Temperature jump complexes

Temperature-jump kinetics. The kinetics of complexation of lutetium(III) with anthrani-late ion was studied by the use of a temperature-jump method.25 The principal reaction is... 

This report has been written in order to demonstrate the nature of spin-state transitions and to review the studies of dynamical properties of spin transition compounds, both in solution and in the solid state. Spin-state transitions are usually rapid and thus relaxation methods for the microsecond and nanosecond range have been applied. The first application of relaxation techniques to the spin equilibrium of an iron(II) complex involved Raman laser temperature-jump measurements in 1973 [28]. The more accurate ultrasonic relaxation method was first applied in 1978 [29]. These studies dealt exclusively with the spin-state dynamics in solution and were recently reviewed by Beattie [30]. A recent addition to the study of spin-state transitions both in solution and the... 

The most significant results obtained for complexes of iron(II) are collected in Table 3. The data derive from laser Raman temperature-jump measurements, ultrasonic relaxation, and the application of the photoperturbation technique. Where the results of two or three methods are available, a gratifying agreement is found. The rate constants span the narrow range between 4 x 10 and 2 X 10 s which shows that the spin-state interconversion process for iron(II) complexes is less rapid than for complexes of iron(III) and cobalt(II). 

Polyether complexation. The kinetics of formation of polyether crown, cryptand and related complexes have received considerable attention. Since formation rates are often quite fast, techniques such as temperature-jump, ultrasonic resonance, and nmr have typically been used for such studies. 

The observation of a single set of resonances in the NMR spectra of [Fe(HB(pz)3)2], spectra that are clearly obtained for a mixture of the high-spin and low-spin forms of the complex, indicates that the equilibrium between the two states is rapid on the NMR time scale [27]. Subsequent solution studies by Beattie et al. [52, 53] using both a laser temperature-jump technique and an ultrasonic relaxation technique have established that the spin-state lifetime for [Fe(HB(pz)3)2] is 3.2xl0 8 s. These studies also established... 

The complexity of the binding dynamics of 1 with DNA became apparent in subsequent temperature jump experiments, where three relaxation processes were observed.112 The fastest relaxation process had a small amplitude (< 14%) and its kinetics were uncoupled from the second and third relaxation processes. This fast process was assigned to the binding of 1 to a minor site with a k+ value of 1.5x10 M s and a value of 6.9 x 10 s. This assignment was problematic because of the possible interference of artifacts for temperature jump experiments when the fluorescence detection is not performed at the magic angle,29 and this kinetic component was not observed in later studies.94,120... 

Studies on the dynamics of complexation for guests with cyclodextrins have been carried out using ultrasonic relaxation,40 151 168 temperature jump experiments,57 169 183 stopped-flow,170,178,184 197 flash photolysis,57 198 202 NMR,203 205 fluorescence correlation spectroscopy,65 phosphorescence measurements,56,206 and fluorescence methods.45,207 In contrast to the studies with DNA described above, there are only a few examples in which different techniques were employed to study the binding dynamics of the same guest with CDs. This probably reflects that the choice of technique was based on the properties of the guests. The examples below are grouped either by a type of guest or under the description of a technique. 

The kinetics of a series of guests that form 2 1 (guest CD) complexes were studied using temperature jump methods.179 183,210 The formation of the 1 1 complex was determined to be fast and to occur within the time resolution of the equipment, while... 

Compounds 30-32 formed 2 1 complexes with CDs (Scheme 13). The formation of the 1 1 complex was fast and for this reason only one relaxation process was observed. In the cases where the 2 2 complex was present its formation was also fast and only one relaxation process for the 2 1 complex was observed in the temperature jump experiments. Since the equilibria are coupled the expression for the observed rate constant includes Kt, (and K22 when the 2 2 complex is present), k21, k2, and the concentrations of guest, 1 1 complex and CD.180 182 The values for the association and dissociation rate constants and equilibrium constants were obtained from the non-linear fit of the dependence of kobs on the total concentration of CD (Table 9). 

The association rate constants were the same within experimental error. The dissociation rate constant for 31 was however an order of magnitude larger than that for 32. The association rate constants determined with fluorescence correlation spectroscopy were similar to the rate constants determined using temperature jump experiments (see above). However, a significant difference was observed for the dissociation rate constants where, for the 1 1 complex, values of 2.6 x 104 and 1.5 x 104s 1 were determined in the temperature jump experiments for 31 and 32, respectively.181,182 The reasons for this difference were not discussed by the authors of the study with fluorescence correlation spectroscopy. One possibility is that the technique is not sensitive enough to detect the presence of higher-order complexes, such as the 1 2 (31 CD) complex observed in the temperature jump experiments. One other possibility is the fact that the temperature jump experiments were performed in the presence of 1.0 M NaCl. 

The results of a temperature jump relaxation study of the complexation of metal cations by dibenzo-30-crown-10 [14] in methanol led Chock (1972) to propose a two-step mechanism. The first step (9) comprises a rapid equilibrium... 

The relaxation approach has played an important role in our understanding of the mechanisms of complex formation in solution (Chap. 4) 39,i4o -pjjg qj computer programs has now eased the study of multiple equilibria. For example, four separate relaxation effects with t s ranging from 100 xs to 35 ms are observed in a temperature-jump study of the reactions of Ni with flavin adenine dinucleotide (fad) (Eqn. (8.121)). The complex relaxation... 

The rate constants and k represent rate constants for a surface reaction and have units m mol s and s respectively. The accelerative effects are about 10 -10 fold. They indicate that both reactants are bound at the surface layer of the micelle (surfactant-water interface) and the enhanced rates are caused by enhanced reactant concentration here and there are no other significant effects. Similar behavior is observed in an inverse micelle, where the water phase is now dispersed as micro-droplets in the organic phase. With this arrangement, it is possible to study anion interchange in the tetrahedral complexes C0CI4 or CoCl2(SCN)2 by temperature-jump. A dissociative mechanism is favored, but the interpretation is complicated by uncertainty in the nature of the species present in the water-surfactant boundary, a general problem in this medium. 

Until 1984, all of the stopped-flow and temperature-jump kinetic studies of alpha cyclodextrin inclusion-complex formation were explainable in terms of a single-step, binding mechanism. According to this mechanism, the observed rate constant, kobs, (for stopped-flow) and the reciprocal relaxation time, 1/t, (for temperature-jump) should show a linear dependence on the edpha cyclodextrin concentration. Sano and coworkers, however, in the case of the iodide-alpha cyclodextrin interaction, and Hersey and Robinson,in the case of various azo dye-alpha cyclodextrin interactions (see Fig. 7), found that certain guest species exhibit a limiting value of kobs and 1/t at high concentrations of alpha cyclodextrin. This behavior can most simply be explained in terms of a mechanism of the type,... 

Further support for the presence of a conformational change has come from the work of Orstan and Wojcik, who also studied azo dye-alpha cyclodextrin complexes by using the temperature-jump technique. The dyes that they investigated showed three different types of behavior. Certain dyes showed a limiting value of 1/t at high alpha cyclodextrin concentrations, others showed a linear dependence of 1/t on alpha cyclo-... 

The formation of a one host-two guests inclusion-complex could proceed by way of two main mechanisms (/) dimerization of the guest, followed by inclusion and (2) stepwise inclusion of two guest molecules. In order to distinguish between these two possibilities, several temperature-jump relaxation kinetic studies have been carried us-... 

During the past year, in association with Manfred Eigen in Gottingen, Germany, I examined a number of substitution reactions of nickel to see if there was indeed a direct relationship between the charge of a complex and its rate of water substitution. The temperature jump method was used to measure the rate of substitution of NH3 for water with various complexes. 

T4 lysozyme 33,497 helix stability of 528, 529 hydrophobic core stability of 533, 544 Tanford j8 value 544, 555, 578, 582-Temperature jump 137, 138, 541 protein folding 593 Terminal transferase 408,410 Ternary complex 120 Tertiary structure 22 Theorell-Chance mechanism 120 Thermodynamic cycles 125-131 acid denaturation 516,517 alchemical steps 129 double mutant cycles 129-131, 594 mutant cycles 129 specificity 381, 383 Thermolysin 22, 30,483-486 Thiamine pyrophosphate 62, 83 - 84 Thionesters 478 Thiol proteases 473,482 TNfn3 domain O-value analysis 594 folding kinetics 552 Torsion angle 16-18 Tbs-L-phenylalanine chloromethyl ketone (TPCK) 278, 475 Transaldolase 79 Tyransducin-o 315-317 Transit time 123-125 Transition state 47-49 definition 55... 

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