温敏性纤维素/聚N-异丙基丙烯酰胺复合水凝胶的固体核磁共振表征及动力学研究

利用半互穿网络方法将具有温度响应的高分子聚N-异丙基丙烯酰胺(PNIPAM)与天然纤维素复合得到温敏性水凝胶. 通过固体核磁共振的 ¹H, ¹³C CP/MAS(交叉极化/魔角旋转)和QCP(定量交叉极化)等实验手段对复合凝胶的结构进行了定性及定量研究, 并利用固体静态变温核磁共振实验和偶极滤波-自旋扩散实验研究了复合凝胶中PNIPAM分子链段的动力学行为.     

新型四苯乙烯衍生物的合成

以4-溴二苯甲酮为起始原料, 利用McMurry等反应构筑分子骨架,设计并合成了3个新型四苯乙烯衍生物,其结构经¹H NMR, ¹³C NMR, EI-MS和元素分析表征。     

The N and C solid state NMR study of intramolecular hydrogen bond in some Schiff bases

In present work set of eight Schiff bases derived from substituted salicylaldehydes and aliphatic and aromatic amines has been studied in the solid state by ¹⁵N and ¹³C CPMAS NMR methods. ¹⁵N CPMAS NMR measurement is especially useful for investigation of the tautomerism in the compounds considered, owing to the large difference in the nitrogen chemical shifts of OH and NH tautomers. In the solid state, four of the compounds examined were shown by ¹⁵N CPMAS NMR to exist as OH tautomeric forms, and the remaining four as the corresponding NH forms with different stage of proton transfer process, from oxygen to nitrogen site.

This was confirmed by ¹³C CPMAS. The results reported were compared with those obtained for only two compounds in CDCl₃ solutions (solubility problems).     

Synthesis and Biological Evaluation of Novel Saccharin Derivatives Containing 1,2,3-Triazole Moiety

A series of novel saccharin derivatives containing 1,2,3-triazole moiety was synthesized in satisfactory yields. The structures of all the compounds were elucidated and confirmed by Fourier transform infrared(FTIR) spectroscopy, ¹H and ¹³C nuclear magnetic resonance(¹H NMR, ¹³C NMR) spectroscopy, and high resolution mass spectrometry(HRMS). The bioassays indicated that most of the title compounds displayed some extent herbicidal activities at 100 μg/mL.     

Eucleanal A and B:Two new napthalene derivatives from Euclea divinorum

Two new naphthalene derivatives named eucleanal A and B（1 and 2） were isolated from Euclea divinorum.The structures of the new compounds were elucidated by detailed spectroscopic analysis such as ¹H,¹³C NMR,COSY,HMQC,HMBC and HREIMS mass spectrometry.     

Synthesis of new N-substituted imidazolyl and 1H-1,2,4-triazolyl derivatives of (η-arene)(η-cyclopentadienyl)iron(II) salts

A series of new imidazolyl and 1H-1,2,4-triazolyl derivatives of (η⁶-arene)(η⁵cyclopentadienyl)iron(II) salts have been prepared by reaction of the corresponding chloroarene complexes with the sodium salts of the heterocycles. Good yields of N-substituted products were obtained in all cases under very mild conditions. In contrast to substitution by primary and secondary amines, both chlorines were displaced from [(η⁵-1,2-dichlorobenzene)(η⁵-Cp)Fe][PF₆], indicating electron withdrawal by the imidazolyl and triazolyl groups. Detailed ¹H and ¹³C NMR analysis confirmed this point. NOE difference spectra were used for ¹³C assignments, and evidence for conformational isomers in the 1,2-disubstituted complexes is presented.     

新型瑞香酮类似物的合成及杀菌活性

以瑞香狼毒中分离的天然产物(E)-1,5-二苯基-2-烯-1-戊酮(A)为先导, 引入色酮片段设计合成了15个新型的瑞香酮类似物, 其结构均经IR, ¹H NMR, ¹³C NMR及元素分析或HRMS确证. 杀菌活性测试结果表明, 在100 mg/mL浓度下, 部分化合物的杀菌活性优于先导化合物A, 其中化合物6d对水稻纹枯病菌和黄瓜灰霉病菌的抑制率分别为87%和86%, 与对照药剂苯醚甲环唑相当, 值得进一步优化研究.     

The structure of the antibiotic hedamycin—III : C NMR spectra of hedamycin and kidamycin

The ¹³C NMR spectra of hedamycin, kidamycin and some of their derivatives have been fully assigned. Proton coupling constants and ¹³C NMR acetylation shifts indicate that the conformations of the highly substituted tetrahydropyran rings in solution are chair forms for ring E, as well as for ring F in isokidamycins, but a twist form for ring F in hedamycins and kidamycins.     

Synthesis and biological activities of some fluorine-and piperazine-containing 1,2,4-triazole thione derivatives

A series of fluorine-and piperazine-containing 1,2,4-triazole thione derivatives were synthesized by the Mannich reaction of triazole intermediates with various substituted piperazines and formaldehyde in high yields. Structures of title compounds were confirmed by melting points, IR, ¹H NMR, ¹³C NMR and elemental analysis. The preliminary bioassays for 17 novel title compounds showed that several compounds have significant fungicidal activity against Cercospora arachidicola, Physalospora piricola and Rhizoctonia cerealis at 50μg/mL.     

Direkte und indirekte metallierung von endo-dicylopentadien. Sn- und C-NMR studie stannylierter folgeprodukte

endo-Dicyclopentadiene (1) can be metalated by use of simple procedures with good overall yields. The attack occurs at the various vinyl, rather than at the allyl, positions of 1 as was confirmed by trapping the carbanions with Me₃SnCl. When t-BuLi/TMEDA are used, the 8- and 9-stannyl derivatives (3 and 4) are formed, whereas an excess of n-BuLi/t-BuOK leads to doubly stannylated derivatives with Me₃Sn groups in position 4/8 (6), 4/9 (7), and 3/9 (8) in addition to 3 and 4. Furthermore the latter reaction yields 5,5-bis(trimethylstannyl)cyclopentadiene (5). With stoichiometric amounts of n-BuLi/t-BuOK the formation of 3 and 4 predominates over that of 5–8. 5 is obtained from 1 after deprotonation at the allyl position, followed by an extremely fast retro-Diels-Alder reaction and then by further deprotonation. This follows from two experiments: (1) exo- and endo-5-trimethylstannyl-endo-dicyclopentadiene (11 and 12) which are synthesized from 1 in three steps give cyclopentadienyllithium and 1 when treated with methyllithium at −78°C; (2) cyclopentadiene reacts with an excess of n-BuLi/t-BuOK and Me₃SnCl to give 5. When 12 is heated syn-10-trimethylstannyl-endo-dicyclopentadiene (13) is obtained. The eight stannyl derivatives of 1 are identified mainly from the following NMR parameters: δ(¹¹⁹Sn), δ(¹³C), δ(¹H), ⁿJ(^119/117Sn---¹³C), and ⁶J(¹¹⁹Sn---^119/117Sn). The ¹³C NMR satellite spectrum of 1 yields the isotope shifts ¹Δ¹³(i(¹³C(j)) and ¹J(¹³C---¹³C). The latter lead to the revision of earlier signal assignments.     

新型3-氨基氮杂环丁烷衍生物的合成

以3-羟基氮杂环丁烷盐酸盐为原料,与4-氟苯乙酮反应制得1-（4-乙酰苯基）-3-羟基氮杂环丁烷（1）; 1经甲磺酰化反应、取代反应、还原反应及酰化反应,合成了6个新型的3-氨基氮杂环丁烷衍生物,其结构经¹H NMR和¹³C NMR表征。     

汉防己甲素衍生物的合成及其生物活性

为寻找更为有效的抗肿瘤药物,改善汉防己甲素的抗肿瘤活性,本文以汉防己甲素为原料,经过Suzuki反应设计并合成了6个新的双苄基异喹啉类衍生物。新化合物经过质谱(MS)、核磁共振氢谱(~1H NMR)、核磁共振碳谱(~(13)C NMR)等技术手段进行了结构确证。采用细胞计数试剂盒(CCK-8)法初步评价了6个新化合物对人肺癌细胞(A549)和小鼠白血病细胞(P388)的抗肿瘤活性。结果表明,化合物均有不同程度的抗肿瘤活性,其中化合物H1、H4、H6对A549细胞的抗肿瘤活性(IC5010μmol/L)明显优于阳性对照汉防己甲素。     

Synthesis and characterization of a new biodegradable polyurethanes with good mechanical properties

In the paper, a new biodegradable polyurethane(PU, PU-I) was prepared: the prepolymer was synthesized via bulk ring-opening polymerization with poly(ethylene glycol)(M_n= 600)(PEG600) as an initiator and L-lactide(L-LA), e-caprolactone(CL) as monomers, and the prepolymer was chain-extended with an isocyanate-terminated urethane triblock(macrodiisocyanate) to prepare the PU. The macrodiisocyanate, prepolymer and PUs were characterized by~1H NMR,~(13)C NMR, FT-IR, high resolution mass spectrometry(HR-MS), gel permeation chromatography(GPC), thermo gravimetric analysis(TGA),and differential scanning calorimetry(DSC). The corresponding PU films showed excellent mechanical properties with a tensile strength of 27.5 MPa and an elongation at break of 996%, and also maintained mechanical properties in physiological saline at 37℃ for more than three weeks, which appeared to be more suitable for biomedical applications.     

新型含嘧啶的苯氧乙酸酯类衍生物的合成

以对羟基苯甲醛和一氯乙酸为起始原料,经羟醛缩合、关环及酯化等反应合成了6个含有嘧啶杂环的新型苯氧乙酸酯类衍生物,其结构经¹H NMR, ¹³C NMR, IR和HR-ESI-MS表征。     

几种咔唑衍生物(有机光导材料)的13C核磁共振谱的研究

我们测定了3-溴咔唑,3,6二溴咔唑,9-(2',3'-环氧丙基)咔唑,9-(2',3'-环氧丙基)-3-溴咔唑和9-(2',3'-环氧丙基)-3,6-二溴咔唑(后分别简称化合物1,2,3,4,5)的宽带去偶谱、偏共振谱和非去偶谱。通过对它们的¹³C核磁共振谱的数据分析比较,就以下几方面进行了归纳总结:①信号的归属方法;②环氧丙基的¹³C化学位移范围;③偶合常数的范围,这些归纳总结有助于确定此类化合物的价键特征和结构。     

Synthesis and thermal properties of novel calix[4]arene derivatives containing 1,2,3-triazole moiety via K2CO3-catalyzed 1,3-dipolar cycloaddition reaction

Two calix[4]arene derivatives containing 1,2,3-triazole moiety were synthesized via K2CO3-catalyzed1,3-dipolar cycloaddition reaction between calix[4]arene-based azide and active methylene compounds in good yields.The structures of the two compounds synthesized herein were fully confirmed by 1HNMR,,（13）C NMR,and MS（ESI）.The thermal analysis showed that the mass losses of the synthesized compounds 4 and 5 containing 1,2,3-triazole groups are similar to each other.     

Design,synthesis and evaluation of novel cis-p-menthane type Schiff base compounds as effective herbicides

p-Menthane type monoterpene derivatives were identified as bio-based compounds with high herbicidal activities. In order to search novel p-menthane type monoterpene derivatives in good performance, a series of novel cis-p-menthane type Schiff base derivatives were designed and synthesized. All target products were easily available novel compounds and characterized by FT-IR, ¹H NMR, ¹³C NMR and ESI⁺- MS. Their pre-emergence herbicidal activities against annual ryegrass were evaluated. The bioassays indicated that most of the target compounds displayed excellent herbicidal activities in pre-emergence treatment.     

酞侧基聚芳醚酮的核磁共振研究(Ⅰ)──链结构及NMR谱的归属

用1D NMR方法研究酞侧基聚芳醚酮(PEK-C)链结构,用二维同核化学位移相关与二维异核化学位移相关实验方法对1D NMR谱峰进行归属,探讨了二维异核远程相关实验在缩聚高分子研究中的应用,为PEK-C修饰机理以及共混相容机理的研究提供重要信息。溶液NMR谱图数据表明,PEK-C具有较规整的链结构。     

两类含有吡唑酮或吲哚酮结构的色满衍生物的合成与结构表征——羰基与醛基的反应活性及化学选择性

以色酮醛为反应物,在四氢吡咯催化条件下分别与甲基吡唑酮或2-吲哚酮发生加成-消除反应,得到两类含有吡唑酮或吲哚酮结构的色满衍生物,并且通过熔点测定、核磁共振(1H NMR、13C NMR)、高效液相色谱(HPLC)和高分辨质谱仪(HRMS)对产物结构进行表征。     

新型高冲击韧性环氧乙烯基酯树脂的合成和表征

通过引入柔性环氧封端聚醚(ETPE)单体, 报道了一种温和且高效制备新型高冲击韧性的乙烯基酯树脂(EVER-2)的方法。 用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(¹H NMR)和碳谱(¹³C NMR)等技术手段对其结构进行了表征, 并对其拉伸强度、弯曲强度和冲击韧性等力学性能和热变形温度进行了测试。 结果表明, 只需少量的ETPE参与反应(约占树脂总质量的7.9%), EVER-2固化产物就具有很高的冲击韧性。 其SEM的冲击断面形貌表明, 新型高冲击韧性乙烯基酯树脂为均相结构, 其与玻璃纤维有很好的粘结能力。 提出了EVER-2及其与玻璃纤维复合材料 EVERL-2可能的增韧机理。