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Spectral measurements

Relaxation kinetics may be monitored in transient studies tlirough a variety of metliods, usually involving some fonn of spectroscopy. Transient teclmiques and spectrophotometry are combined in time resolved spectroscopy to provide botli tire stmctural infonnation from spectral measurements and tire dynamical infonnation from kinetic measurements that are generally needed to characterize tire mechanisms of relaxation processes. The presence and nature of kinetic intennediates, metastable chemical or physical states not present at equilibrium, may be directly examined in tliis way. [Pg.2946]

Figure C3.1.1. The basic elements of a time-resolved spectral measurement. A pump source perturbs tlie sample and initiates changes to be studied. Lasers, capacitive-discharge Joule heaters and rapid reagent mixers are some examples of pump sources. The probe and detector monitor spectroscopic changes associated with absorjDtion, fluorescence, Raman scattering or any otlier spectral approach tliat can distinguish the initial, intennediate and final... Figure C3.1.1. The basic elements of a time-resolved spectral measurement. A pump source perturbs tlie sample and initiates changes to be studied. Lasers, capacitive-discharge Joule heaters and rapid reagent mixers are some examples of pump sources. The probe and detector monitor spectroscopic changes associated with absorjDtion, fluorescence, Raman scattering or any otlier spectral approach tliat can distinguish the initial, intennediate and final...
Che D P, Shapiro D B, Esquerra R M and Kliger D S 1994 Ultrasensitive time-resolved linear dichroism spectral measurements using near-crossed linear polarizers Chem. Rhys. Lett. 224 145-54... [Pg.2970]

The amino add analysis of all peptide chains on the resins indicated a ratio of Pro Val 6.6 6.0 (calcd. 6 6). The peptides were then cleaved from the resin with 30% HBr in acetic acid and chromatogra phed on sephadex LH-20 in 0.001 M HCl. 335 mg dodecapeptide was isolated. Hydrolysis followed by quantitative amino acid analysis gave a ratio of Pro Val - 6.0 5.6 (calcd. 6 6). Cycll2ation in DMF with Woodward s reagent K (see scheme below) yielded after purification 138 mg of needles of the desired cyc-lododecapeptide with one equiv of acetic add. The compound yielded a yellow adduct with potassium picrate, and here an analytically more acceptable ratio Pro Val of 1.03 1.00 (calcd. 1 1) was found. The mass spectrum contained a molecular ion peak. No other spectral measurements (lack of ORD, NMR) have been reported. For a thirty-six step synthesis in which each step may cause side-reaaions the characterization of the final product should, of course, be more elaborate. [Pg.236]

Benz[/]isoindole (125), recently prepared from the p-toluene-sulfonyl derivative (124), proved to be too unstable for isolation, but eould be trapped in solution as the Diels-Alder adduct (127). The corresponding 1-phenyl derivative (126) was also prepared and, aecording to spectral measurements, reacts with maleic anhydride to give the product (128) derived by additive substitution. This subsequently rearranged to the adduct (129). The same behavior is observed in the reaction of (126) with V-phenylmaleimide. This provides the first clear indication that substitution products from isoindole derivatives and dienophiles can be converted into the normal addition products. [Pg.144]

A useful diagnostic tool for investigating possible hydration of cations of bases for which pA is greater than about one is the measurement of their ultraviolet spectra in aqueous acid solutions and also in an anhydrous acidic solvent such as dichloroacetic acid (for which the Hammett acidity function, Hq, is — 0.9, and in which hydration of the cation cannot occur). This technique has been used with quinazoline to obtain spectra approximating those of the hydrated and anhydrous cations, respectively. For weaker bases, spectral measurements in sulfuric acid-water mixtures of increasing acid content may be used to reveal a progressive conversion of hydrated into anhydrous species as the thermodynamic activity of the water decreases. [Pg.48]

Analyzed by IR spectral measurement (Japan Special Reference Lab, Inc,). [Pg.138]

From the rearrangement of tetra-O-acetyl-2-hydroxy-D-galactal in boiling acetic acid it was possible to isolate l,2,4,6-tetra-0-acetyl-2,3-dide-h.ydro-3-deoxy-a-jy-threo-hexose (32) (58%) and a small amount of 1,2,3,4,6-penta-O-acetyl-jS-D-galactopyranose. In the reaction mixture the presence of some a-pentaacetate was demonstrated chromatographically but NMR spectroscopy indicated no resonances corresponding to the / anomer of compound 32. These spectral measurements indicate that compound 32 constituted 80% of the mixture of products. [Pg.162]

High refractory properties, extremely strong sensitivity to moisture and exceptionally high chemical activity of fluoride melts, especially of those containing ions of polyvalent metals, make spectral measurements of such melts extremely complicated. In order to obtain reliable results, the measurement cell must comply with three main requirements ... [Pg.168]

However, valence isomerism in some l//-azepinc-4,5-dicarboxylates, e.g. 3, which is undetectable by NMR spectral measurements, has been confirmed by trapping out the benzene imine tautomers 4, as their bisdipolar cycloadducts 5, with diazomethane.233,234 In contrast, ethyl l//-azepine-l-carboxylate and diethyl l-acetyl-l//-azcpinc-3,5-dicarboxylate, with diazomethane, yield only the C4-C5 dipolar cycloadducts. [Pg.176]

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. [Pg.559]

The nickel(II) dithiocarbamate complexes are neutral, water-insoluble, usually square-planar, species, and they have been studied extensively by a range of physical techniques. The usual methods for the synthesis of dithiocarbamate complexes have been employed in the case of Ni(II), Pd(II), and Pt(II). In addition, McCormick and co-workers (330,332) found that CS2 inserted into the Ni-N bonds of [Ni(aziri-dine)4P+, [Nilaziridinelgf, and [Ni(2-methylaziridine)4] to afford dithiocarbamate complexes. The diamagnetic products are probably planar, but they have properties typical of dithiocarbamate complexes, and IR- and electronic-spectral measurements suggested that they may be examples of N,S-, rather than S,S-, bonded dithiocarbamates. The S,S-bonded complexes are however, obtained, by a slow rearrangement in methanol. The optically active lV-alkyl-iV(a-phenethyl)dithio-carbamates of Ni(II), Pd(II), and Cu(II) (XXIV) have been synthesized, and the optical activity was found to be related to the anisotropy of the charge-transfer transitions (332). [Pg.254]

Another point of contention has been the extent to which, if any, SbFj is reduced to SbFs upon intercalation. Although chemical analyses have shown an F Sb ratio of 5 1 (Lll, M5), Sb Mossbauer measurements (B24) indicated partial reduction of Sb(V) to Sb(III). On the other hand, mass-spectral measurements as a function of temperature (S15) showed only SbFs, evolved in stages, with no fluorocarbons emitted at any time. The latter are usually an indication of partial reduction of the intercalant and fluorination of the graphite host. Wide-line, F-NMR chemical-shifts are consistent with either SbFj or SbFe, but not with SbFs, but the occurrence of fluorine exchange could produce minor amounts of trivalent species (FI 1) this point is thus still controversial, and will be alluded to again. [Pg.310]

A free radical (often simply called a radical) may be defined as a species that contains one or more unpaired electrons. Note that this definition includes certain stable inorganic molecules such as NO and NO2, as well as many individual atoms, such as Na and Cl. As with carbocations and carbanions, simple alkyl radicals are very reactive. Their lifetimes are extremely short in solution, but they can be kept for relatively long periods frozen within the crystal lattices of other molecules. Many spectral measurements have been made on radicals trapped in this manner. Even under these conditions, the methyl radical decomposes with a half-life of 10-15 min in a methanol lattice at 77 K. Since the lifetime of a radical depends not only on its inherent stabihty, but also on the conditions under which it is generated, the terms persistent and stable are usually used for the different senses. A stable radical is inherently stable a persistent radical has a relatively long lifetime under the conditions at which it is generated, though it may not be very stable. [Pg.238]

Stacked together along the a-axis. The long molecular axes are tilted by 13° within the layers. By Raman spectral measurements Tashiro et al. found that the biphenyl group of the compound has a twisted structure in the liquid crystalline state as well as in the a-form. [Pg.172]

Amino acid sequences of eleven homologous sea anemone polypeptides have been elucidated. All possess three disulfide bonds. The six half-cysteine residues always occur in the same positions (7,8). Initial studies concerning the toxin secondary and tertiary structures relied upon circular dichroism, laser Raman, and, to a lesser extent, fluorescence spectral measurements (15—18). The circular dichroism spectra of the four toxins so far examined are essentially superimpos-able and thus indicate a common secondary structure. The only peak observed, a negative ellipticity at 203 nm, largely results from a non-regular ("random")... [Pg.280]

Recent work in our laboratory has shown that Fourier Transform Infrared Reflection Absorption Spectroscopy (FT-IRRAS) can be used routinely to measure vibrational spectra of a monolayer on a low area metal surface. To achieve sensitivity and resolution, a pseudo-double beam, polarization modulation technique was integrated into the FT-IR experiment. We have shown applicability of FT-IRRAS to spectral measurements of surface adsorbates in the presence of a surrounding infrared absorbing gas or liquid as well as measurements in the UHV. We now show progress toward situ measurement of thermal and hydration induced conformational changes of adsorbate structure. The design of the cell and some preliminary measurements will be discussed. [Pg.435]

Secondly, the reaction of 89a, 90a, and K2CO3 under solvent-free conditions was monitored by IR spectral measurement. A mixture of 89a, an equimolar amount of 90a, and twice the molar amount of K2CO3 initially showed vC=0 absorption (C) at 1670 cm assigned to the formation of 93 this absorption decreased gradually and new vC=0 absorption bands appeared at 1696 (D) and 1641 cm" (E) (Fig. 2). After 60 min, the C absorption band disappeared and the D and E absorptions increased. After further reaction at 80 °C for 10 min, the D absorption disappeared and only the E absorption remained in the spectrum (VI in Fig. 2). The spectrum VI is identical to that of the final product 91a. The appearance of the D absorption band together with a strong OH absorption band at 3465 cm" suggests production of a ketoalcohol intermediate. [Pg.21]

Fig. 3 Monitoring for 40 min of the solvent-free benzoylation of 20 with 101b at 80 °C by IR spectral measurements in Nujol mulls... Fig. 3 Monitoring for 40 min of the solvent-free benzoylation of 20 with 101b at 80 °C by IR spectral measurements in Nujol mulls...
This discussion of the structures of diene polymers would be incomplete without reference to the important contributions which have accrued from applications of the ozone degradation method. An important feature of the structure which lies beyond the province of spectral measurements, namely, the orientation of successive units in the chain, is amenable to elucidation by identification of the products of ozone cleavage. The early experiments of Harries on the determination of the structures of natural rubber, gutta-percha, and synthetic diene polymers through the use of this method are classics in polymer structure determination. On hydrolysis of the ozonide of natural rubber, perferably in the presence of hydrogen peroxide, carbon atoms which were doubly bonded prior to formation of the ozonide... [Pg.243]

The first copper(II) complexes prepared with a 2-acetylpyridine thiosemicarbazone were those of the 3-azabicyclononyl-derivative, 4, as well as the analogous selenosemicarbazone [175]. Monomeric [Cu(4-H) A] where A = Cl, Br, I, OAc and NO3 were characterized by their magnetic and spectral measurements. A second report [128] on copper(II) complexes of 4 included [Cu(4) (4-H)]BF4 as... [Pg.24]

Here, B ls = K (KK )" is the final qxp matrix of regression coefficients for converting a spectral measurement into concentration estimates. For KK (pxp) to be invertible K should be of full rank. A first requirement for this is that pchemical components should not exceed the number of wavelengths. Furthermore, the set of pure spectra in K should be independent, i.e. no pure spectrum may be an exact linear combination of the other pure spectra. [Pg.355]

Several precautions were taken to ensure the immobilization chemistry. First, the sulfhydryl groups containing the macromolecular fraction was spectrophotometrically determined according to the literature [15]. We found that every set of 150 base pairs contained approximately one disulfide group. Since the DNA fragment used has hundreds of base pairs, each DNA strand seems to have one disulfide as its terminal group. Next, we made IR spectral measurements in a reflection-absorption (RA) mode [14b]. A freshly evaporated gold substrate was immersed into the DNA solution for 24 h at 5°C. The substrate was carefully rinsed with deionized water, dried under vacuum and was immediately used for the measurements. An Au substrate treated with unmodified, native sonicated CT DNA solution was also prepared as the control measurement. The / -polar-ized radiation was introduced on the sample at 85° off the surface normal and data were collected at a spectral resolution of 4 cm with 2025 scans. [Pg.519]

Several commercial companies now offer process compatible NMR systems. These systems are either low resolution based on relaxation time measurements or high resolution Fourier Transform spectral measurements. The low resolution systems are manufactured by Process Control Technologies (www.pctnmr.com) and Progression, Inc. (www.progression-systems.com). Progression s systems... [Pg.482]

In contrast to the dihalogens, there are only a few spectral studies of complex formation of halocarbon acceptors in solution. Indeed, the appearance of new absorption bands is observed in the tetrabromomethane solutions with diazabicyclooctene [49,50] and with halide anions [5]. The formation of tetrachloromethane complexes with aromatic donors has been suggested without definitive spectral characterization [51,52]. Moreover, recent spectral measurements of the intermolecular interactions of CBr4 or CHBr3 with alkyl-, amino- and methoxy-substituted benzenes and polycyclic aromatic donors reveal the appearance of new absorption bands only in the case of the strongest donors, viz. Act = 380 nm with tetramethyl-p-phenylendiamine (TMPD) and Act = 300 nm with 9,10-dimethoxy-l,4 5,8-... [Pg.151]

No new absorption bands are observed in other cases, largely due to the fact that the strong absorptions of the aromatic donors obstruct the UV-spectral measurements. For the complex between CBr4 and TMPD, the quantitative analyses of the temperature and concentration-dependent absorptions of the new band at 380 nm afford the extinction coefficient of ct = 3.2 x 103 M 1 cm x, as well as the thermodynamic parameters for complex formation AH = - 4.5 kcalM x, AS = - 14 e.u., and Kda = 0.3 M x at 295 K. Such thermodynamic characteristics are similar to those of the dihalogen complexes of as well as those of other acceptors with aromatic donors. Similar results are also obtained for CBr4 associates with halide and thio-cyanide anions [5,53]. [Pg.152]

The introduction of Py at the 2 sugar position of uridine and Ptz at the 5 -end of ODN caused an increase in Tm. The Tm for PtzPy-1 is 39.4 °C, which is 6.9 °C higher than that of unmodified ODN (32.5 °C). Similarly, the introduction of Ptz or Py into ODN showed increases in Tm for Ptz-1 (1.2 °C) and for Py-1 (6.6 °C) compared with unmodified ODN, suggesting that Py intercalated into ODN duplex at the 3 -side, and the 5 -linked-Ptz associated with the 5 -terminus by end-capping [5]. The structures of ODNs conjugated with Py and Ptz were examined by circular dichroism (CD) spectral measurements. The CD spectra of ODNs in 20 mM phosphate buffer were characteristic of the B-form. [Pg.142]

The author thanks the General Electric Research and Development Center for permission to publish this work and thanks Mr. S. T. Rice for many of the yellowness index and UV spectral measurements. Mr. William Delaware of the New York State Department of Environmental Conservation is also thanked for his data. [Pg.105]


See other pages where Spectral measurements is mentioned: [Pg.2949]    [Pg.417]    [Pg.383]    [Pg.161]    [Pg.236]    [Pg.15]    [Pg.81]    [Pg.18]    [Pg.218]    [Pg.300]    [Pg.185]    [Pg.13]    [Pg.258]    [Pg.24]    [Pg.40]    [Pg.134]    [Pg.31]    [Pg.363]    [Pg.601]    [Pg.1217]    [Pg.20]   
See also in sourсe #XX -- [ Pg.119 ]

See also in sourсe #XX -- [ Pg.178 , Pg.185 ]




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