T1–T2 Correlation Spectra Obtained Using a Fast Two-Dimensional Laplace Inversion

Spin relaxation is a sensitive probe of molecular structure and dynamics. Correlation of relaxation time constants, such as T₁ and T₂, conceptually similar to the conventional multidimensional spectroscopy, have been difficult to determine primarily due to the absense of an efficient multidimensional Laplace inversion program. We demonstrate the use of a novel computer algorithm for fast two-dimensional inverse Laplace transformation to obtain T₁–T₂ correlation functions. The algorithm efficiently performs a least-squares fit on two-dimensional data with a nonnegativity constraint. We use a regularization method to find a balance between the residual fitting errors and the known noise amplitude, thus producing a result that is found to be stable in the presence of noise. This algorithm can be extended to include functional forms other than exponential kernels. We demonstrate the performance of the algorithm at different signal-to-noise ratios and with different T₁–T₂ spectral characteristics using several brine-saturated rock samples.     

Voice F0 responses to pitch-shifted auditory feedback: a preliminary study

Auditory feedback has been suggested to be important for voice fundamental frequency (F₀) control. The present study featured a new technique for testing this hypothesis by which the pitch of a subject's voice was modulated, fed back over earphones, and the resultant change in the emitted voice F₀ was measured. The responses of 67 normal, healthy young adults were recorded as they attempted to ignore intermittent upward or downward shifts in pitch feedback while they sustained steady vowel sounds (/a/) or sang musical scales. Ninety-six percent of subjects increased their F₀ when the feedback pitch was decreased, and 78% of subjects decreased their F₀ when the pitch feedback was increased. Latencies of responses ranged from 104 to 223 ms. Results indicate people normally rely on pitch feedback to control voice F₀.     

Application of low field NMR T2 measurements to clathrate hydrates

Low field (2 MHz) Nuclear Magnetic Resonance (NMR) proton spin–spin relaxation time (T₂) distribution measurements were employed to investigate tetrahydrofuran (THF)—deuterium oxide (D₂O) clathrate hydrate formation and dissociation processes. In particular, T₂ distributions were obtained at the point of hydrate phase transition as a function of the co-existing solid/liquid ratios. Because T₂ of the target molecules reflect the structural arrangements of the molecules surrounding them, T₂ changes of THF in D₂O during hydrate formation and dissociation should yield insights into the hydrate mechanisms on a molecular level. This work demonstrated that such T₂ measurements could easily distinguish THF in the solid hydrate phase from THF in the coexisting liquid phase. To our knowledge, this is the first time that T₂ of guest molecules in hydrate cages has been measured using this low frequency NMR T₂ distribution technique. At this low frequency, results also proved that the technique can accurately capture the percentages of THF molecules residing in the solid and liquid phases and quantify the hydrate conversion progress. Therefore, an extension of this technique can be applied to measure hydrate kinetics. It was found that T₂ of THF in the liquid phase changed as hydrate formation/dissociation progressed, implying that the presence of solid hydrate influenced the coexisting fluid structure. The rotational activation measured from the proton response of THF in the hydrate phase was 31 KJ/mole, which agreed with values reported in the literature.     

氢同位素氚水T2O(X1A1)的解析势能函数

获得T₂O(X¹A₁)解析势能函数的主要困难在于Born-Oppenheimer近似下T₂O(X¹A₁)与H₂O(X¹A₁)势能函数的不可区分性.然而,在Born-Oppenheimer近似下,分子势能函数实际上是键长、键角这些 关键词： 2O(X¹A₁)')" href="#">T₂O(X¹A₁) 同位素效应 解析势能函数     

Removal of t(1) noise from metabolomic 2D (1)H-(13)C HSQC NMR spectra by Correlated Trace Denoising

The presence of t(1) noise artefacts in 2D phase-cycled Heteronuclear Single Quantum Coherence (HSQC) spectra constrains the use of this experiment despite its superior sensitivity. This paper proposes a new processing algorithm, working in the frequency-domain, for reducing t(1) noise. The algorithm has been developed for use in contexts, such as metabolomic studies, where existing denoising techniques cannot always be applied. Two test cases are presented that show the algorithm to be effective in improving the SNR of peaks embedded within t(1) noise by a factor of more than 2, while retaining the intensity and shape of genuine peaks.     

Absorption spectrum of nitrous acid for the ν1+2ν3 band studied with continuous-wave cavity ring-down spectroscopy and theoretical calculations

We present the high resolution absorption measurements of gaseous HONO at room temperature using continuous-wave cavity ring-down spectroscopy in the near-infrared region between 6017 and 6067 cm⁻¹ at a resolution of 1 pm (0.037 cm⁻¹). For the trans-HONO isomer an extensive analysis of the ν₁+2ν₃ combination band 6045.8089 cm^–1 was performed starting from the results of a previous study for the 1¹ and 3¹ vibrational states [Guilmot J-M, Godefroid M, Herman M. Rovibrational parameters for trans-nitrous acid. J Mol Spectrosc 1993;160:387–400]. The present combination band is perturbed because of the existence of several dark states of HONO which could not be identified unambiguously. The rotational constants achieved for the 1¹3² state deviate slightly from the values which are predicted from the rotational constants achieved in the previous studies for the 1¹ and 3¹ vibrational states of trans-HONO.     

Delta-P1近似漫反射光学模型的二阶参量灵敏度

基于Delta-P₁近似漫反射光学模型, 推导了双点源近似下空间分辨漫反射解对于Henyey-Greenstein散射相函数的二阶参量γ的灵敏度表达式, 研究了参量γ对漫反射分布的影响. 研究表明, 与漫射近似模型相比, Delta-P₁近似漫反射光学模型不仅含有散射相函数的二阶参量γ, 而且在弱吸收或强吸收的情况下, 参量γ对于光源附近(ρ<1.0 mm)的空间分辨漫反射都存在较大的影响(极值大于30%). 因此利用γ研究漫反射光分布对于获取组织光学信息具有重要的意义.     

Al NMR studies of NpPd5Al2

We present ²⁷Al NMR studies for a single crystal of the Np-based superconductor NpPd₅Al₂. We have observed a five-line ²⁷Al NMR spectrum with a center line and four satellite lines separated by first-order nuclear quadrupole splittings. The Knight shift clearly drops below T_c. The temperature dependence of the ²⁷Al nuclear spin-lattice relaxation rate shows no coherence peak below T_c, indicating that NpPd₅Al₂ is an unconventional superconductor with an anisotropic gap. The analysis of the present NMR data provides evidence for strong-coupling d-wave superconductivity in NpPd₅Al₂.     

A New Two-Dimensional Pulse Sequence for T2* Measurements of Protons in C Isotopomers

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.     

In vivo NMR T2 relaxation of experimental brain tumors in the cat: A multiparameter tissue characterization

Experimental gliomas (F98) were inoculated in cat brain for the systematic study of their in vivo T₂ relaxation time behavior. With a CPMG multi-echo imaging sequence, a train of 16 echoes was evaluated to obtain the transverse relaxation time and the magnetization M(0) at time t = 0. The magnetization decay curves were analyzed for biexponentiality. All tissues showed monoexponential T₂, only that of the ventricular fluid and part of the vital tumor tissue were biexponential. Based on these NMR relaxation parameters the tissues were characterized, their correct assignment being assured by comparison with histological slices. T₂ of normal grey and white matter was 74 ± 6 and 72 ± 6 msec, respectively. These two tissue types were distinguished through M(0) which for white matter was only 0.88 of the intensity of grey matter in full agreement with water content, determined from tissue specimens. At the time of maximal tumor growth and edema spread a tissue differentiation was possible in NMR relaxation parameter images. Separation of the three tissue groups of normal tissue, tumor and edema was based on T₂ with T_2(normal) < T_2(tumor) < T_2(edema). Using M(0) as a second parameter the differentiation was supported, in particular between white matter and tumor or edema. Animals were studied at 1–4 wk after tumor implantation to study tumor development. The magnetization M(0) of both tumor and peritumoral edema went through a maximum between the second and third week of tumor growth. T₂ of edema was maximal at the same time with 133 ± 4 msec, while the relaxation time of tumor continued to increase during the whole growth period, reaching values of 114 ± 12 msec at the fourth week. Thus, a complete characterization of pathological tissues with NMR relaxometry must include a detailed study of the developmental changes of these tissues to assure correct experimental conditions for the goal of optimal contrast between normal and pathological regions in the NMR images.     

T1ρ-weighted MRI using a surface coil to transmit spin-lock pulses

T1rho-weighted MRI is a novel basis for generating tissue contrast. However, it suffers from sensitivity to B1 inhomogeneity. First, excitation with a spatially varying B1 causes flip-angle artifacts and second, spin locking with an inhomogeneous B1 results in non-uniform T1rho contrast. In this study, we overcome the former complication with a specially designed spin-locking pulse sequence and we successfully obtain T1rho-weighted images with a surface coil. In this pulse sequence, the spin-lock pulse was divided into segments of equal duration and alternating phase. This "self-compensating" T1rho-preparatory pulse sequence was analyzed and the effect of an inhomogeneous B1 field was simulated using the Bloch equations. T1rho-weighted MR images of a phantom and a human knee joint in vivo were obtained on a clinical scanner with a surface coil to demonstrate the utility of the pulse sequence. The self-compensating T1rho-prepared pulses sequence resulted in substantially reduced image artifacts compared to the conventional, single-phase spin-lock pulse.     

微观相场法模拟Ni75Al5.3V19.7 中L12和D022结构反位缺陷的演化

运用微观相场法研究Ni₇₅Al_5.3V_19.7合金沉淀过程中L1₂结构和D0₂₂结构反位缺陷发现：在沉淀初期,L1₂结构反位缺陷Al_Ni,V_Ni,Ni_Al,D0₂₂结构反位缺陷V_Ni,Al_Ni关键词： 微观相场 反位缺陷 L1₂结构')" href="#">L1₂结构 D0₂₂结构')" href="#">D0₂₂结构     

Analytical potential energy function for the electronic states 2^∏1/2 and 2^∏3/2 of O^x2 （x=＋1, -1）

The splitting of potential energy levels for ground state X^2∏g of O^x2 （x = ＋1,-1） under spin-orbit coupling （SOC） has been calculated by using the spin-orbit （SO） multi-configuration quasi-degenerate perturbation theory （SO-MCQDPT）. Their Murrell-Sorbie （M S） potential functions are gained, and then the spectroscopic constants for electronic states 2^∏1/2 and 2^∏3/2 are derived from the M S function. The vertical excitation energies for O^x2 （x = ＋1,-1） are v[O2＋1^（2∏3/2→X^2∏1/2）] =195.652cm^-1, and v[O2^-1（2^∏1/2 →X^2∏3/2）] =182.568cm^-1, respectively. All the spectroscopic data for electronic states 2^∏1/2 and 2^∏3/2 are given for the first time.     

Laser stark spectroscopy ofSO2 with the HCN laser

The Far Infrared (FIR) laser Stark spectrum ofSO ₂ was investigated using the 337 m line of the HCN laser. Two distinct families, one originating at low field and the other at high field, were observed. The high field transition is identified as theJ _K–1,K+1=22_5,1721_4,18, v₂=1 transition. A significant fourth-order Stark shift was observed for this transition in the presence of a large second-order Stark shift. The zero-field frequency of the assigned transition was obtained by accounting for the fourth-order contribution.Present Adress: Department of Chemistry, University of Rochester, Rochester, NY 14627.     

Global Entanglement Measures and Quantum Phase Transitions in the 1D J 1? J 2 Model

We have analyzed the behavior of multipartite global entanglement and average bipartite concurrence for the sign of quantum phase transitions in the frustrated J ₁−J ₂ model by using exact diagonalization technique for a chain of 12 qubits. It is found that although the magnitude of two classes of the measures show opposite trends the absolute value of their derivatives show similar structure near critical points.     

光源附近空间分辨漫反射的SP3研究

根据P₃近似对半无限生物组织的空间分辨漫反射理论,研究了强吸收条件下光源附近 光辐射分布的简化表达式SP₃函数.研究表明:组织吸收越强, SP₃函数越能准确描述光源附近空间 分辨漫反射;应用SP₃函数反演强吸收组织光学参数时,由不同起始距离的漫反射数据拟合得到的反演 结果曲线存在极值,极值附近对应的反演结果最接近实际组织光学参数.     

Quasi-two-dimensional magnetism in (CnH2n+1NH3)2CuCl4 studied by electron paramagnetic resonance

The quasi-two-dimensional magnetism in the layered transition metal compound (C_nH_2n+1NH₃)₂CuCl₄ (n=10, 14) was investigated by means of electron paramagnetic resonance (EPR) and superconducting quantum interference device measurements. As a result, the high temperature magnetic phase transitions were reflected in the EPR parameters in a sensitive manner.     

高温无铅BaTiO_3-(Bi_(1/2)Na_(1/2))TiO_3正温度系数电阻陶瓷阻抗和介电谱分析

采用固相反应法制备了Y2O3施主掺杂的92 mol%BaTiO3-8 mol%(Bi1/2Na1/2)TiO3(BBNT8)高温无铅正温度系数电阻(positive temperature coe?cient resistivity,PTCR)陶瓷.利用透射电镜观察材料的显微结构,发现陶瓷的显微结构主要包括晶粒和晶界两部分,观察不到明显的壳层结构.进一步利用交流阻抗谱研究了陶瓷的宏观电学性能,发现陶瓷的总电阻是晶粒和晶界两部分的贡献,而晶粒电阻很小,在居里温度以上变化不大,材料的PTCR效应主要是晶界部分的贡献.当温度高于居里温度时,随着温度的升高,晶界介电常数逐渐减小,导致势垒增加,晶界电阻增大,从而产生正温度系数效应.最后,通过测试材料的介电频谱特性,研究计算了陶瓷的室温电阻率.     

The ν1 and ν3 stretching fundamental bands of PD3

The infrared (IR) spectrum of PD₃ has been recorded in the 1580–1800 cm⁻¹ range at a resolution of 0.0027 cm⁻¹. About 2400 rovibrational transitions with J^′=K^′22 have been measured and assigned to the ν₁ (A₁) and ν₃ (E) stretching fundamentals. These include 506 “perturbation-allowed” transitions with selection rules Δ(k−l)=±3. Splittings of the K^′′=3 lines have been observed. Effects of strong perturbations are evident in the spectrum. Therefore the rovibrational Hamiltonian adopted for the analysis explicitly takes into account the Coriolis and k-type interactions between the v₁=1 and v₃=1 states, and includes also several essential resonances within these states. The rotational structure in the v₁=1 and v₃=1 vibrational states up to J^′=K^′=18 was reproduced by fitting simultaneously all experimental data. Thirty-four parameters reproduced 1950 transitions retained in the final cycle with a standard deviation of the fit equal to 4.9 × 10⁻⁴ cm⁻¹ (about the precision of the experimental measurements).     

三明治结构Tan(B3N3H6)n+1 团簇的磁性和量子输运性质

利用密度泛函理论和非平衡格林函数方法, 本文对小尺寸团簇Ta_n(B₃N₃H₆)_n+1 (n ≤ 4)的磁性和量子输运性质进行了系统的研究. 计算结果表明, 此类体系采用三明治结构作为其基态并且具有较高的稳定性. 体系的磁矩随团簇尺寸的增大而线性增大. 当把Ta_n(B₃N₃H₆)_n+1团簇耦合到Au电极上时, 形成的Au-Ta_n(B₃N₃H₆)_n+1-Au体系在有限偏压下展示出了较强的自旋过滤能力, 因而可以被看做是一类新型的低维自旋过滤器.