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Journal of Rare Earths 2004年第3期22卷 327-330页

作者：杨正银杨汝栋 State Key Laboratory of Applied Organic Chemistry Lanzhou University Lanzhou 730000 China

Oxopentanedioic acid isonicotinoyl hydrazone (H_2L) and its five rare earth complexes were synthesized with a view to further investigating MRI activities of the polycarboxylic Schiff base complexes. The complexes were characterized on the basis of elemental analyses, IR, UV, (()~1H) NMR spectra and thermal analyses. The general formula of the complexes is [Ln(HL)(H_2O)_2]Cl_2·H_2O (where Ln(Ⅲ)=La, Pr, Nd, Eu and Gd). In addition, the relaxivity ( R _1) of the Gd-complex was determined by INVREC Au program.

关键词： inorgonic chemistry MRI contrast agent relaxivity rare earth complexes

NMR relaxivity AND IMAGING OF NEUTRAL MACROMOLECULAR POLYESTER GADOLINIUM(Ⅲ)COMPLEXES

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Chinese Journal of Polymer Science 1999年第5期17卷 471-475页

作者：叶朝辉 Laboratory of Magnetic Resonance and Atomic and Molecular Physics Wuhan Institute of Physics and Mathematics Chinese Academy of Sciences Wuhan 430071 China

Five neutral macromolecular polyester gadolinium (Ⅲ) complexes with pendant hydrophobic alkyland aromatic functional groups were prepared. The longitudinal relaxation rates of these complexes weremeasured. One of these Gd (Ⅲ) complexes was chosen for the acute toxicity test and T_1-weighted imagingmeasurement. Preliminary results showed that. compared with Gd-DTPA. the neutral macromoleculargadolinium (Ⅲ) complexes provide higher T_1 relaxivity enhancement and longer function duration.

关键词： Magnetic resonance imaging (MRI) Neutral contrast agent Macromolecular gadolinium complexes relaxivity Acute toxicity

Observation of the relaxivity and thickness of surface phase in porous rock with the combination of PFG NMR and relaxation measurements

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Science China Mathematics 1996年第9期39卷 974-980页

作者：肖立志杜有如叶朝辉 (Laboratory of Magnetic Resonance and Atomic and Molecular Physics Wuhan Institute of Physics Chinese Academy of Sciences Wuhan 430071 China)

Nuclear magnetic resonance (NMR) relaxation of fluids in porous media is affected by the solid-liquid interface. Quantitative determination of the surface relaxivity is significantly important for both investigation and application of relaxation mechanisms in porous media. A method to estimate the surface relaxivity with the combination of relaxation and diffusion measurements is proposed. According to this method, a criterion for testing the current diffusion and relaxation theory for porous media is available.

关键词： rock surface relaxivity PFG NMR Bi-exponential decomposition.

STUDY　ON　SYNTHESIS　AND　relaxivity　OF　PARAMAGNETIC　POLYESTER　METAL　COMPLEXES　FOR　MRI

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Chinese Journal of Reactive Polymers 1995年第1期4卷 99-106页

作者： Ouyang ming Zhuo Renxi Fu Gongcheng Department of Chemistry Wuhan University Wuhan 430072

Fifteen new polyester ligands were prepared by copolymerndion Of EDTA(ethylenediaminetetraacetic acid ) dianhydride or DTPA (dikthylenetriaminepenlaacetic acid) dianhydrtde and dihydric alcohol or dihydric phenol. Theirparanzagnetic metal complexes were also synthesized. All polyester ligands andmetal complexes were characterized by IHNMR, IR spectra and elemental analyses. Preliminary study showed that the polyester .metal complexes had higher relaxation effectiveness as compared to corresponding small molecular metal complexes.

关键词： Magnetic resonance imaging (MRI) Polyester metal complex relaxivity

Synthesis and in vitro Evaluation of Manganese（Ⅱ）-porphyrin Modified with Chitosan Oligosaccharides as Potential MRI Contrast Agents

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Chemical Research in Chinese Universities 2014年第4期30卷 549-555页

作者： LIU Yun HUANG Yan BOAMAH Peter Osei ZHANG Qi LIU Yuanyuan HUA Mingqing School of Chemistry and Chemical Engineering Jiangsu University Zhenjiang 212013 P. R. China Hainan Provincial Key Lab of Fine Chemistry Hainan University Haikou 570228 P. R. China

Mn-TCPP-CSn（n=6,1 1,20） as a type of potential magnetic resonance imaging（MRI） contrast agents were synthesized via manganese（Ⅱ） meso-tetra（4-carboxyphenyl） porphyrin（Mn-TCPP） modified with chitosan oligosaccharides（CSn）.Experimental data of infared（IR）,UV-Vis,MS,inductively coupled plasma-atomic emission spectrometer（ICP-AES） and size exclusion chromatography evidenced the formation of Mn-TCPP-CSn-The stability results show that Mn-TCPP-CSn in aqueous solution was stable enough to prevent Mn（Ⅱ） ions from *** magnetic properties in vitro indicate that Mn-TCPP-CS20 possesses higher longitudinal relaxivity（r1=10.38 L·mmol^-1·s^-1） in aqueous solution than unmodified porphyrin Mn-TCPPNa4[manganese（Ⅱ） meso-tetra（4-carboxyphenyl） porphyrin,tetrasodium salt]（r1=5.10 L·mmol^-1·s^-1） and the commercial contrast agent Gd-DTPA（r1=4.05 L·mmol^-1·s^-1）.The preliminary T1-weighted flash image studies in vitro show that the contrast and the imaging signal of Mn-TCPP-CSn were superior to those of Mn-TCPPNa4 and Gd-DTPA under the same *** 3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay shows that Mn-TCPP-CSn has a good *** addition,the thermodynamical parameters（ΔH〈0,ΔS〈0,ΔG〈0） of Mn-TCPP-CSn bound to bovine serum albumin（BSA） show that Mn-TCPP-CSn could bind to BSA spontaneously,where the binding complex was stabilized mainly by van der Waals interactions and hydrogen *** results suggest that Mn-TCPP-CSn have the advantage of becoming a potential MRI contrast agent.

关键词： MRI contrast agent Porphyrin Chitosan oligosaccharide relaxivity T1-Weighted flash image

Liver-targeting macromolecular MRI contrast agents

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Science China Chemistry 2001年第4期44卷 344-352页

作者：鄢国平卓仁禧徐勉懿李丽云唐岳枫 Laboratory of Biomedical Polymer Materials of the Ministry of Education Department of Chemistry Wuhan University Wuhan China State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics Wuhan Institute of Physics and Mathematics Chinese Academy of Sciences Wuhan China

Macromolecular ligands with liver-targeting group (pyridoxamine, PM) PHEA-DTPA-PM and PAEA-DTPA-PM were prepared by the incorporation of different amount of diethylenetria-minepentaacetic acid monopyridoxamine group (DTPA-PM) into poly-α, β-[N-(2-hydroxyethyl)-L-aspartamide] (PHEA) and poly-α, β-[N-(2-aminoethyl)-L-aspartamide] (PAEA). The macromolecular ligands thus obtained were further complexed with gadolinium chloride to give macromolecular MRI contrast agents with different Gd(III) contents. These macromolecular ligands and their gadolinium complexes were characterized by1H NMR, IR, UV and elementary analysis. relaxivity studies showed that these polyaspartamide gadolinium complexes possess higher relaxation effectiveness than that of the clinically used Gd-DTPA. Magnetic resonance imaging of the liver in rats and experimental data of biodistribution in mice indicate that these macromolecular MRI contrast agents containing pyridoxamine exhibit liver-targeting property.

关键词： polyaspartamide gadolinium complexes magnetic resonance imaging (MRI) relaxivity liver-targeting

Gadolinium-based contrast agents built of DO3A-pyridine scaffold:Precisely tuning carboxylate group for enhanced magnetic resonance imaging

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Chinese Chemical Letters 2023年第6期34卷 537-540页

作者： Yongyin Geng Tianze Wu Qiuyue Han Yongtai Yang Zhenxia Chen Xuanxuan Li Bo Yin Yaming Zhou Yun Ling Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Department of ChemistryFudan UniversityShanghai 200438China Department of Radiology Huashan Hospital NorthFudan UniversityShanghai 201907China

It is greatly desired to develop novel gadolinium-based contrast agents(GBCAs)as improved platforms for magnetic resonance imaging(MRI).Herein,we report the syntheses of a series of nonionic cyclenbased GBCAs by precisely tuning carboxylate group on DO3A-pyridine scaffold.[Gd-DO3A-4cp]is isolated which adopts an octadentate coordination mode with a free carboxylate group at 4-position of *** shows the r_(1)relaxivity of 5.8(mmol/L)^(-1)s^(-1)(3 T,25℃),which is 75%higher than 3.3(mmol/L)^(-1)s^(-1)of the clinic used[Gd-DOTA].The possible mechanisms behind the enhanced relaxivity are investigated and proposed by structure-property relationship *** validation of low cytotoxicity and considerable kinetic inertness,in-vivo studies are further examined,demonstrating its good MRI performance,biodistribution as well as the way of excretion.

关键词： Gadolinium-based contrast agents Cyclen-based ligand Structure-property relationship relaxivity Magnetic resonance imaging

Syntheses and Characterization of Metal Complexes of　L－Lysine－N，N，N＇，N＇－tetraacetic　Acid　and　L－Lysine－N，N，N＇，N＇－tetramethylenepho　sphonic　Acid

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Chemical Research in Chinese Universities 1995年第3期11卷 276-278页

作者： ZHOU, RX LU, ZR WEN, J WUHAN UNIV DEPT CHEMWUHAN 430072PEOPLES R CHINA

ＳｙｎｔｈｅｓｅｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＭｅｔａｌＣｏｍｐｌｅｘｅｓＯｆＬ－Ｌｙｓｉｎｅ－Ｎ，Ｎ，Ｎ＇，Ｎ＇－ｔｅｔｒａａｃｅｔｉｃＡｃｉｄａｎｄＬ－Ｌｙｓｉｎｅ－Ｎ，Ｎ，Ｎ＇，Ｎ＇－ｔｅｔｒａｍ... 详细信息

ＳｙｎｔｈｅｓｅｓａｎｄＣｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆＭｅｔａｌＣｏｍｐｌｅｘｅｓＯｆＬ－Ｌｙｓｉｎｅ－Ｎ，Ｎ，Ｎ＇，Ｎ＇－ｔｅｔｒａａｃｅｔｉｃＡｃｉｄａｎｄＬ－Ｌｙｓｉｎｅ－Ｎ，Ｎ，Ｎ＇，Ｎ＇－ｔｅｔｒａｍｅｔｈｙｌｅｎｅｐｈＯｓｐｈｏｎｉ...

关键词： L-Lysine Coniplex relaxivity

Water-Soluble Gd(III)−Porphyrin Complexes Capable of Both Photosensitization and Relaxation Enhancement

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Chemical & Biomedical Imaging 2023年第2期1卷 157-167页

作者： Tamas Nemeth Naoko Yoshizawa-Sugata Agnes Pallier Youichi Tajima Yue Ma Éva Tóth Hisao Masai Yoko Yamakoshi Department of Chemistry and Applied Biosciences ETH ZürichCH8093 ZürichSwitzerland Research Center for Genome&Medical Sciences Tokyo Metropolitan Institute of Medical ScienceSetagayaTokyo 156-8506Japan Centre de Biophysique Moléculaire CNRS UPR 4301University of Orléans45071 Cedex 2 OrléansFrance Department of Basic Medical Sciences Tokyo Metropolitan Institute of Medical ScienceSetagayaTokyo 156-8506Japan

With the aim of developing more stable Gd(III)−porphyrin complexes,two types of ligands 1 and 2 with carboxylic acid anchors were *** to the N-substituted pyridyl cation attached to the porphyrin core,these porphyrin ligands were highly water-soluble and formed the corresponding Gd(III)chelates,Gd-1 and ***-1 was sufficiently stable in neutral buffer,presumably due to the preferred conformation of the carboxylateterminated anchors connected to nitrogen in the meta position of the pyridyl group helping to stabilize Gd(III)complexation by the porphyrin center.1H NMRD(nuclear magnetic relaxation dispersion)measurements on Gd-1 revealed high longitudinal water proton relaxivity(r1=21.2 mM^(−1)s^(−1)at 60 MHz and 25℃),which originates from slow rotational motion resulting from aggregation in aqueous *** visible light irradiation,Gd-1 showed extensive photoinduced DNA cleavage in line with efficient photoinduced singlet oxygen ***-based assays revealed no significant dark cytotoxicity of Gd-1,while it showed sufficient photocytotoxicity on cancer cell lines under visible light *** results indicate the potential of this Gd(III)−porphyrin complex(Gd-1)as a core for the development of bifunctional systems acting as an efficient photodynamic therapy photosensitizer(PDT-PS)with magnetic resonance imaging(MRI)detection capabilities.

关键词： Singlet oxygen generation relaxivity Gd(III)chelate water-soluble porphyrin photocytotoxicity

Studies on Hepatocyte-Targeting Magnetic Resonance Imaging Macromolecular Contrast Media

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Chemical Research in Chinese Universities 1997年第4期13卷 56+58-63页

作者： FU Yan jun ZHUO Ren xi Department of Chemistry Wuhan UniversityLaboratory of Biomedical Polymer Materials of the State Education Commission of ChinaWuhan430072

DTPA was covalently conjugated to the copolymer of L lysine and L tyrosine, then transchelated with Gd EDTA,the resultant polymer chelates were further reacted with 6 O bromoacetyl D galactose or methyl lactobionyloxyacetate to give PLT(Gd DTPA) with galactose moiety as liver targeting *** macromolecular MRI contrast agents were characterized by means of FT IR, ICP AES, elementary analyses and UV Vis spectrophotometry. Their in vitro relaxivity and liver targeting property in mice were also investigated.

关键词： MRI macromolecular contrast media(MMCM) Polylysine Hepatocyte targeting relaxivity Biodistribution