Monomode

Aromatic radical anions, such as lithium naphthalene or sodium naphthalene, are efficient difunctional initiators (eqs. 6,7) (3,20,64). However, the necessity of using polar solvents for their formation and use limits their utility for diene polymerization, since the unique abiUty of lithium to provide high 1,4-polydiene microstmcture is lost in polar media (1,33,34,57,63,64). Consequentiy, a significant research challenge has been to discover a hydrocarbon-soluble dilithium initiator which would initiate the polymerization of styrene and diene monomers to form monomodal a, CO-dianionic polymers at rates which are faster or comparable to the rates of polymerization, ie, to form narrow molecular weight distribution polymers (61,65,66). 

However, the largest increase in volume fraction is observed when changing from a monomodal to a bimo-dal system, with successive systems giving a less significant reduction in viscosity, as depicted in Fig. 4. 

Figure 1 and Table 1 show the data obtained using PIB s prepared with the f-BuCl/ Et2AlCl/MeCl system in the -30° to -65 °C range. PIB s prepared in the range from —30° to —45 °C have monomodal MWD while those prepared below -45 °C exhibit bimodal distributions. MWD s broaden with decreasing polymerization temperature. 

Figure 3 and Table 3 give the data for PIB prepared with f-BuCl/Et2AlBr/MeBr in the range from -30° to -65 °C. All GPC traces are monomodal, even for samples prepared below -50 °C (an exception was the sample prepared at -65 °C, which showed a small shoulder). While the molecular weight data are scattered and a trend... 

PIB s prepared at —40 °C were monomodal with MWD = 2.2 0.2 whereas those obtained at —50° and —60 °C were bimodal. For PIB s prepared at —50 °C, both Mn and Mw of the total polymer and the HMWF and LMWF increased with an increase in [MJ. Increasing [M] significantly increases the relative amount of HMWF at the expense of LMWF. 

PIB s prepared with f-BuCl/Et2AlBr have monomodal MWD and polymerization does not occur with Et2AlBr in the absence of added f-BuX, and... 

PIB s prepared using r-BuI/Et2AH show monomodal distribution but slow polymerization occurs even in the absence of purposefully added r-BuX. 

One of the first published microwave-assisted synthesis of benzothiazoles is the condensation of a dinucleophile such as 2-aminothiophenol, with an ortho-ester (neat) in the presence of KSF clay in a mono-mode microwave reactor operating at 60 W under a nitrogene atmosphere [ 12] (Scheme 12). Traditional heating (oil bath, toluene as solvent and KSF clay) gave the expected products in similar yields compared to the microwave experiments but more than 12 h were required for completion. Solvent-free microwave-assisted syntheses of benzothiazoles was also described by attack of the dinucleophiles cited above on benzaldehydes and benzaldoximines [13] (Scheme 12). This methodology was performed in a dedicated monomode microwave reactor... 

The biberty (Fig. 10), a monomode microwave reactor for automated SPPS, was recently introduced by the CEM Corporation [153]. Although this instrument was originally developed for SPPS, it also allows for a broader scale of solid-phase applications. The solid-phase vial is equipped with a polypropylene frit and cap at one end (the entire assembly fitting into the standard 10 mb CEM reaction vessel) to allow the processing of 0.1 to 1.0 mmol quantities of resin attached substrates. An integrated fiber optic probe provides... 

For the synthesis of coumarins, the Pechmann reaction [145] is one of the most popular synthetic routes. As the reaction is conventionally carried out at high temperature, two microwave-assisted versions have been recently described. Besson and co-workers described the cyclocondensation of different m-amino phenols 226 with /1-ketoesters 227 on graphite/montmorillonite KIO support (Scheme 83). The use of graphite was crucial in the development of the reaction conditions. In fact, microwave irradiation of the reagents using different conditions gave poor results in terms of yields and purity. The optimized conditions, using a monomode microwave system, employed... 

If the core only corresponds to one speckle spot the fibre is monomode. Otherwise the waveguide is multimode. This back to the envelop calculation intuitively shows the origin of the mode number. Note that N is wavelength dependent the larger the wavelength, the lower the number of mode. 

Figure 8. Calibration of the fringes contrasts by means of spatial filtering in monomode...

Figure 10. Left Monomode optical fibre acts as a spatial filter. The coupling efficiency is 1/N where N is the input beam number of modes. Right Using a wavefront corrector the coupling efficiency is significant and quite stable (K band CFHT/ GHANA) (Perrin et al., 2000).

Lewin, A. D., "Non-Contact Surface Vibration Analysis Using a Monomode Fiber Optic Interferometer, /. Phys. E Sci. Instrum.,Vol. 18,1985, pp. 604-608. 

The preparation by dispersion polymerization of the microsphere sample employed in this study was previously described [8]. The microsphere sample utilized in this study has a monomodal diameter distribution with mean diameter value d= 3.09 pm and standard deviation dsdev= 0-74 pm. The microsphere surface is covered by a poly(methacrylic acid-co-ethylacrylate) whose percent by weight is 1.1... 

We have been recently studying new pathways leading to polysilanes with low polydispersity and controlled structures. Our research is focused on three areas. The first one is low temperature reductive coupling in the presence of ultrasound. This leads to monomodal polymers with molecular weights in the range from Mn=50,000 to Mn=300,000 and polydispersities as low as Mw/Mn=1.20 (in addition to usually formed cyclic oligomers). 

GPC traces of poly(phenylmethylsilylenes) prepared in the ultrasonication bath are shown in Fig. 1. In contrast to thermal condensation, monomodal high molecular weight polymer is formed. Oligomeric cycles (mostly cyclic pentamer), formed usually in high yield (cf. Table 1), can be very easily separated from the reaction mixture by precipitation with isopropanol. The molecular weight of polysilanes decreases and polydispersity increases with temperature. 

Both polymers 10 and 11 are soluble in common organic solvents, melt without decomposition, and can be drawn into the fibers. Molecular weights of the polymers 10 and 11, determined by gel permeation chromatography with tetrahydrofuran as the eluant after purification by reprecipitation from benzene-ethanol, showed a broad monomodal molecular weight distribution. The degree of polymerization depends on particle size of sodium metal. Polymers with molecular weights of 23,000-34,000 are always obtained, if fine sodium particles are used. 

Microwave irradiation is used to create hot spots on metal clusters in solution, facilitating catalytic cycles in which these clusters participate. An 8x 12 parallel screening system is built based on this concept, and tested using the Heck reaction as a case study. The spatial reproducibility of this system is examined and the pros and cons of monomode and multimode m/w setups are discussed. 

Further, we examined the Heck reaction between w-butyl acrylate and 4-bromobenzotrifluoride 5 in the presence of 2 mol% Pd clusters in a singlevessel monomode m/w oven fitted with an infrared thermometer. 100% conversion with quantitative yield to the cinnamate was obtained after 5 min irradiation at 75 W/240 °C. We then repeated the reaction under conventional heating at 240 °C. After 3.5 min a black tarry gel formed. Extraction followed by GC analysis showed only cinnamate, but the tarry material (probably acrylate polymers/oligomers) could not be analysed. These experiments show that when clusters are present different results are obtained depending whether m/w heating or conventional heating is used. In principle, this could be the result of hot spots created on the metal clusters. 

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