Specialized Techniques

If preclinical pancreatic toxicity is identified, the first step to better understanding the pathogenesis of the lesion is often a 

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Aono M, Hou Y, Souda R, Oshima C, Otani S, Ishizawa Y, Matsuda K and Shimizu R 1982 Interaction potential between He" and Ti in a keV range as revealed by a specialized technique in ion scattering spectroscopy Japan. J. Appl. Phys. Lett. 21 L670-2... 

In hyperspherical coordinates, the wave function changes sign when <]) is increased by 2k. Thus, the cotTect phase beatment of the (]) coordinate can be obtained using a special technique [44 8] when the kinetic energy operators are evaluated The wave function/((])) is multiplied with exp(—i(j)/2), and after the forward EFT [69] the coefficients are multiplied with slightly different frequencies. Finally, after the backward FFT, the wave function is multiplied with exp(r[Pg.60]

For all the different methods of chemical visualization, a lar e number of special techniques arc available, depending on the purpose of visualization. These software programs can be installed on a local computer or can be operated via the Internet. An ovemew of these programs is given in Section 2.12.3. 

The thermodynamic properties that we have considered so far, such as the internal energy, the pressure and the heat capacity are collectively known as the mechanical properties and can be routinely obtained from a Monte Carlo or molecular dynamics simulation. Other thermodynamic properties are difficult to determine accurately without resorting to special techniques. These are the so-called entropic or thermal properties the free energy, the chemical potential and the entropy itself. The difference between the mechanical emd thermal properties is that the mechanical properties are related to the derivative of the partition function whereas the thermal properties are directly related to the partition function itself. To illustrate the difference between these two classes of properties, let us consider the internal energy, U, and the Fielmholtz free energy, A. These are related to the partition function by ... 

Principle. This is essentially a small-scale modification of the macro piethod described on p. 416, the substance being completely oxidised in a sealed tube with fuming nitric acid in the presence of silver nitrate, the halogen being thus converted into silver halide. The collection and weighing of the silver halide require special techniques on the semi-micro scale. 

For the more advanced student, we have extended the section on Quantitative Semi-micro Analysis, and we have included a section dealing with Special Techniques in Separation and Purification, namely Adsorption Chromatography, Paper Chromatography, and Ion- Exchange Processes. 

A matrix with a large condition number is commonly referred to as ill-conditioned and particularly vulnerable to round-off errors. Special techniques. 

Chapter XII is concerned with Semimicro Technique. There can be little doubt that preparations on a smaller scale than has hitherto been customary have many advantages particular reference may be made to cost, time and bench space, all of which are important factors in teaching laboratories and also in training for research. Once the student has mastered the special technique, no difficulty should be experienced in adapting most of the preparations described in the book to the semimicro scale. A few examples of small-scale preparations are included together with a suggested list of experiments for an elementary course. 

Palladium-catalyzed coupling reactions of organic halides with olefins or dienes (R. F. Heck, 1979) are broad in scope and simple to carry out. Anhydrous conditions or any special technique are not required and most functional groups are tolerated. 

Synthesis of large heterocycles usually involves condensation reactions of two difunctional molecules. Such molecules tend to polymerize. So far two special techniques have been described above to avoid this important side-reaaion , namely high dilution and use of templates. The general procedure to avoid polymerizations in reactions between difunctional molecules is, of course, the application of protecting groups as described in sections 4.1.2 and 2.6. 

Section 13 18 One of the special techniques for distinguishing carbons according to the number of their attached hydrogens is called DEPT A series of NMR measurements using different pulse sequences gives normal nulled and inverted peaks that allow assignment of primary secondary tertiary and quaternary carbons... 

Many models can be built with the tools that have already been described Some mod els however require special techniques (or are more easily built) using some of the Spar tanBmld tools described m the following table... 

Porro, T. J. Pattacini, S. C. Sample Handling for Mid-Infrared Spectroscopy, Part 11 Specialized Techniques, Spectroscopy 1993,8(8), 39-44. 

Transient species, existing for periods of time of the order of a microsecond (lO s) or a nanosecond (10 s), may be produced by photolysis using far-ultraviolet radiation. Electronic spectroscopy is one of the most sensitive methods for detecting such species, whether they are produced in the solid, liquid or gas phase, but a special technique, that of flash photolysis devised by Norrish and Porter in 1949, is necessary. 

Special techniques for experimentation with the actinide elements other than Th and U have been devised because of the potential health ha2ard to the experimenter and the small amounts available (15). In addition, iavestigations are frequently carried out with the substance present ia very low coaceatratioa as a radioactive tracer. Such procedures coatiaue to be used to some exteat with the heaviest actinide elements, where only a few score atoms may be available they were used ia the earHest work for all the transuranium elements. Tracer studies offer a method for obtaining knowledge of oxidation states, formation of complex ions, and the solubiHty of various compounds. These techniques are not appHcable to crystallography, metallurgy, and spectroscopic studies. 

Trace contaminants such as host cell proteins (HCPs) and DNA are deterrnined by more specialized techniques. Host cell proteins are generally deterrnined using an immunochemical assay, in which an antibody preparation, raised against a mixture of the HCPs, is used to selectively detect the total level of HCPs in the product. DNA can be deterrnined using a labeled mixture, or probe, of complimentary DNA from the host cell. 

Eabrication techniques must take into account the metallurgical properties of the metals to be joined and the possibiUty of undesirable diffusion at the interface during hot forming, heat treating, and welding. Compatible alloys, ie, those that do not form intermetaUic compounds upon alloying, eg, nickel and nickel alloys (qv), copper and copper alloys (qv), and stainless steel alloys clad to steel, may be treated by the traditional techniques developed for clads produced by other processes. On the other hand, incompatible combinations, eg, titanium, zirconium, or aluminum to steel, require special techniques designed to limit the production at the interface of undesirable intermetaUics which would jeopardize bond ductihty. 

Because of its low melting point and high chemical stabiHty, HDPE is easily processed by most conventional techniques (94—98) specialized techniques have also been described (99—107) (see Plastics processing). 

Rotational Molding. Large containers and some toys are manufactured with a specialized technique caHed rotational mol ding. A rotational mol ding machine contains several large metal molds that can be rotated in two perpendicular planes. A load of fine LLDPE particles is introduced into each mold, and the mold assembly is transferred into an oven. Inside the oven, heated molds rotate at speeds ranging from 10 to 40 rpm. The polymer powder melts and is uniformly distributed on the internal surface of each mold. After the container is formed, the mold assembly is removed from the oven and cooled at which point the plastic containers are removed. 

The alkyls and aryls, R3AI (in monomer form), are colorless Hquids or low melting soHds easily oxidized and hydrolyzed when exposed to the atmosphere. Triethylalurninum (TEA), one of the most commercially important members of this family of chemicals, is so reactive it bursts into flame on contact with air, ie, it is pyrophoric, and it reacts violently with water. This behavior is typical and special techniques are necessary for the safe handling and use of organoalurninum compounds. 

Syntheses of radioactive tracers involve all of the classical biochemical and synthetic chemical reactions used in the synthesis of nonradio active chemicals. There are, however, specialized techniques and considerations required for the safe handling of radioactive chemicals, strategic synthetic considerations in terms of their relatively high cost, and synthesis scale constraints governed by specific activity requirements. 

Radioactive samples requite other, special techniques. Some are discussed in Reference 22 (see Radioactive tracers). 

The presence of polysulfonates in petroleum sulfonates used in lube formulations has a destabilizing effect on the formulation stabiUty and function of the sulfonate in motor oils, etc. Special techniques are utilized to help reduce the carryover of residual sludge components, including the use of hydrocarbon solvents such as hexane or heptane to faciUtate separation of sludge, often with centrihigation. Other desludging procedures include water wash, H2SO4 wash, clay percolation, and filtration. 

Manufacture. The manufacture of sulfur dichloride is similar to that of sulfur monochloride, except that the last stage of chlorination proceeds slowly and must be conducted at temperatures below 40°C. The preparation of a high assay sulfur dichloride requites special techniques, eg, continuous chlorination duriag distillation or distillation with traces of phosphoms trichloride or phosphoms pentasulfide [1314-80-3] (162—164). Cmde product containing 80 wt % sulfur dichloride to which is added 0.1 wt % phosphoms trichloride can be distilled to yield a 98—99 wt % pure sulfur dichloride, which can be stored for weeks at room temperature without appreciable change. 

The bismuth that is found in the lead ore accompanies the lead through the smelting operation right up to the last refining steps. The removal of bismuth then requires special techniques, the most common being the Betterton-KioU and the Betts processes (5). 

Chemically pure calcium carbide [75-20-7] is a colorless solid however, the pure material can be prepared only by very special techniques. 

Removal of Free Fatf Fields. Alkali treatment of the oil is accompHshed by the use of caustic soda solutions to neutralize the excess free fatty acids. Because castor oil readily forms emulsions with water and/or alkaline solutions, special techniques have been developed to neutralize the acids. A continuous counter-current process was developed using a stationary contact reactor (15). Treatment in the presence of a solvent is also utilized (16). 

Experimental techniques to visualize flows have been extensively used to define fluid flow in pipes and air flow over lift and control surface of airplanes. More recently this technology has been appHed to the coating process and it is now possible to visualize the flow patterns (16,17). The dimensions of the flow field are small, and the flow patterns both along the flow and inside the flow are important. Specialized techniques such as utilizing small hydrogen bubbles, dye injection, and optional sectioning, are required to visualize these flows. 

The polysulfide mbbers are capable of beiag electroplated by a special technique. Either copper or silver can be used, but the alkaline silver cyanide plating system gives more rehable results. 

Surfaces. Essentially any electrically conductive surface can be electroplated, although special techniques may be required to make the surface electrically conductive. Many techniques ate used to metalline nonconductive surfaces. These are weU-covered ia the Hterature (3) and can range from coating with metallic-loaded paints or reduced-silver spray, to autocatalytic processes on tin—palladium activated surfaces or vapor-deposited metals. Preparation steps must be optimized and closely controlled for each substrate being electroplated. 

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