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1.
Chem Sci ; 14(48): 14166-14175, 2023 Dec 13.
Article in English | MEDLINE | ID: mdl-38098721

ABSTRACT

Substrate-support interactions play an important role in the catalytic hydrogenation of phenolic compounds by ceria-supported palladium (Pd/CeO2). Here, we combine surface contrast solution NMR methods and reaction kinetic assays to investigate the role of substrate-support interactions in phenol (PhOH) hydrogenation catalyzed by titania-supported palladium (Pd/TiO2). We show that PhOH adsorbs on the catalyst via a weak hydrogen-bonding interaction between the -OH group of the substrate and one oxygen atom on the support. Interestingly, we observe that the addition of 20 mM inorganic phosphate results in a ∼2-fold destabilization of the PhOH-support interaction and a corresponding ∼2-fold inhibition of the catalytic reaction, suggesting an active role of the PhOH-TiO2 hydrogen bond in catalysis. A comparison of the data measured here with the results previously reported for a Pd/CeO2 catalyst indicates that the efficiency of the Pd-supported catalysts is correlated to the amount of PhOH hydrogen bonded to the metal oxide support. Since CeO2 and TiO2 have similar ability to uptake activated hydrogen from a noble metal site, these data suggest that hydrogen spillover is the main mechanism by which Pd-activated hydrogens are shuttled to the PhOH adsorbed on the surface of the support. Consistent with this hypothesis, Pd supported on a non-reducible metal oxide (silica) displays negligible hydrogenation activity. Therefore, we conclude that basic and reducible metal oxides are active supports for the efficient hydrogenation of phenolic compounds due to their ability to hydrogen bond to the substrate and mediate the addition of the activated hydrogens to the adsorbed aromatic ring.

2.
Langmuir ; 38(49): 15361-15371, 2022 Dec 13.
Article in English | MEDLINE | ID: mdl-36459485

ABSTRACT

We experimentally investigate the evaporation characteristics of a sessile ethanol droplet containing Al2O3 and Cu nanoparticles of sizes 25 and 75 nm on a heated substrate using shadowgraphy and infrared imaging techniques. Our results demonstrate that the droplet contact line dynamics resulting from the presence of various nanoparticles plays a dominant role in the evaporation process. This is in contrast to the widely held assumption that the enhanced evaporation rate observed in sessile nanofluid droplets is due to the higher thermal conductivity of the added nanoparticles. We observe that even though the thermal conductivity of Al2O3 is an order of magnitude lower than that of Cu, droplets containing 25-nm-sized Al2O3 exhibit pinned contact line dynamics and evaporate much more rapidly than droplets containing Cu nanoparticles of both sizes and 75 nm Al2O3 nanoparticles that exhibit stick-slip behavior. We also found that the droplets with different nanoparticles display distinct thermal patterns due to the difference in contact line behavior, which alters the heat transfer inside the droplets. We establish this counter-intuitive observation by analyzing the temporal variations of the perimeter, free surface area, and deposition patterns on the substrate.

3.
Langmuir ; 38(15): 4722-4735, 2022 Apr 19.
Article in English | MEDLINE | ID: mdl-35377666

ABSTRACT

We experimentally investigate the evaporation of water-ethanol binary sessile droplets loaded with alumina nanoparticles on a critically inclined heated surface and compare it to the no-loading condition. In contrast to a droplet of pure fluids, several distinct and interesting phenomena observed in a binary-nanofluid droplet on a critically inclined substrate are reported for the first time. The critical angle at which a droplet begins to slide increases for ethanol-rich binary droplets up to 0.6 wt % nanoparticle loading. The critical angle for binary droplets also increases as the substrate temperature increases and as the ethanol concentration decreases for modest loading conditions. It is observed that the advancing side of a binary droplet is pinned in both the loading and no-loading scenarios, whereas the receding side is pinned in the loading case but shrinks continuously in the no-loading case. The pinning effect caused by nanoparticles results in a larger perimeter and surface area for the nanoparticle-laden droplets, enhancing the evaporation rates and significantly decreasing the lifetime of the nanoparticle-containing droplets compared to the no-loading case. Increasing the ethanol percentage in the binary droplet placed on an inclined substrate produces complex thermosolutal Marangoni convection, which becomes more affluent in the case of nanoparticles loading than the no-loading condition. The radial symmetry of the circular coffee ring structure observed on a horizontal surface is shattered in the inclined case because the droplet elongates and preferentially deposits toward the advancing side of the triple line due to the action of the body force. Despite its fundamental nature, the present study can contribute to understanding many practical applications.

4.
Phys Fluids (1994) ; 33(8): 081302, 2021 Aug.
Article in English | MEDLINE | ID: mdl-34471333

ABSTRACT

The World Health Organization has declared COVID-19 a global pandemic. Several countries have experienced repeated periods of major spreading over the last two years. Many people have lost their lives, employment, and the socioeconomic situation has been severely impacted. Thus, it is considered to be one of the major health and economic disasters in modern history. Over the last two years, several researchers have contributed significantly to the study of droplet formation, transmission, and lifetime in the context of understanding the spread of such respiratory infections from a fluid dynamics perspective. The current review emphasizes the numerous ways in which fluid dynamics aids in the comprehension of these aspects. The biology of the virus, as well as other statistical studies to forecast the pandemic, is significant, but they are not included in this review.

5.
Langmuir ; 37(20): 6311-6321, 2021 May 25.
Article in English | MEDLINE | ID: mdl-33983033

ABSTRACT

We investigate the evaporation dynamics of a sessile droplet of ethanol-water binary mixtures of different compositions laden with alumina nanoparticles and compare with the no-loading condition at different substrate temperatures. Shadowgraphy and infrared imaging methods are used, and the experimental images are postprocessed using a machine learning technique. We found that the loading and no-loading cases display distinct wetting and contact angle dynamics. Although the wetting diameter of a droplet decreases monotonically in the absence of loading, the droplet with 0.6 wt % nanoparticle loading remains pinned for the majority of its lifetime. The temporal variation of the normalized droplet volume in the no-loading case has two distinct slopes, with ethanol and water phases dominating the early and late stages of evaporation, respectively. The normalized droplet volume with 0.6 wt % loading displays a nearly linear behavior because of the increase in the heat transfer rate. Our results from infrared imaging reveal that a nanofluid droplet displays far richer thermal patterns than a droplet without nanoparticle loading. In nanoparticle-laden droplets, the pinning effect, as well as the resulting thermo-capillary and thermo-solutal convection, causes more intense internal mixing and a faster evaporation rate. Finally, a theoretical model is also developed that satisfactorily predicts the evaporation dynamics of binary nanofluid droplets.

6.
F1000Res ; 10: 508, 2021.
Article in English | MEDLINE | ID: mdl-35265321

ABSTRACT

Background: Osteoarthritis (OA) and cardiovascular disease (CVD) are prevalent in India. However, there is dearth of literature among Indians studying the relationship between the two. This study was carried out to assess various cardiovascular (CV) risk factors in patients with knee OA with an objective to investigate their association, screening and management.  Methods: In total, 225 patients were included in this cross-sectional study. Participants were diagnosed with knee OA on the basis of the Kellgren and Lawrence (K-L) classification of their radiograph. Participants were also assessed for CV risk factors; age, body mass index, systolic blood pressure, diabetes mellitus, total cholesterol, high-density lipoprotein, smoking. Joint British Society QRisk3 calculator (JBS3) a comprehensive risk score calculator as well as a screening tool, which produces three more variables, namely 10-years risk of developing CVD, physiological heart age and life expectancy, was used. Chi Square, Fishers exact test and one-way ANOVA tests were used to compare the categorical and quantitative variables, respectively.. Multiple regression analysis was done to adjust the multiple con-founders and determine their significance. Results: Patients with severe knee OA had a statistically significantly higher prevalence of CV risk factors (p<0.05). Grade 4 knee OA patients were found to have a mean JBS3 risk of 38%, heart age of 82 years and life expectancy of 77 years as compared to grade 2 patients who had a mean JBS3 risk of 11%, heart age of 63 years and life expectancy of 82 years.  Conclusions: Our study concluded that there is a strong relation between knee OA and CVD, with CV risk score being positively correlated to the severity of OA.


Subject(s)
Cardiovascular Diseases , Osteoarthritis, Knee , Aged, 80 and over , Cardiovascular Diseases/complications , Cardiovascular Diseases/epidemiology , Child , Cross-Sectional Studies , Heart Disease Risk Factors , Humans , Middle Aged , Osteoarthritis, Knee/complications , Osteoarthritis, Knee/epidemiology , Risk Factors
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