Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

A competitive optimization approach for data clustering and orthogonal non-negative matrix factorization

4OR - Partitioning a given data-set into subsets based on similarity among the data is called clustering. Clustering is a major task in data mining and machine learning having many applications...     

Bejan flow visualization of free convection in a Jeffrey fluid from a semi-infinite vertical cylinder

Journal of Thermal Analysis and Calorimetry - This article studies the pattern of heat lines in free convection non-Newtonian flow from a semi-infinite vertical cylinder via Bejan’s heat...     

Direct Introduction of an Alkylsulfonamido Group on C-sites of Isomeric Dicarba-closo-dodecaboranes: The Influence of Stereochemistry on Inhibitory Activity against the Cancer-Associated Carbonic Anhydrase IX Isoenzyme

Carbonic anhydrase IX (CA IX), a tumor-associated metalloenzyme, represents a validated target for cancer therapy and diagnostics. Herein, we report the inhibition properties of isomeric families of sulfonamidopropyl-dicarba-closo-dodecaboranes group(s) prepared using a new direct five-step synthesis from the corresponding parent cages. The protocol offers a reliable solution for synthesis of singly and doubly substituted dicarba-closo-dodecaboranes with a different geometric position of carbon atoms. The closo-compounds from the ortho- and meta-series were then degraded to corresponding 11-vertex dicarba-nido-undecaborate(1−) anions. All compounds show in vitro enzymatic activity against CA IX in the low nanomolar or subnanomolar range. This is accompanied by clear isomer dependence of the inhibition constant (K_i) and selectivity towards CA IX. Decreasing trends in K_i and selectivity index (S_I) values are observed with increasing separation of the cage carbon atoms. Interactions of compounds with the active sites of CA IX were explored with X-ray crystallography, and eight high-resolution crystal structures uncovered the structural basis of inhibition potency and selectivity.     

Aminomethyl Transfer (Mannich) Reactions Between an O-Triethylsilylated Hemiaminal and Anilines,RnC6H5−nNH2 Leading to New Diamines,Triamines, Imines,or 1,3,5-Triazines Dependent upon Substituent R

The reactions of the Mannich reagent Et₃SiOCH₂NMe₂ ( 1 ) with a variety of anilines (mono-substituted RC₆H₄NH₂, R=H, 4-CN, 4-NO₂, 4-Ph, 4-Me, 4-MeO, 4-Me₂N; di-substituted R₂C₆H₃NH₂, R₂=3,5-(CH₃)₂, 3,5-(CF₃)₂; tri-substituted R₃C₆H₂NH₂, R₃=3,5-Me₂-4-Br and a “super bulky” aniline (Ar*NH₂) [Ar*=2,6-bis(diphenylmethyl)-4-tert-butylphenyl]) led to the formation of a range of products dependent upon the substituent. With electron-withdrawing substituents, previously unknown diamines, RC₆H₄NH(CH₂NMe₂) [R=CN ( 2 a ), NO₂ ( 2 b )] and R₂C₆H₃NH(CH₂NMe₂) [R₂=3,5-(CF₃)₂ ( 2 c) ] were formed. Further reaction of 2 a , b , c with 1 yielded the corresponding triamines RC₆H₄N(CH₂NMe₂)₂ (R=CN ( 3 a ), NO₂ ( 3 b ) and R₂C₆H₃N(CH₂NMe₂)₂, R₂=3,5-(CF₃)₂ ( 3 c ). The new polyamines were characterized by NMR spectroscopy, and for 2 a , 2 c _, and 3 c , by single crystal XRD. In the case of electron-donating groups, R=4-OMe, 4-NMe₂, 4-Me, 3,5-Me₂, 3,5-Me₂-4-Br, and for R=4-Ph, the reactions with 1 immediately led to the formation of the related 1,3,5-triazines, R=4-MeO ( 5 a ), 4-Me₂N ( 5 b ), 4-Me ( 5 c ), 3,5-Me₂ ( 5 d ), 3,5-Me₂-4-Br ( 5 e ), 4-Ph ( 5 f ), 4-Cl ( 5 g ). The “super bulky” aniline rapidly produced a single product, namely the corresponding imine Ar*N=CH₂ ( 4 ) which was also characterized by single crystal XRD. Imine 4 is both thermally and oxidatively stable. All reactions are very fast, thus based upon the presence of Si we are tempted to denote the reactions of 1 as examples of “Silick” chemistry.     

The Study of the Behaviors of Zinc and Strontium in Caries-Affected Teeth by Laser-Induced Breakdown Spectroscopy(LIBS) Technique

We report on the application of Laser Induced Breakdown Spectroscopy(LIBS)technique to the study of Ca,P,Zn and Sr evolutions for adult caries-affected teeth using nanosecond laser pulses.The aim of this work is to better understand the behaviors of Zn and Sr as trace-elements in the caries eruption with respect to the behaviors of one of the main compounds of the hydroxyapatite crystal which is the calcium.The study was focused on the investigation of these elements’evolutions from three parts of the enamel surfaces of twenty two adult caries-affected teeth;the healthy part,the dental plaque part and the caries-affected part.The decrease rates of Zn,Sr and P was,also,compared to the Ca one.Comparison concerned normalized emission line intensities.For every species,normalization was done relatively to the emission line intensities of the healthy part.Results showed that abundances of these elements decrease similarly from the healthy parts to the affected-caries parts.The higher decrease rate was noticed for the calcium.The evolutions of Zn and Sr for the three parts of the teeth surfaces cannot inform about the substitution of the calcium by these trace-elements,however the comparison of their decrease rates to the calcium one can be considered as a valuable index of this substitution.     

Validated ecofriendly chromatographic method for quantitative determination of anti‐migraine quaternary mixture

A novel ecofriendly, cost and time saving high‐performance thin‐layer chromatographic method was developed and validated for simultaneous determination of metoclopramide, ergotamine, caffeine, and paracetamol in bulk and pharmaceutical formulation. The separation was carried out on silica gel plates, using ethyl acetate:ethanol:ammonia (9:1:0.1, v/v/v) as a developing system. Ultraviolet detection was carried out at 272 nm. The resulting retention times were 0.15, 0.36, 0.49, and 0.74 min for metoclopramide, ergotamine, caffeine, and paracetamol, respectively. The greenness profile assessment was achieved to the proposed method to evaluate its greenness characters to the environment with acceptable results. Validation parameters were checked according to International Conference of Harmonization guidelines to achieve the international requirements for quality control analysis of the proposed drugs.     

Structure activity relationship of bergenin,p-hydroxybenzoyl bergenin, 11-O-galloylbergenin as potent antioxidant and urease inhibitor isolated from Bergenia ligulata

Ethanol extract of the aerial parts of Bergenia ligulata was subjected to solvent–solvent separation followed by various chromatographic techniques that lead to isolation of bergenine (1), p-hydroxybenzoyl bergenin (2), 11-O-galloylbergenin (3) and methyl gallate (4) as major constituents. Ethyl acetate fraction showed a dose-dependent urease inhibitory pattern with IC₅₀ value of 54μg/mL. Structures of compounds 1 and 3 were established by XRD and 2, 4 by NMR. All these compounds were subjected to DPPH scavenging activity, reducing power assay and urease inhibitory activity. The EC₅₀ 7.45 ± 0.2 μg/mL and 5.39 ± 0.28 μg/mL values in terms of antioxidant and reducing power, respectively, were less for 3. Compounds 1–3 showed moderate to significant urease inhibitory potential with IC₅₀ 57.1 ± 0.7, IC₅₀ 48.4 ± 0.3 and 38.6 ± 1.5. Antioxidant activities and urease inhibitory potential were investigated and compound 3 was found to be the most active.     

One‐dimensional CuII coordination polymers containing C2h‐symmetric 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate linkers

Two new one‐dimensional Cu^II coordination polymers (CPs) containing the C_2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ⁴O,O′:O′′:O′′′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂]·H₂O}_n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ²O³:O^3′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂(H₂O)]·H₂O}_n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the Cu^II ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II).