B‐MWW Zeolite: The Case Against Single‐Site Catalysis

Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron‐containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B₂(OH)_xO_(3?x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM‐22 isomorphously substituted with boron (B‐MWW). Using ¹¹B solid‐state NMR spectroscopy, we show that the majority of boron species in B‐MWW exist as isolated BO₃ units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B‐MWW for ODH of propane falsifies the hypothesis that site‐isolated BO₃ units are the active site in boron‐based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium‐based catalysts and provides an important piece of the mechanistic puzzle.     

Low molecular weight organogelators derived from threefold symmetric tricarbamates

A group of new low molecular weight organogelators based on threefold symmetric tricarbamate were synthesized and characterized. The tricarbamates with long alkyl chains were able to gelate a wide range of polar and nonpolar organic solvents such as acetonitrile and cyclohexane, generally at concentrations lower than 20 g/L. The best organogel formation was obtained using a threefold symmetric tricarbamate in n-dodecane, in which a sufficiently transparent gel was formed at the critical gelation concentration 1 g/L. Intermolecular hydrogen bonding by the tricarbamate in a nonpolar solvent benzene-d₆ was indicated by ¹H NMR spectra. Its maximum UV absorption was 11 nm higher in chloroform than in n-dodecane, and this red shift indicated increased conjugation between the benzene core and the carbamate substituents, which confirmed a change in its conformation from nonpolar to polar solvent. The self-assembling behavior of the tricarbamate in dilute solutions was investigated by TEM. Fiber-like networks were observed in a large range of solution concentrations.     

Accurate mass analysis of ethanesulfonic acid degradates of acetochlor and alachlor using high-performance liquid chromatography and time-of-flight mass spectrometry

Degradates of acetochlor and alachlor (ethanesulfonic acids, ESAs) were analyzed in both standards and in a groundwater sample using high-performance liquid chromatography-time-of-flight mass spectrometry with electrospray ionization. The negative pseudomolecular ion of the secondary amide of acetochlor ESA and alachlor ESA gave average masses of 256.0750+/-0.0049 amu and 270.0786+/-0.0064 amu respectively. Acetochlor and alachlor ESA gave similar masses of 314.1098+/-0.0061 amu and 314.1153+/-0.0048 amu; however, they could not be distinguished by accurate mass because they have the same empirical formula. On the other hand, they may be distinguished using positive-ion electrospray because of different fragmentation spectra, which did not occur using negative-ion electrospray.     

The Measurement of Ultrashort Light Pulses—Simple Devices,Complex Pulses

We review the state of the art of ultrashort-light-pulse measurement using frequency-resolved-optical-gating (FROG). Recent developments have extended the state of the art considerably. FROG devices for measuring the intensity and phase of ultrashort laser pulses have become so simple that almost no alignment is required. In addition, such devices not only operate single shot, but they also yield the two most important spatio-temporal distortions, spatial chirp and pulse-front tilt. With other FROG variations, it is now possible to measure more general ultrashort light pulses (i.e., pulses much more complex than common laser pulses), with time-bandwidth products as large as several thousand and as weak as a few hundred photons, and despite other difficulties such as random absolute phase and poor spatial coherence.     

Newton-Cotes integration for approximating Stieltjes (generalized Euler) constants

In the Laurent expansion

of the Riemann-Hurwitz zeta function, the coefficients are known as Stieltjes, or generalized Euler, constants. [When , (the Riemann zeta function), and .] We present a new approach to high-precision approximation of . Plots of our results reveal much structure in the growth of the generalized Euler constants. Our results when for , and when for (for such as 53/100, 1/2, etc.) suggest that published bounds on the growth of the Stieltjes constants can be much improved, and lead to several conjectures. Defining , we conjecture that is attained: for any given , for some (and similarly that, given and , is within of for infinitely many ). In addition we conjecture that satisfies for 1$">. We also conjecture that , a special case of a more general conjecture relating the values of and for . Finally, it is known that for . Using this to define for all real 0$">, we conjecture that for nonintegral , is precisely times the -th (Weyl) fractional derivative at of the entire function . We also conjecture that , now defined for all real arguments 0$">, is smooth. Our numerical method uses Newton-Cotes integration formulae for very high-degree interpolating polynomials; it differs in implementation from, but compares in error bounding to, Euler-Maclaurin summation based methods.

     

The interaction of a laser-generated cavity with a solid boundary

In this paper new observations of a laser-generated cavitation bubble interacting with an inertial boundary are presented. Employing schlieren photography techniques and a thin film transducer placed on the surface of the boundary, the pressure stresses induced in the solid boundary and the surrounding fluid by collapsing bubbles, created very close to the solid surface, are experimentally measured. Liquid jet development, shock wave emission, and "splash" phenomena are identified. For different creation sites close to the boundary, the relevance of each of these phenomena with respect to potentially damaging pressure stresses in the boundary is speculated on.     

Amalgamation of partitions from multiple segmentation bases: A comparison of non-model-based and model-based methods

The segmentation of customers on multiple bases is a pervasive problem in marketing research. For example, segmentation service providers partition customers using a variety of demographic and psychographic characteristics, as well as an array of consumption attributes such as brand loyalty, switching behavior, and product/service satisfaction. Unfortunately, the partitions obtained from multiple bases are often not in good agreement with one another, making effective segmentation a difficult managerial task. Therefore, the construction of segments using multiple independent bases often results in a need to establish a partition that represents an amalgamation or consensus of the individual partitions. In this paper, we compare three methods for finding a consensus partition. The first two methods are deterministic, do not use a statistical model in the development of the consensus partition, and are representative of methods used in commercial settings, whereas the third method is based on finite mixture modeling. In a large-scale simulation experiment the finite mixture model yielded better average recovery of holdout (validation) partitions than its non-model-based competitors. This result calls for important changes in the current practice of segmentation service providers that group customers for a variety of managerial goals related to the design and marketing of products and services.