乙烯直接氧化制乙酸的研究

采用固定床流动装置考察了乙烯直接氧化制乙酸的新工艺,并对该过程的催化剂进行研究开发。结果表明,以硅胶为载体、铬氧化物为助剂、Ｐｄ和Ｈ３ＰＯ４的质量分数分别为０．０１５和０．３０时（以载体的质量计）,催化剂具有最佳活性,此时乙烯的转化率和乙酸的选择性分别可达４．４％和６８．９％,乙酸的单程时空收６率达１３４ｇ／（Ｌ．ｈ）。     

放射性粒子103 Pd与缓释化疗粒子联合应用靶向治疗肝癌

目的探讨应用放、化疗粒子联合植入法综合治疗肝癌的可行性、安全性及短期疗效。方法自2001年12月～2004年12月，应用放、化疗粒子联合植入法综合治疗复发性直肠癌48例。在治疗计划指导下，交替植入5-Fu缓释化疗粒子和放射性。Pd粒子。放射性粒子的肿瘤匹配周边剂量（Matched Peripheral dose，MPD）为90～130Gy。平均每例使用^103Pd粒子10粒，5-Fu 1000mg。结果48例病人手术均顺利完成，未发生出血、感染等并发症，经摄片证实放射性粒子的位置无变化。疼痛缓解率为95．83％（46／48），平均疼痛缓解时间为5～9d。于术后3～6个月CT复查肿瘤变化，提示瘤体不同程度缩小，其中11例完全缓解，27例部分缓解，9例稳定，局部控制率为79．17％。随访6～28个月，中住生存期为17个月，最长1例随访时间为术后26个月，现仍存活。1例术后6个月死于全身广泛转移。结论放射性^103Pd粒子和5-Fu缓释化疗粒子联合应用局部植入技术具有安全、微创及并发症发生率低的特点，是综合治疗肝癌的较有效手段之一。     

Synthesis of tritium labelled CHS 828 and its prodrug EB 1627

The potent antitumoral cyanoguanidine CHS 828 and its prodrug EB 1627 have successfully been labelled with tritium. The pyridyl‐3,5‐dibromo derivative of CHS 828 was debrominated with tritium‐gas using Pd/C catalyst to give [pyridyl‐3,5‐³H₂]‐CHS 828 with a radiochemical purity of 99.3% and a specific activity of 1960 GBq/mmol. Similarly, the pyridyl‐3‐bromo derivative of the prodrug EB 1627 was debrominated with tritium‐gas to give [pyridyl‐3‐³H]‐EB 1627 with a radiochemical purity of 98.1% and a specific activity of 894 GBq/mmol. Copyright © 2005 John Wiley & Sons, Ltd.     

电感耦合等离子体发射光谱法(ICP-OES)测定枸橼酸托法替布中钯、铑残留量

目的 建立枸橼酸托法替布中钯、铑残留量的测定方法.方法 样品用浓硫酸碳化,加浓硝酸及高氯酸消解后,采用电感耦合等离子体发射光谱法(ICP-OES)测定钯、铑元素含量.结果 各元素线性关系良好,相关系数(r)均大于0.999,钯和铑的方法检出限为分别为0.10 mg·kg-1和0.25 mg·kg-1,加标回收率在88....     

CO Oxidation over Pd Catalyst Supported on Porous TiO2 Prepared by Plasma Electrolytic Oxidation (PEO) of a Ti Metallic Carrier

A porous TiO₂ layer was prepared with the plasma electrolytic oxidation (PEO) of Ti. In a further step, Pd was deposited on the TiO₂ surface layer using the adsorption method. The activity of the Pd/TiO₂/Ti catalyst was investigated during the oxidation of CO to CO₂ in a mixture of air with 5% CO. The structure of the catalytic active layer was studied using a scanning electron microscope equipped with an energy dispersive spectrometer (SEM-EDS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), inductively coupled plasma mass spectrometry (ICP-MS), and X-ray diffraction (XRD). The PEO process provided a porous TiO₂ layer with a uniform thickness in the range of 5–10 µm, which is desirable for the production of Pd-supported catalysts. A TOF-SIMS analysis showed the formation of Pd nanoparticles after the adsorption treatment. The conversion of CO to CO₂ in all samples was achieved at 150–280 °C, depending on the concentration of Pd. The composition of Pd/ TiO₂/Ti was determined using ICP-MS. The optimum concentration of Pd on the surface of the catalyst was approximately 0.14% wt. This concentration was obtained when a 0.4% PdCl₂ solution was used in the adsorption process. Increasing the concentration of PdCl₂ did not lead to a further improvement in the activity of Pd/ TiO₂/Ti.     

Physiologic Characteristics and Clinical Outcomes of Patients With Discordance Between FFR and iFR

ObjectivesThis study evaluated the physiologic characteristics of discordant lesions between instantaneous wave-free ratio (iFR) and fractional flow reserve (FFR) and the prognosis at 5 years.BackgroundFFR or iFR have been standard methods for assessing the functional significance of coronary artery stenosis. However, limited data exist about the physiologic characteristics of discordant lesions and the prognostic implications resulting from these lesions.MethodsA total of 840 vessels from 596 patients were classified according to iFR and FFR; high iFR–high FFR (n = 580), low iFR–high FFR (n = 40), high iFR–low FFR (n = 69), and low iFR–low FFR (n = 128) groups, which were compared with a control group (n = 23). The differences in coronary circulatory indices including the coronary flow reserve (CFR), index of microcirculatory resistance (IMR), and resistance reserve ratio (RRR) (resting distal arterial pressure × mean transit time / hyperemic distal arterial pressure × hyperemic mean transit time), which reflect the vasodilatory capacity of coronary microcirculation, were compared. Patient-oriented composite outcomes (POCO) at 5 years including all-cause death, any myocardial infarction, and any revascularization were compared among patients with deferred lesions.ResultsIn the low iFR–high FFR group, CFR, RRR, and IMR measurements were similar to the low iFR–low FFR group: CFR 2.71 versus 2.43 (p = 0.144), RRR 3.36 versus 3.68 (p = 0.241), and IMR 18.51 versus 17.38 (p = 0.476). In the high iFR–low FFR group, the CFR, RRR, and IMR measurements were similar to the control group: CFR 2.95 versus 3.29 (p = 0.160), RRR 4.28 versus 4.00 (p = 0.414), and IMR 17.44 versus 17.06 (p = 0.818). Among the 4 groups, classified by iFR and FFR, CFR and RRR were all significantly different, except for IMR. However, there were no significant differences in the rates of POCO, regardless of discordance between the iFR and FFR. Only the low iFR–low FFR group had a higher POCO rate compared with the high iFR–high FFR group (adjusted hazard ratio: 2.46; 95% confidence interval: 1.17 to 5.16; p = 0.018).ConclusionsDifferences in coronary circulatory function were found, especially in the vasodilatory capacity between the low iFR–high FFR and high iFR–low FFR groups. FFR–iFR discordance was not related to an increased risk of POCO among patients with deferred lesions at 5 years. (Clinical, Physiological and Prognostic Implication of Microvascular Status; NCT02186093; Physiologic Assessment of Microvascular Function in Heart Transplant Patients; NCT02798731)     

P波最大时限及P波离散度与阵发性心房颤动的关系

目的 探讨P波最大时限（Pmax）与P波离散度（Pd）对特发性阵发性房颤（PM）的预测价值。方法 分别观察30例特发性PAl和40例健康成人的Pmax及Pd,研究Pmax和Pd对特发性PAl诊断的敏感性、特异性和阳性预测值。结果 特发性PM患者的Pmax及Pd明显大于对照组,其差异有高度显著性（P〈0．01）;Pmax〉110ms、Pd〉40ms及两者相结合时预测特发性PM的敏感性分别为86％、84．2％和72．2％,特异性分别为78．3％、85．0％和88．7％,阳性预测值分别为81．6％、85．3％和89．4％。结论 Pmax和Pd在特发性附病人中明显增加,可作为预测特发性眦的有效指标。     

国际放射防护委员会第98号出版物放射安全,前列腺(癌)近距离治疗

近15年来,选择性局限性前列腺癌患者使用永久性粒子(~(125)I或~(103)Pd)治疗已经越来越多的得到采用。每年全世界约有5万以上的患者接受这一治疗,并且这一数字在不久的将来还会进一步增加。尽管迄今为止尚未见有关患者家庭成员或医务人员的损伤或放射事故的报道,这一近距离治疗技术引发了许多放射安全性问题,亟待ICRP的专业意见。回顾涉及植入治疗患者周围人群受照剂量的所有相关资料。剂量数值是直接测量或计算获得。提示在大多数情况下,陪护人员或探视人员的受照剂量保持在推荐限值1 mSv／年以下。仅有极罕见的情况是,在进行植入治疗时患者的同伴正值妊娠期,需要特别谨慎。放射源随尿液、精液或粪便从体内的逸出是非常少见的。应给予患者专业建议以使其能够正确处理这类事件。显然,由于孤立粒子的低活度和较低的光子能量,未见与粒子丢失相关的意外或事故的报道。如果患者在植入术后几个月内死亡,尸体火化时(某些国家较为普遍)涉及到几个问题:(1)患者骨灰残留的放射活度;(2)空气剂量,因为有可能含有微粒子的空气会被火葬场工作人员或公众吸入。现有资料表明,如果在~(125)I植入术后12个月(~(103)Pd后3个月)进行火化是可行的。如果患者在这一时间期内死亡,则必须采取适当防护措施。我们还要告知患者,当其需要采取腹盆腔手术时,患者有义务告知其手术医生曾进行放射性粒子植入术。含有全部植入信息的“皮夹卡”就非常有用。在大多数情况下,接受近距离治疗会导致患者不育。然而,尽管该治疗相关的精液改变可降低生育能力,接受永久性粒子植人术后患者仍应格外小心衍育后代的可能,尽管对孩子遗传效应的影响是有效的。接受永久性粒子植入术的患者应警惕粒子可能会激发某些类型的放射安全检测仪。含有全部植入信息的“皮夹卡”这时候或有所帮助。根据现有前列腺癌近距离治疗和外照射的经验,放射诱发第二原发癌发生率极低。近距离治疗带来的益处显然超过了迄今为止非常有限的(而且主要是理论上的)放射诱发第二原发癌的增加。     

聚氯乙烯多乙烯多胺负载钯配合物对Heck反应的催化性能

目的：研究高分子材料聚氯乙烯负载胺一钯配合物的制备并探讨其催化性能。方法：以聚氯乙烯为原料，通过胺化反应得到聚氯乙烯多乙烯多胺，进一步制得聚氯乙烯多乙烯多胺负载钯配合物（PVC-PP-Pd），观察其在不同反应条件下对碘苯与丙烯酸的Heck反应的催化性能。结果：PVC-PP-Pd在空气氛围中即可有效地催化碘苯与丙烯酸的反应，在100℃和较少的催化剂用量下，可较高产率地生成反式取代产物，而且便于回收，重复使用性能较好。结论：PVC-PP-Pd是Heck反应良好的负载型催化剂。     

Spectrophotometric study of polythiazide—palladium(II) complex

A quantitative spectrophotometric method using Pd(II) chloride as analytical reagent for the determination of polythiazide in pharmaceutical preparations is described in this study. It has been found that polythiazide reacts with Pd(II) chloride in the pH range 3.6–5.8, forming a red, water-soluble (1:1) complex with maximum absorbance at 527 nm. At the optimum pH of 4.8 and an ionic strength μ = 0.1 M, the conditional stability constant of the complex is found to be log K′ = 4.77. The molar absorptivity at 527 nm is 3.2 × 10³ 1 mol⁻¹ cm⁻¹. Good agreement with Beer's law was found for polythiazide concentrations up to 2.2 mmol l⁻¹. The nominal percent recovery of polythiazide was 99.5% (n = 20). The simplicity, selectivity and sensitivity of the method described is suitable for rapid and accurate determinations of polythiazide in tablets.