Ultrasensitive quantification of trace amines based on N-phosphorylation labeling chip 2D LC-QQQ/MS

Trace amines(TAs)are metabolically related to catecholamine and associated with cancer and neurological disorders.Comprehensive measurement of TAs is essential for understanding pathological processes and providing proper drug intervention.However,the trace amounts and chemical instability of TAs challenge quantification.Here,diisopropyl phosphite coupled with chip two-dimensional(2D)liquid chromatography tandem triple-quadrupole mass spectrometry(LC-QQQ/MS)was developed to simultaneously determine TAs and associated metabolites.The results showed that the sensitivities of TAs increased up to 5520 times compared with those using nonderivatized LC-QQQ/MS.This sensitive method was utilized to investigate their alterations in hepatoma cells after treatment with sorafenib.The significantly altered TAs and associated metabolites suggested that phenylalanine and tyrosine metabolic pathways were related to sorafenib treatment in Hep3B cells.This sensitive method has great potential to elucidate the mechanism and diagnose diseases considering that an increasing number of physiological functions of TAs have been discovered in recent decades.

Amine-functionalized mesoporous UiO-66 aerogel for CO_(2) adsorption

A mesoporous UiO-66-NH_(2) aerogel is prepared via a straightforward sol-gel method without using any binders or mechanical pressures, in which the amine groups are directly introduced into the matrix by using 2-aminoterephthalic acid. The novel UiO-66-NH_(2) aerogel also exhibits high specific surface area and mesopore-dominated structure, implying its highly potential use in CO_(2) adsorption. For ulteriorly investigating the effect of amine loading on the CO_(2) adsorption ability, a series of UiO-66-NH_(2) aerogel with different amino content is fabricated by changing the ligand/metal molar ratio. When the molar ratio is 1.45, the CO_(2) adsorption capacity reaches the optimum value of 2.13 mmol·g^(-1) at 25 ℃ and 0.1 MPa, which is 12.2% higher than that of pure UiO-66 aerogel. Additionally, UiO-66-NH_(2)-1.45 aerogel also has noticeable CO_(2) selectivity against N_(2) and CH_(4) as well as good regeneration stability. Such results imply that it has good application prospect in the field of CO_(2) adsorption, and also contains the potential to be applied in catalysis, separation and other fields.

联苯吡菌胺关键中间体3′,4′-二氯-5-氟-1,1′-联苯-2-胺的合成

为获得联苯吡菌胺关键中间体3′,4′-二氯-5-氟-1,1′-联苯-2-胺的适合工业化生产工艺路线,对其合成工艺进行了优化。以3,4-二氯溴苯和2-溴-4-氟苯胺为原料,经格氏和Suzuki偶联2步反应合成了3′,4′-二氯-5-氟-1,1′-联苯-2-胺,其结构经1H NMR、MS表征确证,并对合成条件进行了优化。优化条件下,3′,4′-二氯-5-氟-1,1′-联苯2-胺合成总收率61.9%,纯度98%。该工艺成本低,收率高,具有工业化生产前景。

具有自萃取功能的相变CO_(2)吸收剂体系开发

二氧化碳(CO_(2))捕集工程应用的吸收剂存在再生能耗高、传质速率低、运行损耗大等问题,严重制约了CO_(2)捕集技术的大规模推广应用。为解决这些问题,该文开发适用于低分压CO_(2)捕集的相变吸收剂。该相变吸收体系以亲水性胺N-氨乙基哌嗪(N-aminoethyl piperazine,AEP)为主吸收体系,添加亲脂性分相剂二正丁胺(Di-n-butylamine,DPA)和活化剂(activator,ACT)。通过核磁共振波谱(nuclear magnetic resonance,NMR)和捕集CO_(2)连续测试实验研究该相变吸收剂的性能。实验结果表明,吸收负载达1.082 mol CO_(2)/mol溶液,再生温度降至98.5℃,具有优异的吸收性能和解吸性能。NMR分析表明,反应产物具有氨基甲酸盐分子结构,捕集CO_(2)连续测试实验研究与同浓度3 mol/L一乙醇胺(Monoethanolamine,MEA)溶液进行对比分析可知,相同再生能耗下,单位体积同浓度相变体系相比MEA吸收容量提高33%以上;相同再生能耗下相变体系的再生率比MEA提高15%,相同再生率下相变体系的再生能耗比MEA降低31%以上。结果表明,该相变吸收剂对于低分压CO_(2)捕集具有良好的应用前景。

Capture and separation of CO_(2) from flue gas by coupling free and immobilized amines

A novel system was proposed for the capture and separation of CO 2 from flue gas. In this method, a resin was employed to regenerate the amine capturing CO 2 from flue gas at room temperature. The feasibility for the resin to regenerate amines such as MEA, MAE, TEA, and ammonia was demonstrated. It was also discovered that the resin could be regenerated by hot water.

区域选择性O-烯丙基取代反应合成2-吡啶酮衍生物

报道了一种有机催化合成2-吡啶酮衍生物的方法.以N-取代的3-羟基-2-吡啶酮和Morita-Baylis-Hillman(MBH)碳酸酯为原料,在亲核性有机胺催化下,经区域选择性O-烯丙基取代反应合成一系列含有2-吡啶酮片段的多官能团产物,产率51%~91%.在温和的反应条件下实现了3-羟基-2-吡啶酮类化合物的羟基功能化.

The CO_2 absorption and desorption performance of the triethylenetetramine + N,N-diethylethanolamine + H_2O system

Post-combustion CO_2 capture(PCC) process faces significant challenge of high regeneration energy consumption.Biphasic absorbent is a promising alternative candidate which could significantly reduce the regeneration energy consumption because only the CO_2-concentrated phase should be regenerated. In this work, aqueous solutions of triethylenetetramine(TETA) and N,N-diethylethanolamine(DEEA) are found to be efficient biphasic absorbents of CO_2. The effects of the solvent composition, total amine concentration, and temperature on the absorption behavior, as well as the effect of temperature on the desorption behavior of TETA–DEEA–H2 O system were investigated. An aqueous solution of 1 mol·L-1 TETA and 4 mol·L-1 DEEA spontaneously separates into two liquid phases after a certain amount of CO_2 is absorbed and it shows high CO_2 absorption/desorption performance.About 99.4% of the absorbed CO_2 is found in the lower phase, which corresponds to a CO_2 absorption capacity of 3.44 mol·kg-1. The appropriate absorption and desorption temperatures are found to be 30 °C and 90 °C,respectively. The thermal analysis indicates that the heat of absorption of the 1 mol·L-1 TETA and 4 mol·L-1 DEEA solution is-84.38 kJ·(mol CO_2)-1 which is 6.92 kJ·(mol CO_2)-1 less than that of aqueous MEA. The reaction heat, sensible heat, and the vaporization heat of the TETA–DEEA–H2 O system are lower than that of the aqueous MEA, while its CO_2 capacity is higher. Thus the TETA–DEEA–H2 O system is potentially a better absorbent for the post-combustion CO_2 capture process.

Recent progress of amine modified sorbents for capturing CO2 from flue gas

Under the Paris agreement, China has committed to reducing CO_2 emissions by 60%–65% per unit of GDP by 2030.Since CO_2 emissions from coal-fired power plants currently account for over 30% of the total carbon emissions in China, it will be necessary to mitigate at least some of these emissions to achieve this goal. Studies by the International Energy Agency(IEA) indicate CCS technology has the potential to contribute 14% of global emission reductions, followed by 40% of higher energy efficiency and 35% of renewable energy, which is considered as the most promising technology to significantly reduce carbon emissions for current coal-fired power plants.Moreover, the announcement of a Chinese national carbon trading market in late 2017 signals an opportunity for the commercial deployment of CO_2 capture technologies.Currently, the only commercially demonstrated technology for post-combustion CO_2 capture technology from power plants is solvent-based absorption. While commercially viable, the costs of deploying this technology are high. This has motivated efforts to develop more affordable alternatives, including advanced solvents, membranes,and sorbent capture systems. Of these approaches, advanced solvents have received the most attention in terms of research and demonstration. In contrast, sorbent capture technology has less attention, despite its potential for much lower energy consumption due to the absence of water in the sorbent. This paper reviews recent progress in the development of sorbent materials modified by amine functionalities with an emphasis on material characterization methods and the effects of operating conditions on performance. The main problems and challenges that need to be overcome to improve the competitiveness of sorbent-based capture technologies are discussed.

Amine-silica composites for CO_2 capture: A short review

Amine-silica composite materials for post-combustion COcapture have attracted considerable attention because of their high COuptake at low COconcentrations, excellent COcapture selectivity in the presence of moisture, and lower energy requirements for sorbent regeneration. This review discusses the recent advances in amine-silica composites for COcapture, including adsorbent preparation and characterization, COcapture under dry and moisture conditions at different COpartial pressures, sorbent regeneration, and stability after many cyclic sorption-desorption runs.

The latest development on amine functionalized solid adsorbents for post-combustion CO_(2)capture:Analysis review

Global warming and associated global climate change have led to serious efforts towards reducing CO_(2)emissions through the CO_(2)capture from the major emission sources.CO_(2)capture using the amine functionalized adsorbents is regard as a direct and effective way to reducing CO_(2)emissions due to their large CO_(2)adsorption amount,excellent CO_(2)adsorption selectivity and lower energy requirements for adsorbent regeneration.Moreover,large number of achievements on the amine functionalized solid adsorbent have been recorded for the enhanced CO_(2)capture in the past few years.In view of this,we review and analyze the recent advances in amine functionalized solid adsorbents prepared with different supporting materials including mesoporous silica,zeolite,porous carbon materials,metal organic frameworks(MOF)and other composite porous materials.In addition,amine functionalized solid adsorbents derived from waste resources are also reviewed because of the large number demand for cost-effective carbon dioxide adsorbents and the processing needs of waste resources.Considering the importance of the stability of the adsorbent in practical applications,advanced research in the capture cycle stability has also been summarized and analyzed.Finally,we summarize the review and offer the recommendations for the development of amine-based solid adsorbents for carbon dioxide capture.

胺功能化沸石吸附剂载体的结构性质对CO_(2)吸附性能的影响

为了探究胺功能化沸石吸附剂载体的结构性质对其CO_(2)吸附性能的影响并进一步探索出低成本制备高效CO_(2)吸附剂的有效方法,采用不同的后处理方法对MCM–41沸石的孔道结构进行改造,并将四乙烯五胺(TEPA)负载在这些沸石上制备胺功能化吸附剂。利用N_(2)吸脱附、扫描电镜、X射线衍射、红外光谱等方法对沸石载体进行表征,并利用热重分析仪(TGA)对吸附剂的吸附性能进行评价,系统研究了载体的结构性质、活性胺负载量以及吸附温度对CO_(2)吸附性能的影响,计算了吸附剂的吸附动力学和吸附活化能。最后,通过循环吸脱附实验评估了吸附剂的稳定性。结果表明,通过合理设计载体的结构,可以有效提升基于不同吸附原理的吸附剂的CO_(2)吸附性能。微孔沸石对物理吸附过程更有利,而具有宽孔径分布的多级介孔沸石则比微孔沸石在负载TEPA后表现出更好的化学吸附性能。在80℃和15%(体积分数)CO_(2)条件下,经结构改造并负载TEPA的吸附剂(M–N−T60)的最大吸附容量达到4.04 mmol/g。10次吸脱附循环后,其吸附容量仅下降8.4%,表现出良好的循环稳定性能,这表明M–N−T60为一种有望应用于烟气中CO_(2)捕集的吸附材料。

Enhancement of CO_2 adsorption on nanoporous chromium terephthalate(MIL-101) by amine modification

Carbon dioxide （CO2） adsorption on a standard metal-organic framework MIL-101 and a pentaethylenehexamine modified MIL-101 （PEHA- MIL-101） are investigated and compared in this study. The adsorbent samples were characterized by XRD, FT-IR and nitrogen adsorption- desorption isotherms analysis. CO2 adsorption capacity was measured by a volumetric method. MIL-101 and PEHA-MIL-101 exhibited CO2 adsorption capacities of 0.85 and 1.3 mmO1CO2/gadsorbent at 10 bar and 298 K, respectively. It is observed that CO2 adsorption capacity was fairly improved about 50% after amine modification.

Reaction of 4-Chloro-3,5-Dinitrobenzotrifluoride and 2-Chloro-3,5-Dinitrobenzotrifluoride with Hydro-xylamine Hydrochloride and Hydrazine Hydrate

Introduction It seems to be realized that a number of special reactions would occur owing to the three electron-withdrawing groups in the title compound 1(4-chloro-3,5-dinitrobenzotrifluoride（1;） and 2-chloro-3, 5-dinitrobenzotrifluoride （1;）). Some of

少水胺吸收剂CO_(2)捕集工艺的中试试验与技术经济性评价

化学吸收法是现阶段燃烧后CO_(2)捕集大规模应用的主要技术路线,但其运行和投资成本高是技术难题。该文采用基于有机胺构效关系开发的低再生能耗少水胺吸收剂,在真实燃烧后烟气条件下的中试平台上,试验研究少水胺吸收剂的CO_(2)捕集率、再生能耗、挥发性胺排放等性能,并通过流程模拟与成本测算,评估技术经济性。中试结果表明,烟气流量为260~280 m^(3)/h,CO_(2)浓度(干基)约12%,少水胺体系(水质量浓度约15%)实现稳定运行,CO_(2)捕集率高于90%,再生能耗低至2.35 GJ/t CO_(2),胺挥发排放较高(约110~380 mg/m^(3))。在Aspen Plus建立10000 m^(3)/h烟气CO_(2)捕集工艺流程,相比常规一乙醇胺(monoethanolamine,MEA)工艺,少水胺工艺系统的投资成本降低12%,运行成本降低20%。该少水胺吸收剂具有CO_(2)捕集率高、再生能耗低、系统投资和运行成本低等优势,有望在工业示范中应用。该文研究结果可为万t级/年CO_(2)捕集示范工程的设计提供一定依据。

Synthesis and fungicidal activity of novel strobilurin analogues containing substituted N-phenylpyrimidin-2-amines

A number of novel strobilurin analogues containing substituted N-phenylpyrimidin-2-amines were synthesized. The structures of these new compounds were confirmed by ^1H NMR, IR and elemental analysis. Biological evaluation in the greenhouse showed several compounds have good fungicidal activities at 25 mg/L.

Heat of absorption of CO_2 in aqueous N,N-diethylethanolamine+ N-methyl-1,3-propanediamine solutions at 313 K

Differential heat of absorption of CO_2 in aqueous solutions of N,N-diethylethanolamine(DEEA) and activated DEEA solutions up to a total concentration of 2 mol·L^(-1) was measured as a function of CO_2 loading at 313.15 K using a reaction calorimeter. In order to analyze the performance of N-methyl-1,3-propanediamine(MAPA)as an activator, DEEA blended solutions containing 0.05, 0.1 and 0.2 mol·L^(-1) MAPA were studied. The heat of CO_2 absorption in single DEEA solutions was unaffected by changing the DEEA concentration in the range of(0.5–2) mol·L^(-1). On the other hand, increasing the concentration of MAPA in aqueous amine mixtures of(DEEA + MAPA) raised the heat of absorption.

Impact of solvents and surfactants on the self-assembly of nanostructured amine functionalized silica spheres for CO_(2) capture

Macroscopic SiO2 spheres with a homogeneous amine distribution were synthesized by a one-step emulsion based synthesis approach in a flow column reactor. The CO2 adsorption capacity of the nanostructured amine-functionalized silica spheres was studied in absence and presence of H2O. The structural properties were adjusted by varying solvents and surfactants during the synthesis and, at constant amine loadings, were found to be the main factor for influencing the CO2 sorption capacities. Under water-free conditions CO2 is bound to the amino groups via the formation of carbamates, which require two neighboring amino groups to adsorb one CO2 molecule. At constant amine concentrations sorbents with lower surface area allow to establish a higher amine density on the surface, which enhances the CO2 uptake capacities under dry conditions. In presence of H2O the CO2 adsorption changes to 1：1 stoichiometry due to stabilization of carbamates by protonation of H2O and formation of further species such as bicarbonates, which should in principle double the adsorption capacities. Low concentrations of physisorbed H2O（0.3 mmol/g） did not impair the adsorption capacity of the adsorbents for CO2, while at higher water uptakes（0.6 and 1.1 mmol/g） the CO2 uptake is reduced, which could be attributed to capillary condensation of H2O or formation of bulky reaction products blocking inner pores and access to active sites.

An Exploratory Study of Tridentate Amine Extractants: Solvent Extraction and Coordination Chemistry of Base Metals with <i>Bis</i>((1<i>R</i>-benzimidazol-2-yl)methyl)amine

Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.

异氟尔酮二胺-水二元固-液相变吸收剂捕集CO_(2)机制

固-液相变吸收剂在CO_(2)负荷调控下可发生相变形成固体产物,具有易分离、操作简便的优势,但现有体系大多需有机分相剂调控才能发生固液相变,存在分相剂易挥发损耗、富液黏度大等瓶颈。本研究构建了异氟尔酮二胺(IPDA)-水二元固-液相变吸收体系,无需分相剂,水相溶液吸收CO_(2)后即可发生固液相变。研究表明,1.00 mol·L^(-1)IPDA水溶液在313.15 K下饱和吸收负荷高达0.85 mol CO_(2)·mol^(-1),吸收产物为白色晶体粉末且富集在溶液下层,富液体积占总溶液体积的43.60%,而CO_(2)富集率达93.98%,此时,上层贫相黏度为1.08 mPa·s。富相固体产物分离熔融后在393.15 K温度条件下解吸60 min,再生效率为98.31%。经5次循环吸收-解吸,再生容量仍保持初始容量的80%以上,具有良好的重复利用性。^(13)C核磁共振(NMR)表征分析表明,IPDA与CO_(2)反应生成IPDA-氨基甲酸盐与碳酸氢盐,大多聚集在富相中,仅少量氨基甲酸盐溶于贫相中。解吸完成后,样品未见CO_(2)产物峰,进一步证明了IPDA-H_(2)O可完全解吸。量子化学计算证明,吸收前IPDA与水偶极矩接近,极性相近可互溶,吸收后形成的产物偶极矩低、极性小,产物间的分子内氢键高于产物和水的氢键,产物晶格能增加。因此,产物从溶液中析出,无需分相剂调控,即可在水中发生固液相变。

Synthesis, Crystal Structure and Antitumor Activity of (E)-4-tert-Butyl-N-(2,4-dichlorobenzylidene)-5-(1,2,4-triazol-1-yl)-thiazol-2-amine

The title compound （E）-4-tert-butyl-N-（2,4-dichlorobenzylidene）-5-（1,2,4-triazol-1-yl）-thiazol-2-amine was synthesized by the reaction of 4-tert-butyl-5-（1,2,4-triazol-1-yl）-thiazol-2-amine with 2,4-dichlorobenzaldehyde, and its crystal structure was determined by singlecrystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.9748（4）, b = 10.1803（5）, c = 11.4603（6）, α = 102.882（1）, β = 100.253（1）, γ = 104.457（1）°, V = 850.95（7）3, Z = 2, F（000） = 392, C16H15Cl2N5S, Mr = 380.29, Dc = 1.484 g/cm3, S = 1.095, μ = 0.512 mm-1, the final R = 0.0301 and wR = 0.0965 for 3334 observed reflections （I 〉 2σ（I））. The preliminary antitumor activity shows that for the title compound the IC50 of Hela is 0.175 μmol/mL and that of Bel7402 is 0.156 μmol/mL.