基于咔唑-靛红双-硫代碳酰腙衍生物的NMR研究

采用多种核磁共振（NMR）技术（包括¹H NMR、¹³C NMR、¹H-¹H COSY、¹H-¹³C HSQC、¹H-¹³C HMBC），对基于咔唑-靛红双-硫代碳酰腙新型衍生物2，即1-[（3Z）-2-氧代吲哚-3-亚基]-5-[（9-己基-3-咔唑基）亚基]硫代碳酰腙的¹H和¹³C NMR信号进行了全归属，确定了其结构．     

N-异丁酰基-3'-O-(1-氟-1,1,3,3-四异丙基-1,3-二硅氧烷-3-基)-2'-苄氧羰基鸟苷的NMR研究

本文采用氢氟酸吡啶鎓在5′-位选择性断裂1,1,3,3-四异丙基二硅氧烷基保护基的方法得到了核苷衍生物N-异丁酰基-3′-O-（1-氟-1,1,3,3-四异丙基-1,3-二硅氧烷-3-基）-2′-苄氧羰基鸟苷（化合物1）,并应用液相色谱串联质谱（LC-MS）、气相色谱-高分辨质谱（GC-HRMS）、液体1D和2D NMR谱（包括¹H NMR、¹³C NMR、¹⁹F NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC）,对产物的¹H、¹³C和¹⁹F NMR信号进行了归属,确定了其结构．     

苦皮藤中两个新的 β-二氢沉香呋喃型化合物的 NMR 数据解析

从南蛇藤属植物苦皮藤中分离出两个新的β-二氢沉香呋喃型化合物：1β,2β,15-三乙酰氧基-8α-(α-甲基)-丁酰氧基-9β-苯甲酰氧基-4α,6α-二羟基-β-二氢沉香呋喃（化合物I）和1β,15-二乙酰氧基-8α-(α-甲基)-丙酰氧基-2β,9β-二苯甲酰氧基-4α,6α-二羟基-β-二氢沉香呋喃（化合物II）．通过核磁共振（NMR，包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、NOESY、HSQC、HMBC）技术对化合物所有的¹H和¹³C NMR信号进行了全归属和详细解析.     

含苯并咪唑环N-酰腙衍生物的NMR研究

应用¹H NMR、¹³C NMR、¹H-¹H COSY、NOESY、¹H-¹³C HSQC、¹H-¹³C HMBC和变温¹H NMR等多种NMR技术,对新化合物1,即N'-[（4-N,N-二甲基）苯基]亚甲基-2-（4-甲基苯氧甲基）苯并咪唑-1-乙酰肼的两种异构体（E/trans和E/cis）的¹H和¹³C NMR信号进行了全归属,测量了相应的偶合常数（J值）以及异构体所占的比例.实验结果表明,此新化合物在DMSO-d₆中存在着E/trans和E/cis两种异构体的互变,且E/cis异构体含量为74.2%.     

新型连翘脂素-布洛芬酯合物的波谱学数据解析

以连翘脂素和布洛芬为原料,通过Schotten-Baumann酯化合成了酯合物——连翘脂素-布洛芬酯.对其紫外吸收光谱（UV）、红外吸收光谱（IR）、基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF-MS）、1D和2D核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹H NOESY、¹H-¹³C HSQC和¹H-¹³C HMBC）进行了解析,对其¹H和¹³C NMR谱峰进行了全归属.     

二氢沉香呋喃倍半萜的2D NMR研究

利用¹H-¹³C相关(¹H-¹³C COSY)谱对1β-乙酰氧基-2β(α-甲基丁酰氧基)-6α-羟基-8β,9α-二苯甲酰氧基-β-二氢沉香呋喃(A),和1β-乙酰氧基-2β(α-甲基丁酰氧基)-6α-羟基-8β(β-呋喃甲酰氧基)-9α-苯甲酰氧基-β-二氢沉香呋喃(B)的¹³C NMR谱化学位移进行了全指定,利用¹H-¹H远程相关(¹H-¹H COSYLR)谱确定了化合物A和B中6-Ha和7-He,8-He和9-He的弱偶合,以及7-He和9-He的弱W型远程偶合.     

靶向新药吉非替尼的核磁共振波谱研究

应用1D、2D NMR实验技术（¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HMQC、¹H-¹³C HMBC等）研究了靶向新药吉非替尼的结构,对其1H NMR和¹³C NMR谱峰作了全归属,并讨论了F原子对吉非替尼的¹H、¹³C NMR的影响.     

硼替佐米的波谱学数据解析

对抗肿瘤药硼替佐米的紫外吸收光谱（UV）、红外吸收光谱（IR）、电喷雾离子源-质谱（ESI-MS）、核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC）数据进行了解析,对其¹H和¹³C NMR谱峰进行了全归属,通过多种谱学技术确证了硼替佐米的结构.     

一种1,4-噻嗪酰胺类FKBPs配体的波谱学数据解析

（3R）-4-[（4-甲基苯磺酰基）]-1,4-噻嗪-3-酰基-[（2R）-2-氨基-4-甲基]-戊酸异丙酯（代号：HD5-6）,是一个拥有完全自主知识产权的FK506结合蛋白家族（FKBPs）配体,具有显著的促神经再生作用,有望在临床实现对神经退行性疾病和肌萎缩侧索硬化、脑卒中的有效治疗.本文采用多种核磁共振（NMR）技术,包括¹H NMR、¹³C NMR、DEPT、1D NOESY、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC等,并结合质谱（MS）、紫外光谱（UV）和红外光谱（IR）等方法对此化合物进行解析,对其¹H和¹³C NMR谱峰进行全归属,通过多种谱学技术确证了该化合物的化学结构.     

依卡倍特钠的波谱学数据解析

对胃粘膜保护剂依卡倍特钠的紫外吸收光谱（UV）、红外吸收光谱（IR）、高分辨-质谱（HR-MS）、核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC和¹H-¹³C HMBC）数据进行了解析,对其所有的¹H和¹³C NMR谱信号进行了归属,通过多种谱学技术确证了依卡倍特钠的结构.     

A multinuclear magnetic resonance study of intramolecular hydrogen bonding in some Schiff and Schiff-Mannich bases in solution and in the solid state

Two Schiff bases; N, N′-bis(5-bromosalicylidene)-1,2-diaminoethane, BS, and 7-[(1-{5-bromo-2-hydroxyphenyl} methylidene)amino]-4-methylcoumarin, Sc, and two appropriate Schiff–Mannich bases, N, N′-bis{5-bromo-3-[(diethylamino)methyl]salicylidene}-1,2-diaminoethane, BSM, and 7-[(1-{5-bromo-3-[(diethylamino)methyl]-2-hydroxyphenyl} methylidene)amino]-4-methylcoumarin, SMc, capable of intramolecular hydrogen bonding have been investigated by multinuclear magnetic resonance methods in both solid and liquid phases. In all of the compounds under investigation tautomeric equilibrium involving an intramolecular hydrogen bond has been found. The Schiff–Mannich bases, which can form two different kinds of H bonds at room temperature, form relatively weak H bonds with the imino nitrogen atoms. At low temperatures the tautomeric proton exchange becomes slow on the NMR time scale and both hydrogen-bonded forms can be observed by ¹H, ¹³C, and ¹⁵N NMR methods. In the solid state the tautomeric process is frozen and only one H-bonded form is present. On the basis of 13C and ¹⁵N CPMAS NMR spectra this is identified as the form with hydrogen bonds involving the imino groups. This conclusion is in good agreement with previous results obtained by X-ray diffraction methods.

The investigated Schiff bases (BS and Sc) form relatively weak H bonds. The proton position in the hydrogen bridge, estimated from ¹⁵N and ¹³C chemical shifts, is very similar in both the solution and solid phases. In chloroform solution the observed tautomeric equilibria are almost insensitive to a temperature change within the range 223 to 303 K.     

3,22-二羟基何伯烷的单晶结构及波谱学数据

利用三异丁基硼氢化锂（L-selectride）试剂还原3-氧代-22-羟基何伯烷得到单一构型的3α,22-二羟基何伯烷和3β,22-二羟基何伯烷.在此基础上,通过X-射线单晶衍射实验确认了3β,22-二羟基何伯烷的绝对构型,并完整归属了该类化合物的¹H和¹³C NMR数据.本文的方法亦可用以制备其他使用常规方法难以分离的α-和β-异构体.     

A new upper bound formula for the ground state energies of N-boson systems

The energy E_N of an N-body system of pairwise interacting bosons is shown to satisfy the inequality, E_N < [N(N − 1)/n(n − 1)] E_n, where N > n 2. This inequality generalizes the Bruch-Sawada result, E₃ < 3E₂, and is superior in its predictive ability to Lim et al.'s .     

Isomerism in Ag and non-yrast levels in Pd and Rh, studied in β decay

The β decay of ⁹⁶Ag (Z=47,N=49) was investigated by measuring positrons, X rays as well as β-delayed protons and γ rays. The γ radiation was studied by means of germanium detectors and a NaI total-absorption spectrometer. Two β-decaying isomers in ⁹⁶Ag were established with half-lives of 4.40(6) and 6.9(6) s and tentative spin–parity assignments of (8⁺) and (2⁺), respectively. For both isomers, the intensities of β transitions to low-lying levels of ⁹⁶Pd (Z=46,N=50) and β-delayed proton decays to levels in ⁹⁵Rh (Z=45,N=50) were measured. Several new ⁹⁶Pd levels were firmly established. The level energies, their γ decays and the Gamow–Teller decay of ⁹⁶Ag are compared to shell-model predictions. A new low-lying level in ⁹⁵Rh was found at 680 keV excitation energy. Through a comparison with low-lying states of N=50 isotones, this level is interpreted as the first excited 7/2⁺ state built on the proton 9/2⁺ ground state. The assignments of further excited states in ⁹⁵Rh are discussed.     

新型吡唑并[3,4-d]嘧啶-4-酮类衍生物的结构表征和镇痛活性

本文以2-氰基-3-乙氧基丙烯酸乙酯与3,4-二甲基苯肼为原料,通过多步反应合成了三种新型吡唑并[3,4-d]嘧啶-4-酮类衍生物（A~C）,通过核磁共振（NMR,包括¹H NMR、¹³C NMR）和液相色谱-质谱联用（LC-MS）技术表征确证了其结构,并完整归属了三种化合物的¹H NMR数据．对所合成的化合物1-(3,4-二甲基苯基)-6-甲基-5-[3-(哌啶-1-基)丙氧基]-1,5-二氢-4H-吡唑并[3,4-d]嘧啶-4-酮（A）,通过小鼠脑部质谱成像和福尔马林实验进行了初步的体内镇痛活性评价,我们发现化合物A能透过血脑屏障,并产生显著且剂量依赖的镇痛活性．本研究为以吡唑并[3,4-d]嘧啶-4-酮为骨架的镇痛药物的研发提供了结构和体内活性的基础研究数据．     

含手性膦配体3-MBPA的铂(Ⅱ)配合物的2D NMR研究

利用一维和二维NMR技术,对含有手性膦配体的铂配合物trans-[Pt(3-MBPAH)₂Cl₂](1)和trans-(Pt(3-MBPA)(3-MBPAH)Cl)(2)进行¹H和¹³C NMR谱分析,否定了化合物(2)的结构为trans-[Pt(3-MBPA)₂]的可能,归属了所有的¹H和¹³C NMR谱线,并根据磷和铂及磷与磷的偶合常数确定它们是反式构型.     

Development of laser photoelectron spectroscopy based on resonantly enhanced multiphoton ionization

This review article is mainly concerned with laser photoelectron spectroscopy based on REMPI (resonantly enhanced multiphoton ionization), consisting of two parts. One is associated with the measurement of photoelectron kinetic-energy distribution and the other is associated with the measurement of zero-kinetic-energy (ZEKE) photoelectrons in very high resolution. These two techniques are complementary to each other. During the last three decades, the author and co-workers have carried out photoelectron spectroscopic studies of molecules in the gas phase, using the HeI 584 Å resonance line and a nanosecond tunable UV–visible laser. In this article, firstly the author’s background in the field of molecular photoelectron spectroscopy is described briefly, by mentioning three topics of HeI photoelectron spectroscopy. Secondly, the principle and characteristics of laser photoelectron kinetic-energy spectroscopy and its application to several typical topics, namely, one-photon forbidden states (O₂), autoionization from a super-excited state (NO), and small van der Waals molecules (NO–Ar and the NO₂ dimer), and some others. Thirdly, the principle and characteristics of ZEKE photoelectron spectroscopy are described, together with its application to the following several topics: (1) rotational spectra of NO⁺, (2) vibrational coupling of (naphthalene)⁺, (3) large-amplitude torsional motion of (tolane)⁺, (4) rotational isomers of (cis and trans n-propylbenzene)⁺ and structural isomers of (2-hydroxypyridine)⁺, (5) proton tunneling of (tropolone)⁺ and (9-hydroxyphenalenone)⁺, (6) intramolecular vibrational redistribution of trans stilbene, and (7) cation van der Waals molecules of aniline–Ar_n (n=1,2) and azulene–Ar. All the results mentioned as examples are those obtained in the author’s laboratory.     

Rotational bands in Ho

The excited states of the deformed odd-proton nucleus ¹⁶¹Ho have been studied in the reactions ¹⁵⁹Tb(, 2n), ¹⁶¹Dy(d, 2n) and ¹⁶¹Dy(p, n). Gamma-ray spectra in single and coincidence modes as well as angular distributions and excitation functions of the transitions were measured. The proposed level scheme of ¹⁶¹Ho contains besides of the ground state band ⁻[523] the bands ⁺[404], ⁺[411], ⁺[411] and ⁻ [541] (band heads at 252.7, 298.7, 211.2 and 423.9 keV, respectively). An attempt was made to estimate the influence of Coriolis coupling between the bands ⁺ [411] and ⁺ [411], which are very close in energy. The ⁺ [404] band was found to de-excite by very fast E1 transitions to the ground state band ⁻[523]. Nilsson retardation factors of about 0.03 for these transitions were deduced using the E2/E1 branching ratios. An investigation has also been made of the independent feeding of the levels from high-lying states.     

苄基保护甘露糖羧酸酯的NMR研究

应用NMR技术研究了1-0-(3,5-二硝基苯甲酰基)-2、3、4、6-四-0-苄基-D-吡喃甘露糖的α、β异构体的构型和糖环上碳氢归属情况,总结了苄基保护甘露糖羧酸酯构型的确证方法及影响糖环上碳氢化学位移的一些规律;并对其它13种四苄基甘露糖羧酸酯的NMR谱进行了研究,提供了这些化合物的¹³C和¹H NMR数据.     

一个含苯并咪唑环的酰氨基硫脲NMR研究

该文合成了一个新的在医药方面具有潜在应用价值的含苯并咪唑环的酰氨基硫脲化合物,即4-(4-甲氧基苯基)-1-[2-(4-硝基苯氧基甲基)-苯并咪唑-1-基\]甲酰基氨基硫脲,并利用元素分析、IR和NMR对其结构进行了表征. 通过NOESY谱确定了其两种异构体(A和B)的构型,并利用2D NMR技术对它们的¹H NMR 和¹³C NMR谱进行了全归属,给出了相应的偶合常数和两种异构体的含量.