跨海集群工程节能减排关键技术研究

港珠澳大桥跨海集群工程囊括跨海桥梁、沉管隧道、离岸人工岛等多个领域。跨海集群工程由于建设期及运营期能耗巨大,国内外尚无节能减排的成套技术指导工程建设,成为制约跨海集群工程持续发展的瓶颈之一。本文依托港珠澳大桥跨海集群工程建设和运营过程,采用理论研究、数值分析及模拟测试等多种方法,开展了集群工程节能减排指标体系和长大沉管隧道通风、照明、人工岛运营节能减排关键技术研究,成果支撑了工程项目节能减排目标的实现

Application of Accelerated Solvent Extraction Technique for Analysis of Active Components in Traditional Chinese Medicinal Herbs

以两种药材为研究实例,对加速溶剂萃取法(ASE)在中药材有效成分提取研究中的应用进行了简要介绍。采用正交试验法考察了提取丹参中丹酚酸B的提取条件(萃取温度、静态萃取时间、萃取溶剂以及料液比),确定了较好的实验条件。比较了ASE、水蒸气蒸馏法、超声波提取法及索氏提取法对木香挥发油的提取效果,结果表明ASE对木香挥发油的提取效果最好。The application of accelerated solvent extraction(ASE) technique for the Analysis of active components in traditional Chinese medicinal herbs was introduced by using two kinds of herbs as examples.The conditions including extraction temperature,static extraction time,the ratio of material to solvent and solvent of ASE for extraction of salvianolic acid B in Salvia miltiorrhiza were optimized by orthogonal experiments,and the optimal conditions were obtained.Different extraction methods(ASE,steam distillation,ultrasonic wave and Soxhlet extraction) were used to extract volatile oil in Aucklandia lappa Decne.Results of the comparative experiments indicated that ASE was the most effective method in this case.All the results from these studies demonstrate that ASE is indeed a powerful tool in the preparation of herbal extracts for downstream chromatographic analysis.青岛“2004将才计划”(04-3-JJ-11);; 共建生物医药研发测试中心(LS-05-KJZX-76)资

Study on the Elements and Element Speciation in the Extract of Taizishen

目的对太子参水提液中3种金属元素Cu,Mn,Zn进行形态研究。方法采用电感耦合等离子体质谱(ICP-MS)测定太子参及太子参水提液中3种金属元素的含量,并用反相高效色谱(RP-HPLC)-电感耦合等离子体质谱(ICP-MS)联用技术对太子参水提液中的Cu,Mn,Zn元素进行形态分析。结果太子参水提液中金属元素Cu,Mn,Zn含量较高,其中Cu,Mn,Zn均主要以结合态形式存在。结论该实验所建立的HPLC-ICP-MS分析方法是太子参水提液中金属元素形态分析的良好方法。ObjectiveTo develop a modern analysis method for speciation of metal elements(Cu,Mn,Zn) in Taizishen.MethodsThe contents of three elements in Taizishen and the extract of Taizishen were determined by ICP-MS,and the coupling of high performance liquid chromatography(HPLC) with inductively coupled plasma mass spectrometry(ICP-MS) was applied for elemental speciation.ResultsIn the extract of Taizishen,the contents of Cu,Mn,Zn were high,and the organic speciation of Cu,Mn,Zn were the main speciation.ConclusionThe HPLC-ICP-MS method is efficient to separate inorganic speciation and organic speciation of the metal elements in Taizishen.国家自然科学基金资助项目(No.20235020

西洋参多糖及总皂苷中无机元素的ICP/MS法测定

采用电感耦合等离子发射光谱—质谱联用法(ICP/MS),对西洋参样品、西洋参多糖、西洋参总皂苷中无机元素Mg、Al、P、Ca、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Se、Sr、Mo、Cd、Pb的含量进行测定分析。结果表明,西洋参多糖中各种元素的含量均明显高于西洋参样品,而不同方法提取的多糖中元素含量有一定差异;西洋参总皂苷中Cr、Ni、Cu、Zn、Pb元素的含量明显高于西洋参样品,而其它元素含量较低。这就为西洋参多糖、西洋参皂苷的综合开发利用及其药效提供理论依据

Content of gentiopicroside and loganic acid in Radix gentianae and their fingerprints

To develop a HPLC-DAD-ESI-TOF/MS analysis method for the determination of gentiopicroside and loganic acid in Radix gentianae samples and for the research of their fingerprints.The samples were extracted using ASE for 10 min under 100 ℃ and 9.65 MPa,and divided into water phase and chloroform phase and analyzed them with HPLC-DAD-ESI-TOF/MS method respectively.Based on this method,the HPLC fingerprints of Radix gentianae were established.Comparing the spectrogram and mass spectrum of the chromatogram peak with the reference value,three compounds in water phase were identified as gentiopicroside,asafetida acid and loganic acid.There is no report of the compounds in chloroform phase.The content of gentiopicroside and loganic acid in samples of different groups were determined,separately.The fingerprints were compared by the software of the similarity evaluation system for chromatographic fingerprint.The water phase fingerprint congruence coefficients of samples from six different areas were above 0.90,however,the chloroform phase fingerprint congruence coefficients were within 0.62-0.99.This method can be used for determination of potent component in Radix gentianae and its quality control.Radix gentianae from different producing areas have the largest diversities,and the diversities embodied in the content of chloroform phase compounds.青岛“2004将才计划”(04-3-JJ-11);; 国家海洋局青年基金资助项目(2005602);; 崂山区政府区校共建生物医药研发测试中心资助(LS-05-KJZX-76)

Determination of Gentiopicroside and Loganic Acid in Radix Gentianae by MEKC and MEEKC Mode

目的建立胶束电动毛细管色谱(MEKC)和微乳液毛细管电动色谱(MEEKC)分析龙胆药材中龙胆苦苷和马钱子苷酸含量的方法。方法采用加速溶剂萃取法(ASE)对龙胆药材进行提取,萃取温度:100℃,压力:9.65MPa,萃取时间:10min。采用未涂层熔融石英毛细管(内径75μm,有效长度50cm)。分别考察了两种分离模式下电泳介质的构成和电泳过程中的各操作参数对样品分离过程的影响,优化了MEKC和MEEKC的分析条件,在各自对应的缓冲液体系下,MEKC和MEEKC分离电压分别为30和22kV,柱温均为25℃,检测波长均为238nm。结果在选定的工作条件下,龙胆苦苷和马钱子苷酸与其他组分达到了基线分离,两种成分的浓度与其响应信号值之间具有较好的线性相关性,加标回收率在96.3%～105.1%之间,检测限均低于10mg·L-1,对6处不同产地的龙胆药材进行了分析,并对测定结果进行了t检验,结果表明,两种模式下,测定结果之间不存在显著性差异,而不同产地的龙胆药材的龙胆苦苷和马钱子苷酸含量之间存在较大差异。结论本方法简便,准确,快速,重现性较好,可用于龙胆药材有效成分的含量测定和质量控制。OBJECTIVE To develop MEKC and MEEKC modes for the determination of gentiopicroside and loganic acid in extracts of Radix Gentianae. METHODS The analyte was extracted from Radix Gentianae samples by accelerated solvent extraction, and the extraction conditions were optimized. Separation and determination were carried out on a bared fused silica capillary(50 cm×75 μm) with corresponding buffer. The run voltage of MEKC and MEEKC were 30kV and 22 kV respectively. Detection wavelength of DAD was at 238 nm and column temperature was 25 ℃. RESULTS The developed ASE-HPCE method was simple and reliable for the determination of gentiopicroside and loganic acid in Radix Gentianae samples with a broad linear dynamic range, a recovery range of 96.3%～105.16%,and the detection limit was below 10 mg·L-1. The contents of gentiopicroside and loganic acid in six samples from different regions were determined by the developed method in two modes. T-test value indicated that the determined contents of gentiopicroside and loganic acid by MEKC and MEEKC were consistent. CONCLUSION The method is simple,accurate,rapid and with good reproducibility.It can be used to determine active components in Radix Gentianae.国家自然科学基金重点项目(20235020);; 青岛“2004将才计划”(04-3-JJ-11);; 崂山区校区共建生物医药研发测试中心资助(LS-05-KJZX-76

Methodologic Study of HPCE Fingerprints of Radix paeoniae Alba and Radix paeoniae Rubra

目的确定赤芍和白芍的高效毛细管电泳分析方法,建立赤芍和白芍的高效毛细管电泳法(HPCE)指纹图谱。方法HPCE工作条件:采用未涂层熔融石英毛细管(内径75μm,有效长度50 cm),分离电压为25 kV,柱温25℃,二极管阵列检测器(DAD)检测波长为220 nm,缓冲液为30 mmol/L硼砂(pH=9.0)溶液。按此条件对来自不同产地的7种赤芍样品和8种白芍样品进行了分析。结果建立了赤芍和白芍HPCE指纹图谱,采用中药指纹图谱相似度计算软件,以系统生成的对照指纹图谱为对照模板对不同样品的图谱进行相似度计算。结论该方法简捷、有效,可以用于赤芍和白芍药材的质量控制。Objective To set up a modern High Performance Capillary Electrophoresis analysis method for separating and detecting Radix paeoniae Alba and Radix paeoniae Rubra and establish their fingerprints.Methods Seven samples of Radix paeoniae Alba and eight samples of Radix paeoniae Rubra were carried out by HPCE under the following conditions: bared fused silica capillary(50 cm ×75 μm i.d.),30 mmol/L borate(pH = 9.0) as buffer,the run voltage is +25 kV,detection wavelength of UV at 220 nm,and column temperature of 25℃.Results The fingerprints were confirmed and compared by the software of the similarity evaluation system for chromatographic fingerprint.Conclusion The results showed that the method of HPCE fingerprint is reliable and accurate to control the quality of two Chinese traditional medicines.国家自然科学基金重点项目(No.20235020);; 青岛“2004将才计划”(No.04-3-JJ-11);; 青岛市崂山区科技计划项目(No.LS-05-KJZX-76

Concentration and distribution of polycyclic aromatic hydrocarbons in surface sediments collected in the Southern Yellow Sea

采用气相色谱与质谱联用(gC/MS)技术,在一个航次内对南黄海表层沉积物中16种优先监控的PAHS的污染状况进行了调查,采用菲/蒽、荧蒽/芘、荧蒽/(荧蒽+芘)、吲哚芘/(吲哚芘+苯并(g,H,I)苝)等特定比值对PAHS来源进行了分析.结果表明,南黄海表层沉积物中检出PAHS的总含量为90.4~732.65ng·g-1,各站点均以4~6环为主;与其它站位相比,倾废区的H01站位受到PAHS污染较为明显,无论是16种PAHS总量还是高分子量组分最高值都出现在该站点,虽然该海区沉积物中PAHS的含量没有超出生物影响低值,但苯并(b)荧蒽、吲哚芘和苯并(g,H,I)芘等一些没有最低安全标准的PAHS也有不同程度的检出,对海洋生物具有潜在的毒副作用.PAHS可能来源于原油、生物和煤燃烧造成的污染.The concentrations of sixteen representative Polycyclic Aromatic Hydrocarbons(PAHs) in surface sediment samples collected from the Southern Yellow Sea were determined by GC-MS.The distribution and potential sources of PAH contamination in the region were investigated.The types of PAHs found in the surface sediments were mainly 4～6 ring PAHs,and they are unevenly distributed among the different sampling sites covering an area of 139 km2.The area is known for continuous waste dumping activities in recent years,and indeed sites adjacent to such activities were found to have high levels of PAHs.Some high molecular weight PAH compounds such as benzo$$b$$fluoranthene,dibenzo$$a,h$$anthracene and benzo$$g,h,i$$perylene were detected in some samples.The health implication of these contaminants needs careful assessment since toxicity guidelines are not available for these species.The potential sources of PAHs are discussed using various source-specific PAH indexes such as Phenathrene/Anthracene、Fluoranthene/Pyrene、Fluoranthene/(Fluoranthene+Pyrene) and Indeno [1,2,3-cd] pyrene/(Indeno[1,2,3-cd] pyrene+Benzo [g,h,i] perylene).The composition of the observed PAHs reflects that they originate from both petroleum utilization and incomplete combustion.海洋公益性行业科研专项(No.200705011);中国海监技术支撑体系项目;2008年海洋环境保护及节能减排专项---

Comparison of Recoveries of PAHs Obtained by Ultrasound-assisted Extraction from Wet and Freeze-dried Marine Sediment

以美国环保局(EPA)优先控制的16种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)为研究对象,建立了湿法超声波辅助萃取技术提取沉积物中痕量PAHs的可靠方法,对萃取剂、萃取功率、萃取次数和萃取时间进行了优化。并与传统干法超声辅助萃取进行了比较,湿法超声波辅助萃取的PAHs回收率为57%～125%,而干法超声波辅助萃取PAHs的回收率为48%～113%,对相对分子质量小的PAHs如萘～芴的回收率,湿法明显高于干法。该文建立的湿法超声辅助萃取适用于沉积物和泥土中痕量PAHs的快速测定。An ultrasound-assisted extraction method for the extraction of 16 trace PAHs(USEPA priority pollutant) from wet(i.e.untreated) marine sediment was developed.The effects of solvent type,power of ultrasound,and extraction time were studied and optimized.The developed method was compared with the traditional ultrasound-assisted extraction for freeze-dried sediment.The results showed that recoveries of sixteen PAHs extracted from the wet marine sediment ranged from 57% to 125%,whereas those extracted from the freeze-dried marine sediment ranged from 48% to 113%.The results also indicated that the recoveries of PAHs with smaller relative molecular mass(e.g.naphthalene and fluorine) extracted from the wet sediment were higher than those from the freeze-dried sediment.Thus the developed method was appropriate for rapid determination of trace PAHs in marine sediment and soil.海洋公益性行业科研专项(200705011);; 中国海监技术支撑体系项目;; 2008年海洋环境保护及节能减排专

大孔吸附树脂分离纯化龙胆药材中龙胆苦苷和马钱子苷酸的研究

目的:建立利用大孔吸附树脂对龙胆药材中龙胆苦苷和马钱子苷酸进行富集和分离纯化的方法。方法:采用加速溶剂萃取法对龙胆药材中两种有效成分进行高效提取,比较了D301,AB-8,D101,XDA-1四种大孔树脂对龙胆苦苷和马钱子苷酸的吸附性能,最终确定采用D301型大孔对脂对二者进行富集吸附,对其工艺参数进行优化,全程采用高效液相色谱进行目标化合物浓度检测。结果:化优后的工艺参数为:上样浓度:0.2 g/mL,最大上样量:0.25 g龙胆药材/g树脂,最佳静态吸附时间:8 h,采用8%和55%的乙醇溶液对龙胆苦苷和马钱子苷酸分别进行洗脱;龙胆苦苷和马钱子苷酸分别富集在8%和55%的乙醇洗脱液中,洗脱液浓缩后冷冻干燥,可得到纯度分别为74.3%和80.9%的粗产物,龙胆苦苷和马钱子苷酸的回收率分别为70.11%和67.82%。结论:此法效率较高,操作简便,即可用于实验室制备少量的难以购置的标准品,也可进行放大研究,用于工业生产。国家自然科学基金重点项目(20235020);; 青岛“2004将才计划”(04-3-JJ-11);; 共建生物医药研发测试中心(LS-05-KJZX-76)资