Post-synthesis modification of porous organic polymers with amine： a task-specific microenvironment for CO2 capture

A porous organic polymer named FC-POP was facilely synthesized with extraordinary porosity and excellent stability. Further covalent incorporation of various amines including single amine group, multi-amine groups of diethylenediamine （DETA）, and poly-amine groups of polyethylenimine （PEI） to the network gave rise to task-specific modification of the microenvironments to make them more suitable for CO2 capture. As a result, significant boost of CO2 adsorption capacity of 4.5 mmol/g （for FC-POP-CH2DETA, 273 K, 1 bar） and the CO2/N2 selectivity of 736.1 （for FC- POP-CH2PEI） were observed after the post-synthesis amine modifications. Furthermore, these materials can be regener- ated in elevated temperature under vacuum without apparent loss of CO2 adsorption capacity.

Syntheses, Structures and Fluorescent Properties of Two 1D Chain Organic Amines and Metal Iodine Organic-inorganic Hybrid Compounds

Two bifunctional amines, 4-(2-aminoethyl)morpholine and histamine, were heated with PbI_2 and BiI_3 in concentrated HI aqueous solution to give one-dimensional(1D) organicinorganic hybrid compounds [(C_6H_(16)N_2O)PbI4]n(1) and [(C_(16)H_(20)N_(20))Bi_2I_(10)](2), respectively. In 1, the [PbI6] octahedra formed double chain anions through sharing-corner and-edge, and the protonated(C_6H_(16)N_2O)^(2+) cations were located at the vicinity of the double chains by hydrogen bonds. In 2, the [BiI_6] octahedra firstly formed dimeric [Bi_2I_(10)]^(4-) anion through sharing edge, and subsequently, the protonated histamine cations worked as bridge to link alternately with [Bi_2I_(10)]^(4-) anion by hydrogen bonds to form organic-inorganic hybrid 1D chains. In addition, compound 1 emitted a green light at the excitation wavelength of 400 nm and the maximum emission wavelength is at 503 nm.

Synthesis,Crystal Structure and Blue Photoluminescence of a Metal-organic Framework Constructed from Triangular [Zn_3(μ_3-OH)] Clusters with Bis(tetrazole)amine Ligands

A new metal-organic framework, {Zn[Zn3（BTA）3（μ3-OH）（H2O）3]2}n 1, has been synthesized under hydrothermal reaction of ZnCl2 and bis（5-tetrazolyl）amine （H2BTA）, and characterized by elemental analysis, FT-IR, Raman spectrum, X-ray single-crystal diffraction, TGA and photoluminescence measurements. Compound 1 crystallizes in the trigonal system, space group P-3cl, a = 13.667（3）, c = 12.981（3） A, V = 2099.6（8） A3 and Z = 2. The BTA2- ligand in 1 assumes theμ3 tetradentate mode with both 1,2- and 1,4-tetrazole bridges, generating an unusual 2-D layer, in which the [Zn3（μ3-OH）] triangular motifs act as three-connecting nodes and the mononuclear Zn atoms as six-connecting nodes that are inter-linked by organic ligands. Adjacent 2-D metal-organic layers are linked by strong hydrogen bonds to form a novel 3-D supramolecular framework. Complex 1 exhibits blue fluorescence emission in the solid state at ambient temperature.

In-situ preparation of Cu-BTC modified with organic amines for H_(2)S removal under ambient conditions

Amine modification is an effective strategy to improve the H_(2)S removal performance of Cu-BTC.In order to avoid the problem of pore blockage after amine modification in post synthesis impregnation,herein a series of Cu-BTC modified with organic amine adsorbents were prepared via an in-situ one-pot method and the H_(2)S removal performance under ambient conditions was tested.It is found that the introduced organic amines,depending on the types of amine selected,have a significant influence on the growth of Cu-BTC and its textural properties.The H_(2)S removal performance on the as-prepared materials suggested that the amine modified samples remarkably improved the H_(2)S removal capacities with an order of BA-Cu-BTC>TEA-Cu-BTC>TEOA-Cu-BTC>Cu-BTC.Besides the enlarged surface area and the increased mesopores volumes,BA has the advantages of smaller steric hindrance and-NH_(2)groups,among which the former increased the accessibility of Cu active sites while the latter acted as additional active sites for H_(2)S capturing,thus affording BA-Cu-BTC highest breakthrough capacity of 77.3 mg S/g.Overall,this study elaborates the effect of organic amines in-situ modification on the Cu-BTC structure and desulfurization.

Recent advances in fluorescent and colorimetric sensing for volatile organic amines and biogenic amines in food

Volatile organic amines and biogenic amines produced by the amino acid degradation can undeniably affect the food quality and safety,and thus causes serious health problems.It is of great urgency to exploit reliable and sensitive detection methods for amines to ensure food safety and public health.The fluorescent and colorimetric sensors offer simple and robust means to monitor amines with high sensitivity and selectivity,quick response,facile operation and low cost.Herein,we briefly review the past five years’progress in fluorescent and colorimetric sensing for monitoring organic and biogenic amines in food.The architectures of sensing materials ranging from small molecules to frameworks to polymers or self-assembly materials have been highlighted.Moreover,the main challenges and perspective of various sensing materials are presented to inspire further research and development.In the end,the development trend of new sensing materials and devices for real-time monitoring of food quality is also forecasted.This review is expected spur more research interest in design of novel amine sensing materials for future application transformation research.

Effects of biogenic amines on the testicular development in mud crabs Scylla serrata

The regulation of three biogenic amines over the reproductive neuroendoerine activity of the male Scylla serrata was investigated by in vivo injection and in vitro incubation. The testicular index, the ratio of the mature sections in testes, and the ratio of Type B cells in androgenic gland were taken as the quantitative indexes. The in vivo injections indicated that： 5-HT can significantly promote the testicular development and the secretion of the androgenic gland in S. serrata; DA can inhibit the testicular development, but no influence on the secretion of the androgenic gland was found; no significant difference was observed between the OA-injected group and the concurrent control group. In vitro incubations showed that： 5-HT can stimulate the secretion of the brain and the thoracic ganglia, thus accelerating that of the androgenic gland; however, neither OA nor DA showed any significant influence on the secretion of the brain and the thoracic ganglionic mass. As to the optic ganglia, the three biogenic amines hardly have any effect on its secretion. It is the first time to report the regulation of biogenic amines over the reproductive neuroendocrine of male crustaceans through vitro experiments. Results corroborate that 5-HT activates the brain and the thoracic ganglia to secret GSH first, then promote the testicular development through the activity of the androgenic gland.

THE SYNERGISTIC INHIBITION STUDIES OF SEVERAL AMINES AND CHLORIDE ION ON IRON IN THE ACIDIC PERCHLORIDE SOLUTIONS

The effect of chloride ion on the corrosion inhibition of iron caused by dencylamine(DA), dipentylamine(DDA) and dodecylamine(DPA) has been investigated by measuring the inhibitory coefficients for the anodic and cathodic processes at corrosion potential. It has been shown that the major synergistic inhibition effects between amines and chloride ions occur in the cathodic process, very weak in the anodic process. The anodic inhibition mechanism follows the competing adsorptive model, while the cathodic inhibition mechanism follows the cooperative adsorptive model.

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.

Extraction of Tungsten and Molybdenum by Various Organic Compounds as Extractants

Seventy organic compounds including various organophosphorus esters, amines and oxygen-based ligands were investigated as extractants. The experiment results show that amines are excellent extractants for W and Mo. Their sequence of extraction ability for W is as follows: quarternary amine > tertiary amine > secondary amine > primary amine. Acidic organophosphorus extractants do not extract W, but can extract Mo with high extraction ability from the acidic solution. These extractants could provide a potential process for separating W from Mo.

{[K.18-Crown-6]Br_3}_n:A tribromide catalyst for the catalytic protection of amines and alcohols

{[K.18-Crown-6]Br3}n,a unique tribromide-type catalyst,was utilized for the N-boc protection of amines and trimethylsilylation(TMS)and tetrahydropyranylation(THP)of alcohols.The method is general for the preparation of N-boc derivatives of aliphatic(acyclic and cyclic)and aromatic,and primary and secondary amines and also various TMS-ethers and THP-ethers.The simple separation of the catalyst from the product is one of the many advantages of this method.

Preparation and Performance of the Hyperbranched Polyamine as an Effective Shale Inhibitor for Water-Based Drilling Fluid

Seeking effective solutions to control and mitigate the interaction between drilling fluids and clay formations has been a challenge for many years, and various shale inhibitors have shown excellent results in problematic shale formations around the world. Herein, the hyperbranched polyamine (HBPA) inhibitor with a higher ratio of amine groups and obvious tendentiousness in protonation was successfully synthesized from ethylenediamine, acryloyl chloride and aziridine by five steps, in which the metal-organic framework (MOF) was employed as a catalyst for ring-open polycondensation (ROP). The structure and purity were confirmed by nuclear magnetic resonance hydrogen spectroscopy and high-performance liquid chromatography (HPLC) respectively. The HBPA displays more excellent performance than EDA and KCl widely applied in the oil field. After aging at 80°C and 180°C, the YP of a slurry system containing 25 wt.% bentonite and 2 wt.% HBPA are just 8.5 Pa and 5.5 Pa (wt.%: percentage of mass), respectively. The swelling lengths of 2 wt.% HBPA are estimated to be 1.78 mm, which falls by 70% compared with that of freshwater. Under a hot rolling aging temperature of 180°C, the HBPA system demonstrates a significant inhibition with more than 85% shale cuttings recovery rate and is superior to conventional EDA and KCl. Mechanism analysis further validates that the HBPA can help to increase the zeta potential.

Effect of organic amine alkali and inorganic alkali on benzotriazole removal during post Cu-CMP cleaning

Benzotriazole(BTA), an anticorrosion agent of slurry, is the main organic pollutant remaining after CMP of multilayer copper wiring, and also the main removal object of post CMP cleaning. The adsorption of BTA onto the copper could form a dense Cu-BTA film, which makes the copper surface strongly passivated. According to this characteristic, quantitative analysis of BTA residue after cleaning is carried out by contact angle measurement and electrochemical measurement in this paper. A scanning electron microscope(SEM) with EDX was used to observe and analyze the BTA shape and elements. The efficiencies of organic alkali and inorganic alkali on the removal of BTA were studied. The corresponding reaction mechanism was also analyzed. The results show that the adsorption structure of Cu(I)-BTA cannot be destroyed in an alkaline environment with a pH less than 10; the effect of BTA removal by inorganic alkali is worse than that of the organic amine alkali with the coordination structure under the same pH environment; the FA/O Ⅱ chelating agent with the fraction of 200 ppm can effectively remove BTA residue on the surface of copper wafer.

Ruthenium(Ⅱ)-cored supramolecular organic framework-mediated recyclable visible light photoreduction of azides to amines and cascade formation of lactams

Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reduction of phenyl, benzyl, 2-phenylethyl and 3-phenylpropyl azides in acetonitrile to produce the corresponding amines in good to high yields. For the last two kinds of azides that bear a CO2Me group at the para-position of the benzene ring, cascade reactions take place to generate the corresponding lactams in high yields. Compared with homogeneous control [Ru(bpy)3]Cl2, SMOF-1 exhibits remarkably increased photocatalysis activity as a result of synergistic effect of the [Ru(bpy)3]2+ units that form cubic cages to host the azide molecules and related intermediates. Moreover, SMOF-1 displays high recyclability and considerable photocatalysis activity after 3 to 12 runs.

2D-π-A Type Organic Dyes Based on N,N-Dimethylaryl Amine and Rhodamine-3-acetic Acid for Dye-sensitized Solar Cells

Three organic dyes XS17--19 based on N,N-dimethylaryl amine and rhodamine-3-acetic acid moieties are designed and synthesized. These dyes were applied into nanocrystalline TiOa dye-sensitized solar cells through standard operations, showing strong absorption bands at around 320--650 rim, and exhibiting broad IPCE responses. Cell based on XS17 gave a Jsc of 3.7 mA/cm2, an open circuit voltage of 550 mV, and a fill factor of 0.68, corresponding to an overall conversion efficiency of 1.4%. The low overall conversion efficiency is due to the modest IPCE and Voc values, which mainly stem from the acceptor of rhodanine-3-acetic acid.

A Triformylphloroglucinol-based Covalent Organic Polymer:Synthesis,Characterization and Its Application in Visible-light-driven Oxidative Coupling Reactions of Primary Amines

A triformylphloroglucinol-based AiB2-typed covalent organic polymer(TFG-BPTH)was successfully constructed by the condensation reaction of triformylphloroglucinol(TFG)and 2.5-bis(2-propynyloxy)terephthalo-hydrazide(BPTH)under solvothermal conditions.The structure of the TFG-BPTH was confirmed by spectra tech-niques including FTIR and solid-state IC CP/MAS NMR spectroscopy.The mophological features of TFG-BPTH were analyzed using scanning electron microscopy(SEM)and transmission electron microscopy(TEM).The TFG-BPTH possessed good thermal and chemical stability,and exhibited good photocatalytic activity as a metal-free heterogeneous catalyst for oxidation of amines to valuable imines under visible light irradiation using O2 as greer oxidant.In addition,the catalyst could be readily recovered from the reaction mixture by simple filtration and reused for at least five cycles without any observable change in structure and catalytic activity.

Small organic amine assisted synthesis of an extra-large pore containing open-framework zinc-cobalt phosphate templated by a chain-type polyamine

An open-framework zinc-cobalt phosphate CoZnPO4-V with 16-ring extra-large-pore channels has been obtained in the presence of chain-type polyamines as the structure directing agent (SDA). Its large single crystal suited for structure refinement has been prepared with the assistance of small organic amines. Single-crystal X-ray diffraction analysis has shown that CoZnPO4-V is a novel metal phosphate. It crystallizes in monoclinic space group P21/c (No. 14), with a = 31.936(3) , b = 8.3775(7) , c = 15.7874(13) , α = γ = 90°, β = 97.0530(10)°, V = 4191.8(6) 3, and Z = 4 with R1 = 0.0455,wR2 = 0.0869. Its three-dimensional framework can be considered as stacking from two-dimensional nets and one-dimensional units as linkers. Between the stacking nets and linkers are located extra-large channels with 16-ring apertures.

Olefin-linked covalent organic frameworks with twisted tertiary amine knots for enhanced ultraviolet detection

Though Olefin-linked covalent organic frameworks(oCOFs)possess excellentπ-electron delocalization,the barely reversible olefin linkage brings challenges for oCOFs’synthesis and functionalization.Here,we synthesize new oCOFs with tertiary amine knots which have twisted configuration and electron-donating nature.Investigation into the structural variation and photoelectric performance shows that the twisted configuration of oCOF-TFPA could favor to the intramolecular charge transfer process and reduce the pos-sibility of aggregation-caused quenching.Photoelectrical measurements and electric band structure cal-culation both verify the superiority of this oCOFs’structure in photoelectric sensing.

Scaffold-like 3D networks fabricated via the organogelation of β-diketone-boron for fluorescent sensing organic amine vapors

A new compoud based on carbazole functionalized β-diketone-boron difluoride(1) was synthesized.It is found that compoud 1 can gel toluene,ethylbenzene and some mixed solvents,and 3D networks consisting lots of nanofibers were observed using SEM and fluorescence microscopy.The molecular packing model in xerogel 1 was proposed according to the results of XRD,UV/Vis absorption and semiempirical calculations.The obtained nanofibers prepared through organogelation can emit strong orange light under irradiation.It is interesting that the fluorescence of the nanofiber-based film can be quenched quickly and significantly upon exposed to the vapors of n-butylamine,dibutylamine,triethylamine,triethylamine,cyclohexylamine,aniline and pyridine instead of other common reagents.Notably,the response time of the nanofiber-based film to aniline vapor reached ca.0.59 s,and the detection limit for aniline was as low as ca.0.83 mL/m 3.

气相条件下Criegee中间体与痕量酸碱物种的双分子反应研究进展

气相臭氧化反应是不饱和烯烃在大气中重要的降解途径之一.反应会生成一个关键的Criegee中间体,该中间体有非常活跃的反应活性,可以发生单分子分解反应生成羟基自由基和烷氧自由基,也可以与大气中其他化合物发生双分子反应,生成复杂的反应产物.受测量手段的限制和大气丰度的影响,关于Criegee中间体双分子反应的研究主要集中在与H_(2)O、(H_(2)O)2及SO_(2)的反应.大气中的无机酸、有机酸、氨和有机胺是大气中痕量、具有高反应活性的化合物,在维持大气酸碱平衡、新粒子生成及二次有机气溶胶形成过程中发挥重要作用.近年的研究指出,Criegee中间体与这些痕量酸碱气体反应速率接近碰撞极限,并生成低挥发性有机物,颠覆了以往研究中认为的反应可以忽略的结论.结合前人的研究成果,对Criegee中间体双分子反应机理做了简要总结,着重阐述了Criegee中间体与无机酸和有机酸以及与氨和有机胺在大气中的双分子反应过程.从文献的梳理中我们发现Criegee中间体与有机酸和有机胺的双分子反应均可以无势垒发生,并且有低聚产物生成,这些机理的提出对于现有的全球化学传输模型和新粒子形成模型可能有重要影响.

离子色谱法同时测定脱硫液中8种有机胺类物质

有机胺脱硫工艺因高效、经济等优点,应用越来越广泛。不同配比的有机胺对二氧化硫脱除效果不同。因此,对脱硫液中的不同有机胺成分进行准确测定具有重要意义。离子色谱法检测有机胺不需要衍生步骤,前处理简单,并且可同时测定多种有机胺。本研究采用离子色谱法同时测定乙醇胺(MEA)、二乙基乙醇胺(DEEA)、N-甲基二乙醇胺(MDEA)、2-氨基-2-甲基-1-丙醇(AMP)、羟乙基乙二胺(AEEA)、哌嗪(PZ)、N-羟乙基哌嗪(HEPZ)、二乙烯三胺(DETA)等8种有机胺。实验对比不同型号色谱柱、淋洗液和柱温条件对8种有机胺的分离效果,最终采用IonPac CS17色谱柱,柱温35℃,甲基磺酸(MSA)水溶液梯度淋洗,抑制电导法进行测定。脱硫液样品采用超纯水稀释,过0.22μm尼龙微孔滤膜和OnGuardⅡRP柱后进样分析,样品前处理简便。8种有机胺在一定范围内具有良好的线性关系,判定系数R~2≥0.998 0。以信噪比(S/N)=3时对应的有机胺质量浓度为检出限(LOD),以S/N=10时对应的有机胺质量浓度为定量限(LOQ)。在进样量1.0μL时,LOD即可达到0.02~0.08 mg/L, LOQ为0.07~0.27 mg/L。实际样品的加标回收率为93.0%~111%,相对标准偏差(RSD,n=5)为0.31%~1.2%,说明方法具有良好的准确性和精密度,适用于脱硫液中多种有机胺的测定。