2006
DOI: 10.1016/j.jmr.2005.11.001
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The time-dependence of exchange-induced relaxation during modulated radio frequency pulses

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Cited by 12 publications
(18 citation statements)
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“…The time-dependent magnitude of the effective frequency vector is given by, ω eff ( t ) = ω 1 2 ( t ) + ( ω 0 ω R F ( t ) ) 2 . In accordance with the 2SX model, with two water populations ( P A and P B , where P A + P B = 1) coupled by equilibrium exchange, the rate constant describing longitudinal rotating frame relaxation ( R 1ρ,obs =( T 1ρ,obs ) -1 ) during an adiabatic pulse is given by (Michaeli et al 2004; Sorce et al 2006) R ¯ 1 ρ , italicobs = P A T P 0 T P R 1 ρ A , d d ( t ) d t + P B T P 0 T P R 1 ρ B , d d ( t ) d t + 1 T P 0 T P R 1 ρ , italicex ( t ) d t , where T P is the length of individual pulses. Contributions from dipolar fluctuations (first and second terms of Eq.…”
mentioning
confidence: 75%
“…The time-dependent magnitude of the effective frequency vector is given by, ω eff ( t ) = ω 1 2 ( t ) + ( ω 0 ω R F ( t ) ) 2 . In accordance with the 2SX model, with two water populations ( P A and P B , where P A + P B = 1) coupled by equilibrium exchange, the rate constant describing longitudinal rotating frame relaxation ( R 1ρ,obs =( T 1ρ,obs ) -1 ) during an adiabatic pulse is given by (Michaeli et al 2004; Sorce et al 2006) R ¯ 1 ρ , italicobs = P A T P 0 T P R 1 ρ A , d d ( t ) d t + P B T P 0 T P R 1 ρ B , d d ( t ) d t + 1 T P 0 T P R 1 ρ , italicex ( t ) d t , where T P is the length of individual pulses. Contributions from dipolar fluctuations (first and second terms of Eq.…”
mentioning
confidence: 75%
“…The formalism was initially formulated to describe relaxation during CW SL experiments, where ω eff and α are constant during the RF irradiation [1,2,16,17]. Recently, the theoretical expressions of R 1ρ ( t ) and R 2ρ ( t ) have been generalized to the case of time-dependent ω eff ( t ) and α( t ) [6,18,19]. It has been shown that the relaxations during adiabatic rotation in the weak field approximation could be represented as an average of instantaneous time-dependent contributions due to the different relaxation channels:trueR1,2ρ=1Tnormalp0TnormalpR1,2ρ,ex(t)dt+1Tnormalp0TnormalpR1,2ρ,dd(t)dt,where R 1,2ρ,dd and R 1,2ρ,ex are the rotating frame relaxations due to dipolar interactions and anisochronous exchange, respectively.…”
Section: B Theoretical Overviewmentioning
confidence: 99%
“…The difference in chemical shifts between sites m and q is defined by δω in rad/s. Here k 1 and k -1 represent the forward and backward exchange rate constants obeying the McConnell relationship [21]:τex=Pnormalmk1=Pnormalqk1,and for anisochronous exchange in the fast regimeτex=1kex<<δω1.Exchange-induced R 1ρ,ex and R 2ρ,ex under CW SL irradiation were derived in [1,2]:R1ρ,ex=PnormalmPnormalqδω2sin2ατex1+(ωeffτex)2,R2ρ,ex=PnormalmPnormalq(δω)2true[cos2ατex+12sin2ατex1+(ωeffτex)2true].The corresponding time-dependent relaxation functions during adiabatic rotation were detailed in [19]. Theory shows R 1ρ,ex and R 2ρ,ex to be dependent on the choice of the amplitude- and frequencymodulation functions of adiabatic pulses via their α( t ) and ω eff ( t ) dependencies.…”
Section: B Theoretical Overviewmentioning
confidence: 99%
“…Previous work from our laboratory focused on the derivation of exchange-induced relaxations during adiabatic pulses of the hyperbolic secant (HS n ) family [3], where the theoretical treatment of exchange-induced relaxation was given in the effective field frame, H 1 (t) [12, 13]. Following our nomenclature, H 1 is the effective field in first rotating frame (FRF), and thus upon convention the H 1 (here we adapted terminology used in [4]) is the vector sum of ω 1 (t) x⃗ ' and Δω ( t ) z⃗ '.…”
Section: Theorymentioning
confidence: 99%
“…We note that the symbol ± indicates the taking of the hermitian adjoint, and in particular we adopt the convention: T1q±=false(1false)qT1q Using Eqs. (15–19) and using the secular approximation [27], we find: dtruetrueσ˜˜˜false(tfalse)dt=0true{δfalse(tfalse)δfalse(tτfalse)true}q2=11q1=11italicexpfalse(iτq2H2false(tfalse)false)false(dq1q2false(1false)false(α2false(tfalse)false)false)2false(d0q1false(1false)false(α1false(tfalse)false)false)2false(1false)q2false[T1q2,false[T1q2,truetrueσ˜˜˜false(tfalse)false]dτ. We assume an exponential dependence for the correlation function: false{δfalse(tfalse)δfalse(tτfalse)false}italicexpfalse(τ/τexfalse), where τ ex is the lifetime of the spin in either of the two exchanging sites [13, 14]. Then, by carrying out the integration, we derive the spectral density function: Jfalse(q2H2false(tfalse)false)=kexτexfalse(1+false(false(q2H…”
Section: Theorymentioning
confidence: 99%