The Formation of Pd Nanocrystals from Pd2(dba)3 Microcrystals

As‐grown platelets formed from tris‐(dibenzylideneacetone) dipalladium(0) [Pd₂(dba)₃] precursor in the presence of Pd17 RNA are investigated before and after thermal annealing. Results show that as‐grown platelets are disordered crystals of Pd₂(dba)₃ containing 1?2 nm Pd clusters and platelets grown in the absence of RNA are morphologically and structurally similar to those formed with RNA. The initially formed crystals are so sensitive to environmental variables that the degree of crystallinity can not be determined accurately by electron diffraction. X‐ray crystallography on as‐grown platelets gives a crystal structure consistent with Pd₂(dba)₃, but reveals a composition of ≈Pd_1.07(dba)₃, indicating one Pd atom in Pd₂(dba)₃ is lost from the structure. Both electron beam and thermally induced decomposition of as‐grown Pd₂(dba)₃ platelets having a hexagonal habit on the micrometer scale produces elemental Pd platelets having a hexagonal habit on the nanometer scale. These hexagonal platelets are composed of a partially sparse form of Pd₂(dba)₃ that is initially crystalline but rapidly degrades due to the loss of Pd atoms from organic ligand cages. Once released, Pd atoms aggregate to form Pd clusters, which grow and transform into well‐formed Pd nanocrystals under electron‐beam irradiation or through thermal annealing.     

Bessel capacities and rectangular differentiation in Besov spaces

We consider the differentiation of integrals of functions in Besov spaces with respect to the basis of arbitrarily oriented rectangular parallelepipeds in Rn. We study almost everywhere convergence with respect to Bessel capacities. These outer measures are more sensitive than n-dimensional Lebesgue measure, and therefore we improve the positive results in [H. Aimar, L. Forzani, V. Naibo, Rectangular differentiation of integrals of Besov functions, Math. Res. Lett. 9 (2-3) (2002) 173-189].     

Activation du methyl-2 benzothiazole par metallation

The α-metalation of 2-methylbenzothiazole is studied with the aim of obtaining quantitatively an anionic intermediate which is able to react fully with benzaldehyde. The relative importance of the factors which influence the formation and reactivity of this intermediate are examined: the nature of the metalating agent, the solvent, the temperature and the reaction time.Butyllithium and phenyllithium, in the presence of linear or cyclic ethers at ?78°C, allow quantitative transformation into 2-benzothiazolylmethyllithium, a highly reactive agent at low temperatures (?78 to ?35°C), but non-reactive at 0°C. The addition of complexing bases raises the maximum temperature at which the reaction is possible. This method is applicable to 2-benzylbenzothiazole and induces a stereoselective attack on benzaldehyde.     

Evaluating Re-order Levels and Probabilities of Stockout during a Lead Time for Some Stock-Control Models

When several suppliers are concurrently used to replenish one stock item, it is often of interest to compute the mean and the variance of the effective lead time, i.e., the minimum of all lead times. However, in many cases, especially with non-identical lead time distributions, these quantities do not have closed form expressions and their calculation can be complicated. Difficulty in computation also arises in evaluating demand during lead time, even if there is only one supplier. This paper presents a numerical integration method using Gaussian quadrature to evaluate the effective lead time mean and variance, re-order level and the probability of stockout during the effective lead time. The Gaussian quadrature rules are easy to implement and several data sets are used in the paper to demonstrate the method.     

Characterization of proton NMR relaxation times in normal and pathological tissues by correlation with other tissue parameters

To help understand which tissue parameters best account for the water proton NMR relaxation times, the longitudinal relaxation time (T₂), the transverse relaxation time (T₂), and the water content of 16 tissues from normal adult rats were measured at 10.7 MHz and 29°C. Regression analyses between the above and other tissue parameters were performed. These other tissue parameters included: the amounts of various organic and inorganic components, protein synthetic rate, oxygen consumption rate, and morphological composition. In addition, the differences in T₁, T₂, and water content values between normal liver and malignant tumor (Morris #7777 a transplantable hepatoma) were studied to help understand how a disease state can be detected and characterized by NMR spectroscopy. The results of this study and information from the literature allow the following generalizations to be made about tissue T₁ and T₂ values: (1) Each normal tissue has rather consistent and characteristic T₁ and T₂ relaxation times which are always shorter than the T₁ and T₂ of bulk water; (2) tissues with higher water content tend to have longer T₁ relaxation times; (3) tissue T₂ values are not, however, as well correlated with water content as T₁ values; (4) tissues with shorter T₁ values have higher calculated hydration fractions, greater amounts of rough endoplasmic reticulum, and a greater rate of protein synthetic activity; (5) tissues with higher lipid content, associated with intracellular non-membrane bounded lipid droplets, tend to have longer T₂ values; (6) tissues with greater overall surface area, whether in the form of cellular membranes or intracellular or extracellular fibrillar macromolecules, tend to have shorter T₂ values; (7) the differences between T₁ and T₂ values between tumor and normal tissues correlated with differences in the volume fraction (amounts) of extracellular fluid volumes and in the amounts of membrane and fibrillar surface area in the cells. The above generalizations should be useful in predicting T₁ and T₂ changes associated with specific tissue pathologies.     

Studies in nuclear magnetic resonance—XII: Complete analysis of the proton spectra of tert-butylcyohexane-3,3,4,4,5,5-d6 and -3,3,5,5-d4

Accurate parameters for the two title compounds have been obtained by the aid of a spectral subtraction technique in conjunction with analysis by LAOCN3. It is observed that J_{1eq, 6eq} and J_{1ax, 2ax} are abnormally large and small, respectively, and the significance of these and other coupling constants are discussed in terms of the probable geometry of tert-butylcyclohexane. The tert-butyl group affects the chemical shifts of the 4-protons, indicating that tert-butylcyclohexyl derivatives are poor models for fixed conformers of monosubstituted cyclohexanes. The deuterium isotope effects on proton chemical shifts appear to be influenced by the same factors as proton-proton coupling constants.     

Matrix screening of substituted N-aryl-1,8-naphthalimides reveals new dual fluorescent dyes and unusually bright pyridine derivatives

A 3 x 14 matrix of substituted N-aryl-1,8-naphthalimides was synthesized for the evaluation and discovery of dual fluorescence. Because of their unique photophysical properties, these dual fluorescent systems represent an exception to the widely studied TICT (Twisted Internal Charge Transfer) fluorescent dyes or tautomeric benzofluorescein class of two-color dyes. The matrix library was designed to investigate the effects of heterocycles, particularly pi-excessive and pi-deficient systems. Of the 42 compounds surveyed, five displayed well-resolved two-color emission in solvents as nonpolar as hexane. Based on the observed trends in fluorescence lambda(max) and quantum yield, a new model is proposed that predicts LW and SW emission for these systems. In addition, this model provides potential design features for the synthesis of new dual fluorescent species.     

Spectroscopic studies of Lewis acid-base complexes: Part V. Raman and infrared spectra,assignments and normal coordinate analysis for difluorophosphine borane

Raman spectra of five isotopic species of HPF₂BH₃ have been obtained in the liquid and solid states together with infrared spectra of the same species in the gaseous and solid states. Vibrational assignments have been made with the aid of a normal coordinate analysis utilizing compliance constants. Both compliance and force constants are reported. The force field is quite similar to that of PF₃BH₃ despite the marked difference in stability of the two compounds.