聚氯乙烯辐射效应的NMR研究

用¹H 和¹³C NMR谱,FT-IR光谱等方法研究了聚氯乙烯(PVC)在限量空气氛室温下经⁶⁰Coγ 射线辐照后的辐照效应．结果表明PVC 大分子链的脱HCl 方式,受辐射剂量的影响．当辐射剂量达到2.8×10⁵Gy 时,PVC 以大分子链内脱HCl为主,产生部分－CH＝CH－结构,使得－CHCl的运动受阻,表现为T_２减小．不同溶剂对聚合物质子自旋-自旋弛豫时间（T_２）的影响,反映出溶剂效应和聚合物链在溶剂中的“伸展”状态．而水质子峰随着辐照剂量的增大而逐渐向低场位移,则是由于HCl与溶剂中的H₂O在微酸性溶液中发生了快速的质子交换之故．     

紫外光辐照聚乙烯醇的1H NMR研究

用¹H NMR谱,自旋-晶格弛豫时间（T₁）和X-射线衍射研究了聚乙烯醇(PVA)在紫外光（UV）辐照后-OH基团与溶剂中残余水质子间氢键的生成与质子交换. 结果表明随着UV光辐照时间的增长,水峰与-OH质子峰逐渐相互靠近,同时水峰逐渐变宽,向低场方向移动,这与-OH基团与溶剂DMSO中残余水的质子之间既有氢键生成又有质子交换有关. 对辐照前后的PVA的DMSO溶液进行变温氢谱的研究,表明随着温度的升高,二者的-OH基团共振峰均逐渐变弱,溶剂残余水峰与-OH基团峰逐渐移向高场. PVA辐照前后随着浓度增大,羟基质子峰“变钝”. 辐照后的PVA的X-射线衍射表明聚集态结构中部分分子间氢键受到了破坏.     

固体高分辨NMR研究PPU/PMAs,AB-交联聚合物中的分子运动和相容性

本文使用固体高分辨NMR测量了PPU/PMAs,AB-交联聚合物中PPU的侧甲基的¹³C自旋-晶格弛豫时间(T₁)。使用内旋转运动的平均谱密度函数分析了PPU侧甲基的内旋转和PMA的侧基的多重内旋转运动。结果表明PMA中的侧基距主链越远,其旋转速度越快并且PPU侧甲基的内旋转速度随ABCP中PMA侧链长度增加而变快。还使用质子的T_1ρ和T₂及自旋扩散研究了体系的相容性和相行为。得到了有关相应尺度下的每相的组成和软相微区尺度的信息。     

大分子中磁偶极弛豫的分离

提出采用仅与偶极弛豫有关的¹³C核同¹H核之间的核交叉弛豫速率来考察分子内部运动状况。给出了实际用于考察分子运动状况的关系式,从理论上阐明了本文方法比传统上直接采用常规测定的¹³C核纵向弛豫时间T₁、演向弛豫时间T₂及NOE增强因子η来研究分子运动状况的方法要合理。建立了既适用于小分子又适用于大分子自旋系统¹³C核总自旋弛豫中偶极弛豫分离的公式.     

有机磷化合物的NMR研究——Ⅱ0,0-二烷基膦酸酯的1H、13C和31PNMR谱

本文报道了21个0,0一二烷基膦酸酯类化合物的¹H、¹³C和³¹P NMR参数。研究和讨论了不等价的二烷基¹H、¹³C化学位移和磷碳偶合常数与立体化学的关系。测定了(CH₃CH₂O)₂P(O)CH(CH₂NO₂)(p-OCH₃C₆H₄)的¹³C自旋一晶格弛豫时间T₁,二乙基¹³C T₁间的差别,说明在类似化合物中,含有化学位移各向异性对弛豫的贡献。     

AB-交联聚合物(PPU/PS)中分子运动和相容性的固态高分辨NMR研究

本文用固体高分辨NMR技术测量了AB-交联聚合物(即ABCP)PPU/PS(聚氨酯/聚苯乙烯)中侧甲基的¹³C弛豫时间T₁。使用分子内旋转的平均谱密度函数分析了ABCP中CH₃侧基的内旋转运动。结果表明PPU/PS,ABCP中PPU的CH₃侧基运动与PS的含量有关。当体系发生相反转时,侧甲基的运动也发生一转变。这反映了侧甲基的运动与ABCP的宏观性质密切相关。对该ABCP体系还进行了¹H T_1ρ的测量,分析了其相容性。     

新疆长绒棉辐射效应的谱学研究

用¹³C CP/MAS NMR谱、ESR谱和质子弛豫时间等方法,研究了经γ射线在室温下辐照后新疆长绒棉纤维的辐射效应. 结果表明随着辐照剂量的增加,长绒棉纤维内的自由基浓度明显的增大,并产生了多种自由基的混合物. 由辐照前后的长绒棉纤维的¹³C CP/MAS NMR谱可以得出,随着辐射剂量的增加,C1峰的谱宽趋向增宽,表明了自由基存在的位置. 各类弛豫时间的改变则反映出长绒棉纤维内部聚集态结构和大分子链运动随辐射剂量的变化.     

羰基化合物分子距边矢量与其13C NMR δC的关系

通过对155个羰基化合物中羰基碳原子的¹³C NMR谱与其分子距离-边数矢量(MDE)、立体效应参数(γ 效应)关系的研究，发现羰基化合物羰基碳的¹³C NMR谱化学位移可表示为：
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δ_C=a+bμ₅₁+cμ₅₂+dμ₅₃+eμ₅₄+fγ
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此式不仅在一定程度上表明了羰基化合物¹³C NMR谱化学位移与其分子结构信息之间的关系，同时也提供了一种计算羰基化合物¹³C NMR化学位移的新方法，并对解析和预测其¹³C NMR谱提供了理论依据.      

丙烯酰胺-甲基丙烯酸共聚物结构的NMR研究

用¹H NMR谱,¹³C NMR谱,DEPT谱,gHMQC,gHMBC二维谱和质子弛豫时间等方法研究了在紫外光辐照条件下丙烯酰胺(AM) -甲基丙烯酸(MAA)共聚合反应,讨论了AM-MAA共聚合反应时间与转化率的关系、共聚单体的连接方式、共聚物序列结构以及不同辐照时间下形成的共聚物链运动. 结果表明在紫外光辐照条件下,AM-MAA共聚物链节中同时存在多种连接方式,当反应时间为45 min时,共聚合转化率可达100%. 从自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）测定中得出,在辐照1小时范围内,时间越长聚合物长链分子运动速度越快,但主链的链段运动变化不明显.     

PAMAM树状大分子与5-氟尿嘧啶相互作用的NMR研究

本文利用多种核磁共振（NMR）技术研究了聚酰胺-胺树状大分子（PAMAM）与5-氟尿嘧啶（5-FU）在水溶液中的相互作用.¹H NMR化学位移滴定结果表明5-FU分子结合在PAMAM分子表面,¹³C NMR化学位移滴定分析结果表明5-FU分子通过氢键或疏水间相互作用进入到PAMAM的内部疏水空腔.¹H核和¹⁹F核自旋-晶格弛豫时间（T₁）的测定结果也说明了二者之间存在相互作用.NOESY实验进一步验证了5-FU分子进入到PAMAM分子的内部空腔.本研究为研究树状大分子和药物小分子的相互作用提供了系统的NMR分析方法.     

EPR Investigation of Radical-Production Cross Sections for Sucrose and L-alanine Irradiated with X-rays and Heavy-ions

Using electron paramagnetic resonance (EPR), we investigated stable radical-production cross sections (σ) of sucrose and L-alanine radicals produced by heavy-ion irradiations with various linear energy transfers (LET). The heavy-ion irradiation results were compared with those of X-ray irradiation at the same dose. The EPR signal areas for the two compounds showed a linear relation with the absorbed dose, as well as a logarithmic correlation with the LET. Further analysis was carried out for the radical-production cross section, which showed that stable radicals of the two compounds were produced through collisions of several particles with a single molecule. The relative σ value of sucrose for C ion irradiation was (1.29 ± 0.64) × 10⁻¹² μm². The σ value of alanine for C ion irradiation was (6.83 ± 0.42) × 10⁻¹³ μm². Considering the structural molecular sizes of sucrose and alanine, the σ values are similar. In addition, a comparison of the EPR results for the C ions and X-rays at 50 Gy dose was made. Sucrose spin concentrations produced by C ions at the LET value of 13.1 keV/μm and X-rays were similar unlike alanine. Thus, the noble EPR results with X-ray and heavy-ion irradiations imply that sucrose can be useful as a radiation indicator.     

Fast Dissolution Dynamic Nuclear Polarization NMR of 13C-Enriched 89Y-DOTA Complex: Experimental and Theoretical Considerations

The yttrium complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(1′-¹³C-acetic acid) [¹³C]DOTA was synthesized. Fast dissolution dynamic nuclear polarization (DNP) nuclear magnetic resonance (NMR) studies revealed that the ⁸⁹Y, ¹³C, and ¹⁵N nuclei present in the complex could be co-polarized at the same optimum microwave irradiation frequency. The liquid-state spin–lattice relaxation time T ₁ of these nuclei were found to be reasonably long to preserve some or most of the DNP-enhanced polarization after dissolution. The hyperpolarized ¹³C and ⁸⁹Y NMR signals were optimized in different glassing mixtures. The overall results are discussed in light of the thermal mixing model of DNP.     

Spectroscopic and thermal studies of gamma irradiated polypropylene polymer

Thin films of polypropylene have been irradiated with different doses of gamma radiation from a ⁶⁰Co source. IR, UV-VIS spectra of this polymer before and after irradiation have been recorded and from the spectral data some modifications in the properties have been investigated. The spectra indicated that polypropylene film was oxidised at the dose of 10⁶ Gy. Due to the removal of additives, total destruction of the polymer takes place at this dose. Isotactic arrangement of the polymer is no longer present after irradiation. Growth of carbon cluster takes place above a gamma dose of 10² Gy. Thermal stability of the polymer changes due to irradiation and the polymer seems to decompose in four different steps at the highest dose of 10⁶ Gy.     

A localization method for the measurement of fast relaxing13C NMR signals in humans at high magnetic fields

Nuclear magnetic resonance (NMR) signals with shortT ₁ andT ₂, such as the¹³C signal of glycogen, are difficult to localize in three dimensions without major signal loss. A pulse sequence that accomplishes the spatial localization of¹H-decoupled¹³C NMR signals on a whole-body scanner within the Food and Drug Administration guidelines for specific absorption rates was designed. The method uses an optimized three-dimensional outer volume suppression scheme combined with one-dimensional image-selected in vivo spectroscopy and surface coil detection. The localization performance of the sequence was validated at 4 T with double chambered phantoms and¹³C magnetic resonance imaging. Localized¹³C spectra were acquired from human brain and muscle.     

Satellite structure of DNP enhanced 13C NMR spectra in diamond

The P1 nitrogen defect centres in natural type Ia diamonds have been exploited in dynamic nuclear polarization (DNP) of the ¹³C nuclei (1.1% abundant) via the solid-effect. We have achieved sufficiently large ¹³C polarizations in some diamonds to observe weak satellite lines in the ¹³C NMR spectra by using long microwave irradiation times. A study of the dependence of the NMR spectra on the crystal orientation with respect to the applied magnetic field reveals that the satellite structure originates from the small fraction of ¹³C nuclei that are involved in nearest neighbour dipole interactions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Optorelaxers: Achieving real-time control of NMR relaxation

We present an approach to increase the detection sensitivity of NMR by shortening the spin-lattice relaxation time using transient paramagnetic species created by light irradiation of “optorelaxer” molecules. In the ultimate implementation of this concept, not yet realized here, these transient species are absent during the detection period, thereby avoiding the loss of spectral resolution caused by inhomogeneous broadening from paramagnetic species. Real-time control of NMR relaxation by visible light is demonstrated with Fe(II)(ptz)₆(BF₄)₂, (ptz = 1-propyltetrazole), abbreviated FePTZ. Illumination of FePTZ at 30 K results in a decrease of the ¹H NMR spin-lattice relaxation time T₁ due to formation of a high spin photoexcited state. The ¹H NMR of polystyrene containing a low concentration of FePTZ molecules shows a similar reduction in T₁, establishing that FePTZ can act as an optorelaxer for the protons of a matrix. Numerical modeling of the spin-diffusion processes from the protons in a FePTZ core to those in a shell of polystyrene accounts for the observed T₁ effects under both dark and light conditions. Additionally, ¹H MAS (magic-angle spinning) NMR results for pure FePTZ provide information on the isotropic and anisotropic portions of the electron-nuclear hyperfine interactions.     

Application of High-Resolution NMR Spectroscopy in Analyzing Ionites

The ¹H and ¹³C NMR spectra of granulated carboxylic cationite MAC-3 and fibrous anionites FIBAN (A-5, A-7, and A-9) have been investigated. The dependence of the chemical shifts and times of spin–spin relaxation of the water protons and carbon nuclei of MAC-3 on the water content in a sample has been investigated. A comparison of the carbon spectra of polyelectolytes and FIBAN fibrous anionites swollen in water has been made. It is shown that the carbon spectra of the ionites swollen in water represent fairly narrow lines practically for all groups of the skeleton, and therefore the structure of the ionites can be analyzed using a high-resolution NMR.