Directing Reaction Pathways through Controlled Reactant Binding at Pd–TiO2 Interfaces

Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO₂ films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface.     

Evaluation of tetracationic salts as gas‐phase ion‐pairing agents for the detection of trivalent anions in positive mode electrospray ionization mass spectrometry

In previous studies, new electrospray ionization mass spectrometry (ESI‐MS) approaches were developed for the highly sensitive detection of singly and doubly charged anions in positive mode ESI‐MS by using specially synthesized dicationic and tricationic ion‐pairing agents, respectively. By detecting the positively charged ion complex in the positive mode, limits of detection (LODs) for the anions can be lowered by several magnitudes. In this work, we used eighteen newly synthesized tetracationic ion‐pairing agents, constructed with different geometries, linkages and cation moieties, for the detection of eighteen triply charged anions of different structural motifs. The LODs for these anions were from ten to several thousand times lower in the positive selective ion monitoring (SIM) mode than in the negative mode. These tetracationic agents also were shown to be useful for the detection of ?1 and ?2 anions. In addition, the LODs for ?3 anions can be further lowered by monitoring the product fragments of the ion‐pairing complexes in the single reaction monitoring (SRM) mode. Copyright © 2010 John Wiley & Sons, Ltd.     

An optimization‐based undeflated PLS (OUPLS) method to handle missing data in the training set

Advances in sensory systems have led to many industrial applications with large amounts of highly correlated data, particularly in chemical and pharmaceutical processes. With these correlated data sets, it becomes important to consider advanced modeling approaches built to deal with correlated inputs in order to understand the underlying sources of variability and how this variability will affect the final quality of the product. Additional to the correlated nature of the data sets, it is also common to find missing elements and noise in these data matrices. Latent variable regression methods such as partial least squares or projection to latent structures (PLS) have gained much attention in industry for their ability to handle ill‐conditioned matrices with missing elements. This feature of the PLS method is accomplished through the nonlinear iterative PLS (NIPALS) algorithm, with a simple modification to consider the missing data. Moreover, in expectation maximization PLS (EM‐PLS), imputed values are provided for missing data elements as initial estimates, conventional PLS is then applied to update these elements, and the process iterates to convergence. This study is the extension of previous work for principal component analysis (PCA), where we introduced nonlinear programming (NLP) as a means to estimate the parameters of the PCA model. Here, we focus on the parameters of a PLS model. As an alternative to modified NIPALS and EM‐PLS, this paper presents an efficient NLP‐based technique to find model parameters for PLS, where the desired properties of the parameters can be explicitly posed as constraints in the optimization problem of the proposed algorithm. We also present a number of simulation studies, where we compare effectiveness of the proposed algorithm with competing algorithms. Copyright © 2014 John Wiley & Sons, Ltd.     

Nitric oxide release mediated by calix[4]hydroquinones

Calix[4]monohydroquinone has been used as a supramolecular system for the generation of NO gas. In a one-electron reduction scheme involving NO+ subsetcalix[4]monohydroquinone complex, NO is released without the presence of an external reducing agent. Free calix[4]monoquinone, thus obtained, can be reused for a new NO-releasing cycle after NaBH4-reduction to calix[4]monohydroquinone.     

Syntheses and excitation transfer studies of near-orthogonal free-base porphyrin-ruthenium phthalocyanine dyads and pentad

A new series of molecular dyads and pentad featuring free-base porphyrin and ruthenium phthalocyanine have been synthesized and characterized. The synthetic strategy involved reacting free-base porphyrin functionalized with one or four entities of phenylimidazole at the meso position of the porphyrin ring with ruthenium carbonyl phthalocyanine followed by chromatographic separation and purification of the products. Excitation transfer in these donor-acceptor polyads (dyad and pentad) is investigated in nonpolar toluene and polar benzonitrile solvents using both steady-state and time-resolved emission techniques. Electrochemical and computational studies suggested that the photoinduced electron transfer is a thermodynamically unfavorable process in nonpolar media but may take place in a polar environment. Selective excitation of the donor, free-base porphyrin entity, resulted in efficient excitation transfer to the acceptor, ruthenium phthalocyanine, and the position of imidazole linkage on the free-base porphyrin could be used to tune the rates of excitation transfer. The singlet excited Ru phthalocyanine thus formed instantly relaxed to the triplet state via intersystem crossing prior to returning to the ground state. Kinetics of energy transfer (k(ENT)) was monitored by performing transient absorption and emission measurements using pump-probe and up-conversion techniques in toluene, respectively, and modeled using a F?rster-type energy transfer mechanism. Such studies revealed the experimental k(ENT) values on the order of 10(10)-10(11) s(-1), which readily agreed with the theoretically estimated values. Interestingly, in polar benzonitrile solvent, additional charge transfer interactions in the case of dyads but not in the case of pentad, presumably due to the geometry/orientation consideration, were observed.     

Detection of nucleotides in positive-mode electrospray ionization mass spectrometry using multiply-charged cationic ion-pairing reagents

Nucleotides are a class of molecules that play an essential role in biological systems. A new method has been developed in the detection of nucleotides. These molecules can exist as monomers or constituents of oligomers and polymers. As such, they carry from one to several negative charges. In this study, different cationic ion-pairing reagents were used to complex with each of the 28 nucleotide monomers and nucleotide containing compounds. By using this method, this discrete set of anions was able to be detected in the positive-mode electrospray ionization mass spectrometry, as positively charged complexes. Tandem mass spectrometry experiments were also completed on the ion-pairing reagents that performed the best in the single ion monitoring (SIM) ion mode, and the sensitivity was lowered even further for most of the anions. Limits of detection for compounds such as thymidine diphosphate were improved as much as 100 times compared to the positive SIM mode, and 750 times when compared to the negative mode. A few nucleotides did not show a significant increase in sensitivity when analyzed in the positive ion mode, but in general the new method developed herein resulted in a much greater sensitivity than traditional detection in the negative mode.     

Bonded ionic liquid polymeric material for solid-phase microextraction GC analysis

Four new ionic liquids (IL) were prepared and bonded onto 5-μm silica particles for use as adsorbent in solid-phase microextraction (SPME). Two ILs contained styrene units that allowed for polymerization and higher carbon content of the bonded silica particles. Two polymeric ILs differing by their anion were used to prepare two SPME fibers that were used in both headspace and immersion extractions and compared to commercial fibers. In both sets of experiments, ethyl acetate was used as an internal standard to take into account adsorbent volume differences between the fibers. The polymeric IL fibers are very efficient in headspace SPME for short-chain alcohols. Immersion SPME also can be used with the IL fibers for short-chain alcohols as well as for polar and basic amines that can be extracted at pH 11 without damage to the IL-bonded silica particles. The sensitivities of the two IL fibers differing by the anion were similar. Their efficacy compares favorably to that of commercial fibers for polar analytes. The mechanical strength and durability of the polymeric IL fibers were excellent.      

Synthesis, molecular and electronic structure, and TDDFT and TDDFT-PCM study of the solvatochromic properties of (Me2Pipdt)Mo(CO)4 complex (Me2Pipdt = N,N'-dimethylpiperazine-2,3-dithione)

The synthesis, spectroscopic, and structural characterization of the (Me2Pipdt)Mo(CO)4 complex (Me2Pipdt = N,N'-piperazine-2,3-dithione) are presented in this paper. The title complex crystallizes in the P2(1)/n space group with a = 25.541(3) A, b = 10.3936(14) A, c = 10.9012(12) A, beta = 92.261(9) degrees , V = 2891.6(6) A(3), and Z = 8. Gas- and solution-phase structural and electronic features of (Me2Pipdt)Mo(CO)4 and Me2Pipdt have been investigated using density functional theory. The molecular structure underscores the flexibility of the NC(S)C(S)N fragment in both the free ligand and the metal complex. On the basis of structural, spectroscopic, and theoretical results, the bidentate ligand in (Me2Pipdt)Mo(CO)4 is considered to be in the dithione, not dithiolate, form. Time-dependent density functional theory has been used for the investigation of the excited states and solvatochromic properties of (Me2Pipdt)Mo(CO)4. The calculated vertical excitation energies in solution are consistent with the experimental data, showing that the metal-to-ligand charge-transfer transitions, in both the visible and UV regions, dominate over the ligand-based pi-pi transitions.     

The quadratic assignment problem with a monotone anti-Monge and a symmetric Toeplitz matrix: Easy and hard cases

This paper investigates a restricted version of the Quadratic Assignment Problem (QAP), where one of the coefficient matrices is an Anti-Monge matrix with non-decreasing rows and columns and the other coefficient matrix is a symmetric Toeplitz matrix. This restricted version is called the Anti-Monge—Toeplitz QAP. There are three well-known combinatorial problems that can be modeled via the Anti-Monge—Toeplitz QAP: (Pl) The Turbine Problem, i.e. the assignment of given masses to the vertices of a regular polygon such that the distance of the center of gravity of the resulting system to the center of the polygon is minimized. (P2) The Traveling Salesman Problem on symmetric Monge distance matrices. (P3) The arrangement of data records with given access probabilities in a linear storage medium in order to minimize the average access time. We identify conditions on the Toeplitz matrixB that lead to a simple solution for the Anti-Monge—Toeplitz QAP: The optimal permutation can be given in advance without regarding the numerical values of the data. The resulting theorems generalize and unify several known results on problems (P1), (P2), and (P3). We also show that the Turbine Problem is NP-hard and consequently, that the Anti-Monge—Toeplitz QAP is NP-hard in general. © 1998 The Mathematical Programming Society, Inc. Published by Elsevier Science B.V.Dedicated to the memory of Gene LawlerThis research has been supported by the Spezialforschungsbereich F 003 Optimierung und Kontrolle, Projektbereich Diskrete Optimierung.     

Comparison of stationary phases for packed column supercritical fluid chromatography based upon ionic liquid motifs: a study of cation and anion effects

A class of stationary phases for packed column supercritical fluid chromatography (SFC), referred to as immobilized ionic liquids (IILs), is evaluated with a two-part study: (1) a cation effect study and (2) an anion effect study. The former study compares six different IILs (tripropylphosphonium, tributylphosphonium, methyl-imidazolium, benzyl-imidazolium, triphenylphosphonium, and 4,4′-bipyridyl) on silica gel, evaluating their performance in SFC with all the counter anions as trifluoroacetate (TFA⁻). In the latter study, the stationary phase consisted of a bonded tributylphosphonium cation and varying counter anions (acetate, TFA⁻, chloride, NTf₂⁻, and perchlorate). An order of retentivity was established for the cation effect study, and the favorable behavior of phosphonium-based stationary phases is reported for the first time in SFC. It was not possible to always assign a retentivity order for the anion effect study, but wide variations in selectivity are noted for different anions showing the tunable nature of this class of stationary phases.