Elucidating the Nature of the External Acid Sites of ZSM-5 Zeolites Using NMR Probe Molecules

The identification of acid and nonacid species at the external surface of zeolites remains a major challenge, in contrast to the extensively-studied internal acid sites. Here, it is shown that the synthesis of zeolite ZSM-5 samples with distinct particle sizes, combined with solid-state NMR and computational studies of trimethylphosphine oxide (TMPO) adsorption, provides insight into the chemical species on the external surface of the zeolite crystals. ¹H–³¹P HETCOR NMR spectra of TMPO-loaded zeolites exhibit a broad correlation peak at δ_P ∼35–55 ppm and δ_H ∼5–12 ppm assigned to external SiOH species. Pore-mouth Brønsted acid sites exhibit ³¹P and ¹H NMR resonances and adsorption energies close to those reported for internal acid sites interacting with TMPO. The presence of an external tricoordinate Al-Lewis site interacting strongly with TMPO is suggested, resulting in ³¹P resonances that overlap with the peaks usually ascribed to the interaction of TMPO with Brønsted sites.     

An expansion formula for fractional derivatives of variable order

In this work we extend our previous results and derive an expansion formula for fractional derivatives of variable order. The formula is used to determine fractional derivatives of variable order of two elementary functions. Also we propose a constitutive equation describing a solidifying material and determine the corresponding stress relaxation function.     

On double cycling for container port productivity improvement

How quay cranes (QC) are scheduled is vital to the productivity of seaside container port operations. Double cycling concept is an operation strategy of loading the containers into ships as they are unloaded, thus improving the efficiency of a QC as well as the container port. Goodchild and Daganzo (Transp Sci 40(4):473–483, 2006) first described QC double cycling problem and solved the problem after formulating it into a two machine flow shop problem. Song (Port Technol Int 36:50–52, 2007) studied the formula to determine the optimal starting sequence for double cycling while reflecting on the practical issue of QC working direction. The above studies focused on a single QC double cycling and their empirical trials showed the double cycling could improve the productivity of each QC approximately by between 10 and 20 %. In Zhang and Kim (Comput Ind Eng 56(3):979–992, 2009), a multiple QC double cycling model was first suggested by formulating a mixed integer programming model to maximise the number of double cycles between multiple QCs. In the present paper we point out a flaw with the existing multiple QC double cycling model that lets cycles that are not implementable. In addition, the paper discusses the need for imposing constraints arising from real world requirements to the formulations aiming at double cycling.     

Synthesis of Polylactide: Effect of Dispersion of the Initiator

The ring opening polymerization of L-lactide was studied in bulk using stannous octoate as initiator. In some experiments, triphenylphosphine, a Lewis base was also used as co-initiator. The polymerization was carried out at 130°C up to 29 h. The monomer was used after recrystallizing three times with dry toluene. Experiments were carried out using a wide range of monomer to initiator ratio. The averages and distributions of molar masses of resulting PLA have been determined by means of size exclusion chromatography, SEC. It is shown that the (mode, process) procedure of dispersion of the catalyst in polymerization system affects the molar mass distribution of the product as is evidenced by the bimodality or even trimodality observed in the SEC chromatograms.     

Synthesis and Stereochemistry of Some new Derivatives of 1,2-O-Cyclohexylidene-α-D-Xylofuranuronic Acid

Abstract

1,2-O-Cyclohexylidene-α-d-xylofuranuronic acid (2) has been converted into its 3-O-acetyl derivative and consecutively to the corresponding acid chloride and ethyl ester. Direct reaction of 2 with ethanol in the presence of p-to-luene sulphonic acid gave the ethyl ester. Reaction of 2 with phosphorus pentachloride in dry ether gave the acid chloride of 1,2-O-cyclohexylidene-3-O-dichlorophosphoryl–α-d-xylofuranuronic acid. Conformational data have been obtained from ¹H and ¹³C NMR measurements.     

Pressure jumps due to flow interruptions as source of system peaks in liquid chromatography with mixed eluents

Summary Brief pressure changes take often place within a liquid chromatography column, e.g., during sample injection. It is shown that pressure jumps may cause local changes in the composition of a mixed effluent and the rise of system peaks in the chromatogram. This is a consequence of the dependence of sorption equilibrium on pressure.     

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Key side products due to reactivity of dimethylmaleoyl moiety as amine protective group

Dimethylmaleoyl (DMM) moiety has become an important amine protective group in sugar chemistry. We disclose herein that DMM-containing D-glucosamine analogues, because of their electrophilic nature, are prone to reactions with strong nucleophiles, such as hydrazine, resulting in a set of undesired side products that are difficult to detect, yet proved to be problematic for organic synthesis.     

Model of quasi-ductile deformations that bridges the scales

This study proposes a model of the deformation of materials susceptible to microcracking that is based on the thermodynamics of irreversible processes and fracture mechanics. The study considers the process on the atomic-, micro-, meso- and macroscales that are connected by the process of homogenization. The limitations of the process are carefully spelled out.