spite of its importance, the electronic structure of this open-shell ion has remained ambiguous in the literature. In particular, computed values for both the thermodynamics of hydration and the vibrational signatures of the mono- and dihydrates have shown prohibitively large errors compared to values from recent experimental measurements. In this work, the source of this discrepancy is demonstrated to be the propensity of this ion to exist between traditional Cu(I) and Cu(II) oxidation-state limits. The spin density of the radical is accordingly shown to delocalize between the metal center and surrounding ligands, and increasing the hydration serves to exacerbate this behavior. Equation-of-motion coupled-cluster methods demonstrated the requisite accuracy to resolve the thermodynamic discrepancies. Such methods were also needed for spectral simulations, although the latter also required a direct simulation of the role of the deuterium "tag" molecules that are used in modern predissociation spectroscopy experiments. This nominally benign tag molecule underwent direct complexation with the open-valence metal ion, thereby forming a species akin to known metal-H 2 complexes and strongly impacting the resulting spectrum. Thermal populations of this configuration and other more traditional noncovalently bound isomers led to a considerable broadening of the spectral lineshapes. Therefore, at least for the CuOH + (H 2 O) 0-2 hydrates, these benchmark ions should be considered to be delocalized radical systems with some degree of multireference character at equilibrium. They also serve as a cautionary tale for the spectroscopy community, wherein the role of the D 2 tag is far from benign.

Chemical activation of water by a single chlorine atom was examined computationally for clusters of chlorine radicals and water in a size regime just prior to internal hydration of water/ions, Cl · (H 2 O) n =4-8,17 . This investigation follows a recent analysis of this radical-molecule interaction [Christensen et al. J. Phys. Chem. A 2019, 123, 8657] for n = 1-4, which demonstrated that n = 4 marked a transition in which an oxidized-water structural motif became viable, albeit high in energy. Thousands of unique isomers were computed in the present analysis, which resulted in three structural classes of isomers, including intact hydrated chlorine, hydrogen-transferred (HCl)(OH · )(H 2 O) n -1 , and charge-transferred (Cl - )(H 3 O + )(OH · )(H 2 O) n -2 configurations. The electronic structures of these classes were investigated, along with harmonic vibrational signatures that probed the degree of water-network perturbations and generated experimentally verifiable computational predictions. The main outcome of this analysis is that the charge-transferred isomers were stabilized considerably upon increased hydration-leading to an energetic crossover with the hydrogen-transferred forms-but the degree of hydration was surprisingly still not sufficient to achieve crossover between the intact chlorine-water complexes and these charge-separated configurations. Internal hydration of the ions appears to be necessary in order to achieve this separation, which will likely occur at larger cluster sizes.

The partial chemical activation of water by reactive radicals was examined computationally for small clusters of chlorine and water, Cl • (H 2 O) n =1-4 . Using an automated isomer-search procedure, dozens of unique, stable structures were computed. Among the resulting structural classes were intact, hydrated-chlorine isomers, as well as hydrogen-abstracted (HCl)(OH)(H 2 O) n -1 configurations. The latter showed increased stability as the degree of hydration increased, until n = 4, where a new class of structures was discovered with a chloride ion bound to an oxidized water network. The electronic structure of these three structural classes was investigated, and spectral signatures of this hydration-based evolution were connected to these electronic properties. An ancillary outcome of this detailed computational analysis, including coupled-cluster benchmarks, was the calibration of cost-effective quantum chemistry methods for future studies of these radical-water complexes.

Antibiotics are frequently administered orally to treat bacterial infections not necessarily related to the gastrointestinal system. This has adverse effects on the commensal gut microbial community, as it disrupts the intricate balance between specific bacterial groups within this ecosystem, potentially leading to dysbiosis. We hypothesized that modulation of community composition and function induced by antibiotics affects intestinal integrity depending on the antibiotic administered. To address this a total of 60 Wistar rats (housed in pairs with 6 cages per group) were dosed by oral gavage with either amoxicillin (AMX), cefotaxime (CTX), vancomycin (VAN), metronidazole (MTZ), or water (CON) daily for 10-11 days. Bacterial composition, alpha diversity and caecum short chain fatty acid levels were significantly affected by AMX, CTX and VAN, and varied among antibiotic treatments. A general decrease in diversity and an increase in the relative abundance of Proteobacteria was observed for all three antibiotics. Additionally, the relative abundance of Bifidobacteriaceae was increased in the CTX group and both Lactobacillaceae and Verrucomicrobiaceae were increased in the VAN group compared to the CON group. No changes in microbiota composition or function were observed following MTZ treatment. Intestinal permeability to 4 kDa FITC-dextran decreased after CTX and VAN treatment and increased following MTZ treatment. Plasma haptoglobin levels were increased by both AMX and CTX but no changes in expression of host tight junction genes were found in any treatment group. A strong correlation between the level of caecal succinate, the relative abundance of Clostridiaceae 1 family in the caecum, and the level of acute phase protein haptoglobin in blood plasma was observed. In conclusion, antibiotic-induced changes in microbiota may be linked to alterations in intestinal permeability, although the specific interactions remain to be elucidated as changes in permeability did not always result from major changes in microbiota and vice versa.

TL1A is a proinflammatory cytokine, which is prevalent in the gut. High TL1A concentrations are present in patients with inflammatory bowel disease (IBD) and in IBD mouse models. However, the role of TL1A during steady-state conditions is relatively unknown. Here, we used TL1A knockout (KO) mice to analyse the impact of TL1A on the intestinal immune system and gut microbiota. The TL1A KO mice showed reduced amounts of small intestinal intraepithelial TCRγδ(+) and CD8(+) T cells, and reduced expression of the activating receptor NKG2D. Moreover, the TL1A KO mice had significantly reduced body weight and visceral adipose tissue deposits, as well as lower levels of leptin and CXCL1, compared with wild-type mice. Analysis of the gut microbial composition of TL1A KO mice revealed a reduction of caecal Clostridial cluster IV, a change in the Firmicutes/Bacteroidetes ratio in caecum and less Lactobacillus spp. in the mucosal ileum. Our results show that TL1A deficiency impacts on the gut microbial composition and the mucosal immune system, especially the intraepithelial TCRγδ(+) T-cell subset, and that TL1A is involved in the establishment of adipose tissue. This research contributes to a broader understanding of TL1A inhibition, which is increasingly considered for treatment of IBD., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Consumption of prebiotics may modulate gut microbiota, subsequently affecting the bacterial composition, metabolite profile, and human health. Previous studies indicate that also changes in intestinal integrity may occur. In order to explore this further we have investigated the effect of the putative prebiotic xylo-oligosaccharides (XOS) on the gut microbiota and intestinal integrity in male Wistar rats. As changes in intestinal integrity may be related to the expected bifidogenic effect of XOS, we additionally addressed effects of supplementation with a commensal Bifidobacterium pseudolongum (BIF) isolated from the same breed of laboratory rats., Results: Changes in faecal and caecal bacterial composition determined by 16S rRNA gene sequencing and quantitative PCR for selected bacterial groups revealed that the overall bacterial composition did not differ markedly between the control (CON), XOS, and BIF groups, when correcting for multiple comparisons. However as hypothesised, the relative abundance of Bifidobacterium spp. was increased in XOS-fed rats as compared to CON in faecal samples after the intervention. Also Lactobacillus spp. was increased in both the XOS and BIF groups in caecum content compared to CON. Intestinal permeability determined in vivo by FITC-dextran permeability and in vitro using extracted caecum water in trans-epithelial resistance (TER) assay showed no effect on intestinal integrity in either the XOS or the BIF groups. However, the expression of occludin, which is part of the tight junction complex, was increased in the XOS group compared to the CON group., Conclusions: Supplementation with XOS or a commensal Bifidobacterium pseudolongum had very limited effects on intestinal integrity in rats as only significant change in expression of a single tight junction protein gene was found for the XOS group.

Background/objectives: Consumption of whole-grain products is known to have beneficial effects on human health. The effects of whole-grain products on the intestinal microbiota and intestinal integrity have, however, only been studied limitedly. We investigate changes of the human gut microbiota composition after consumption of whole-grain (WW) or refined wheat (RW) and further study effects on gut wall integrity., Subjects/methods: Quantitative PCR was used to determine changes in the gut bacterial composition in postmenopausal women following a 12-week energy-restricted dietary intervention with WW (N=38) or RW (N=34). Intestinal integrity was determined by measuring trans-epithelial resistance (TER) across a Caco-2 cell monolayer, following exposure to faecal water., Results: No significant differences in microbiota composition were observed between the two dietary groups; however, the whole-grain intervention increased the relative abundance of Bifidobacterium compared to baseline, supporting a prebiotic effect of whole-grain wheat. Faecal water increased TER independent of dietary intervention, indicating that commensal bacteria produce metabolites that generally provide a positive effect on intestinal integrity. Combining microbiota composition data from the run-in period with its effect on TER revealed a tendency for a negative correlation between the relative abundance of Bifidobacterium and TER (P=0.09). This contradicts previous findings but supports observations of increased Salmonella infection in animal models following treatment with bifidogenic prebiotics., Conclusions: The present study shows that whole-grain wheat consumption increases the abundance of bifidobacteria compared to baseline and may have indirect effects on the integrity of the intestinal wall.

The human food-borne pathogen Listeria monocytogenes is capable of persisting in food processing plants despite cleaning and sanitation and is likely exposed to sublethal biocide concentrations. This could potentially affect susceptibility of the bacterium to biocides and other antimicrobial agents. The purpose of the present study was to determine if sublethal biocide concentrations affected antibiotic susceptibility in L. monocytogenes. Exposure of L. monocytogenes strains EGD and N53-1 to sublethal concentrations of Incimaxx DES (containing peroxy acids and hydrogen peroxide) and Triquart Super (containing quaternary ammonium compound) in four consecutive cultures did not alter the frequency of antibiotic-tolerant isolates, as determined by plating on 2× the MIC for a range of antibiotics. Exposure of eight strains of L. monocytogenes to 1 and 4 μg/ml triclosan did not alter triclosan sensitivity. However, all eight strains became resistant to gentamicin (up to 16-fold increase in MIC) after exposure to sublethal triclosan concentrations. Gentamicin-resistant isolates of strains N53-1 and 4446 were also resistant to other aminoglycosides, such as kanamycin, streptomycin, and tobramycin. Gentamicin resistance remained at a high level also after five subcultures without triclosan or gentamicin. Aminoglycoside resistance can be caused by mutations in the target site, the 16S rRNA gene. However, such mutations were not detected in the N53-1-resistant isolates. A combination of gentamicin and ampicillin is commonly used in listeriosis treatment. The triclosan-induced resistance is, hence, of great concern. Further investigations are needed to determine the molecular mechanisms underlying the effect of triclosan.