不均匀场下空间编码超快速高分辨NMR研究进展

二维核磁共振(2D NMR)的提出和发展,为NMR技术的研究和应用提供了广阔的空间. 然而当样品或磁场本身不均匀时,高分辨的2D NMR谱难以获得. 此外,常规2D NMR实验通常需要长的采样时间. 空间编码超快速采样方法利用空间编码技术,只需单次扫描即可获得2D甚至多维NMR谱,极大地缩短了采样时间. 目前相位补偿、相干转移和分子间多量子相干等技术与空间编码技术相结合,已成功实现不均匀场下超快速获得高分辨NMR谱. 该文对不均匀场下空间编码超快速NMR方法进行了介绍,对其未来发展进行了展望.     

Photoluminescence and electroluminescence investigations at Ge-rich SiO2 layers

Strong blue and violet photo (PL) and electroluminescence (EL) at room temperature was obtained from SiO₂-films grown on crystalline Si, which were either single (SI) or double implanted (DI) with Ge ions and annealed at different temperatures. The PL spectra of Ge-rich layers reach a maximum after annealing at 500–700°C for DI layers or 900–1000°C for SI layers, respectively. Both, PL and EL of 500 nm thick Ge-rich layers are easily visible by the naked eye at ambient light due to their high intensity. Based on excitation spectra we tentatively interpret the blue PL as due to the oxygen vacancy in silicon dioxide.

The EL spectrum of the Ge-implanted oxide correlates very well with the PL one and shows a linear dependence on the injected current over three orders of magnitude. For DI layers much higher injection currents than for SI layers can be achieved. An EL efficiency in the order of 10⁻⁴ for Ge⁺-implanted silicon dioxide was determined.     

迭代最小二乘法气体光谱自动水汽差减算法

傅里叶红外光谱法具有测量速度快、信噪比高、检测范围广等优势,在针对污染源废气排放的快速检测及长时间在线监测中具有巨大的发展潜力。水汽是红外光谱污染气体检测中的主要干扰物,影响NO_X,SO₂等重要污染物的检测,差减水汽背景谱消除光谱中水汽干扰可提高这些污染物的检测精度,具有重要意义。气体光谱中水汽吸收峰由于受到水分子团簇、仪器线型函数等影响,通过数值方法对其计算的误差较大;为此,水汽背景谱一般需采用同一台光谱仪实测获得。主要有两种方法： 第一种是通过反复调节水汽/氮气混合气中的水汽浓度,使水汽背景谱中的水汽吸收峰与污染气体光谱中水汽吸收峰相同,此方法耗时较长,且受环境条件制约很难在现场检测中使用;第二种方法是预先测量不同浓度的水汽光谱,在检测污染气体时选取两幅与污染气体光谱中水汽吸收峰最为接近且将其夹在中间的水汽光谱作为参考谱,使用这两幅参考谱线性拟合与污染气体光谱中水汽吸收峰相同的水汽背景谱,此方法可获得高度近似的水汽背景谱,但当前缺乏相关自动算法妨碍了其在快速自动消除水汽干扰方面的应用。为此,提出一种选取水汽参考谱及拟合水汽背景谱的自动算法,用于自动差减消除水汽干扰。在参考谱选取中,使用污染气体光谱依次减去浓度由低至高的水汽光谱,依据差减后光谱中水汽吸收峰所在波数的吸光度正负性来选取参考谱。在水汽背景谱计算中,基于迭代最小二乘法逐步剔除光谱中受污染物吸收峰干扰的波数,采用剩余波数上的数据拟合水汽背景谱,使其与污染气体光谱中水汽吸收峰相一致。使用水汽背景谱对污染气体光谱进行差减即可消除污染气体光谱中的水汽干扰。对含有NO₂的污染气体光谱进行了差减消除水汽干扰实验,结果表明所提出的自动算法可快速准确消除水汽干扰;NO₂在消除水汽干扰后可由其位于1 629 cm-1的强吸收峰检测,相比消除水汽干扰前使用不受水汽干扰的位于2 917 cm-1的弱吸收峰检测,其检出限得到了大幅提高。     

通过向量角转换校正拉曼光谱中乘性干扰

拉曼光谱强度与物质量存在的线性关系会受到许多复杂因素破坏,包括激发光源、聚焦、散射、折射等,导致定量效果不佳。各种因素的干扰效应,总体上分成加性和乘性效应,而消除乘性效应的难度会更大一些。光谱序列信号可视为向量,信号强度对应向量的模量,而体现向量本质的方向属性不会受模量变化的影响。根据这一原理,利用向量的方向确定性,将信号的强度度量转换成空间角度度量,建立了一种消除乘性效应的方法。首先,选择一个与待定量组分相近而与背景空间近似正交的基准向量,并定义移动窗口; 然后,计算移动窗口内的光谱向量与基准向量的夹角,所得值存储为矩阵,完成角度描述转换。角度矩阵消除了乘性效应的干扰,而定量关系仍然近似线性,只要将该矩阵的秩满足多元统计建模要求,就可以用于多元校正,并得到良好结果。研究采用甲醇-乙醇-异丙醇混合体系,验证了消除乘性效应后改进的定量效果,对于积分时间波动的预测值与实际值,直接PLS方法的相关系数r为0.911 9,预测标准偏差（RMSEP）为0.110 2; 采用MSC预处理的r为0.906 0,RMSEP为0.100 8; 而本文提出的VAPLS的r为0.998 7,RMSEP为0.015 2。结果表明向量角转换度量处理后,光谱的乘性干扰得到了有效校正,拉曼定量分析准确性得到了提高。     

Statistical isotropy of the cosmic microwave background

The breakdown of statistical homogeneity and isotropy of cosmic perturbations is a generic feature of ultra-large scale structure of the cosmos, in particular, of non-trivial cosmic topology. The statistical isotropy (SI) of the cosmic microwave background temperature fluctuations (CMB anisotropy) is sensitive to this breakdown on the largest scales comparable to, and even beyond the cosmic horizon. We propose a set of measures,K _l (l = 1, 2,3,...) which for non-zero values indicate and quantify statistical isotropy violations in a CMB map. We numerically compute the predictedK _l spectra for CMB anisotropy in flat torus universe models. Characteristic signatures of different models in theK _l spectrum are noted.     

Selective excitation and suppression of coherent anti-Stokes Raman scattering by shaping femtosecond pulses

Femtosecond coherent anti-Stokes Raman scattering (CARS) suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump (or Stokes) spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump (or Stokes) spectrum with the $\pi $ spectral phase step.     

Influence of the regime of plastic deformation on the magnetic properties of single-crystal silicon Cz-Si

A variation has been revealed in electron paramagnetic resonance spectra of single-crystal silicon Cz-Si plates plastically deformed by bending and torsion. The plastic deformation of the silicon plates is accompanied by the introduction of dislocations (∼10⁷ cm⁻²) and leads to the appearance of new lines in the electron paramagnetic resonance spectrum of the sample. The paramagnetic centers introduced during bending and torsion, as well as their electron paramagnetic resonance spectra, differ from those previously studied under conditions of uniaxial deformation. The plastic deformation results in a significant increase in the diamagnetic component of the magnetic susceptibility, which exceeds the increase in the paramagnetic component for the magnetic susceptibility of the Cz-Si crystals.     

茶粉均质性的红外光谱相似度评价研究

非均质固态样品的充分均质化前处理是取得可靠分析结果的前提,这对于单次测试取样量约1 mg的红外光谱（KBr）分析而言尤为重要。通过对不同茶类、粒径茶粉的多角度红外光谱相似度评价,揭示茶粉粒径与均质化程度的关系并用于指导茶叶的均质化粉碎,确保采集的红外光谱能准确反映茶粉的化学组成信息。选取普洱生茶（Raw-PE）、普洱熟茶（Riped-PE）、滇红茶（YNBT）三类茶制成的A,B,C和D四种不同粒径茶样,以透射法（KBr）及衰减全反射法（ATR）分别平行五次采集茶样的红外光谱（FTIR）,利用夹角余弦值（r）对所得红外光谱开展相似度评价研究,考察粉碎粒径、光谱采集方式、茶叶类别等因素对r值的影响。不同茶类光谱相似度评价结果显示,基于普洱生茶所得的r值明显高于普洱熟茶和滇红茶,不同粒径滇红茶的r值波动幅度高达18%。不同光谱采集方式评价结果显示,基于ATR谱所得的r值更为集中,而基于KBr谱的结果则更分散。不同粒径茶粉评价结果显示,粒径越小,所得的r值越高,250目以上的茶样对应的r值通常大于0.999。ATR谱具有更好的重现性,而KBr谱则具有更强的差异识别能力,后者更适于组成高度相似的样本间的差异分析。茶粉的均质性不仅与粉碎粒径密切相关,还可能与茶样本身的基质相关,但均可以通过缩小粉碎粒径提高均质性。一般而言,60目以下的粉碎粒径难以满足红外光谱分析方法对茶叶均质性的要求。120目以上的茶粉粒径可让平行KBr谱间r＞0.995,但若基于ATR谱进行分析,最好将茶样粉碎至250目以上。     

1-D and 2-D NMR of broad-line solids: an application to quasicrystals

Nuclear magnetic resonance (NMR) techniques for measuring one-dimensional absorption spectra and two-dimensional exchange spectra of solids with extremely inhomogeneously broadened lines are discussed. Among various “broad-line” solids, quasicrystals represent alloys of metallic elements, the structures of which include “forbidden” symmetry elements. NMR absorption lines of quasicrystals exhibit a strong electric-quadrupole-induced inhomogeneous broadening that originates from the lack of translational periodicity of the otherwise perfectly long-range-ordered quasiperiodic lattice. Recording an NMR spectrum of a quasicrystalline sample requires a magnetic field-sweep technique. The two-dimensional exchange experiment on quasicrystals can be performed on selectively excited portions of the NMR spectrum only. Due to the off-resonance effects in a selective excitation, the use of a simple three-pulse stimulated-echo exchange sequence is preferred. The²⁷Al spectra of the Al-Pd-Mn and Al-Pd-Re families show interesting features like temperature-dependent frequency shifts and exchange effects due to atomic motion.     

Spectrum of vibrational frequencies of crystalline tungsten at temperatures of 293 and 2400 K

The slow neutron inelastic scattering spectra for a refractory (T _melt = 3680 K) Group VI transition metal of the Periodic Table, namely, tungsten, were measured for the first time in the range from room temperature to 2400 K. Measurements of the neutron scattering spectra of tungsten were performed on a DIN-2PI time-of-flight spectrometer installed at the IBR-2 reactor (Dubna, Russia). The sample was heated in a TS3000 K high-temperature thermostat. The spectrum of vibrational frequencies of the crystal lattice of tungsten at temperatures of 293 and 2400 K was determined from the measured neutron scattering spectra by the iterative method. A softening of the frequency spectrum of tungsten was observed with increasing temperature. This was explained by the increasing role of vibrational anharmonicity effects at high temperatures. The experimental results were compared with model calculations of the frequency spectrum of tungsten.     

Magnetostatic modes in antiferromagnetic resonance

Measurements of the antiferromagnetic resonance (AFMR) spectra of MnF₂ spheres are reported, and the principal magnetostatic modes (MSMs) in these spectra are identified. To interpret the observed spectra it is necessary to take into account, in addition to the theoretical MSM solution, the effects of impurities, finite sample size (propagation effects), and radiation damping. Expressions for the predicted relative intensities of the modes are developed for particular choices of symmetry of the exciting rf field and compared to observations. The observed shifts and intensities are larger than predicted. This discrepancy is explained by analysis of the role of the magnetic susceptibility of a sample near resonance. New observations are reported which improve the understanding of radiation damping in AFMR.     

Study on Infrared Transmission Spectrum of Sildenafil Citrate Mixed in Traditional Chinese Medicine

The infrared transmission spectrum has been studied on the mixed medicine sample composed of sildenafil citrate (SDF or Viagra) and traditional Chinese medicine(TCM). The measured infrared spectra are composed of several broad absorption bands and many sharp absorption lines. Then the broad absorption bands are changed from sample to sample. It is identified that the sharp and broad absorption bands are from the Viagra and TCM, respectively. A numerical best fitting process has been used to extract the absorption spectrum from the spectrum of mixed sample. Combined with the numerical analysis, the Viagra component can be extracted from the mixed material even with a changeable broad absorption bands' background. It shows that the infrared transmission spectroscopy is a useful method to extract the component of chemical medicine from the mixed medicine.     

不需制备样品与获得期望强度的红外单光束谱

为扣除溶剂或其他背景组分的干扰,测量红外光谱时常常需要获得期望强度的高质量背景单光束谱。通常,实验上获得期望强度的背景谱是极其困难的。为实现这一重要且十分困难的目标,引进了杂化单光束谱的概念。同一溶液但不同厚度的b₁和b₂的两样品的单光束谱分别为Φ_b1和Φ_b2,则定义它们的线性组合Φ_α=αΦ_b1+(1-α)Φ_b2为杂化单光束谱,其中α(0≤α≤1)称为组分因子。调整组分因子α数值,就可以精确调控杂化谱的强度。在合适的条件下,杂化谱Φ_α与厚度为b₂-αb₂+αb₁的真实样品的光谱高度类似,即Φ_b2-αb2+αb1≈Φ_α。因此,不用制备厚度为b₂-αb₂+αb₁的样品,其单光束谱可以用Φ_α来替代。随着α变化,可以得到不同的Φ_α,厚度在b₁和b₂间的真实样品的单光束谱都可用相应的Φ_α来替代。实验结果证实,杂化谱提供了一种简单和易操作的扣除背景干扰的高效方法。     

Methods of calculating the band structure and low-energy secondary electron spectroscopy of iridium

A theoretical interpretation is put forward for the fine structure of the secondary electron emission spectra of Ir normal to the (111) surface and the total current spectrum of an Ir polycrystal. The calculations took into account the energy dependence of the broadening of the energy band levels, the electron-electron and electron-plasmon contributions to the nonequilibrium electron distribution function, and the isotropic component of the current from the electrons scattered at the surface. It is shown that the fine structure of the secondary electron emission spectrum and the total current spectrum is mainly attributable to the electron structure of the final states into which the electrons enter or from which they are emitted so that the characteristics of the band configuration in the energy band structure can be reconstructed directly from the experimental data. This method can be used to separate bulk effects from surface effects in the secondary electron emission and total current spectra. It is confirmed that the fine structure of the secondary electron emission and total current spectra depends on the geometric structure and the degree of ordering of the crystals. A reduction in the intensity of the fine structure serves as a measure of the defect structure in the surface region of the sample which can be successfully used to monitor the surface state during treatment. Zh. Tekh. Fiz. 69, 94–96 (June 1999)     

A fast variant of (1)H spectroscopic U-FLARE imaging using adjusted chemical shift phase encoding

So far, fast spectroscopic imaging (SI) using the U-FLARE sequence has provided metabolic maps indirectly via Fourier transformation (FT) along the chemical shift (CS) dimension and subsequent peak integration. However, a large number of CS encoding steps N(omega) is needed to cover the spectral bandwidth and to achieve sufficient spectral resolution for peak integration even if the number of resonance lines is small compared to N(omega) and even if only metabolic images are of interest and not the spectra in each voxel. Other reconstruction algorithms require extensive prior knowledge, starting values, and/or model functions. An adjusted CS phase encoding scheme (APE) can be used to overcome these drawbacks. It incorporates prior knowledge only about the resonance frequencies present in the sample. Thus, N(omega) can be reduced by a factor of 4 for many (1)H in vivo studies while no spectra have to be reconstructed, and no additional user interaction, prior knowledge, starting values, or model function are required. Phantom measurements and in vivo experiments on rat brain have been performed at 4.7 T to test the feasibility of the method for proton SI.     

温度对叶片近红外光谱的影响

近红外光谱分析技术是发展最快的定性和定量分析技术之一,在各个领域得到了广泛应用。但近红外谱区自身信息的特点决定了其吸收强度弱、信噪比低、谱峰严重重叠等缺点,这使得近红外光谱易受样品来源、样品种类、样品状态、装样条件和样品温度等的影响,造成光谱的不确定性。文章以温度对叶片近红外光谱的影响为研究内容,详细考察了不同温度下样品的叶绿素的校正和预测模型。结果发现温度对模型精度有一定的影响,样品的温度在10和20℃下模型的精度较高,10℃下模型精度效果最好,但是所用的主成分也较多。当实验温度达到25℃时,模型的校正和预测精度都相对较差。利用判别分析对各个温度下的光谱进行分类。发现20℃下采集的光谱没有分到其他温度区外,其他的都有不同程度的跨区,这说明除20℃外,其他温度下测得的光谱差异不明显。试验对叶片近红外检测的条件和应用做了初步的探索性工作,为今后提出温度修正模型提供理论基础。     

常态中子深度分析物理模型

带电离子在样品内输运过程中的能量岐离、探测立体角有效范围及探测系统噪声都将改变中子深度分析（NDP）的多道离子能谱分布。假定上述三种因素导致的离子探测谱能量展宽都可以采用高斯函数描述，基于一般条件下的NDP装置设计，建立了预测一定深度核素产生的离子测量谱的探测器响应函数物理模型。该模型的理论分析结果与实验测量能谱的峰位、半高宽均符合良好，能够作为中子深度分析测量谱反演分析的基础。     

Micromagnetic simulation on the dynamic susceptibility spectra of cobalt nanowires arrays: the effect of magnetostatic interaction

<正>Micromagnetic simulations have been performed to obtain the dynamic susceptibility spectra of 4×4 cobalt nanowire arrays with different spatial configurations and geometries.The susceptibility spectra of isolated wires have also been simulated for comparison purposes.It is found that the susceptibility spectrum of nanowire array bears a lot of similarities to that of an isolated wire,such as the occurrences of the edge mode and the bulk resonance mode. The simulation results also reveal that the susceptibility spectrum of nanowire array behaves like that of single isolated wire as the interwire distance grows to an extent,which is believed due to the decrease of magnetostatic interaction among nanowires,and can be further confirmed by the static magnetic hysteresis simulations.In comparison with single nanowire,magnetostatic interaction may increase or decrease the resonance frequencies of nanowire arrays assuming a certain interwire distance when the length of array increases.Our simulation results are also analysed by employing the Kittel equation and recent theoretical studies.     

近红外等效光谱测量方法研究

便携式近红外光谱仪器测量低反射率或透过率样品的漫反射率或透过率光谱时,由于仪器噪声的影响,光谱数据小、信噪比低,即使采用降噪数据处理,所得光谱数据仍无法满足分析精度的要求。因此研究了近红外等效光谱测量方法：根据低反射率或透过率样品在常规测量条件下反射信号的强度,增大仪器测量时光源电流以增大样品扫描信号、减小参比反射或透射光强以避免参比信号超量程,并计算得与常规测量方法相同的等效光谱,以提高样品近红外反射率或透过率光谱数据的信噪比。理论分析和实验结果表明采用近红外等效光谱测量方法,可获得与常规测量方法的光谱数据相同、且信噪比增大的等效光谱。     

7-羟基喹啉在二甲基亚砜中的荧光光谱

7-羟基喹啉(7-HQ)是一种具有激发态质子转移(ESPT)效应的有机分子。它溶于乙醇溶剂中,在紫外光的激励下,将发生ESPT反应,荧光光谱出现2个荧光带。7-HQ溶于二甲基亚砜(DMS)溶剂中,则不能发生ESPT反应,其荧光光谱只出现单一荧光带。但样品被强紫外光照射后,其荧光光谱也出现2个荧光带。文章首次报道了这一现象,并通过对7-HQ的乙醇、二甲基亚砜和二甲基甲酰胺溶液的吸收光谱和荧光光谱的研究,探讨产生这一现象的机理。认为7-HQ溶于DMS中被强紫外光照射后荧光光谱的变化是由于DMS被光解并生成水而使7-HQ发生ESPT反应的结果。