Nucleophilic Solvent Participation in the Solvolysis of Tertiary Bromoalkanes

The solvolysis of 2‐bromo‐2‐methylpropane ( 1B ), 2‐bromo‐2‐methylbutane ( 2B ), 2‐bromo‐2, 3‐di‐methylbutane ( 3B ), 2‐bromo‐2, 3, 3‐trimethylbutane ( 4B ), 3‐bromo‐3‐methylpentane ( 5B ), 3‐bromo‐2, 3‐dimethylpentane ( 6B ), 3‐bromo‐2, 2, 3‐trimethylpentane ( 7B ), 3‐bromo‐3‐ethylpentane ( 8B ), 3‐bromo‐3‐ethyl‐2‐methylpentane ( 9B ) and 2‐bromo‐2, 4, 4‐trimethylpentane ( 11B ) in 15 to 21 solvents was studied, and correlation analyses by using the single‐ and dual‐parameter Grunwald‐Winstein equations (Eqns 1 and 2) were examined. Substrates 7B, 9B and 11B showed excellent linear relationship (R ≥ 0.997) in the logk ‐ Y_Br plots and indicated limiting S_N1 mechanism for the solvolysis. On the other hand, bromides 1B‐6B and 8B gave linear correlations (R = 0.987–0.996) with the dual‐parameter (Y_Br and N_OTs) equation (2) only, which indicated the presence of significant nucleophilic solvent participation. Normal trends of reactivity due to the relief of B‐strain could be found in the poorly nucleophilic trifluoroethanol. Similar to the corresponding chlorides, the overwhelming influence of nucleophilic solvent assistance results in the observed inverse order of reactivity: k( 2B ) > k( 3B ), k( 5B ) > k( 6B ) and k( 8B ) > k( 9B ).     

The genetic incorporation of a distance probe into proteins in Escherichia coli

The unnatural amino acid p-nitrophenylalanine (pNO2-Phe) was genetically introduced into proteins in Escherichia coli in response to the amber nonsense codon with high fidelity and efficiency by means of an evolved tRNA/aminoacyl-tRNA synthetase pair from Methanocuccus jannaschii. It was shown that pNO2-Phe efficiently quenches the intrinsic fluorescence of Trp in a distance-dependent manner in a model GCN4 basic region leucine zipper (bZIP) protein. Thus, the pNO2-Phe/Trp pair should be a useful biophysical probe of protein structure and function.     

Cross-point analysis for a multimode fiber sensor based on surface plasmon resonance

A novel analysis based on surface plasmon resonance (SPR) with a side-polished multimode fiber and a white-light (halogen light) source is presented. The sensing system is a multimode optical fiber in which half of the core has been polished away and a 40 nm gold layer is deposited on to the polished surface by dc sputter. The SPR dip in the optical spectrum is investigated with an optical spectrum analyzer (OSA). In our SPR fiber sensor, the use of liquids with different refractive indices leads to a shift in the spectral dip in the SPR curve. The cross point (CP) of the two SPR spectra obtained from the refractive-index liquid and the deionized water measurements was observed with the OSA. The CP is shifted sensitively in wavelength from 630 to 1300 nm relative to a change in the refractive index of the liquid from 1.34 to 1.46. High sensitivities of 1.9 x 10(-6) refractive-index units (RIUs) in the range of the refractive index of the liquid from 1.40 to 1.44 of 5.7 x 10(-7) RIUs above the value of 1.44 are proposed and demonstrated in our novel SPR analysis.     

Characteristics Measurement of A FLM-Grating Cavity WDM Fiber Laser

In this paper, we study an FLM-grating cavity WDM fiber laser with dynamic polarization compensation technique for maintaining the output polarization states. We observe the characteristics and obtain the optimal experimental results.     

Cationic copolymerization of isobutene and conjugated small-ring dienes

1-Methyl-3-methylenecyclobutene (MMCB) and 1,2-dimethylenecyclobutane (DMCB) copolymerized readily with isobutene with aluminum chloride as initiator in methyl chloride solution at temperatures from ?95 to ?78°C. No polymers were obtained with methylenecyclobutene (MCB) under similar conditions. The copolymerization of MMCB with isobutene took place through a 1,5-addition reaction while that of DMCB through both 1,2- and 1,4-addition reactions. Large amounts of gel were present in the copolymers obtained from DMCB if the reaction was carried to high conversion. The commonly observed effects of dienes (i.e., rate retardation and molecular weight depression) on cationic copolymerization reactions were observed but to a much higher degree with these small ring dienes. The thermal crosslinking behavior of the resulting copolymers was investigated. In conjunction with the copolymerization studies, homopolymers of MMCB, DMCB, and 3,3-dimethyl-1-isopropylidene-2-methylenecyclobutane (IMCB) were prepared and their chemical structures examined.     

Multiphoton vibrational pumping on optically prepared NO2 molecules

Reported is the collisionless infrared multiphoton excitation of NO₂ molecules initially prepared in an electronically excited state. From the shape of the infrared induced blue-shifted fluorescence spectrum the probability distribution P(n) for the net absorption of n photons has been deduced.     

A continuous approximation approach for the integrated facility-inventory allocation problem

In today’s retail business many companies have a complex distribution network with several national and regional distribution centers. This article studies an integrated facility location and inventory allocation problem for designing a distribution network with multiple distribution centers and retailers. The key decisions are where to locate the regional distribution centers (RDCs), how to assign retail stores to RDCs and what should be the inventory policy at the different locations such that the total network cost is minimized. Due to the complexity of the problem, a continuous approximation (CA) model is used to represent the network. Nonlinear programming techniques are developed to solve the optimization problems. The main contribution of this work lies in developing a new CA modeling technique when the discrete data cannot be modeled by a continuous function and applying this technique to solve an integrated facility location-allocation and inventory-management problem. Our methodology is illustrated with the network from a leading US retailer. Numerical analysis suggests that the total cost is significantly lower in the case of the integrated model as compared with the non-integrated model, where the location-allocation and inventory-management problems are considered separately. This paper also studies the effects of changing parameter values on the optimal solutions and to point out some management implications.     

Branching features of photonic bandgaps in Fibonacci dielectric heterostructures

We propose branching features of photonic band gaps in one-dimension Fibonacci dielectric heterostructures with arbitrary generation orders and thicknesses based on the gap map diagram, which is determined by the band edge formalism to avoid numerical instability. We find that the gap map diagram can be divided by the half-wave lines into several regions, each of which has similar gap pattern. The branching rules including the existence condition and the frequency range of each major gap as well as the number of all minor gaps in each region for systems with arbitrary thicknesses and generations are proposed. The number of major gaps in each region for the Fibonacci systems equals two rather than one for traditional binary layers. Moreover, the conditions of maximum gapwidth for the Fibonacci systems are not near the quarter wavelength, although the ones for traditional binary layers are at the quarter wavelength.     

Glycerol from the tubers of Jerusalem artichoke

The search for alternate sources of chemicals has resulted in a re-evaluation of many carbohydrates for conversion to oxychemicals. Inulin is an example of a carbohydrate receiving an increased amount of attention for use in industrial processes. This polymer is composed almost exclusively of fructofuranose structural units, making it very attractive for conversion into high fructose syrup and ethanol. Inulin can also be oxidized and reduced by a number of methods, and therefore lends itself well as feedstock for the exclusive conversion to glycerol. The advantages of inulin, coupled with a renewable supply, make it a very attractive source for industrial processes.