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1.
A novel implementation of the water flipback technique employing a 45 degrees flip-angle water-selective pulse is presented. The use of this water flipback technique is shown to significantly enhance signal in 3D 15N-edited ROESY in a 20 kDa complex of the vnd/NK-2 homeodomain bound to DNA. The enhancement is seen relative to the same experiment using weak water presaturation during the recovery delay. This enhancement is observed for the signals from both labile and nonlabile protons. ROESY and NOESY pulse sequences with 45 degrees water flipback are presented using both HMQC and HSQC for the 15N dimension. The 45 degrees flipback pulse is followed by a gradient, a water selective 180 degrees pulse, and another gradient to remove quadrature images and crosspeak phase distortion near the water frequency. Radiation damping of the water magnetization during the t1 and t2 evolution periods is suppressed using gradients. Water resonance planes from NOESY-HMQC and NOESY-HSQC spectra show that the HMQC version of the pulse sequences can provide stronger signal for very fast exchanging protons. The HSQC versions of the ROESY and NOESY pulse sequences are designed for the quantitative determination of protein-water crossrelaxation rates, with no water-selective pulses during the mixing time and with phase cycling and other measures for reducing axial artifacts in the water signal.  相似文献   

2.
Three-dimensional image-selected in vivo spectroscopy (ISIS) was combined with phase-cycled 1H–15N heteronuclear multiple-quantum coherence (HMQC) transfer NMR for localized selective observation of protons J-coupled to 15N in phantoms and in vivo. The ISIS–HMQC sequence, supplemented by jump–return water suppression, permitted localized selective observation of 2–5 μmol of [15Nindole]tryptophan, a precursor of the neurotransmitter serotonin, through the 15N-coupled proton in 20–40 min of acquisition in vitro at 4.7 T. In vivo, the amide proton of [5-15N]glutamine was selectively observed in the brain of spontaneously breathing 15NH4+-infused rats, using a volume probe with homogeneous 1H and 15N fields. Signal recovery after three-dimensional localization was 72–82% in phantoms and 59 ± 4% in vivo. The result demonstrates that localized selective observation of 15N-coupled protons, with complete cancellation of all other protons except water, can be achieved in spontaneously breathing animals by the ISIS–HMQC sequence. This sequence performs both volume selection and heteronuclear editing through an addition/subtraction scheme and predicts the highest intrinsic sensitivity for detection of 15N-coupled protons in the selected volume. The advantages and limitations of this method for in vivo application are compared to those of other localized editing techniques currently in use for non-exchanging protons.  相似文献   

3.
The effect of proton exchange on the measurement of1H–1H,1H–2H, and2H–2H residual dipolar interactions in water molecules in bovine Achilles tendons was investigated using double-quantum-filtered (DQF) NMR and new pulse sequences based on heteronuclear and homonuclear multiple-quantum filtering (MQF). Derivation of theoretical expressions for these techniques allowed evaluation of the1H–1H and1H–2H residual dipolar interactions and the proton exchange rate at a temperature of 24°C and above, where no dipolar splitting is evident. The values obtained for these parameters at 24°C were 300 and 50 Hz and 3000 s−1, respectively. The results for the residual dipolar interactions were verified by repeating the above measurements at a temperature of 1.5°C, where the spectra of the H2O molecules were well resolved, so that the1H–1H dipolar interaction could be determined directly from the observed splitting. Analysis of the MQF experiments at 1.5°C, where the proton exchange was in the intermediate regime for the1H–2H dipolar interaction, confirmed the result obtained at 24°C for this interaction. A strong dependence of the intensities of the MQF signals on the proton exchange rate, in the intermediate and the fast exchange regimes, was observed and theoretically interpreted. This leads to the conclusion that the MQF techniques are mostly useful for tissues where the residual dipolar interaction is not significantly smaller than the proton exchange rate. Dependence of the relaxation times and signal intensities of the MQF experiments on the orientation of the tendon with respect to the magnetic field was observed and analyzed. One of the results of the theoretical analysis is that, in the fast exchange regime, the signal decay rates in the MQF experiments as well as in the spin echo or CPMG pulse sequences (T2) depend on the orientation as the square of the second-rank Legendre polynomial.  相似文献   

4.
A new two-dimensional pulse sequence for T2* measurement of protons directly coupled to 13C spins is proposed. The sequence measures the tranverse relaxation time of heteronuclear proton single-quantum coherence under conditions of free precession and is therefore well suited to evaluate relaxation losses of proton magnetization during preparation delays of heteronuclear pulse experiments in analytical NMR. The relevant part of the pulse sequence can be inserted as a “building block” into any direct or inverse detecting H,C correlation pulse sequence if proton spin–spin relaxation is to be investigated. In this contribution, the building block is inserted into a HETCOR as well as into a HMQC pulse sequence. Experimental results for the HETCOR-based sequence are given.  相似文献   

5.
Double quantum (DQ) filtering is shown to lead to an effective separation of the NMR signals from the para (I = 1) and ortho (I = 2) molecules in solid deuterium. The separation is achieved by the pulse sequence 90φ°tpr–90φ°tev–90x°t, where the phase-cycled first two pulses create the DQ coherence. Two components are observed after the third pulse; the para signal shows the maximum at a short time t while the ortho signal reaches the maximum at a longer t. The observed signal can be expressed as ∑I [FI(tprt) − FI(tpr + t)], where FI(t) is a proper fitting function for the free induction signal of the para and ortho molecules (with I = 1 or 2, respectively). Numerical fits to experimental data at 4.2 and 2 K show that this method can be used to determine the ratio F1(0)/F2(0) and thus, because the initial value FI(0) is proportional to the respective magnetization before the pulse sequence, the ortho and para concentrations in solid deuterium.  相似文献   

6.
Two-dimensional pulse sequences for the determination of heteronuclear long-range coupling constants are presented. The sequences are based on the HMQC/HMBC or HSQC technique with subsequent optional homonuclear I-spin transfer. However, they yield tilted cross-peak patterns displaying antiphase heteronuclear coupling constants in the projections of both dimensions, which allow accurate determination of the couplings even in cases where the linewidth is of comparable magnitude. Two characteristic pulse-sequence elements were implemented to shape theF1domain: the first element allows an arbitrary scaling of the heteronuclear coupling splittings relative to S-spin chemical-shift differences, whereas the second element achieves homonuclear broadband decoupling among the I spins in the HMQC/HMBC experiments and thus allows purely absorptive representations of such spectra. In comparison with established (ω1) X-half-filtered TOCSY spectra, the signal dispersion inF1is significantly improved and largely under experimental control. Furthermore, heteronuclear couplings of (I1, S) pairs where S is either quaternary or carries one or more I spins that do not belong to the same I-coupling network as I1can also be measured. The implementation of pulsed field gradients results in good suppression of spectral artifacts.  相似文献   

7.
Proton-magnetic-resonance measurements have been carried out on juvenile porcine peripheral lung parenchyma. The free-induction-decay signal contained a motionally restricted component which decayed in a few tens of microseconds and a mobile component with aT2time greater than 1 ms. The average second moment,M2, for the motionally restricted signal was found to be 3.42 ± (0.25) × 109s−2. TheT2distribution for the mobile signal consistently showed four resolvable components ofT2range: 2–6, 10–40, 80–110, and 190–400 ms. The 2–6 ms component was present in a fully dehydrated preparation and was therefore assigned to a nonaqueous lung constituent. The motionally restricted FID component had aT1= 0.772 ± 0.11 s and the mobile component had aT1= 0.967 ± 0.02 s. The hydrogen content per unit mass for lung parenchyma and water were estimated in two ways: (1) on the basis of chemical content and (2) on the basis of comparison of restricted and mobile signals to the gravimetric (G) water content for a lung sample studied at a wide range of water contents. Lung wet/dry weight ratios were estimated from the free-induction decays and compared with gravimetric measurement. The ratio of (wet/dry)NMR/(wet/dry)Gwas 1.00 ± 0.08 and 1.00 ± 0.05 for the two methods of estimation.  相似文献   

8.
The Ag2O–TiO2–SiO2 glasses were prepared by Ag+/Na+ ion-exchange method from Na2O–TiO2–SiO2 glasses at 380–450 °C below their glass transition temperatures (Tg), and their electrical conductivities were investigated as functions of TiO2 content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R2xTiO2·(80−x)SiO2 with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10−5 or 10−4 S cm−1 and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10−7 to 1.3×10−4 S cm−1 at 200 °C by Ag+/Na+ ion exchange among them. When the ion-exchange ratio was changed in 20R2O·30TiO2·50SiO2 system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10−8 S cm−1 around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The Tg of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.  相似文献   

9.
Applications of selective, multiselective, and semiselective pulses with pulsed field gradients are described. The use of multiple-selective excitation and PFGs for coherence selection in the selective one-dimensional experiments results in spectra devoid of artifacts and with remarkable solvent suppression. Multiple-selective excitation is also employed in an experiment called Multigate, a variant of the well-known WATERGATE experiment, in order to achieve multiple solvent signal suppression. Finally, new pulse sequences are shown for recording pure absorption ω1semiselective PFG NOESY, ROESY, and TOCSY experiments. The merits and limitations of these experiments are discussed.  相似文献   

10.
The improper ferroelastic phase letovicite (NH4)3H(SO4)2 has been studied by 1H MAS NMR as well as by static 14N NMR experiments in the temperature range of 296–425 K. The 1H MAS NMR resonance from ammonium protons can be well distinguished from that of acidic protons. A third resonance appears just below the phase transition temperature which is due to the acidic protons in the paraelastic phase. The lowering of the second moment M2 for the ammonium protons takes place in the same temperature range as the formation of domain boundaries, while the signals of the acidic protons suffer a line narrowing in the area of Tc. The static 14N NMR spectra confirm the temperature of the motional changes of the ammonium tetrahedra. Two-dimensional 1H NOESY spectra indicate a chemical exchange between ammonium protons and the acidic protons of the paraphase.  相似文献   

11.
A new technique is presented for generating myocardial tagging using the signal intensity minima of the transition zones between the bands of 0° and 360° rotations, induced by a tandem of two adiabatic delays alternating with nutations for tailored excitation (DANTE) inversion sequences. With this approach, the underlying matrix corresponds to magnetization that has experienced 0° or 360° rotations. The DANTE sequences were implemented from adiabatic parent pulses for insensitivity of the underlying matrix to B1 inhomogeneity. The performance of the proposed tagging technique is demonstrated theoretically with computer simulations and experimentally on phantom and on the canine heart, using a surface coil for both RF transmission and signal reception. The simulations and the experimental data demonstrated uniform grid contrast and sharp tagging profiles over a twofold variation of the B1 field magnitude.  相似文献   

12.
The spin–lattice relaxation times and spin–spin relaxation times for 1H and M in M5H3(SO4)4·H2O (M=Na, K, Rb, and Cs) single crystals grown using the slow-evaporation method were measured as functions of temperature. Two kinds of protons were identified in the M5H3(SO4)4·H2O structure: acid protons and water protons. Our experimental results show that the acid and water protons in Cs5H3(SO4)4·H2O are involved in phase transitions of this crystal, whereas neither type of proton is involved in the phase transitions of the other three crystal type (M5H3(SO4)4·H2O; M=Na, K, and Rb). Moreover, the relaxation times for the M (=Na, K, and Rb) nuclei in these crystals were found to decrease with increasing temperature and can be described with (k=2). The T1 results for M (=Na, K, and Rb) in M5H3(SO4)4·H2O crystals can be explained in terms of a relaxation mechanism in which the lattice vibrations are coupled to the nuclear electric quadrupole moments.  相似文献   

13.
Macroscopic magnetic field inhomogeneities might lead to image distortions, while microscopic field inhomogeneities, due to susceptibility changes in tissues, cause spin dephasing and decreasing T2 relaxation time. The latter effects are especially observed in the trabecular bone and in regions adjacent to air-containing cavities when gradient-echo sequences are applied. In conventional MRI, these susceptibility-related signal voids can be avoided by applying spin-echo (SE) techniques. In this study, an alternative method for the examination and control of susceptibility-related effects by spin-lock (SL) radiofrequency pulses is presented: SL pulses were applied in two different susceptibility-sensitive sequence types: (a) between the jump and return 90° pulses in a 90°xτ−90°x magnetization-prepared Fast Low Angle Shot (FLASH) sequence and (b) between the 90° pulse and the 180° pulse in an asymmetric SE sequence. The range of Larmor frequencies used for spin locking can be determined for different B1 amplitudes of the SL pulses, allowing control of image contrast by the amplitude of the SL pulses.  相似文献   

14.
A multiple-pulse technique for complete dipolar decoupling of directly bonded13C-labeled sites is described. It achieves significant spectral simplifications in a recently introduced two-dimensional double-quantum solid-state NMR experiment for determining torsion angles. Both homonuclear and heteronuclear dipolar couplings are removed by combining a13C multiple-pulse sequence with continuous-wave irradiation on the protons. The13C sequence has a fundamental 10-pulse cycle which is a significantly modified magic-sandwich-echo sequence. The crucial heteronuclear decoupling is achieved by breaking the 360° “inner” pulses in the magic sandwich into 90° pulses and spacing them by1H 360° pulse lengths. Spectral artifacts typical of multiple-pulse sequences are eliminated by phase shifts between cycles. In contrast to many other multiple-pulse decoupling sequences, the long window in the cycle is the dwell time and can be longer than the inverse dipolar coupling, which makes the sequence practical for direct detection even with long pulse ring-down times. A modification of the sequence to scale the chemical shift and increase the effective spectral width is also presented. The 1D and double-quantum 2D experiments are demonstrated on polyethylene with 4%13C–13C spin pairs. The potential of this approach for distinguishing segmental conformations is illustrated by spectral simulations of the two-dimensional ridge patterns that correlate double-quantum and single-quantum chemical-shift anisotropies.  相似文献   

15.
A modified version of the echo-planar imaging technique incorporating a Carr–Purcell train of 180° rf pulses (PEPI) has been implemented on a standard spectrometer. It is demonstrated that artifacts in the image due to cumulative errors in the rf field can be reduced by replacing each 180° pulse by a composite sequence of three rf pulses. Artifact-free 3D images at 94 μm voxel resolution are obtained within 15 min. This technique has been applied to study the drying process in an initially water-saturated model porous medium with characteristicT*2of order 700 μs.  相似文献   

16.
Total cross sections of π±, K±, p and on protons and deuterons have been measured at 6 momenta between 200 and 370 GeV/c.  相似文献   

17.
The transverse relaxation rates R 2 = 1/T 2 of protons can be determined by spin-echo sequences with multiple refocusing pulses using moderate radio-frequency field strengths and properly chosen inter-pulse delays so as to suppress echo modulations due to homonuclear scalar couplings. Combination with 2D heteronuclear correlation spectroscopy (HSQC) allows one to measure R 2 of arbitrary protons attached to nitrogen-15 or carbon-13 nuclei. Decays of six amide protons in the protein Ubiquitin that is nitrogen-15 enriched (but not deuterated) were measured at different temperatures.  相似文献   

18.
A non-localizing pulse sequence to quantify the total amount of N-acetylaspartate (NAA) in the whole brain (WBNAA) was introduced recently [Magn. Reson. Med. 40, 684–689 (1998)]. However, it is known that regional magnetic field inhomogeneities, ΔB0s, arising from susceptibility differences at tissue interfaces, shift and broaden local resonances to outside the integration window, leading to an underestimation of the true amount of NAA in the entire brain. To quantify the upper limit of this loss, the whole-head proton MR spectrum (1H-MRS) of the water was integrated over the same frequency width as the NAA. The ratio of this area/total-water-line was 75 ± 5% in 5 volunteers. The procedure was repeated with the brain-only water peak, obtained by summing signals only from voxels within that organ from a three-dimensional chemical-shift-imaging (3D CSI) set. It indicated that <10% of the water signal loss occurred in the brain. Therefore, by analogy, WBNAA accounts for >90% of that metabolite.  相似文献   

19.
The potential of heteronuclear MAS NMR spectroscopy for the characterization of 15N chemical shift (CS) tensors in multiply labeled systems has been illustrated, in one of the first studies of this type, by a measurement of the chemical shift tensor magnitude and orientation in the molecular frame for the two 15N sites of uracil. Employing polycrystalline samples of 15N2 and 2-13C,15N2-labeled uracil, we have measured, via 15N–13C REDOR and 15N–1H dipolar-shift experiments, the polar and azimuthal angles (θ, ψ) of orientation of the 15N–13C and 15N–1H dipolar vectors in the 15N CS tensor frame. The (θNC, ψNC) angles are determined to be (92 ± 10°, 100 ± 5°) and (132 ± 3°, 88 ± 10°) for the N1 and N3 sites, respectively. Similarly, (θNH, ψNH) are found to be (15 ± 5°, −80 ± 10°) and (15 ± 5°, 90 ± 10°) for the N1 and N3 sites, respectively. These results obtained based only on MAS NMR measurements have been compared with the data reported in the literature.  相似文献   

20.
AD-32和DM是蒽环类抗肿瘤抗生素,临床上用于治疗难治性膀胱癌、淋巴瘤、间皮瘤、乳癌、卵巢癌、头颈部癌、小细胞肺癌、睾丸癌、骨髓癌、结肠癌、血管肉瘤、子宫颈癌、肝癌等.本文在进行AD-32和DM的化学合成和工艺研究的基础上,应用  相似文献   

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