Ligand Design for Catalytic Dehydrogenation of Formic Acid to Produce High-pressure Hydrogen Gas under Base-free Conditions.

A series of Cp*Ir (Cp* = pentamethylcyclopentadienyl anion) complexes with amino-functionalized ligands were developed for the production of high-pressure H2 via catalytic dehydrogenation of formic acid (DFA) in water under base-free conditions. The Ir complexes with 2,2'-bipyridine (bpy) ligands bearing amino or alkylamino groups at the para positions exhibited high activity and stability for DFA compared with complexes containing bpy ligands bearing para-hydroxyl groups. In addition, para-amino groups afforded superior catalytic stability under high-pressure conditions compared with ortho-amino groups. By exploiting these amino-functionalized Cp*Ir complexes, it was possible to continuously produce high-pressure CO-free H2 via selective DFA in water upon the addition of concentrated FA (>99.5 wt %) to the base-free solution. Systematic investigation of the ligand effects on DFA revealed that the presence of alkylamino groups on the bpy ligand enhanced the catalytic activity (initial turnover frequency, TOF), although the stability decreased with increasing alkyl chain length on the amino groups. According to a Hammett plot, the increased catalytic activity of the Ir complexes after the introduction of amino-functionalized ligands may be attributable to the electron-donating effect of para-amino groups on the bpy ligand. Based on the experimental results, a reaction mechanism is proposed that involves a hydride intermediate whose stability is affected by the position of the amino groups on the bpy ligand, as confirmed through NMR studies.

Evaluation of atrial natriuretic peptide and cardiac troponin I concentrations for assessment of disease severity in dogs with naturally occurring mitral valve disease.

OBJECTIVE: To evaluate and compare the clinical usefulness of plasma atrial natriuretic peptide (ANP) and cardiac troponin-I (cTnI) concentrations for assessment of disease severity in dogs with naturally occurring mitral valve disease (MVD). ANIMALS: 316 dogs with MVD and 40 healthy control dogs. PROCEDURES: Each dog underwent a physical examination and echocardiographic and thoracic radiographic assessments. Blood samples were obtained and processed for measurement of plasma ANP and cTnI concentrations. Dogs with MVD were categorized into 3 groups (stages B1 [no clinical signs or evidence of cardiac enlargement], B2 [no clinical signs with evidence of cardiac enlargement], and C [history of congestive heart failure and pulmonary edema]) on the basis of American College of Veterinary Internal Medicine guidelines. Receiver operating characteristic curve analysis was used to evaluate the accuracy of plasma ANP and cTnI concentrations for assessment of MVD severity. RESULTS: Plasma ANP and cTnI concentrations increased as disease severity increased. Median plasma ANP concentrations for all 3 MVD groups and median plasma cTnI concentrations for the stage B2 and C groups were significantly greater than the corresponding concentrations for the control group. Plasma ANP concentration, but not cTnI concentration, appeared to be useful for detection of dogs with subclinical (stages B1 and B2) MVD, whereas both concentrations appeared useful for detection of dogs with stage C MVD. CONCLUSIONS AND CLINICAL RELEVANCE: Results indicated that plasma ANP and cTnI concentrations should not be used independently to diagnose MVD but can be used to assess MVD severity and supplement echocardiographic findings.

Ligand Effect on the Stability of Water-Soluble Iridium Catalysts for High-Pressure Hydrogen Gas Production by Dehydrogenation of Formic Acid.

Aiming to develop a highly effective and durable catalyst for high-pressure H2 production from dehydrogenation of formic acid (DFA), the ligand effect on the catalytic activity and stability of Cp*Ir (Cp*:pentamethylcyclopentadienyl anion) complexes were investigated using 5 different kinds of N,N'-bidentate ligands (bipyridine, biimidazoline, pyridyl-imidazoline, pyridyl-pyrazole and picolinamide). The Ir complex with biimidazoline ligand exhibited the highest catalytic activity, but deactivation occurred readily at high pressure. The pyridine moiety in the ligand can enhance the stability of Ir complex catalysts for the high-pressure reaction. The Ir complex catalyst containing pyridyl-imidazoline ligand showed the high activity and best stability under the high-pressure conditions.

Epidemiological study of indirect blood pressure measured using oscillometry in clinically healthy cats at initial evaluation.

We investigated the clinical characteristics of healthy cats in accordance with the target organ damage (TOD) risk category, on the basis of systolic blood pressure (SBP). This prospective multi-center study included 137 healthy cats. Indirect blood pressure was measured using an oscillometric technique. The median SBP in all cats was 147 mmHg (interquartile range: 134-158). On the basis of the TOD risk category, 57.7, 19.7, 21.9, and 0.7% of the cats were classified into categories I-IV, respectively. Age, sex, and body weight did not affect the SBP. This study provides basic information on the distribution of TOD risk categories in clinically healthy cats.

Diagnostic utility of cardiac troponin I in cats with hypertrophic cardiomyopathy.

BACKGROUND: Cardiac troponin I (cTnI) is useful for assessing hypertrophic cardiomyopathy (HCM) in cats. OBJECTIVE: To measure plasma cTnI concentrations in healthy cats and evaluate the clinical utility of cTnI in determining the severity of HCM. ANIMALS: Clinically healthy cats (n = 88) and cats with HCM (n = 93). METHODS: Multicenter prospective study. Cats with HCM, including hypertrophic obstructive cardiomyopathy at various stages, were diagnosed using echocardiography. Plasma cTnI concentrations were analyzed by a commercial laboratory. Receiver-operating characteristic curve analysis was used to evaluate the accuracy of plasma cTnI concentrations to detect HCM. RESULTS: The median cTnI concentration was 0.027 ng/mL (interquartile range, 0.012-0.048 ng/mL) in healthy cats. Concentrations were significantly higher in diseased cats than in healthy controls, and concentrations were significantly higher in cats with heart failure than in asymptomatic cats. A plasma cTnI concentration of 0.163 ng/mL had a sensitivity of 62.0% and specificity of 100% when used to distinguish normal cats from asymptomatic HCM cats without left atrial dilatation. A cutoff of 0.234 ng/mL had high sensitivity (95.0%) and specificity (77.8%) for assessing heart failure. The areas under the receiver-operating characteristic curves were 0.85 and 0.93, respectively. CONCLUSIONS AND CLINICAL IMPORTANCE: Increased cTnI concentrations reflect the severity of HCM. If other causes of cardiac injury are ruled out, plasma cTnI concentration may be useful for predicting the severity of HCM in cats.

Relationship between indirect blood pressure and various stages of chronic kidney disease in cats.

Chronic kidney disease (CKD) is a common cause of secondary systemic hypertension in cats. We investigated the relationship between indirect blood pressure and the prevalence of systemic hypertension in various CKD stages in cats. Client-owned cats (24 control cats and 77 cats with CKD) were included. Biochemical examinations of plasma were conducted by a commercial laboratory. Diseased cats were divided into two groups based on the International Renal Interest Society (IRIS) guidelines (II and III-IV). Indirect blood pressure was measured using an oscillometric technique. Severe hypertension was diagnosed if systolic blood pressure (SBP) was ≥180 mmHg. Indirect blood pressures were significantly higher in IRIS stage III-IV than in the control cats. Of 77 cats with CKD, 25 (32.5%) had severe hypertension. The frequency of severe hypertension increased with an increase in IRIS stage; 0% in the controls, 27.6% in the IRIS stage II, and 47.4% in the IRIS stage III-IV, respectively. The indirect SBP was weakly correlated with urea nitrogen (r=0.27) and creatinine (r=0.23) concentrations in plasma. Binary logistic regression analysis showed that if plasma creatinine concentration is >3.7 mg/dl, cats with CKD had an increased risk for developing severe hypertension (P<0.001). Our results suggest that indirect blood pressure was correlated with the severity of CKD, and the prevalence of severe hypertension increased in cats with severe CKD. The risk of severe hypertension may be high in cats with severe CKD.

Effect of the ortho-Hydroxyl Groups on a Bipyridine Ligand of Iridium Complexes for the High-Pressure Gas Generation from the Catalytic Decomposition of Formic Acid.

The hydroxyl groups of a 2,2'-bipyridine (bpy) ligand near the metal center activated the catalytic performance of the Ir complex for the dehydrogenation of formic acid at high pressure. The position of the hydroxyl groups on the ligand affected the catalytic durability for the high-pressure H2 generation through the decomposition of formic acid. The Ir complex with a bipyridine ligand functionalized with para-hydroxyl groups shows a good durability with a constant catalytic activity during the reaction even under high-pressure conditions, whereas deactivation was observed for an Ir complex with a bipyridine ligand with ortho-hydroxyl groups (2). In the presence of high-pressure H2 , complex 2 decomposed into the ligand and an Ir trihydride complex through the isomerization of the bpy ligand. This work provides the development of a durable catalyst for the high-pressure H2 production from formic acid.

Kinetic Studies on Formic Acid Dehydrogenation Catalyzed by an Iridium Complex towards Insights into the Catalytic Mechanism of High-Pressure Hydrogen Gas Production.

Kinetic studies on the catalytic reaction mechanism of formic acid (FA) dehydrogenation were performed in the presence of a water-soluble iridium complex bearing a 4,4'-dihydroxy-2,2'-bipyridine ligand. Determination of kinetic isotope effects revealed that a shift of the rate-limiting step at low and high concentrations of FA can be caused by the pH dependence of the reaction steps. The proposed equation for the reaction rate corresponds well with the experimental results concerning the shift phenomena. Towards industrial application in future hydrogen fueling stations, this will able the design of a dehydrogenation system catalyzed by the iridium complex.

Dehydrogenation of Formic Acid Catalyzed by a Ruthenium Complex with an N,N'-Diimine Ligand.

We report a ruthenium complex containing an N,N'-diimine ligand for the selective decomposition of formic acid to H2 and CO2 in water in the absence of any organic additives. A turnover frequency of 12 000 h-1 and a turnover number of 350 000 at 90 °C were achieved in the HCOOH/HCOONa aqueous solution. Efficient production of high-pressure H2 and CO2 (24.0 MPa (3480 psi)) was achieved through the decomposition of formic acid with no formation of CO. Mechanistic studies by NMR and DFT calculations indicate that there may be two competitive pathways for the key hydride transfer rate-determining step in the catalytic process.

Carbon Dioxide to Methanol: The Aqueous Catalytic Way at Room Temperature.

Carbon dioxide may constitute a source of chemicals and fuels if efficient and renewable processes are developed that directly utilize it as feedstock. Two of its reduction products are formic acid and methanol, which have also been proposed as liquid organic chemical carriers in sustainable hydrogen storage. Here we report that both the hydrogenation of carbon dioxide to formic acid and the disproportionation of formic acid into methanol can be realized at ambient temperature and in aqueous, acidic solution, with an iridium catalyst. The formic acid yield is maximized in water without additives, while acidification results in complete (98 %) and selective (96 %) formic acid disproportionation into methanol. These promising features in combination with the low reaction temperatures and the absence of organic solvents and additives are relevant for a sustainable hydrogen/methanol economy.

Development of an Iridium-Based Catalyst for High-Pressure Evolution of Hydrogen from Formic Acid.

A highly efficient and recyclable Ir catalyst bearing a 4,7-dihydroxy-1,10-phenanthroline ligand was developed for the evolution of high-pressure H2 gas (>100 MPa), and a large amount of atmospheric pressure H2 gas (>120 L), over a long term (3.5 months). The reaction proceeds through the dehydrogenation of highly concentrated aqueous formic acid (FA, 40 vol %, 10 mol L-1 ) at 80 °C using 1 µmol of catalyst, and a turnover number (TON) of 5 000 000 was calculated. The Ir catalyst precipitated after the reaction owing to its pH-dependent solubility in water, and 94 mol % was recovered by filtration. Thus, it can be treated and recycled like a heterogeneous catalyst. The catalyst was successfully recycled over 10 times for highpressure FA dehydrogenation at 22 MPa without any treatment or purification.

Dissolution of mechanically milled chitin in high temperature water.

Chitin is high in crystallinity in its natural form and does not dissolve into high temperature water (HTW), which often leads to decomposition reactions such as hydrolysis, deacetylation and dehydration when hydrothermally processed. In this work, we investigated the reactions of mechanically milled chitin in HTW. Mechanical milling pretreatment combined with HTW treatment improved the liquefaction of chitin giving a maximum water soluble fraction of 80%, where the untreated chitin was 55%. The reaction mechanism of the milled and raw chitin in HTW was shown to be different. For milled chitin, the dissolution of chitin occurred during the heating period to supercritical water conditions (400°C) at short reaction times (1 min). Extended reaction time (10 min) led to decomposition products and aromatic char formation. For raw chitin, the dissolution of chitin in HTW did not occur, due to its high crystallinity, so that liquefaction proceeded via decomposition reactions.

Dissolution and recovery of cellulose from 1-butyl-3-methylimidazolium chloride in presence of water.

The dissolution and recovery of microcrystalline cellulose from 1-butyl-3-methylimidazolium chloride, [bmIm][Cl], were studied. At 90 °C and 5 h dissolution time, the regenerated cellulose could be recovered above 80 wt% with a less than 10% decrease in the value of the viscosity-average degree of polymerization, DP(v), regardless of water content. Recovery ratio and DP(v) of regenerated cellulose at 120 °C decreased with time regardless of water content. The regenerated cellulose after dissolution at 120 °C for 10 h regardless of water content had cellulose II structure. Regenerated cellulose at short dissolution times or low temperature had high amorphous content. Both [bmIm][Cl] and [bmIm][Cl] with water act as a non-derivatizing solvent for microcrystalline cellulose at 90 °C, and as a derivatizing solvent at 120 °C. The main effect of added water on the dissolution of cellulose at high temperature was the promotion of cello-oligosaccharide and levoglucosan formation.