Adsorbent-adsorbate interactions in the adsorption of organic and?inorganic species on ozonized activated carbons: a?short?review

This objective of this work was to summarize the main results obtained in previous papers related to the adsorbent-adsorbate interactions involved in the adsorption of naphthalenesulphonic acids and heavy metals (Cd(II) or Hg(II)) by modified activated carbons. The adsorption of organic compounds (1-naphthalenesulphonic acid, 1,5-naphthalenedisulphonic acid and 1,3,6-naphthalenetrisulphonic acid) and inorganic species (Cd(II) and Hg(II)) was studied on a series of ozonized activated carbon in aqueous phase. Commercial activated carbon (Filtrasorb 400) was treated with different ozone doses to study the effect of ozone treatment on its surface properties and investigate the behavior of the treated carbon samples in the above adsorption processes. After ozonation, carbonyl- and carboxyl-type groups were generated on the carbon surface. The action of ozone also affected the textural characteristics of the carbon; thus, the surface area diminished due both to the ozone attack and to the increase in oxygenated groups, which prevented the diffusion of nitrogen by obstructing micropore entrances. The capacity of activated carbon to adsorb naphthalenesulphonic acids sharply decreased with a greater number of sulphonic groups in the aromatic rings of these acids. As the concentration of oxygenated electron-withdrawing groups on the carbon surface increased, a significant reduction in adsorption capacity was observed. In all cases, the adsorption uptake decreased with higher solution pH. The adsorption of metallic ions, Cd(II) and Hg(II), by this series of ozonized activated carbons was also studied. In the case of Cd(II), the adsorption capacity and affinity of the adsorbents increased with a higher concentration of acid oxygenated groups on the activated carbon surface. In the case of Hg(II), the adsorption diminished with an increase in the degree of oxidation of the activated carbon. The adsorption of 1,3,6-naphthalenetrisulphonic acid on the ozonized carbons was also studied in the presence of Cd(II) and Hg(II). The presence of Cd(II)) in the medium enhanced the sulphonic acid uptake, mainly for the most ozonized activated carbon sample, whereas the presence of Hg(II) had no significant effect on the adsorption.     

Playing with peptides: how to build a supramolecular peptide nanostructure by exploiting helix···helix macrodipole interactions

A novel method to build bicomponent peptide self-assembled monolayers (SAMs) has been developed, by exploiting helix···helix macrodipole interactions. In this work, a peptide-based self-assembled monolayer composed of two helical peptides was immobilized on a gold surface. Specifically, a pyrene-containing octapeptide, devoid of any sulfur atom (A8Pyr), and a hexapeptide, functionalized at the N-terminus with (S,R) lipoic acid, for binding to gold substrates (SSA4WA) via a Au-S linkage, have been employed. Both peptides investigated attain a helical structure, because they are almost exclusively formed by strongly folding inducer C(α)-tetrasubstituted α-amino acids. We demonstrate that the two peptides generate a stable supramolecular nanostructure (a densely packed bicomponent peptide monolayer), where A8Pyr is incorporated into the SSA4WA palisade by exploiting helix···helix macrodipole interactions. The presence of both peptides on the gold surface was investigated by spectroscopic and electrochemical techniques, while the morphology of the monolayer was analyzed by ultra high-vacuum scanning tunnelling microscopy. The composition of the bicomponent SAM on the surface was studied by a combination of electrochemical and spectroscopic techniques. In particular, the amount of Au-S linkages from the sulfur-containing peptides was quantified from reductive desorption of the peptide-based SAM, while the amount of A8Pyr was estimated by fluorescence spectroscopy. The antiparallel orientation of the A8Pyr and SSA4WA peptide chains minimizes the interaction energy between the helix dipoles, suggesting that this kind of electrostatic phenomenon is the driving force that stabilizes the bicomponent SAM.     

Volatile organic compound adsorption on a nonporous silica surface: how do different probe molecules sense the same surface?

In this work, we compare experimental results to molecular simulation results of volatile organic compound (VOC) adsorption on nonporous silica. We adopted an effective model for the rough solid surface, obtained by a temperature annealing scheme, plus an experimental/simulation nitrogen adsorption tuning process over the silica energetic oxygen parameter. The measurement/prediction of selected VOCs, specifically, n-pentane and methylcyclohexane, is presented in terms of adsorption isotherms, with an emphasis on the angle distribution analysis of the three studied probe molecules with respect to the same modeled surface.     

Why is the linking C-C bond in tetrahedranyltetrahedrane so short?

[structure: see text]. The block-localized wave function (BLW) method has been employed to probe the origin of the very short linking C-C bond (1.436 A) in tetrahedranyltetrahedrane. Computations show that the vicinal hyperconjugative interactions between the two tetrahedranyl groups is stronger than the conjugation in butadiene, and if there were no hyperconjugation effect, the bond distance would be 1.491 A. Thus, both the hybridization mode and hyperconjugative interactions contribute to the shortening of the central C-C bond in tetrahedranyltetrahedrane.     

Water adsorption on tin hydrodioxide and its effect on the contour of the infrared absorption band ν(OH)

Tin hydrodioxide SnO₂ · nH₂O (THO, n = 1.5) pellets in potassium bromide were studied by IR absorption spectroscopy. Water adsorption by tin hydrodioxide was shown to give rise to a prominent strong and broad band of stretching vibrations ν(OH) with a peak at 3430 cm^?1. Absorption intensity of this band decreases with distance from the peak rapidly toward higher frequencies and very slowly toward lower frequencies; therefore, the contour is distinguished by very high asymmetry. Analysis of the reasons for this asymmetry taking into account the computer decomposition of the contour into components implies that the unresolved bands from two types of water molecules in THO are superimposed onto the weak bands from two types of hydroxide groups. First type molecules are involved in physisorption to form, with one another, hydrogen bonds that are similar to weak bonds in zeolite and liquid water. Second type molecules are involved in chemisorption and are coordinated to tin ions. Coordination enhances the strengthening of acidic properties and promotes the appearance of strong H-bonds. The peak intensity of the THO ν(OH) band depends primarily on the contribution of vibrational transitions of first type molecules and to a lesser extent on the contribution of vibrational transitions of the first type hydroxide groups. The vibrational transitions in second type molecules and second type groups influence the curvature of the contour on the low-frequency side of the peak.     

The ester group: how hydrofluoroalkane-philic is it?

Pressurized metered-dose inhalers (pMDIs) have been recognized as potential devices for the delivery of systemically acting drugs, including biomolecules, to and through the lungs. Therefore, the development of novel excipients capable of imparting stability to suspension formulations in hydrofluoroalkane (HFA) propellants is of great relevance because many of the drugs of interest are poorly soluble in HFAs. In this work, we use ab initio calculations and chemical force microscopy (CFM) to determine the HFA-philicity of the biodegradable and biocompatible ester moiety quantitatively. The complementary information obtained from the binding energy calculations and adhesion force measurements are used to gain microscopic insight into the relationship between the chemistry of the moiety of interest and its solvation in HFA. A lactide (LA)-based copolymer surfactant was synthesized and characterized, and its ability to stabilize a dispersion of micronized budesonide in HFA227 was demonstrated. These results corroborate the ab initio calculations and CFM and show that the LA-based moiety is a suitable candidate for enhancing the stability of dispersions in HFA-based pMDIs.     

NO and dichloroethene reactivity on single crystal and supported Cu nanoparticles: just how big is the materials gap?

Infrared and molecular beam experiments are used to compare and contrast the adsorption and reaction of NO and trans-1,2-dichloroethene on Cu(110) and on Cu nanoclusters deposited on a 5 A thick Al(2)O(3) film. The overall reaction of NO, leading to decomposition, is almost identical in the two systems, with both types of Cu surfaces promoting the formation of NO dimers, which are precursors to the dissociation products N(2)O, N(2) and O. Although the overall reaction is independent of surface structure, the IR spectra clearly show differences in the adsorption sites occupied on the single crystal and the clusters, a disparity that is also shown by CO adsorption experiments. In contrast, the reaction pathway of dichloroethene does show differences on the two types of Cu surfaces. On both surfaces, the initial reaction step is insensitive to structure and efficient dechlorination leads to the production of adsorbed acetylene. However, the fate of this intermediate depends critically on the underlying surface. On Cu(110), the acetylene trimerises readily into benzene at 350 K. However, this reaction shows a significant size dependent behaviour on the supported nanocluster systems, with the probability for trimerisation diminishing with decreasing cluster size.     

Structural requirements for the interaction of combretastatins with tubulin: how important is the trimethoxy unit?

A series of combretastatins possessing both a trimethoxy unit and other substituents on ring A has been synthesised and tested for cytotoxicity and their ability to interact with the protein tubulin. All previous studies have indicated that the trimethoxy unit is essential for interaction with tubulin. The studies herein show that molecules possessing functionalities other than trimethoxy can also interact with tubulin. Importantly a trimethyl substituted agent 52a has shown reduced cytotoxicity, but increased potency in its ability to inhibit the assembly of tubulin.     

Beta-phenyl quenching of triplet excited ketones: how critical is the geometry for deactivation?

The phenomenon of beta-phenyl quenching has been examined by laser-flash photolysis in a series of alpha- and/or beta-substituted ketones 4-8 with similar excited-state characteristics. It is found that alpha-substitution markedly increases the triplet lifetimes in contrast to beta-substitution. The force field calculations for the various staggered conformers of ketones 4-6 and 8-syn show that the lowest-energy conformation in all these ketones has the carbonyl group and the beta-phenyl ring gauche to each other. Despite this geometrical requirement, the longer lifetimes observed are interpreted as being due to the influence of the alpha-substituent on the rotational freedom of the planar benzoyl moiety as a whole. The experimental results are suggestive of the attainment of what appears to be a critical geometry for quenching. This scenario may be likened to Norrish type II reactions, where the alpha-substituent has long been known to suppress the elimination pathway and promote Yang cyclization. In addition, we have shown that the diastereomers of alpha,beta-disubstituted ketones exhibit distinct lifetimes.     

When is a molecule properly solvated by a continuum model or in a cluster ansatz? A first-principles simulation of alanine hydration

In order to test the validity of the cluster ansatz approach as well as of the continuum model approach and to learn about the solvation shell, we carried out first-principles molecular dynamics simulations of the alanine hydration. Our calculations contained one alanine molecule dissolved in 60 water molecules. Dipole moments of individual molecules were derived by means of maximally localized Wannier functions. We observed an average dipole moment of about 16.0 D for alanine and of about 3.3 D for water. In particular, the average water dipole moment in proximity of alanine's COO(-) group decayed continously with increasing distance, while, surprisingly, close to the CH3 and NH3+ group, the dipole moment first rose before its value dropped. In a cluster ansatz approach, we considered snapshots of alanine surrounded by different water molecule shells. The dipole moments from the cluster approaches utilizing both maximally localized Wannier functions as well as natural population analysis served to approximate the dipole moments of the total trajectory. Sufficient convergence of the cluster ansatz approach is found for either of the two solvent shells around the polar groups and one solvent shell around the apolar groups or two solvent shells around the polar groups surrounded by a dieletric continuum.     

N-terminal derivatization and fragmentation of neutral peptides via ion--molecule reactions with acylium ions: toward gas-phase Edman degradation?

The gas-phase ion-molecule reactions of neutral alanylglycine have been examined with various mass-selected acylium ions RCO(+) (R= CH(3), CD(3), C(6)H(5), C(6)F(5) and (CH(3))( 2)N), as well as the transacylation reagent O-benzoylbenzophenone in a Fourier transform ion cyclotron resonance mass spectrometer. Reactions of the gaseous dipeptide with acylium ions trapped in the ICR cell result in the formation of energized [M + RCO](+) adduct ions that fragment to yield N-terminal b-type and C-terminal y-type product ions, including a modified b(1) ion which is typically not observed in the fragmentation of protonated peptides. Judicious choice of the acylium ion employed allows some control over the product ion types that are observed (i.e., b versus y ions). The product ion distributions from these ion--molecule reactions are similar to those obtained by collision-activated dissociation in a triple quadrupole mass spectrometer of the authentic N-acylated alanylglycine derivatives. These data indicate that derivatization of the peptide in the gas-phase occurs at the N-terminal amine. Ab initio molecular orbital calculations, performed to estimate the thermochemistry of the steps associated with adduct formation as well as product ion formation, indicate that (i) the initially formed adduct is energized and hence likely to rapidly undergo fragmentation, and (ii) the likelihood for the formation of modified b(1) ions in preference to y(1) ions is dependent on the R substituent of the acylium ion. The reaction of the tetrapeptide valine--alanine--alanine--phenylalanine with the benzoyl cation was also found to yield a number of product ions, including a modified b(1) ion. This result suggests that the new experimental approach described here may provide a tool to address one of the major limitations associated with traditional mass spectrometric peptide sequencing approaches, that is, determination of the identity and order of the two N-terminal amino acids. Analogies are made between the reactions observed here and the derivatization and N-terminal cleavage reactions employed in the condensed-phase Edman degradation method.     

What is the correct form of BET isotherm for modeling liquid phase adsorption?

In this work subtleties of application of BET isotherm for liquid phase adsorption is presented. It has been shown that direct use of the classical BET equation (which was developed for gas phase adsorption) to liquid phase adsorption leads to ambiguous and erroneous results. Some cases of misuse of BET equation for liquid phase adsorption have been revisited. By close examination of the development of the classical equation, the causes of misunderstandings were elucidated and the suitable form of the BET equation for liquid phase adsorption was developed. As case studies, the classical form of the BET equation along with the correct form of the equation for liquid phase have been applied for modeling liquid phase adsorption of methyl tert-butyl ether (MTBE) on perfluorooctyl alumina, phenol on activated carbon and pentachlorophenol on carbonized bark. It has been shown that direct application of the classical BET isotherm to liquid phase adsorption results in poor and erroneous estimation of the equation parameters. For example, in aqueous phase adsorption of MTBE on perfluorooctyl alumina, the monolayer adsorption capacity of the adsorbent was calculated as 9.7 mg/g instead of 3.3 mg/g or the saturation concentration of MTBE in water was calculated as 1212 mg/L instead of 42000 mg/L.     

Catalytic hunsdiecker reaction of alpha,beta-unsaturated carboxylic acids: how efficient is the catalyst?

UV-vis spectrophotometry is utilized to measure the relative efficiency of lithium acetate, tetrabutylammonium trifluoroacetate, and triethylamine as catalysts for the conversion of 4-methoxycinnamic acid to 4-methoxy-beta-bromostyrene. In acetonitrile-water as solvent, the efficiency order is lithium acetate > triethylamine > tetrabutylammonium trifluoroacetate. For triethylamine as catalyst, solvent-dependent order is acetonitrile-water > dichloromethane > acetonitrile. Using triethylamine as catalyst (5-20 mol %), cinnamic acids, and propiolic acids are converted to corresponding beta-bromostyrenes and 1-halo-1-alkynes in 60-98% isolated yields within 1-5 min.     

Lysozyme adsorption on polyethylene surfaces: why are long simulations needed?

The adsorption of lysozyme onto a polyethylene (PE) surface in an aqueous environment was investigated via molecular dynamics (MD) simulation. The adsorption can be divided into three processes: diffusion to the surface, dehydration induced by hydrophobic surface-protein interactions, and denaturation. The dehydration process is very long, around 70 ns. Structural deformations start soon after the protein reaches the surface and continue during the whole trajectory. The hydrophobic residues are slowly driven toward the surface, inducing changes in the protein's secondary structure. The protein's secondary structural components near the surface are more disturbed than those farther away from the surface. The lysozyme is adsorbed with its long axis parallel to the surface and displays an anisotropic mobility on the surface that is probably due to the intrinsic structure of the PE surface. Our study demonstrates the need for long-time atomistic simulation in order to gain a complete understanding of the adsorption process.     

Quantum-chemical modeling of gas-phase adsorption of the hydroxyl radical on IB metal clusters Me n (n = 2–8)

The structure of the most stable Me _n clusters and Me _n OH complexes (Me = Cu, Ag, Au; n = 2–8) was calculated using the density functional theory. The enthalpy and Gibbs energy of the interaction of OH^· with metal clusters were calculated. It was shown that the hydroxyl radical is predominantly adsorbed into the bridge position on the metal IB clusters. During the adsorption of the hydroxyl radical, the frequency and intensity of the stretching vibrations of the O-H bond increased relative to the corresponding values for the isolated state; the frequency shift changed in the series Ag < Cu < Au.     

Syntheses of dendritic branches based on L-lysine: is the stereochemistry preserved throughout the synthesis?

This paper reports the syntheses of individual dendritic branches based on L-lysine and functionalised with either Boc or Bz surface groups. Convergent and divergent synthetic approaches were employed and the preservation of stereochemistry during the syntheses was monitored using polarmetry, NMR and HPLC. In addition, racemic dendritic branches based on D,L-lysine were synthesised for comparative purposes. It was observed that the preservation of stereochemistry in the dendritic peptide was dependent on the method of synthesis, with divergent methodology being preferred. The results are discussed in terms of the known stereochemical outcomes of traditional peptide coupling processes, and are generalised to the synthesis of other dendritic peptides. Such observations about the chirality of dendritic peptides are of relevance to chemists developing dendritic systems for applications where single enantiomer dendrimers would clearly be preferred, such as enantioselective catalysis or pharmaceutical chemistry.     

Communication: Where does the first water molecule go in imidazole?

Supersonic jet FTIR spectroscopy supplemented by (18)O substitution shows unambiguously that water prefers to act as an O-H···N hydrogen bond donor towards imidazole, instead of acting as a N-H···O acceptor. Previous matrix isolation, helium droplet, and aromatic substitution experiments had remained ambiguous, as are standard quantum chemical calculations. The finding is supported by a study of the analogous methanol complexes and by higher level quantum chemical calculations.     

X-ray tomography: how to evaluate the reconstruction quality?

Different reconstruction techniques are used to reconstruct the distribution of the physical characteristics, describing a sample under investigation, from a set of tomographic projections. We present a technique for the evaluation of the reconstruction quality. The technique is based on the comparison of two images (phantom and reconstructed image) by means of the correlation coefficient and of the mean square error between them. In parallel, the correlation coefficient and mean square error are calculated for the wavelet transforms of the phantom and reconstructed images. The scales for the wavelet transform are chosen in agreement with the major geometric parameters of the phantom. Then the correlation coefficient of the wavelet transform with the chosen scale yields an evaluation of the quality of the phantom parameters reconstruction. The accuracy of the parameters reconstruction is determined by the mean square error for the selected scale. The phantom used for the analysis is a medium with randomly distributed grains. The distribution is characterized by two parameters: grain size and grain density (average number of grains per unit area). The parameters are used as the scales for the wavelet transform calculation. We make a comparison of the Algebraic Reconstruction Technique (ART) and the Filtered Back Projection Algorithm.