Soret

The coefficients, L., are characteristic of the phenomenon of thermal diffusion, i.e. the flow of matter caused by a temperature gradient. In liquids, this is called the Soret effect [12]. A reciprocal effect associated with the coefficient L. is called the Dufour effect [12] and describes heat flow caused by concentration gradients. The... 

Soret band of the macrocycle, a ti to tt transition, is excited instead. It has been found that the vinyl groups do not participate in the conjugated system [4]. This is based on the fact that the vinyl C=C stretch does not... 

Figure C3.1.7. Time-resolved optical absorjDtion data for the Soret band of photo lysed haemoglobin-CO showing six first-order (or pseudo-first-order) relaxation phases, I-VI, on a logaritlimic time scale extending from nanoseconds to seconds. Relaxations correspond to geminate and diffusive CO rebinding and to intramolecular relaxations of tertiary and quaternary protein stmcture. (From Goldbeck R A, Paquette S J, Bjorling S C and Kliger D S 1996 Biochemistry 35 8628-39.)...

L. Holmia, for Stockholm). The special absorption bands of holmium were noticed in 1878 by the Swiss chemists Delafontaine and Soret, who announced the existence of an "Element X." Cleve, of Sweden, later independently discovered the element while working on erbia earth. The element is named after cleve s native city. Holmia, the yellow oxide, was prepared by Homberg in 1911. Holmium occurs in gadolinite, monazite, and in other rare-earth minerals. It is commercially obtained from monazite, occurring in that mineral to the extent of about 0.05%. It has been isolated by the reduction of its anhydrous chloride or fluoride with calcium metal. 

Iron Porphyrins. Porphyrias (15—17) are aromatic cycHc compouads that coasist of four pyrrole units linked at the a-positions by methine carbons. The extended TT-systems of these compounds give rise to intense absorption bands in the uv/vis region of the spectmm. The most intense absorption, which is called the Soret band, falls neat 400 nm and has 10. The TT-system is also responsible for the notable ring current effect observed in H-nmr spectra, the preference for planar conformations, the prevalence of electrophilic substitution reactions, and the redox chemistry of these compounds. Porphyrins obtained from natural sources have a variety of peripheral substituents and substitution patterns. Two important types of synthetic porphyrins are the meso-tetraaryl porphyrins, such as 5,10,15,20-tetraphenylporphine [917-23-7] (H2(TPP)) (7) and P-octaalkylporphyrins, such as 2,3,7,8,12,13,17,18-octaethylporphine [2683-82-1] (H2(OEP)) (8). Both types can be prepared by condensation of pyrroles and aldehydes (qv). 

The Ni and V concentrated into the vacuum resid appear to occur in two forms. Erom 10 to 14% of each of these two metals can be distilled in the 565—705°C boiling range, where they exhibit the strong visible Soret bands associated with the porphyrin stmcture. This tetrapyrrole stmcture (48,49), possibly derived from ancient chlorophyll, has been confirmed by a variety of analytical techniques. 

The e.m.f. of a thermogalvanic cell is the result of four main effects (a) electrode temperature, (b) thermal liquid junction potential, (c) metallic thermocouple and (d) thermal diffusion gradient or Soret. 

Cytochrome P450 monooxygenases are characterized through the presence of the heme (protoporphyrin IX) prosthetic group (Scheme 10.1) that is coordinated to the enzyme through a conserved cysteine ligand. They have obtained their name from the signature absorption band with a maximum near 450 nm in the difference spectrum when incubated with CO. The absorption arises from the Soret Jilt transition of the ferrous protoporphyrin IX-CO complex. 

If a temperature gradient is maintained in a binary gaseous mixture, a concentration gradient is established with the light component collecting preferentially at the hot end and the heavier one at the cold end. This phenomenon, known as the Soret effect, may be used as the basis of a separation technique of commercial significance in the separation of isotopes. 

Chlorophylls c have characteristic bands between 578 and 630 nm and between 443 and 450 mn that correspond to the Q-band and the Soret band, respectively. ... 

The spectral characteristics of bacteriochlorophyUs differ from each other, depending on their peripheral side chains, and the Q band varies between 646 and 795 nm, while the Soret band ranges between 365 and 456 mn. BacteriochlorophyUs absorb in the infrared, in addition to the blue part of the spectrum. ... 

Comparative studies of the widely employed spectrophotometric readings at the Soret and Q bands (405 and 630 nm, respectively) and the elemental analysis of copper and nitrogen showed that the spectrophotometric assay based only on the Soret band can overestimate the purity of a preparation. Erroneous data were attributed to an increase in absorptivity at the Soret band when other colored compounds like metal-free analogs and carotenoids are present. Indeed, copper-free chlorin e6 exhibits a specific absorbance 3.6 times greater than that of its coppered counterpart. Therefore, measurements at the Q band (630 mn) and the establishment of the S Q ratio are preferred. 

However, it was pointed out that two other observations are out of line with the iron(I) formulation and more consistent with an iron(II)-porphyrin radical anion [290] (1) the low-intensity red-shifted Soret band in the UV-VIS spectrum with broad maxima in the a,(3-region compared to, for instance, Fe(TPP) in THF, is typical of a porphyrin radical, and (2) the bond lengths of the porphyrin core indicate population of the (antibonding) LUMO of the ligand (i.e., the presence of an extra electron in the re-system). The presence of porphyrin radical character in the electronic ground state was also inferred from the paramagnetic NMR-shifts of the pyrrole protons at the meso and p-carbon atoms [291]. 

The second reduction step of Fe(II)(TPP) yields an extremely air-sensitive green product which can be assigned the formula [Fe(I)(TPP) ] because of the red shift of the Soret band in the UV-VIS spectrum. The pure material is diamagnetic (S = 0) but this does not allow one to distinguish between the three possible descriptions as an iron(O) / -porpyhrin, a spin-coupled S = 1/2 iron(I)-porphyrin... 

FIG. 16 Photocurrent spectra corresponding to the photo-oxidation of DCMFc by ZnYPPC" at the water-DCE interface under chopped illumination and lock-in detection. The main features of the spectra coincide with the onset of the Soret band and the Q-bands of the porphyrin ring. (From Ref. 73. Reproduced by permission of the Royal Society of Chemistry.)... 

While the control resins were deep red in color due to the presence of soluble porphyrin complexes, the methacrylate resins obtained after removal of the polyethylene-supported catalysts varied from light yellow to nearly water-white (APHA < 25). UV-Vis spectrophotometric analysis of the yellow resins indicated an absorption signal for the cobalt porphyrin complex Soret band (wavelength of cobalt(ll) porphyrin species appears at -415 nm free porphyrin ligand is formd at -423 tun). Resin samples that visttally appear as water-white show little or no porphyrin species present in the spectrum. Measured catalyst activity and PDl of the polyethylene-supported porphyrin complexes are in the expected range for soluble porphyrin CCT catalysts (PDl = M /Mn - 1.2- 2.0)." The screening resrrlts clearly... 

Sanders (14) has exploited the strong and selective coordination of phosphine donor groups to Ru(II) to construct hetero-dimetallic porphyrin dimers (17, Fig. 5). An alkyne-phosphine moiety introduced on the periphery of a free base or metalloporphyrin (M = Zn or Ni) spontaneously coordinates to a Ru(II)(CO) porphyrin when the two porphyrins are mixed in a 1 1 ratio. Coordination is characterized by a downfield shift of the 31P resonance (A<531P = 19 ppm). There is no evidence of self-coordination of the zinc porphyrin at 10 6 m in toluene, there is no shift in the Soret band in the UV-Vis absorption spectrum. The Ni-Ru dimer was observed by MALDI-TOF mass spectrometry. Heating the Ru(II)CO porphyrin with 2 equivalents of the phosphine porphyrins led to quantitative formation of trimeric assemblies. 

The Soret, a and j3 bands in the visible spectra of platinum(IV) porphyrin complexes occur at longer wavelengths than their platinum(II) analogues,482 H NMR resonances are all shifted downfield,482 the 13C resonances of the a carbons are shifted upheld, and the H-195Pt and 13C-195Pt coupling constants are reduced.480 Whereas excitation of platinum(II) porphyrin complexes... 

Per Theodor Cleve (1840-1905) independently Marc Delafontaine (1837-1911) and J.-L. Soret (1827-1890). 

LDMS is particularly well suited for the analysis of porphyrins.35-39 The heme molecule—a 22 rc-electron conjugated protoporphyrin system (Figure 8.1)—is an efficient photo-absorber in the visible and near UV (with an absorption maximum—the Soret band—near 400nm). This feature, concurrently with its low ionization potential, warrants that direct LDMS will possess extremely low limits for heme detection. The uses of IR or UV LDMS for structural characterization of natural porphyrins and their metabolites, synthetic monomeric porphyrins (e.g., used in photodynamic therapy), porphyrin polymers, and multimeric arrays, have been well documented.41148 In addition fast atom bombardment MS has been used to characterize purified hemozoin, isolated from the spleens and livers of Plasmodium yoelii infected mice.49... 

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