Experimental simulation of H2 coinjection via a high-pressure reactor with natural gas in a low-salinity deep aquifer used for current underground gas storage.

If dihydrogen (H2) becomes a major part of the energy mix, massive storage in underground gas storage (UGS), such as in deep aquifers, will be needed. The development of H2 requires a growing share of H2 in natural gas (and its current infrastructure), which is expected to reach approximately 2% in Europe. The impact of H2 in aquifers is uncertain, mainly because its behavior is site dependent. The main concern is the consequences of its consumption by autochthonous microorganisms, which, in addition to energy loss, could lead to reservoir souring and alter the petrological properties of the aquifer. In this work, the coinjection of 2% H2 in a natural gas blend in a low-salinity deep aquifer was simulated in a three-phase (aquifer rock, formation water, and natural gas/H2 mix) high-pressure reactor for 3 months with autochthonous microorganisms using a protocol described in a previous study. This protocol was improved by the addition of protocol coupling experimental measures and modeling to calculate the pH and redox potential of the reactor. Modeling was performed to better analyze the experimental data. As in previous experiments, sulfate reduction was the first reaction to occur, and sulfate was quickly consumed. Then, formate production, acetogenesis, and methanogenesis occurred. Overall, H2 consumption was mainly caused by methanogenesis. Contrary to previous experiments simulating H2 injection in aquifers of higher salinity using the same protocol, microbial H2 consumption remained limited, probably because of nutrient depletion. Although calcite dissolution and iron sulfide mineral precipitation likely occurred, no notable evolution of the rock phase was observed after the experiment. Overall, our results suggested that H2 can be stable in this aquifer after an initial loss. More generally, aquifers with low salinity and especially low electron acceptor availability should be favored for H2 costorage with natural gas.

Theoretical description of hydride-hydride interactions in selected hydrogen storage materials.

The high content of hydride-hydride contacts Hδ-···Î´-H in hydrogen storage materials appears to be relevant for hydrogen formation. At present time there is no consensus whether these contacts are attractive or repulsive. Accordingly, the main goal of this article is to shed light on physical factors which constitute homopolar hydride-hydride interactions Hδ-···Î´-H in selected transition metal complexes i.e. HCoL4, L = CO,PPh3,PH3. In order to achieve this goal, the charge and energy decomposition ETS-NOCV approach along with the Interacting Quantum Atoms (IQA) and reduced density gradient (NCI) are applied for the bonded adducts L4CoH···HCoL4. Based on DFT and correlated methods it has been shown, that hydride-hydride interactions might be attractive and even far stronger than classical hydrogen bonds. The stability of the adducts is increased by phosphine ligand installation: overall Hδ-···Î´-H bonding energy changes in the order: CO << PPh3 ~ PH3. It has been revealed that depending on monomer's conformations Hδ-···Î´-H bonds are dominated by charge delocalization or London dispersion forces and the electrostatic term is also relevant. It is finally determined by IQA energy decomposition, that diatomic hydride-hydride interaction CoH···HCo is chameleon-like, namely, it is attractive in CO4CoH···HCoCO4, whereas the repulsion is unveiled in (CO)3(PPh3)CoH···HCo(CO)3(PPh3).

Light-induced H2 generation in a photosystem I-O2-tolerant [FeFe] hydrogenase nanoconstruct.

The fusion of hydrogenases and photosynthetic reaction centers (RCs) has proven to be a promising strategy for the production of sustainable biofuels. Type I (iron-sulfur-containing) RCs, acting as photosensitizers, are capable of promoting electrons to a redox state that can be exploited by hydrogenases for the reduction of protons to dihydrogen (H2). While both [FeFe] and [NiFe] hydrogenases have been used successfully, they tend to be limited due to either O2 sensitivity, binding specificity, or H2 production rates. In this study, we fuse a peripheral (stromal) subunit of Photosystem I (PS I), PsaE, to an O2-tolerant [FeFe] hydrogenase from Clostridium beijerinckii using a flexible [GGS]4 linker group (CbHydA1-PsaE). We demonstrate that the CbHydA1 chimera can be synthetically activated in vitro to show bidirectional activity and that it can be quantitatively bound to a PS I variant lacking the PsaE subunit. When illuminated in an anaerobic environment, the nanoconstruct generates H2 at a rate of 84.9 ± 3.1 µmol H2 mgchl-1 h-1. Further, when prepared and illuminated in the presence of O2, the nanoconstruct retains the ability to generate H2, though at a diminished rate of 2.2 ± 0.5 µmol H2 mgchl-1 h-1. This demonstrates not only that PsaE is a promising scaffold for PS I-based nanoconstructs, but the use of an O2-tolerant [FeFe] hydrogenase opens the possibility for an in vivo H2 generating system that can function in the presence of O2.

Diamond-Reinforced Al(H2PO4)3@Epoxy Hybrid Thermal Adhesive With Ultra-High Thermal Conductivity and Bonding Strength.

The miniaturization, integration, and increased power of electronic devices have exacerbated serious heat dissipation issues. Thermally conductive adhesives, which effectively transfer heat and firmly bond components, are critical for addressing these challenges. This paper innovatively proposed a composite comprising inorganic phosphate/alumina as a matrix and diamond as filler. The composite achieved an isotropic thermal conductivity (TC) of up to 18.96 W m-1 K-1, significantly surpassing existing reports while maintaining electrical insulation. First-principles calculations and experimental tests confirmed that the high TC of phosphate and excellent interface contact ensured efficient heat transfer. To optimize bonding performance, a modified-diamond/Al(H2PO4)3@epoxy hybrid composite is subsequently developed using an organic modification method. The unique hybrid structure, combining inorganic thermal pathways and an organic adhesive network, enabled the hybrid composite to simultaneously possess a high TC (3.23 W m-1 K-1) and strong adhesion (14.35 MPa). Compared to previous reports, the comprehensive performance of this hybrid thermally conductive adhesive is exceptionally remarkable. The superior heat dissipation capability of the hybrid thermal adhesive is demonstrated in chip cooling scenarios. This organic/inorganic hybrid approach offered a new direction for obtaining advanced thermal interface materials, demonstrating significant application potential in chip soldering, packaging, and heat dissipation.

Effect of storage time on chemical structure of a single-bottle and a two-bottle experimental ceramic primer and micro-shear bond strength of composite to ceramic.

PURPOSE: This study assessed the effect of storage time on chemical structure of a single-bottle and a two-bottle experimental ceramic primer and micro-shear bond strength (µSBS) of composite to ceramic. MATERIALS AND METHODS: This study was conducted on 60 sintered zirconia and 60 feldspathic porcelain blocks. Half of the specimens (n = 30) were subjected to surface treatment with the single-bottle Clearfil ceramic primer (n = 15) and two-bottle experimental primer (n = 15) after 24 hours. The remaining half received the same surface treatments after 6 months storage in distilled water. Composite cylinders were bonded to the ceramics, and they were then subjected to µSBS test. Also, the primers underwent Fourier-transform infrared spectroscopy (FTIR) after 24 hours and 6 months to assess their chemical structure. Data were analyzed with 3-way ANOVA and adjusted Bonferroni test (alpha = 0.05). RESULTS: The µSBS of both ceramics significantly decreased at 6 months in one-bottle ceramic primer group (P = .001), but it was not significantly different from the two-bottle experimental primer group (P = .635). FTIR showed hydrolysis of single-bottle primer, cleavage of silane and 10-MDP bonds, and formation of siloxane bonds after 6 months. CONCLUSION: Six months of storage caused significant degradation of single-bottle ceramic primer, and consequently had an adverse effect on µSBS.

Comparison of the crystal structures of the JAK1/2 inhibitor ruxolitinib and its hydrate and phosphate.

Ruxolitinib {RUX; systematic name: (3R)-3-cyclopentyl-3-[4-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]propanenitrile, C17H18N6} is an orally bioavailable JAK1/2 inhibitor approved for treating intermediate- or high-risk myelofibrosis (MF) and high-risk polycythemia vera (PV). Recent patents claim that RUX can exist in many different forms, information for which is important for the clinical utilization of RUX, especially for the formulation and bioavailability of the drug. But there has been no detailed study on its forms so far. Herein crystals of RUX and its dihydrate (RUX-2H; C17H18N6·2H2O) and phosphate (RUX-P; systematic name: 4-{1-[(1R)-2-cyano-1-cyclopentylethyl]-1H-pyrazol-4-yl}-7H-pyrrolo[2,3-d]pyrimidin-3-ium dihydrogen phosphate, C17H19N6+·H2PO4-) were prepared successfully and their structures studied in detail for the first time. Our study shows that the three crystals of RUX differ in the orientation of the pyrimidine ring relative to the pyrazole ring of the RUX molecule, and in their hydrogen-bond interactions. The water molecules in RUX-2H and the dihydrogen phosphate anion in RUX-P enrich the hydrogen-bond networks in these forms. The expected proton transfer occurs in RUX phosphate and the protonated N atom is engaged in a charge-assisted hydrogen bond with the counter-anion. Hydrogen-bonding interactions dominate in the crystal packing of the three forms. The detailed conformations and packing of the three forms were compared through the calculation of both Hirshfeld surfaces and fingerprint plots.

Trade-off between sulfidated zero-valent iron reactivity and air stability: Regulation of iron sulfides by ammonium dihydrogen phosphate.

The reactivity and stability of zero-valent iron (ZVI) and sulfidated zero-valent iron (S-ZVI) are inherently contradictory. Iron sulfides (FeSX) on the S-ZVI surface play multiple roles, including electrostatic adsorption and catalyzing reduction. We proposed to balance the reactivity and air stability of S-ZVI by regulating FeSX. Benefiting from the superior coordination and accelerate electron transport capabilities of phosphate, herein, eco-friendly ammonium dihydrogen phosphate (ADP) was employed to synthesize N, P, and S-incorporated ZVI (NPS-ZVI) and regulate the FeSX. Raman, FTIR, XPS, and density functional theory (DFT) calculations were combined to reveal that HPO42- acts as the main P species on the Fe surface. The superior reactivity of NPS-ZVI was quantified by kobs, kSA, and kM of Cr(VI), which were 210.77, 27.44, and 211.17-fold than ZVI, respectively. NPS-ZVI demonstrated excellent reusability, with no risk of secondary pollution. Critically, NPS-ZVI could effectively maintain FeSX stability under the combination of diffusion limitation and surface protection mechanisms of ADP. The superior reactivity of NPS-ZVI was attributed to the fact that ADP maintains FeSX stability and accelerates electron transport. This study provides a novel strategy in balancing the reactivity and air stability of S-ZVI and offers theoretical support for material modification.

Seven-Coordinate Group 6 Metal Hydrides Obtained by H2 Activation at B(C6F5)3 Adducts of N2 Complexes: Frustrated Lewis Pair-Type Reactivity of The B-N Linkage.

The adducts 2M,R of general formula trans-[(L)M{R2P(CH2)2PR2}2{N2B(C6F5)3}] (L=ø or N2, M=Mo or W, R=Et or Ph), formed from Lewis acid-base pairing of B(C6F5)3 to a dinitrogen ligand of zero-valent group 6 bis(phosphine) complexes trans-[M{R2P(CH2)2PR2}2(N2)2] are shown to react with dihydrogen to afford hepta-coordinated bis(hydride) complexes [M(H)2{R2P(CH2)2PR2}{N2B(C6F5)3}] 3M,R which feature the rare ability to activate both dinitrogen and dihydrogen at a single metal center, except in the case where M=Mo and R=Ph for which fast precipitation of insoluble [Mo(H)4(dppe)2] (dppe=1,2-bis(diphenylphosphino)ethane) occurs. The frustrated Lewis pair (FLP)-related reactivity of the B-N linkage in compounds 3W,R was explored and led to distal N functionalization without involvement of the hydride ligands. It is shown in one example that the resulting bis(hydride) diazenido compounds may also be obtained through a sequence involving first FLP-type N-functionalization followed by oxidative addition of H2. Those oily compounds were found to have limited stability in solution or in their isolated states. Finally, treatment of 3W,Et with the Lewis base N,N-dimethylaminopyridine (DMAP) affords the simple but unknown bis(hydride)-dinitrogen species [W(H)2(depe)2(N2)] 11Et (depe=1,2-bis(diethylphosphino)ethane) which direct, selective formation from trans-[W(N2)2(depe)2] is not possible.

Monohydrides of the Group 13 Elements M=B, Al and Ga: Axial Bi-Nucleophilicity and the Propensity to Form Both H-M⋠⋠⋠HX and M-H⋠⋠⋠HX Hydrogen Bonds (X=F, Cl, Br, I, CN, CCH, CP).

Equilibrium dissociation energies De of the hydrogen-bonded complexes HAl⋅⋅⋅HX and HGa⋅⋅⋅HX (X=F, Cl, Br, I, CN, CCH, and CP) were calculated ab initio at the CCSD(T)-(F12c)/cc-pVDZ-F12 level of theory. The gradients of graphs of De versus the electrophilicity EHX of the Lewis acids HX yielded the nucleophilicities NM-X of the Group 13 atoms M in these diatomic molecules. Molecular electrostatic surfaces potentials reveal that H-Al and H-Ga are bi-nucleophilic and that the H ends of these H-M molecules are more nucleophilic than the M ends for M=Al and Ga, but not when M=boron. Therefore, the complexes M-H⋅⋅⋅HX were investigated using the same approach. It was concluded for M=Al and Ga that, for a given X, the M-H⋅⋅⋅HX complexes were more strongly bound than the corresponding H-M⋅⋅⋅HX complexes for both M=Al and Ga but the reverse order applies for M = boron. The effects of substituting the H atoms in the M-H molecules by F atoms and by methyl groups were investigated to measure the -I and +I inductive effects relative to H, respectively, on the nucleophilicities of the molecules M-H when M is acting as hydrogen-bond acceptor in complexes H-M⋅⋅⋅H-X.

Structural Flexibility is a Decisive Factor in FLP Dihydrogen Cleavage with Tetrahedral Lewis Acids: A Silane Case Study.

Dihydrogen activation is the paradigmatic reaction of frustrated Lewis pairs (FLPs). While trigonal-planar Lewis acids have been well established in this transformation, tetrahedral Lewis acids are surprisingly limited. Indeed, several cases were computed as thermodynamically and kinetically feasible but exhibit puzzling discrepancies with experimental results. In the present study, a computational investigation of the factors influencing dihydrogen activation are considered by large ensemble sampling of encounter complexes, deformation energies and the activation strain model for a silicon/nitrogen FLP and compared with a boron/phosphorous FLP. The analysis adds the previously missing dimension of Lewis acids' structural flexibility as a factor that influences preexponential terms beyond pure transition state energies. It sheds light on the origin of "overfrustration" (defined herein), indicates structural constraint in Lewis acids as a linchpin for activation of weak donor substrates, and allows drawing a more refined mechanistic picture of this emblematic reactivity.

The impact of six-week dihydrogen-pyrroloquinoline quinone supplementation on mitochondrial biomarkers, brain metabolism, and cognition in elderly individuals with mild cognitive impairment: a randomized controlled trial.

OBJECTIVES: To assess the impact of medium-term supplementation with dihydrogen and pyrroloquinoline quinone (PQQ) on mitochondrial biomarkers, brain metabolism, and cognition in elderly individuals diagnosed with mild cognitive impairment. DESIGN: A parallel-group, randomized, placebo-controlled, double-blind experimental design, maintaining a 1:1 allocation ratio between the experimental group (receiving the dihydrogen-producing minerals and PQQ) and the control group (receiving the placebo) throughout the trial. SETTING AND PARTICIPANTS: Thirty-four elderly individuals with mild cognitive impairment (mean age 71.9 ± 3.8 years; 28 females) voluntarily provided written consent to participate in this trial. Participants were assigned in a double-blind parallel-group design to receive either a dihydrogen-PQQ mixture (Alpha Hope®, CalerieLife, Irvine, CA) or placebo twice daily for a 6-week intervention period. METHODS: The primary endpoint was the change in serum brain-derived neurotrophic factor (BDNF) from baseline to the 6-week follow-up; secondary outcomes included cognitive function indices, specific metabolites in brain tissue, brain oxygenation, and the prevalence and severity of side effects. Interaction effects (time vs. intervention) were evaluated using two-way ANOVA with repeated measures and Friedman's 2-way ANOVA by ranks, for normally distributed data with homogeneous variances and non-homogeneous variances, respectively. RESULTS: Dihydrogen-PQQ resulted in a significant elevation in serum BDNF levels at the six-week follow-up (P = 0.01); conversely, no changes in BDNF levels were observed in the placebo group throughout the study duration (P = 0.27). A non-significant trend in the impact of interventions on BDNF levels was observed (treatment vs. time interaction, P = 0.14), suggesting a tendency for dihydrogen-PQQ to upregulate BDNF levels compared to the placebo. A significant interaction effect was observed for the Alzheimer's Disease Assessment Scale-Cognitive subscale (ADAS-Cog) scores in the orientation domain (P = 0.03), indicating the superiority of dihydrogen-PQQ over placebo in enhancing this cognitive aspect. Cerebral oxygenation saturation exhibited a significant increase following the administration of the dihydrogen-PQQ mixture, from 48.4 ± 7.2% at baseline to 52.8 ± 6.6% at 6-week post-administration (P = 0.005). In addition, brain N-acetyl aspartate levels significantly increased at seven out of thirteen locations post-intervention in participants receiving the mixture (P ≤ 0.05). CONCLUSIONS: Despite the limited number of participants included in the study for interpreting clinical parameters, the dihydrogen-PQQ mixture blend shows promise as a potential dietary intervention for enhancing mental orientation and brain metabolism in individuals with age-related mild cognitive decline.

The acute effects of rumen pulse-dosing of hydrogen acceptors during methane inhibition with nitrate or 3-nitrooxypropanol in dairy cows.

Dietary methane (CH4) mitigation is in some cases associated with an increased hydrogen (H2) emission. The objective of the present study was to investigate the acute and short-term effects of acceptors for H2 (fumaric acid, acrylic acid, or phloroglucinol) supplemented via pulse-dosing to dairy cows fed CH4 mitigating diets (using nitrate or 3-nitrooxypropanol), on gas exchange, rumen gas, and VFA composition. For this purpose, 2 individual 4 × 4 Latin square experiments were conducted with 4 periods of 3 d (nitrate supplementation) and 7 d (3-nitrooxypropanol supplementation), respectively. In each study, 4 rumen-cannulated Danish Holstein cows were used. Each additive for CH4 mitigation was included in the ad libitum-fed diet within the 2 experiments (exp. 1 and exp. 2), to which the cows were adapted for at least 14 d. Acceptors for H2 were administered twice daily in equal portions through the rumen fistula immediately after feeding of the individual cow. In exp. 1 (nitrate), the treatments were CON-1 (no H2-acceptor), FUM-1 (fumaric acid), ACR-1 (acrylic acid), and FUM+ACR-1 (50% FUM-1 + 50% ACR-1). In exp. 2 (3-nitrooxypropanol), the 3 treatments, CON-2, FUM-2, and ACR-2, were similar to CON-1, FUM-1 and ACR-1 treatments, however the fourth treatment was PHL-2 (phloroglucinol). Gas exchanges were measured in respiration chambers, and samples of rumen liquid and headspace gas were taken in time series relative to feeding and dosing on specific days. Headspace gas was analyzed for gas composition, and rumen liquid was analyzed for VFA composition and dissolved gas concentrations. Headspace gas composition and dissolved gas concentration were only measured in exp. 2. Dry matter intake was reduced upon acrylic acid supplementation. There were no significant effects of any treatments in any experiments on H2 emission, except for a decrease in hourly H2 emission rate (g/h) at 1 h after feeding in both experiments. In exp. 2, H2 headspace proportions increased with ACR-2 supplementation, whereas dissolved concentrations were unaffected. In exp. 1, cows on ACR-1 increased propionate proportion at 1 h after feeding. In exp. 2, both FUM-2 and ACR-2 increased rumen propionate proportion in the hours after feeding and dosing. There was no effect on rumen acetate for cows on PHL-2. There was a strong positive correlation between rumen dissolved CH4 and headspace CH4 (r = 0.84), whereas the equivalent correlation was weaker for H2 (r = 0.41). For the relationship between dissolved concentrations and emissions of CH4 and H2, there was a moderate positive correlation for CH4 (r = 0.54), whereas it was weak for H2 (r = 0.28) with zero slope. In conclusion, the results suggested that fumaric acid and acrylic acid to some extent was reduced to propionate without associative effects on measures for H2 redirection. Furthermore, phloroglucinol seemed not to be metabolized in the rumen in the present study, because no effects on rumen acetate or measures of H2 were observed. Changes in H2 headspace and emission may be a poor proxy for actual changes in the rumen fluid concentration of H2.

Imparting Stable and Ultrahigh Proton Conductivity to a Layered Rare Earth Hydroxide via Ion Exchange.

Proton conductors are essential functional materials with a wide variety of potential applications in energy storage and conversion. In order to address the issues of low proton conductivity and poor stability in conventional proton conductors, a simple and valid ion-exchange method was proposed in this study for the introduction of stable and ultrahigh proton conductivity in layered rare earth hydroxides (LRHs). Test analyses by solid-state nuclear magnetic resonance, Fourier transform infrared spectroscopy, and powder X-ray diffraction revealed that the exchange of H2PO4- not only does not disrupt the layered structure of LRHs, but also creates more active proton sites and channels necessary for proton transport, thereby creating a high-performance proton conductor (LRH-H2PO4-). By utilizing this ion-exchange method, the proton conductivity of LRHs can be significantly enhanced from a low level to an ultrahigh level (>10-2 S·cm-1), while maintaining excellent long-term stability. Moreover, through methodically manipulating the guest ions and molecules housed within the interlayers of LRHs, a comprehensive explanation has been presented regarding the proficient mechanism of proton conduction in LRH-H2PO4-. As a result, this investigation presents a feasible and available approach for advancing proton conductor.

Frustrated Lewis Pair-Type Reactivity of Intermolecular Rare-Earth Aryloxide and N-Heterocyclic Carbene/Olefin Combinations.

This work reports the cooperative reactivity of rare-earth aryloxide complexes with N-heterocyclic carbene (NHC) or N-heterocyclic olefin (NHO), showcasing their synergistic effect on the activation of H2 and diverse organic substrates. Reactions of RE(OAr)3 (RE=La, Sm, and Y; Ar=2,6-tBu2-C6H3) with unsaturated NHC ItBu (:C[N(R)CH]2, R=tBu) isolated abnormally bound RE metal NHC complexes RE/aNHC. In contrast, no metal-NHO adducts were formed when RE(OAr)3 were treated with NHO (R2C=C[N(R)C(R)]2, R=CH3). Both RE/aNHC and RE/NHO Lewis pairs enabled cooperative H2 activation. Furthermore, RE(OAr)3 were found to catalyze the hydrogenation of the exocyclic C=C double bond of NHO under mild conditions. Moreover, treatment of the La/aNHC complex with benzaldehyde produced a La/C4 1,2-addition product. The La/NHO Lewis pair could react with (trimethylsilyl)diazomethane and α, ß-conjugated imine, affording an isocyanotrimethylsilyl lanthanum amide complex and a La/C 1,4-addition product, respectively.

Development and Characterization of Bio-Based Formaldehyde Free Sucrose-Based Adhesive for Fabrication of Plywood.

In order to solve the problem of excessive consumption of petrochemical resources and the harm of free formaldehyde release to human health, biomass raw materials, such as sucrose (S) and ammonium dihydrogen phosphate (ADP) can be chemically condensed in a simple route under acidic conditions to produce a formaldehyde free wood adhesive (S-ADP), characterized by good storage stability and water resistance, and higher wet shear strength with respect to petroleum based phenolic resin adhesive. The dry and boiling shear strength of the plywood based on S-ADP adhesive are as high as 1.05 MPa and 1.19 MPa, respectively. Moreover, is Modulus of Elasticity (MOE) is as high as 4910 MPa. Interestingly, the plywood based on the developed S-ADP adhesive exhibited good flame retardancy. After burning for 90 s, its shape remains unchanged. Meanwhile, it can be concluded from thermomechanical analysis (TMA) and thermogravimetric analysis (TGA) that the S-ADP acquired excellent modulus of elasticity (MOE) and good thermal stability. It is thus thought promisingly that the use of S-ADP adhesive as a substitute for PF resin adhesive seems feasible in the near future.

Effects of type of substrate and dilution rate on fermentation in serial rumen mixed cultures.

Forages and concentrates have consistently distinct patterns of fermentation in the rumen, with forages producing more methane (CH4) per unit of digested organic matter (OM) and higher acetate to propionate ratio than concentrates. A mechanism based on the Monod function of microbial growth has been proposed to explain the distinct fermentation pattern of forages and concentrates, where greater dilution rates and lower pH associated with concentrate feeding increase dihydrogen (H2) concentration through increasing methanogens growth rate and decreasing methanogens theoretically maximal growth rate, respectively. Increased H2 concentration would in turn inhibit H2 production, decreasing methanogenesis, inhibit H2-producing pathways such as acetate production via pyruvate oxidative decarboxylation, and stimulate H2-incorporating pathways such as propionate production. We examined the hypothesis that equalizing dilution rates in serial rumen cultures would result in a similar fermentation profile of a high forage and a high concentrate substrate. Under a 2 × 3 factorial arrangement, a high forage and a high concentrate substrate were incubated at dilution rates of 0.14, 0.28, or 0.56 h-1 in eight transfers of serial rumen cultures. Each treatment was replicated thrice, and the experiment repeated in two different months. The high concentrate substrate accumulated considerably more H2 and formate and produced less CH4 than the high forage substrate. Methanogens were nearly washed-out with high concentrate and increased their initial numbers with high forage. The effect of dilution rate was minor in comparison to the effect of the type of substrate. Accumulation of H2 and formate with high concentrate inhibited acetate and probably H2 and formate production, and stimulated butyrate, rather than propionate, as an electron sink alternative to CH4. All three dilution rates are considered high and selected for rapidly growing bacteria. The archaeal community composition varied widely and inconsistently. Lactate accumulated with both substrates, likely favored by microbial growth kinetics rather than by H2 accumulation thermodynamically stimulating electron disposal from NADH into pyruvate reduction. In this study, the type of substrate had a major effect on rumen fermentation largely independent of dilution rate and pH.

Molecular Dihydrogen Activation by (C5Me5)M/N (M=Rh, Ir) Transition Metal Frustrated Lewis Pairs: Reversible Proton Migration to, and Proton Abstraction from, the C5Me5 Ligand.

The masked transition-metal frustrated Lewis pairs [Cp*M(κ3N,N',N''-L)][SbF6] (Cp*=η5-C5Me5; M=Ir, 1, Rh, 2; HL=pyridinyl-amidine ligand) reversibly activate H2 under mild conditions rendering the hydrido derivatives [Cp*MH(κ2N,N'-HL)][SbF6] observed as a mixture of the E and Z isomers at the amidine C=N bond (M=Ir, 3Z, 3E; M=Rh, 4Z, 4E). DFT calculations indicate that the formation of the E isomers follows a Grotthuss type mechanism in the presence of water. A mixture of Rh(I) isomers of formula [(Cp*H)Rh(κ2N,N'-HL)][SbF6] (5 a-d) is obtained by reductive elimination of Cp*H from 4. The formation of 5 a-d was elucidated by means of DFT calculations. Finally, when 2 reacts with D2, the Cp* and Cp*H ligands of the resulting rhodium complexes 4 and 5, respectively, are deuterated as a result of a reversible hydrogen abstraction from the Cp* ligand and D2 activation at rhodium.

Metal-Free B-B Dehydrocoupling Reaction of a Simple Borane Adduct: Convenient Access to a Nucleophilic Diborane(4).

The selective formation of homonuclear bonds is of key importance in synthetic chemistry. Especially, dehydrocoupling reactions are attractive as ecologically and economically friendly alternatives to established reductive bond forming reactions, since they do not require the use of stoichiometric amounts of a reducing reagent and produce only valuable dihydrogen as by-product. Here, we report on a metal-free B-B dehydrocoupling reaction that starts directly from a simple, easily accessible BH3 adduct, providing convenient access to a new nucleophilic dihydridodiborane in excellent yield. The dihydridodiborane in turn activates dihydrogen, allowing to obtain quantitatively the dideuteridodiborane from the dihydridodiborane by D2 activation. On the basis of detailed quantum-chemical calculations, the mechanism of this unprecedented reaction is elucidated. Some key points that are essential for metal-free dehydrocoupling are disclosed, paving the way for their systematic evaluation and application.

Shear bond strength of orthodontic brackets bonded to high-translucent dental zirconia with different surface treatments: An in vitro study.

PURPOSE: The objective of this study was to compare the shear bond strengths of orthodontic brackets bonded to translucent dental zirconia samples which are anatomically accurate and treated with various surface treatments. METHODS: This in vitro study included 156 samples from 3 brands of high-translucent zirconia split into a control group and 4 surface treatment groups: 9.6% hydrofluoric acid etching, 50-micron aluminium oxide particle air abrasion, and 30-micron tribochemical silica coating (TBS) particle air abrasion with and without silane application. After surface treatment, all groups were primed with a 10-MDP primer and bonded to metal orthodontic brackets. Shear bond strength (SBS) was tested and results were compared between all groups. Data analysis consisted of a balanced two-factor factorial ANOVA, a Shapiro-Wilks test, and a non-parametric permutation test. The significance level was set at 0.05. RESULTS: Among all surface treatments, aluminium oxide particle abrasion produced significantly higher SBS (P≤0.002). Lava™ Plus zirconia samples had significantly higher SBS than Cercon® samples (P<0.0001). TBS surface treatment produced significantly higher SBS on Lava™ Plus samples than it did on the other zirconia brands (P=0.032). CONCLUSIONS: This study indicated that mechanical abrasion using aluminium oxide in combination with a 10-MDP primer creates a higher SBS to high-translucent zirconia than the bond created by tribochemical silica coating. Also, there was no significant difference in ARI regardless of zirconia brand or surface preparation.

Facile preparation of high-performance plywood adhesive from gelatinized corn starch crosslinked with ammonium dihydrogen phosphate.

A flame retardant high-performance gelatinized starch (GS)-ammonium dihydrogen phosphate (ADP) wood adhesive, named GS-ADP adhesive was prepared by condensation of GS and ADP under acidic condition. The preparation process of GS-ADP adhesive is very simple by mixing and stirring GS and ADP evenly at room temperature. The results revealed that the GS-ADP adhesive has good storage stability and water resistance, and its wet shear strength is much higher than that of phenolic resin (PF) adhesive. Markedly, the cone calorimeter test results show that G-ADP adhesive has good flame retardancy, and the plywood based on GS-ADP adhesive has good flame retardancy. Meanwhile, it can be seen from dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) that GS-ADP has excellent modulus of elasticity (MOE), high glass transition temperature (Tg) and good thermal stability. The findings suggest that GS-ADP could be a viable substitute for PF resin in structural wood fabrication.