- Synthesis and study on magnetic resonance imaging performance of Gd(III)-DTPA-bisfuran-2-carbohydrazide as a potential MRI contrast agent
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One novel ligand, diethylenetriamine-N, N?-bi(acetyl-furan-2-carbohydrazide)-N, N?, N?-triacetic acid (H3L), has been synthesized in high yield by the reaction of bicyclic anhydride of diethylenetraiaminepentaacetic acid (DTPA) with furan-2-carbohydrazide. It has three carboxylic groups, and the corresponding nonion complex of Gd(III)-L holding promise of magnetic resonance imaging (MRI) was obtained by treating these ligand with Gd2O3 in water. The efficacy of the contrast agent was assessed by measuring the longitudinal relaxivity (r1) and T1 weighted magnetic resonance imaging in vitro. The r1 of Gd(III)-DTPA-bisfuran-2- carbohydrazide was up to 5.92 mM-1￠s-1, which was 1.27 times higher than that of the analogous MRI contrast agent Gd(III)-DTPA(4.65 mM-1￠s-1) in clinical application. T1 weighted magnetic resonance imaging in vitro showed that proton signal intensity increased with Gd(III) complex concentration and the imaging effect of Gd(III)-DTPA-bisfuran-2-carbohydrazide was superior to that of Gd(III)-DTPA in the same condition. These results showed that the complex might be considered as a potential MRI contrast agent.
- Wan, Fuxian,Zhang, Tiankai,Li, Changcheng,Jiang, Lin
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- A dual-excitation fluorescent probe EuIII-dtpa-bis(HBT) for hydrazine detection in aqueous solutions and living cells
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Based on the esterification of 2-(2-hydroxyphenyl)benzothiazole (HBT) and a rare-earth metal ion complex EuIII-dtpa, a novel dual-excitation fluorescence probe, EuIII-dtpa-bis(HBT), was developed for the detection of hydrazine (N2H4). The structure of dtpa-bis(HBT) was characterized via FT-IR and NMR, and its optical properties were studied via UV-vis absorption and fluorescence spectroscopy. Influencing factors including solution acidity, interfering substances and N2H4 concentrations were considered for the detection of N2H4 using EuIII-dtpa-bis(HBT). EuIII-dtpa-bis(N2H4) and HBT emit significant fluorescence at 470 nm (λex = 270 nm) and 480 nm (λex = 325 nm), respectively. The detection limit of EuIII-dtpa-bis(HBT) with N2H4 was 0.283 μM (14 ppb) and 0.182 μM (9 ppb) upon excitation at 270 nm and 325 nm, which is close to and lower than the EPA standard (10 ppb), respectively. The mechanism for the detection of N2H4 by EuIII-dtpa-bis(HBT) was deduced from the experimental results and theoretical calculations. Also, cytotoxicity and cell imaging experiments of EuIII-dtpa-bis(HBT) were performed. The experimental results showed that the fluorescent probe EuIII-dtpa-bis(HBT) can be applied to detect N2H4 in aqueous solution and living cells.
- Liu, Wenfang,Wang, Bingqiang,Jia, Haishuang,Wang, Jun,Song, Youtao
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- Synthesis and Characterization of Amphiphilic Gd(III) Complexes: Gd-DTPA-BA
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Magnetic resonance imaging (MRI) is widely used to identify different diseases. MRI contrast agents, used to enhance the MRI signal, have been studied extensively for precise diagnosis. Based on the advantages of macromolecular MRI contrast agents of higher contrast imaging ability and a longer cycle time, this article modified the most common micromolecular contrast agent (Gd-diethylene triamine pentaacetic acid [DTPA]). 2 long saturated aliphatic chains were attached to both sides of DTPA. DTPA derivatives with 12, 14, and 16 carbon lengths were synthesized and chelated to Gd3+. 3 amphiphilic MRI contrast agents were obtained and their structures were characterized using mass spectrometry, 1H NMR, and Fourier transform infrared. Furthermore, the surface tension of the compounds was measured, and liposomes were prepared by mixing the synthesized amphiphilic molecules with egg lecithin and cholesterol. The assembly behavior of the liposomes was studied using transmission electron microscopy (TEM), dynamic light scattering (DLS), and zeta potential measurements. TEM showed that the liposomes possessed bilayer vesicle structures. The liposome size distribution determined by DLS was from 10 to 1000 nm, and as the aliphatic chain length increased, the polydispersity index (PDI) and zeta potential increased. No obvious changes in the PDI and zeta potential of the liposomes were observed after 5 days at room temperature, suggesting that they possess good stability.
- Zhao, Zheng,Fang, Hui,Qiao, Weihong
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- Synthesis soluble non-ion transition metal manganese(II), cobalt(II), nickel(II) complexes of diethylenetriamine-N,N′,N″-tri(acetyl-p-hydroxybenzoyl hydrazine)- N,N″- bisacetic acid as potential contrast enhancement agent
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A novel ligand, diethylenetriamine-N,N′,N″-tri(acetyl-p-hydroxybenzoyl hydrazine)-N,N″-bisacetic acid, and its three soluble non-ion transition metal complexes, ML· nH2O (M = Mn, n = 4; M = Co, Ni, n = 2) have been synthesized and characterized on the basis of elemental analysis, molar conductivities, 1H NMR, FAB-MS, TG-DTA analysis, and IR methods. In addition, relaxivity of complexes are determined, The relaxivity (R1) of MnL, CoL, NiL, and Gd(DTPA)2- used as control are 6.33, 2.71, 2.60, and 4.34L·mmol-1·s-1, respectively. The spin-lattice relaxivity of MnL are larger than that of Gd(DTPA)2-. The results showed that complex of MnL may be a potential MRI contrast agent with high spin-lattice relaxivity, good solubility, low osmotic pressure due to non-ion complex.
- Zhang, Xue-Li,Zhang, Ding-Wa,Zhang, Hui-Jiao,He, Shi-Ni,Chen, Yao-Ting
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- Design and synthesis of novel adenine fluorescence probe based on Eu(III) complexes with dtpa-bis(guanine) ligand
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A novel adenine (Ad) fluorescence probe (EuIII-dtpa-bis(guanine)) was designed and synthesized by improving experimental method based on the Eu(III) complex and dtpa-bis(guanine) ligand. The dtpa-bis(guanine) ligand was first synthesized by the acylation action between dtpaa and guanine (Gu), and the corresponding Eu(III) complex was successfully prepared through heat-refluxing method with dtpa-bis(guanine) ligand. As a novel fluorescence probe, the EuIII-dtpa-bis(guanine) complex can detect adenine (Ad) with characteristics of strong targeting, high specificity and high recognition ability. The detection mechanism of the adenine (Ad) using this probe in buffer solution was studied by ultraviolet-visible (UV–vis) and fluorescence spectroscopy. When the EuIII-dtpa-bis(guanine) was introduced to the adenine (Ad) solution, the fluorescence emission intensity was significantly enhanced. However, adding other bases such as guanine (Gu), xanthine (Xa), hypoxanthine (Hy) and uric acid (Ur) with similar composition and structure to that of adenine (Ad) to the EuIII-dtpa-bis(guanine) solution, the fluorescence emission intensities are nearly invariable. Meanwhile, the interference of guanine (Gu), xanthine (Xa), hypoxanthine (Hy) and uric acid (Ur) on the detection of the adenine using EuIII-dtpa-bis(guanine) probe was also studied. It was found that presence of these bases does not affect the detection of adenine (Ad). A linear response of fluorescence emission intensities of EuIII-dtpa-bis(guanine) at 570?nm as a function of adenine (Ad) concentration in the range of 0.00–5.00?×?10??5?mol?L??1 was observed. The detection limit is about 4.70?×?10??7?mol?L??1.
- Tian, Fengyun,Jiang, Xiaoqing,Dou, Xuekai,Wu, Qiong,Wang, Jun,Song, Youtao
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- Design and synthesis of a novel fluorescent probe, euiii-dtpa-bis(Adenine), and application for the detection of orotic acid in urine
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For detection of orotic acid (OA), a novel fluorescent probe, EuIII-dtpa-bis(adenine), was designed and synthesized based on the complementation base pairing principle. The dtpa-bis(adenine) ligand was characterized by nuclear magnetic resonance spectroscopy (1H NMR and13C NMR), Fourier transform infrared spectra (FTIR), and elemental analysis. Then, the effects of solution pH values and some coexisting interfering substances on OA detection using EuIII-dtpa-bis(adenine) as a fluorescent probe were investigated. The linear relationship of F0/F and OA concentration in the range of 10–150 μmol/L was obtained, where F0 and F are the fluorescence intensities of EuIII-dtpa-bis(adenine) at 320 nm in the absence and presence of OA, respectively. The calculated limit of detection is about 0.807 μmol/L. The detection mechanism of OA was proposed. In addition, the detection of OA in urine samples has also been studied. It was found that the designed and synthesized fluorescent probe is effective for the detection of OA in urine samples.
- Yu, Zhiyue,Jia, Haishuang,Li, Na,Liu, Wenfang,Wang, Jun,Song, Youtao
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- Synthesis, biological evaluation and molecular docking studies of high-affinity bone targeting N,N'-Bis (alendronate) diethylenetriamene-N,N'-triacetic acid: A bifunctional bone scintigraphy agent
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A bisphosphonate derivative DTPA-bis(alendronate) conjugate has been synthesized and evaluated as potential radiopharmaceutical for bone imaging. The compound was synthesized by the covalent coupling of DTPA-bis(anhydride) with alendronate and was char-acterized on the basis of IR, NMR and mass spectroscopy. It was labelled with 99mTc with 96% efficacy and was found stable for about 24 h under physiological conditions. Blood kinetic studies of 99mTc DTPA-bis(alendronate) showed a biexponential pattern as well as quick washout from the blood circulation. The biological t1/2(F) and t1/2(S) were found to be 50 min ± 0.001 and 6 h 30 min ± 0.005, respectively. Imaging and biodistribution studies showed a significant accumulation of 99mTc DTPA-bis(alendronate) conjugate at bone site. Bone-to-muscles ratios were 12.08 ± 0.001 at 1 h, 45.33 ± 0.001 at 4 h and 35.83 ± 0.001 at 24 h after post-injection, respectively. The receptor binding of the 99mTc-DTPA-bis (alendronate) was established on human bone cell line (Soas-2) revealed KD = 0.86 nm. The preliminary result of the 99mTc-DTPA-bis(alendronate) is encouraging to carrying out further in vivo experiment for targeted bone imaging because of good-bone-to-normal-organ contrast. Further docking analysis with molecular targets, farnesyl diphosphate synthase, geranylgeranyl pyrophosphate and osteocalcin revealed the high affinity of -17.419 and thus represents strong potential of bone-imaging agent.
- Chadha, Nidhi,Sinha, Deepa,Tiwari, Anjani K.,Chuttani, Krishna,Mishra, Anil K.
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- Synthesis of novel macrocyclic lanthanide chelates derived from bis-pyrazolylpyridine.
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[structure: see text] New macrocyclic chelates based on bis-pyrazolylpyridine and diethylenetriaminepentaacetic acid are synthesized, and the remarkable luminescence properties of their lanthanide chelates are reported.
- Brunet, Ernesto,Juanes, Olga,Sedano, Rosa,Rodriguez-Ubis, Juan-Carlos
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- Lanthanide-containing polycations for monitoring polyplex dynamics via lanthanide resonance energy transfer
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Theranostic nanomaterials have emerged in the past decade that combine therapeutic delivery and diagnostic imaging into one package. Such materials offer the opportunity to aid diagnosis, track therapeutic biodistribution, and monitor drug release. We have developed a series of nucleic acid delivery polymers containing oligoethylene amines that are able to be protonated at physiological pH (for binding/compacting pDNA) and a lanthanide-chelating domain, which imparts diagnostic functionality. Diamine monomers (containing between 3 and 6 Boc-protected ethyleneamines) were prepared via a multistep procedure involving the selective protection and deprotection of primary and secondary amines. The polymer structures were then synthesized by step-growth polymerization of the oligoethylene diamines with a bisanhydride of diethylenetriamine pentaacetic acid (DTPA-BA), yielding degrees of polymerization between 18 and 24. Chelation of the polymers with gadolinium and terbium was performed to offer MRI contrast agent and luminescence properties, respectively. All of the polymer chelates were found to house approximately one water coordination site, as calculated by the Horrocks equation and possess longitudinal relaxivities (r1, on a per Gd basis) at least twice that of Magnevist, a clinical contrast agent. All the structures formed polyplexes with pDNA with highly positive zeta potentials and hydrodynamic diameters around 50-80 nm. Lanthanide resonance energy transfer (LRET) was used to monitor polyplex association and dissociation. Polyplexes were formed using the donor-acceptor pair comprising of terbium-chelated polymer with five ethyleneamines within the repeat unit (6c-Tb) and tetramethyl rhodamine (TMR)-labeled pDNA. Association/dissociation in the presence of heparin and NaCl was monitored. The effect of amine number along the polymer backbone on transfection efficiency and cytotoxicity was also investigated. None of the polymers revealed cytotoxic effects with cultured cells; however, the polymer with six ethyleneamines clearly offered the highest transfection efficiency. This preliminary study offers insight into the development of materials with the ability to monitor polyplex unpackaging over time within the cellular environment.
- Kelkar, Sneha S.,Xue, Lian,Turner, S. Richard,Reineke, Theresa M.
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- A caged lanthanide complex as a paramagnetic shift agent for protein NMR
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A lanthanide complex, named CLaNP (caged lanthanide NMR probe) has been developed for the characterisation of proteins by paramagnetic NMR spectroscopy. The probe consists of a lanthanide chelated by a derivative of DTPA (diethylene-triaminepentaacetic acid) with two thiol reactive functional groups. The CLaNP molecule is attached to a protein by two engineered, surface-exposed, Cys residues in a bidentate manner. This drastically limits the dynamics of the metal relative to the protein and enables measurements of pseudocontact shifts. NMR spectroscopy experiments on a diamagnetic control and the crystal structure of the probe-protein complex demonstrate that the protein structure is not affected by probe attachment. The probe is able to induce pseudocontact shifts to at least 40 A from the metal and causes residual dipolar couplings due to alignment at a high magnetic field. The molecule exists in several isomeric forms with different paramagnetic tensors; this provides a fast way to obtain long-range distance restraints.
- Prudencio, Miguel,Rohovec, Jan,Peters, Joop A.,Tocheva, Elitza,Boulanger, Martin J.,Murphy, Michael E. P.,Hupkes, Hermen-Jan,Kosters, Walter,Impagliazzo, Antonietta,Ubbink, Marcellus
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- Design and preparation of gadolinium-reservoir microcapsules for neutron-capture therapy by means of the wurster process
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Gadolinium (Gd)-containing microcapsules designed for neutron-capture therapy (NCT) were prepared by a spouted bed coating process. Microcapsules were designed as a Gd-reservoir. They were prepared with the following properties: particle size was smaller than 50 μm, Gd-content was as high as possible, and release of Gd was suppressed as long as possible. Calcium carbonate (20-32 μm) was selected as a seed particle. As a Gd-source, gadoliniun diethylenetriaminepentaacetic acid (Gd-DTPA) or a synthesized water-insoluble Gd-DTPA derivative, Gd-DTPA-distearylamide (Gd-DTPA-SA), was layered onto the seed particles. The release-suppressing layer was composed of aqueous acrylic latex of 9:9:4 poly(ethyl acrylate/methyl methacrylate]2- hydroxyethyl methacrylate). In preliminary studies, Gd-DTPA microcapsules with 41-45 μm (mass median diameter) were prepared; they released Gd with a short lag-time and 3h-prolongation. Complete release suppression was, however, difficult to achieve because of high water-solubility of Gd-DTPA. Hence, a hydrophobic derivative, Gd-DTPA-SA, was next used as a Gd source. Gd-DTPA-SA microcapsules could he prepared with a mass median diameter of 52 μm. Gd-DTPA-SA content of the microcapsules was 38% and release of Gd was suppressed to less than 0.2% over 60d.
- Miyamoto, Masahito,Ichikawa, Hideki,Fukumori, Yoshinobu,Akine, Yasuyuki,Tokuuye, Koichi
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- O-nitrobenzyl liposomes with dual-responsive release capabilities for drug delivery
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To improve the therapeutic efficacy of anticancer drugs and reduce its toxic side effects, we synthesized a series of amphiphilic o-nitrobenzyl molecules 4-(4-N,N,N,N-dicarboxymethyl-diethylenetriamino)acetoxymethyl-3-nitro-N,N-dialk-ylbenzamide (N,N-NB-DTPA) with good photolysis property and acid sensitivity. Simultaneously, N, N-NB-DTPA liposomes composed of the o-nitrobenzyl molecules have good biocompatibility, low hemolysis rate and cytotoxicity, and the drug encapsulation efficiency of the liposomes exceeds 70%. N, N-NB-DTPA-DOX liposomes possess good stability and can keep uniform distribution in PBS solution for 10 days. The drug release rate of these drug-loaded liposomes reaches to the maximums under pH 5.0 and 30 min UV irradiation, revealing pH/UV dual-responsiveness of these drug-loaded liposomes. The low pH makes DOX separate from these drug-loaded liposomes, and the UV irradiation leads to o-nitrobenzyl ester bond cleave, which contribute to accelerate the release of drug from drug-loaded liposomes. Furthermore, N, N-NB-DTPA-DOX liposomes after UV irradiation have better therapeutic effect than single DOX·HCl, which may result from the production of nitrosobenzaldehyde derivatives after UV irradiation.
- Yao, Weihe,Liu, Chenyu,Wang, Ning,Zhou, Hengjun,Shafiq, Farishta,Yu, Simiao,Qiao, Weihong
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- Synthesis and Characterization of GaIII, InIII and LuIII Complexes of a Set of dtpa Bis-Amide Ligands
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The synthesis and characterization of five new diethylenetriaminepentaacetic acid (dtpa) ligands, (dtpa)-N,N"-bis(alkoxyphenylamide), and their complexation with GaIII, InIII and LuIII are reported. The procedures for the synthesis of all complexes in aqueous media are described as well as a synthetic pathway for the preparation of GaIII complexes in chloroform. All substances were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and HPLC. Single-crystal structure analysis was performed where applicable, which revealed the presence of hepta- and octa-coordinated isomers for InIII complexes and a nine-fold coordination of LuIII ions in the solid state. Additional NMR experiments suggested a hepta-coordinated InIII species in solution, whereas the GaIII complexes appear to be hexa-coordinated and the LuIII complexes to be octa-coordinated. Both NMR and HPLC studies indicated the presence of a single isomer in every complex. The synthesis and characterization of new GaIII, InIII and LuIII complexes of five dtpa bis-amides are described. As determined by single-crystal structure analysis, the InIII complexes are hepta- or octa-coordinated, whereas the LuIII are nona-coordinated in the solid state. NMR studies were undertaken to characterize the coordination behaviour of the complexes in solution.
- Greiser, Julia,Hagemann, Tino,Niksch, Tobias,Traber, Philipp,Kupfer, Stephan,Gr?fe, Stefanie,G?rls, Helmar,Weigand, Wolfgang,Freesmeyer, Martin
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- A multifunctional lipid that forms contrast-agent liposomes with dual-control release capabilities for precise MRI-guided drug delivery
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Monitoring of nanoparticle-based therapy in vivo and controlled drug release are urgently needed for the precise treatment of disease. We have synthesized a multifunctional Gd-DTPA-ONB (GDO) lipid by introducing the Gd-DTPA contrast agent moiety into an o-nitro-benzyl ester lipid. By design, liposomes formed from the GDO lipid combine MRI tracking ability and dual-trigger release capabilities with maximum sensitivity (because all lipids bear the cleavable moiety) without reducing the drug encapsulation rate. We first confirmed that both photo-treatment and pH-triggered hydrolysis are able to cleave the GDO lipid and lyse GDO liposomes. We then investigated the efficiency of drug release via the combined release processes for GDO liposomes loaded with doxorubicin (DOX). Relative to neutral pH, the release efficiency in acidic environment increased by 10.4% (at pH = 6.5) and 13.3% (at pH = 4.2). This pH-dependent release response is conducive to distinguishing pathological tissue such as tumors and endolysosomal compartments. The photo-induced release efficiency increases with illumination time as well as with distance of the pH from neutral. Photolysis increased the release efficiency by 13.8% at pH = 4.2, which is remarkable considering the already increased amount of drug release in the acidic environment. In addition, the relaxation time of GDO liposomes was 4.1 times that of clinical Gd-DTPA, with brighter T1-weighted imaging in vitro and in vivo. Real-time MRI imaging and in vivo fluorescence experiments demonstrated tumor targeting and MRI guided release. Furthermore, significant tumor growth inhibition in a treatment experiment using DOX-loaded GDO liposomes clearly demonstrated the benefit of photo-treatment for efficacy: the tumor size in the photo-treatment group was 3.7 times smaller than in the control group. The present study thus highlights the benefit of the design idea of combining efficient imaging/guiding, targeting, and triggerable release functions in one lipid molecule for drug delivery applications.
- Liu, Chenyu,Ewert,Wang, Ning,Li,Safinya, Cyrus R.,Qiao, Weihong
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- Platinum(II)-gadolinium(III) complexes as potential single-molecular theranostic agents for cancer treatment
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Theranostic agents are emerging multifunctional molecules capable of simultaneous therapy and diagnosis of diseases. We found that platinum(II)-gadolinium(III) complexes with the formula [{Pt(NH3)2Cl}2GdL](NO3)2 possess such properties. The Gd center is stable in solution and the cytoplasm, whereas the Pt centers undergo ligand substitution in cancer cells. The Pt units interact with DNA and significantly promote the cellular uptake of Gd complexes. The cytotoxicity of the Pt-Gd complexes is comparable to that of cisplatin at high concentrations (≥0.1 mm), and their proton relaxivity is higher than that of the commercial magnetic resonance imaging (MRI) contrast agent Gd-DTPA. T1-weighted MRI on B6 mice demonstrated that these complexes can reveal the accumulation of platinum drugs in vivo. Their cytotoxicity and imaging capabilities make the Pt-Gd complexes promising theranostic agents for cancer treatment.
- Zhu, Zhenzhu,Wang, Xiaoyong,Li, Tuanjie,Aime, Silvio,Sadler, Peter J.,Guo, Zijian
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- Synthesis, relaxivity, and T1 relaxation enhancement of binuclear gadolinium(III) complexes based on DTPA or EDTA and long-chain alkyl esters of L-lysine
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Eight novel diamino-ester ligands were synthesized by amidation reaction of long-chain alkyl esters of l-lysine with diethylenetriamine pentaacetic acid monoanhydride or ethylenediamine tetraacetic acid monoanhydride. The corresponding dimeric Gd(iii) complexes were obtained by treating these ligands with GdCl3?6H2O. All ligands and complexes were characterized by 1H NMR, FT-IR, and elemental analysis. The longitudinal relaxation time (T1) was measured, and all relaxivity values (R1) of these dimeric Gd(iii) complexes are higher than that of Magnivest (Gd-DTPA). One of these complexes, possessing the highest relaxivity in the DTPA series, was chosen to test the acute toxicity and T 1-weighted imaging. It was found that this dimeric Gd(iii) complex exhibits no acute toxicity, and offers highly enhanced MRI signal and increases intention time in the rat liver tissue compared to Magnivest. CSIRO 2007.
- Yu, Kaichao,Hamdan, Yousef,Wan, Fuxian,Li, Yinxia,Huang, Kaixun,Zhou, Jinlan
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- Detection and quantification of lanthanide complexes in cell lysates by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry
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Gadolinium (III) complexes are under intense scrutiny as contrast agents for magnetic resonance imaging. Although currently used mainly as extracellular agents, there is a growing interest to exploit their contrast enhancing ability in the intracellular environment To ascertain the preservation of their chemical integrity upon the intracellular entrapment, it is necessary to have a method for their dosage in the cell lysates. Herein, a mass spectrometric method for detection and quantification of gadolinium complexes in cell lysates is reported. The detection by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) was carried out by using a non-acidic matrix (2,4,6-trihydroxyacetophenone), which does not allow any leakage of gadolinium from the complex. Quantification has been possible by using as an internal standard an ytterbium complex with the same ligand of the analyte. Ytterbium was chosen because, among the lanthanides, it is the one with the isotopic distribution pattern the most similar to that of gadolinium. Sensitivity was enough to detect low micromolar quantities of a cationic complex and high micromolar quantities of a neutral complex in cell lysates of rat hepatoma cells. In the case of anionic complexes, sensitivity was too low for quantitative analysis. To the best of our knowledge, this is the first report concerning the quantification of metal complexes by MALDI-TOF-US.
- Corpillo, Davide,Cabella, Claudia,Crich, Simonetta Geninatti,Barge, Alessandro,Aime, Silvio
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- Lanthanide (Eu3 +, Tb3 +, Gd3 +) hybrid system with functionalized diethylenetriamine pentaacetic acid: Coordination bonding assembly, luminescence and MRI contrast agent property
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A bridge molecule (abbreviated as DTPA-AM, DTPA-bi(4′-acrylamide)) orignated from the diethylenetriamine pentaacetic acid (DTPA) derivative (DTPAA, diethylene-triaminepentaacetic anhydride) after the modification by acrylamide though its amino group group. Subsequently, the lanthanide (Eu3 +, Tb3 +, Gd3 +) polymer hybrid material systems have been assembled with coordination bonds, which present luminescence for Eu 3 +, Tb3 + system and MRI (magnetic resonance imaging) contrast agent property for Gd3 + system, respectively.
- Yan, Bing,Sheng, Chao,Guo, Lei
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- Synthesis, characterization, thermodynamics stability constant, and relaxation properties of neutral gadolinium(III) complex with derivatives from diethylene triamine pentaacetic acid and m -hydroxybenzoyl hydrazine
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A novel ligand, diethylenetriamine-N,N″-bis(acetyl-m-hydroxybenzoyl hydrazine)-N, N′, N″-triacetic acid (H3L), was synthesized and characterized on the basis of elemental analysis, molar conductivities, 1H NMR, FAB-MS, TG-DTA analysis, and IR methods. Its complex of Gd(III) holding promise of magnetic resonance imaging(MRI) was synthesized, and relaxivity of GdL and Gd(DTPA)2- used as compare were determined in water solution, respectively. The relaxivity of GdL (R 1 = 6.02 L·mmol-1·s-1) was larger than that of Gd(DTPA)2-(R1 = 4.34L·mmol -1·s-1). The relaxivity of GdL had also been investigated in human serum albumin (HSA) solution, the relaxivity of GdL was enhanced from 6.02 L·mmol-1·s-1 in water solution to 7.10 L·mmol-1·s-1 in HSA solution. In addition, thermodynamics stability constant of GdL complex was determined. The results showed that GdL is a prospective MRI contrast agent, although the thermodynamic stability constant of GdL complex(KGdL = 1019.92) was a little less than that of Gd(DTPA) 2-(KGd-DTPA = 1020.73).
- Zhang, Ding-Wa,Liu, Yin-Qiu,Yang, Ya-Jun,Zhong, Fan
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- Studies on preparation and characterization of novel MRI contrast agents for targeting organs and blood vessels
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To improve the poor properties of currently clinically used MRI contrast agent of Gd-DTPA (Gadolinium-Diethylenetriamine-N,N,N',N",N"- pentaacetic acid) complex, sugar dendritic derivatives which contains Gd-DTPA as the core part and four or twelve sugars as the terminal part, dendrimer 8(Gd-DTPA-D1Glc(OAc)) or dendrimer 10(Gd-DTPA-D2Glc(OAc)), respectively, were prepared. From the result of relaxivity profile of these Gd complexes depending on temperature and magnitude of magnetic field, the smaller size MRI contrast agent of Gd-DTPA, 8(Gd-DTPA-D1Glc(OAc)), showed similar behavior to that of Gd-DTPA and the dendrimer constructs DDS of Gd-DTPA and was proven to have the improved properties for MR imaging of blood vessel (MRA) as well as for targeting specific organs.
- Yu, Gang,Yamashita, Mitsuji,Aoshima, Kengo,Kobayashi, Masatsugu,Kato, Tatsunori,Kamikage, Nao,Takahashi, Masaki,Takayanagi, Hisao,Oshikawa, Tatsuo,Laurent, Sofie,Burtea, Carmen,Vander Elst,Muller, Robert N.,Takehara, Yasuo,Sakahara, Harumi
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- Physicochemical characterization of the dimeric lanthanide complexes [en{Ln(DO3A)(H2O)}2] and [pi{Ln(DTTA)(H 2O)}2]2-: A variable-temperature 17O NMR study
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The Gd(III) complexes of the two dimeric ligands [en(DO3A)2] {N,N′-bis[1,4,7-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecan-10-yl- methylcarbonyl]-N,N′-ethylenediamme} and [pi(DTTA)2] 8- [bisdiethylene-triaminepentaacetic acid (trans-1,2- cyclohexanediamine)] were synthesized and characterized. The 17O NMR chemical shift of H2O induced by [en{Dy(DO3A)}2] and [pi{Dy(DTTA)}2]2- at pH 6.80 proved the presence of 2.1 and 2.2 inner-sphere water molecules, respectively. Water proton spin-lattice relaxation rates for [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H2O)}2]2- at 37.0 ± 0.1°C and 20 MHz are 3.60 ± 0.05 and 5.25 ± 0.05 mM -1 s-1 per Gd, respectively. The EPR transverse electronic relaxation rate and 17O NMR transverse relaxation time for the exchange lifetime of the coordinated H2O molecule and the 2H NMR longitudinal relaxation rate of the deuterated diamagnetic lanthanum complex for the rotational correlation time were thoroughly investigated, and the results were compared with those reported previously for other lanthanide(III) complexes. The exchange lifetimes for [en{Gd(DO3A)(H 2O)}2] (769 ± 10 ns) and [pi{Gd(DTTA)(H 2O)}2]2- (910 ± 10 ns) are significantly higher than those of [Gd(DOTA)(H2O)]- (243 ns) and [Gd(DTPA)(H2O)]2- (303 ns) complexes. The rotational correlation times for [en{Gd(DO3A)(H2O)}2] (150 ± 11 ps) and [pi{Gd(DTTA)(H2O)}2]2- (130 ± 12 ps) are slightly greater than those of [Gd(DOTA)(H2O)] - (77 ps) and [Gd(DTPA)(H2O)]2- (58 ps) complexes. The marked increase in relaxivity (r1) of [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H 2O)}2]2- result mainly from their longer rotational correlation time and higher molecular weight. Copyright
- Lee, Tzu-Ming,Cheng, Tsan-Hwang,Ou, Ming-Hung,Chang, C. Allen,Liu, Gin-Chung,Wang, Yun-Ming
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- A luminescent europium(III)-platinum(II) heterometallic complex as a theranostic agent: A proof-of-concept study
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A luminescent heterometallic multifunctional theranostic Eu-Pt2 complex [{cis-PtCl2(DMSO)}2Eu(L)(H2O)] has been synthesized, possessing two therapeutic Pt-centers as covalent DNA binders and one emissive Eu3+-center which is sensitized by platinum-based metal-to-ligand charge-transfer excited states.
- Chandra, Anirban,Singh, Khushbu,Singh, Swati,Sivakumar, Sri,Patra, Ashis K.
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Read Online
- MRI-guided targeting delivery of doxorubicin with reduction-responsive lipid-polymer hybrid nanoparticles
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In recent years, there has been increasing interest in developing a multifunctional nanoscale platform for cancer monitoring and chemotherapy. However, there is still a big challenge for current clinic contrast agents to improve their poor tumor selectivity and response. Herein, we report a new kind of Gd complex and folate-coated redox-sensitive lipid-polymer hybrid nanoparticle (Gd-FLPNP) for tumor-targeted magnetic resonance imaging and therapy. Gd-FLPNPs can simultaneously accomplish diagnostic imaging, and specific targeting and controlled release of doxorubicin (DOX). They exhibit good monodispersity, excellent size stability, and a well-defined core-shell structure. Paramagnetic nanoparticles based on gadolinium-diethylenetriaminepentaacetic acid-biscetylamine have paramagnetic properties with an approximately two-fold enhancement in the longitudinal relaxivity compared to clinical used Magnevist. For targeted and reduction-sensitive drug delivery, Gd-FLPNPs released DOX faster and enhanced cell uptake in vitro, and exhibited better antitumor effect both in vitro and in vivo.
- Wu, Bo,Lu, Shu-Ting,Deng, Kai,Yu, Hui,Cui, Can,Zhang, Yang,Wu, Ming,Zhuo, Ren-Xi,Xu, Hai-Bo,Huang, Shi-Wen
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Read Online
- Novel fluorescent probe, preparation method thereof and application of novel fluorescent probe in detecting sulfadimidine in honey
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The invention belongs to the field of analytical chemistry, and particularly discloses a novel fluorescent probe, a preparation method thereof and application of the novel fluorescent probe in detecting sulfadimidine in honey. The preparation method comprises the following steps: stirring and refluxing diethylenetriamine pentaacetic acid, acetic anhydride and pyridine at 65 DEG C for 24 hours; cooling, carrying out reduced pressure suction filtration, washing and drying; reacting the obtained diethylenetriamine pentaacetic acid dianhydride (dtpaa) with adenine (adenine), taking triethylamine as an acid acceptor and dimethyl formamide (DMF) as a solvent, and stirring and refluxing for 24 hours at the temperature of 100 DEG C; cooling, carrying out suction filtration, washing and carrying out vacuum drying to obtain Dtpa-bis (adenine) white powder; heating and stirring with Eu (NO3) 3.6 H2O at the temperature of 60 DEG C for 2 hours to obtain a target product Eu-dtpa-bis (adenine).According to the invention, the sulfadimidine is detected by using the fluorescence probe and a fluorescence spectrum method. The method is simple, novel, low in cost and high in efficiency, and can be applied to actual honey samples.
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Paragraph 0034-0037; 0041
(2021/03/13)
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- Luminescent lanthanide(III) complexes of DTPA-bis(amido-phenyl-terpyridine) for bioimaging and phototherapeutic applications
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We report here a series of coordinatively-saturated and thermodynamically stable luminescent [Ln(dtntp)(H2O)] [Ln(III) = Eu (1), Tb (2), Gd (3), Sm (4) and Dy (5)] complexes using an aminophenyl-terpyridine appended-DTPA (dtntp) chelating ligand as cell imaging and photocytotoxic agents. The N,N″-bisamide derivative of H5DTPA named as dtntp is based on 4′-(4-aminophenyl)-2,2′:6′,2″-terpyridine conjugated to diethylenetriamine-N,N′,N″-pentaacetic acid. The structure, physicochemical properties, detailed photophysical aspects, interaction with DNA and serum proteins, and photocytotoxicity were studied. The intrinsic luminescence of Eu(III) and Tb(III) complexes due to f → f transitions used to evaluate their cellular uptake and distribution in cancer cells. The solid-state structure of [Eu(dtntp)(DMF)] (1·DMF) shows a discrete mononuclear molecule with nine-coordinated {EuN3O6} distorted tricapped-trigonal prism (TTP) coordination geometry around the Eu(III). The {EuN3O6} core results from three nitrogen atoms and three carboxylate oxygen atoms, and two carbonyl oxygen atoms of the amide groups of dtntp ligand. The ninth coordination site is occupied by an oxygen atom of DMF as a solvent from crystallization. The designed probes have two aromatic pendant phenyl-terpyridine (Ph-tpy) moieties as photo-sensitizing antennae to impart the desirable optical properties for cellular imaging and photocytotoxicity. The photostability, coordinative saturation, and energetically rightly poised triplet states of dtntp ligand allow the efficient energy transfer (ET) from Ph-tpy to the emissive excited states of the Eu(III)/Tb(III), makes them luminescent cellular imaging probes. The Ln(III) complexes show significant binding tendency to DNA (K ~ 104 M?1), and serum proteins (BSA and HSA) (K ~ 105 M?1). The luminescent Eu(III) (1) and Tb(III) (2) complexes were utilized for cellular internalization and cytotoxicity studies due to their optimal photophysical properties. The cellular uptake studies using fluorescence imaging displayed intracellular (cytosolic and nuclear) localization in cancer cells. The complexes 1 and 2 displayed significant photocytotoxicity in HeLa cells. These results offer a modular design strategy with further scope to utilize appended N,N,N-donor tpy moiety for developing light-responsive luminescent Ln(III) bioprobes for theranostic applications.
- Dasari, Srikanth,Singh, Swati,Abbas, Zafar,Sivakumar, Sri,Patra, Ashis K.
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supporting information
(2021/04/12)
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- Preparation of double-excitation fluorescent probe and application of double-excitation fluorescent probe in detection of hydrazine in water
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The invention discloses a double-excitation fluorescence probe and a preparation method and application thereof in detection of hydrazine in water. The preparation method includes: taking diethylenetriamine pentaacetic acid, acetic anhydride and pyridine, stirring and heating for 24h at 65 DEG C, cooling, filtering, washing and drying; well mixing obtained diethylenetriamine pentaacetic acid dianhydride with triethylamine, DMF (dimethyl formamide) and fluorescein, heating and stirring for 24h at a constant temperature of 100 DEG C, cooling, filtering, and drying; dissolving obtained diethylenetriamine pentaacetic acid-bis(fluorescein) into Tris-HCl/DMSO (10mmol.L, v/v=9:1) buffer solution with pH equal to 7.5, mixing with Tb(NO3)3.6H2O, and heating or placing for more than two hours toobtain a target product. Uric acid detection is realized by combination of Tb-dtpa-bis(fluorescein) as a double-excitation probe and a fluorescence method. The method is simple, novel, high in efficiency and low in cost, and applicability to practical water samples is realized.
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Paragraph 0034; 0036; 0037
(2019/08/21)
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- Amphiphilic molecule containing o-nitrobenzyl ester photo-degradation group
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The invention discloses a novel photodegradable amphiphilic molecule and a synthetic method thereof, and belongs to the field of surfactants. The synthetic method comprises the five steps that (1) diethylenetriamine pentaacetic acid is taken as a raw material, acetic anhydride is taken as a dehydrating agent, and pyridine catalytic dehydration is performed to produce diethylenetriamine pentaaceticdianhydride; (2) methylene of 6-nitropiperonal is removed under the action of aluminum chloride and hydrobromic acid; (3) 4,5-dihydroxy-2-nitrobenzaldehyde and bromoalkane are subjected to an etherification reaction under an alkaline condition; (4) the 4,5-dihydroxy-2-nitrobenzaldehyde is reduced to 4,5-dihydroxy-2-nitrobenzyl alcohol under the action of a reducing agent; (5) the 4,5-dihydroxy-2-nitrobenzyl alcohol and the excess diethylenetriamine pentaacetic dianhydride are subjected to an esterification reaction to obtain the o-nitrobenzyl ester amphiphilic molecule. The novel photodegradable amphiphilic molecule and the synthetic method thereof have the advantages that the reaction condition of an o-nitrobenzyl alcohol derivative and the diethylenetriamine pentaacetic dianhydride is mild, the excess diethylenetriamine pentaacetic dianhydride is used for reducing the occurrence of side reactions, and the amphiphilic molecule has good ultraviolet photodegradability.
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Paragraph 0038-0040
(2019/08/20)
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- A new bis-(3-hydroxy-4-pyridinone)-DTPA-derivative: Synthesis, complexation of di-/tri-valent metal cations and in vivo M3+ sequestering ability
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A new polyaminocarboxylic bis-(3-hydroxy-4-pyridinone), derivative of DTPA, DTPA(PrHP)2, was synthesized starting from maltol by means of a coupling reaction of a protected 3-hydroxy-4-pyridinone and DTPA bis-anhydride. The DTPA(PrHP)2 acid-base behavior was investigated by UV–Vis spectrophotometry and spectrofluorimetry at I = 0.15 mol L?1 in NaCl(aq) at T = 298.15 K and T = 310.15 K. To confirm the speciation scheme, also 1H NMR measurements were performed at T = 298.15 K. The protonation constants obtained from the cited different analytical techniques showed good accordance and were also in agreement with data reported in the literature. The complexing ability of DTPA(PrHP)2 towards divalent (Ca2+, Cu2+, Zn2+) and trivalent (Al3+, Fe3+) cations was studied by potentiometric, UV–Vis spectrophotometric and 1H NMR titrations at T = 298.15 K and I = 0.15 mol L?1 in NaCl(aq). The fitting analysis of experimental data led to the determination of different speciation models consisting of MpLqHr (pn+r-5q) species with different stoichiometry and protonation stages, hydrolytic mixed and polynuclear complexes. The equilibrium model and complex formation constants, obtained from various analytical techniques, are in good agreement. The sequestering ability of the ligand towards the metal cations was assessed through the determination of the pL0.5 and pM parameters at different pH values and pH = 7.4, respectively, which showed to follow the trend Fe3+ > Al3+ > Cu2+ > Ca2+ > Zn2+. Finally, biodistribution studies were carried out in mice previously injected with the radiotracer 67Ga–citrate to evaluate the in vivo ability of DTPA(PrHP)2 as chelating agent towards trivalent metal cations.
- Irto, Anna,Cardiano, Paola,Chand, Karam,Cigala, Rosalia Maria,Crea, Francesco,De Stefano, Concetta,Gano, Lurdes,Gattuso, Giuseppe,Sammartano, Silvio,Santos, Maria Amélia
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p. 280 - 294
(2019/02/27)
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- Fluorescent probes for detecting xanthine, and preparation method and application thereof
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The invention discloses fluorescent probes for detecting xanthine, and a preparation method and an application thereof. The preparation method comprises the following steps: taking diethylenetriaminepentaacetic acid, acetic anhydride and pyridine, performing stirring and refluxing, cooling the obtained solution, carrying out reduced pressure filtration, and washing and drying the obtained reactionproduct; stirring and refluxing the obtained diethylenetriaminepentaacetic acid dianhydride, triethylamine, dimethyl formamide, adenine and/or cytosine, cooing the obtained solution, carrying out rotary evaporation, washing and drying the obtained reaction product, and stirring and heating the obtained intermediate and Tb(NO3)3.6H2O at 60 DEG C for 2 h to obtain the target products. Tb-dtpa-2A, Tb-dtpa-2C and Tb-dtpa-AC which are used as probes are combined with a fluorescence method to detect xanthine. The probes have the advantages of simple and novel process, low cost and high efficiency, and can be applied to actual urine samples.
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Paragraph 0040-0041
(2019/01/20)
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- Preparation method of near-infrared light-controlled visual medicine carrier
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The invention discloses a near-infrared light-controlled medicine carrier, namely a carrier with medicine carrying ability which is formed by o-nitrobenzyl ester amphiphilic molecule vesicles encapsulating water-soluble upconversion nanoparticles (Ligand-UCNPs), and belongs to the field of surfactants. The total number of alkyl carbon atoms of a fatty chain is 6 to 36. A preparation method of thecarrier comprises the following three steps of synthesizing oil-soluble upconversion nanoparticles (OA-UCNPs); synthesizing the water-soluble upconversion nanoparticles (Ligand-UCNPs); encapsulatingthe upconversion nanoparticles by the o-nitrobenzyl ester amphiphilic molecules. The near-infrared light-controlled medicine carrier has the advantages that the o-nitrobenzyl ester amphiphilic molecules have ultraviolet light crackability; by introducing the upconversion nanoparticles (UCNPs) which have large tissue penetration depth and can convert the near-infrared light with little injury to ahuman body into the ultraviolet light, the defects of small penetration depth and large injury to the human body of the ultraviolet light are overcome, and the purpose of medicine release by photolysis is realized; the near-infrared light-controlled medicine carrier is a potential near-infrared light-controlled medicine release carrier.
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Paragraph 0070-0071
(2019/09/17)
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- Preparation of polycarboxylic acid-functionalized silica supported Pt catalysts and their applications in alkene hydrosilylation
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A series of novel immobilized platinum catalysts was prepared by loading Pt onto silica particles modified with polycarboxylic acid groups such as diethylenetriaminepentaacetic acid (DTPA), nitrolotriacetic acid (NTA) and succinic acid (SA). The three modified heterogeneous Pt catalysts were characterized using infrared spectroscopy (IR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS) and atomic absorption spectroscopy (AAS). The residual H2PtCl6 solutions were characterized using ultraviolet spectroscopy (UV). The polycarboxylic acid-functionalized silica supported Pt catalysts were used to catalyze alkene hydrosilylation and 1-hexene was chosen as a model alkene. The data indicated that the catalytic performance was strongly dependent on the properties of the polycarboxylic acid group bonded to the silica particles. Among them, DTPA-functionalized silica supported Pt (SiO2-DTPA-Pt) showed the best catalytic activity and reusability. Furthermore, some hydrosilylation reactions between other linear alkenes (1-heptene, 1-octene, 1-decene, 1-do-decene, 1-tetra-decene, 1-hexa-decene, 1-octa-decene, styrene or cis-hex-2-ene), or ring type alkenes (norbornene) with methyldichlorosilane could be catalyzed in the presence of these three Pt catalysts. Their high activities were more than 90%, and their selectivities were more than 99%, which were apparently better than homogeneous Pt catalysts. In addition, reactions with cyclohexene were also successfully catalyzed by the Pt catalysts. These results indicate that the polycarboxylic acid-functionalized silica gel supported Pt catalysts have potential value in industrial hydrosilylation reactions.
- Shao, Dongyun,Li, Youxin
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p. 20379 - 20393
(2018/06/11)
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- T1/T2 dual-mode magnetic resonance imaging contrast agent, and preparation method and use thereof
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The invention discloses a T1/T2 dual-mode magnetic resonance imaging contrast agent. The expression of the T1/T2 dual-mode magnetic resonance imaging contrast agent is Gd:CA-DTPA-PEG-DIB-Fe3O4, and the structural formula of the T1/T2 dual-mode magnetic resonance imaging contrast agent is shown in the description; and in the structural formula, CA is cholic acid, DTPAA is diethylenetriaminepentaacetic acid dianhydride, DIB is 3,4-dihydroxybenzaldehyde, and PEG is polyethylene glycol. Two contrast agents are loaded into a nano-composite material, and the contrast agents have different contrast modes, so the two contrast agents interact with each other under an external magnetic field in order to achieve accurate imaging. The contrast agent has a high relaxation rate and a liver targeting characteristic.
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Paragraph 0038; 0040
(2018/10/19)
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- 19F CEST imaging probes for metal ion detection
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For detecting metal ions with 19F chemical exchange saturation transfer magnetic resonance imaging (19F CEST MRI), a class of novel fluorinated chelators with diverse fluorine contents and chelation properties were conveniently synthesized on gram scales. Among them, a DTPA-derived chelator with high sensitivity and selectivity was identified as a novel 19F CEST imaging probe for simultaneously detecting multiple metal ions.
- Peng, Qiaoli,Yuan, Yaping,Zhang, Huaibin,Bo, Shaowei,Li, Yu,Chen, Shizhen,Yang, Zhigang,Zhou, Xin,Jiang, Zhong-Xing
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p. 6441 - 6446
(2017/08/10)
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- Novel fluorescent probe, preparation method thereof and application of novel fluorescent probe to detection of 6-thioguanine
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The invention discloses a novel fluorescent probe, a preparation method thereof and application of the novel fluorescent probe to detection of 6-thioguanine (6-TG). The preparation method comprises the following steps: taking DTPA (Diethylene Triamine Pentoacetic Acid), acetic anhydride and pyridine, slowly stirring and heating at the temperature of 65 DEG C for 24 hours; cooling to room temperature, filtering, washing with anhydrous ether, performing suction filtration, and performing vacuum drying to obtain DTPAA (Diethylenetriaminpentacetic Acid); taking the DTPAA, triethylamine, DMF (Dimethyl Formamide) and cytosine, keeping the temperature at 100 DEG C, heating and stirring for 24 hours; cooling to the room temperature, filtering, and performing vacuum drying to obtain DTPA-bis(cytosine); taking the DTPA-bis(cytosine), dissolving the DTPA-bis(cytosine) in a Tris-HCl buffer solution of which the pH is equal to 7.4, washing Eu(NO3)3.6H2O with the solution, collecting washing liquid, and heating or standing for a long time to obtain the fluorescent probe. When the fluorescent probe is applied to the detection of the 6-TG together with a fluorescence method, a simple and novel method is provided, high efficiency is achieved, the cost is low, and environmental pollution is avoided.
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Paragraph 0030; 0031
(2017/08/28)
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- Synthesis and study on magnetic resonance imaging performance of Gd(III)-DTPA-bisbenzothiazol hydrazide
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In this paper, 2-hydrazino-6-methoxy-1,3-benzothiazole was introduced into diethylenetriamine pentaacetic ( DTPA) by acylation reaction. The corresponding non-ion Gd(III) complex holding promise of a single molecule magnetic resonance imaging (MRI) contrast agent was obtained by treating this ligand with GdCl3·6H2 O. The efficacy of the contrast agent was assessed by measuring the longitudinal relaxivity (r1), the r1 of Gd(III)-DTPA-bisbenzothiazole hydrazide was up to 6.44 mM-1·s-1, which was 1.8 times higher than that of the analogous MRI contrast agent Gd(III)-DTPA(r1 = 3.64 mM-1·s-1 ) in commercial use. In addition, in vitro MR images on a 0.5 T magnetic field exhibited a remarkable enhancement of signal contrast for Gd(III)-DTPA-bisbenzothiazole hydrazide than Gd(III)-DTPA. These results demonstrate that this non-ion Gd(III) complex acts as a potentially MRI contrast agent.
- Wan, Fu-Xian,Zhang, Tian-Kai,Li, Ying,Li, Chang-Cheng,Jiang, Lin
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p. 2861 - 2863
(2016/10/12)
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- TARGETED CONTRAST AGENTS COMPRISING A HYDRAZIDE FUNCTIONAL GROUP
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Described herein is a contrast agent for administration to a subject. The contrast agent includes a targeting portion that includes a hydrazide functional group; a metal ion bound to a metal-complexable portion; and a linker joining the targeting portion and the metal- complexable portion of the contrast agent. The portion that is not bound to a metal ion localizes the contrast agent to necrotic tissue in the subject.
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Paragraph 00109
(2016/11/07)
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- Magnetofluorescent Nanoaggregates Incorporating Terbium(III) Complexes as Potential Bimodal Agents for Magnetic Resonance and Optical Imaging
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Terbium(III) ions were coordinated to two diethylenetriaminepentaacetic acid (DTPA) amphiphilic bisamide ligands, and the complexes were assembled into micellar nanoaggregates. The magnetic and optical properties of the resulting nanoaggregates were examined in detail. Upon excitation into the ligand levels at 265 nm, the complexes show characteristic TbIII emission at 546 nm with quantum yields of up to 7.6 %. Nuclear magnetic relaxation dispersion (NMRD) measurements have shown that the transverse relaxivity r2 at 500 MHz and 310 K reaches a maximum value of 9.4 s-1 mM-1. The efficient T2 relaxivity at high magnetic field strengths is sustained by the increased rotational correlation time of the nanoaggregates and high magnetic moment of the terbium ion.
- Harris, Michael,Carron, Sophie,Vander Elst, Luce,Laurent, Sophie,Parac-Vogt, Tatjana N.
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p. 4572 - 4578
(2015/10/06)
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- DTPA DI-ETHYL ESTERS, COMPOSITIONS THEREOF, AND METHODS OF USING THE SAME
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The present invention relates to trisodium diethylenetriamine pentaacetic acid (DTPA) di-ethyl esters. The invention further relates to compositions comprising DTPA di-ethyl esters and methods of using the same.
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Page/Page column 21
(2014/06/11)
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- Controlling multivalency and multimodality: Up to pentamodal dendritic platforms based on diethylenetriaminepentaacetic acid cores
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A highly versatile synthetic strategy is described to generate multimodal and multivalent platforms based on a diethylenetriaminepentaacetic (DTPA) core. Compounds with different functionalization patterns, from mono- to pentamodal, have been prepared using robust and simple chemistry.
- Pulido, Daniel,Albericio, Fernando,Royo, Miriam
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supporting information
p. 1318 - 1321
(2014/04/03)
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- Lanthanide(III) complexes of diethylenetriaminepentaacetic acid (DTPA)-bisamide derivatives as potential agents for bimodal (Optical/Magnetic Resonance) imaging
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Diethylenetriaminepentaacetic acid (DTPA)-bisamide derivatives functionalized with p-toluidine, 6-aminocoumarin, 1-naphthalene methylamine and 4-ethynylaniline were synthesized and fully characterized by mass spectrometry, NMR spectroscopy, FTIR spectroscopy and elemental analysis. LnIII complexes (Ln = Gd, Eu, Tb, Y) of the ligands DTPA-bis-p-toluidineamide (DTPA-BTolA), DTPA-bis-6-coumarinamide (DTPA-BCoumA), DTPA-bis-1- naphthylmethylamide (DTPA-BNaphA) and DTPA-bis-4-ethynylphenylamide (DTPA-BEthA) were prepared and studied for their bimodal magnetic resonance imaging/optical properties. EuIII and TbIII derivatives in aqueous solutions exhibit characteristic red and green emission, respectively, with quantum yields of 0.73 % for EuIII-DTPA-BNaphA and 2.5 % for Tb III-DTPA-BEthA. Ligand-centred photophysical properties of the GdIII complexes were investigated to gain insight into energy-transfer processes that take place in these systems. The GdIII complexes were also analyzed by nuclear magnetic relaxation dispersion (NMRD) techniques. The relaxivity (r1) at 20 MHz and 310 K equals 4.1 s -1 mM-1 for Gd-DTPA-BTolA, 5.1 s-1 mM -1 for Gd-DTPA-BCoumA, 6.4 s-1 mM-1 for Gd-DTPA-BNaphA and 5.7 s-1 mM-1 for Gd-DTPA-BEthA. These values are higher than the value of 3.8 s-1 mM-1 for Gd-DTPA (Magnevist). The improved relaxivity is due to the increase in the rotational tumbling time τR with a factor of 1.6 for Gd-DTPA-BTolA, 2.1 for Gd-DTPA-BCoumA, 3.1 for Gd-DTPA-BNaphA and 6.5 for Gd-DTPA-BEthA. In a 4 % human serum albumin solution, the apparent relaxivity at 20 MHz increases to values of 13.9 and 19.1 s-1 mM-1 for Gd-DTPA-BNaphA and Gd-DTPA-BEthA, respectively. All these features assist the search for optimal bimodal optical and magnetic resonance imaging probes. Copyright
- Debroye, Elke,Eliseeva, Svetlana V.,Laurent, Sophie,Vander Elst, Luce,Petoud, Stephane,Muller, Robert N.,Parac-Vogt, Tatjana N.
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p. 2629 - 2639
(2013/07/11)
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- Synthesis neutral rare earth complexes of diethylenetriamine-N, N″-bis(acetyl-O-hydroxybenzoyl hydrazide)-N, N′, N-triacetic acid as potential contrast enhancement agents for magnetic resonance imaging
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A novel ligand (H3L), diethylenetriamine-N,N″-bis(acetyl- o-hydroxybenzoyl hydrazide)-N, N′, N″-triacetic acid and its four rare earth (La, Eu, Gd, Tb) complexes have been synthesized and characterized on the basis of elemental analyses, molar conductivities, 1H NMR spectra, FAB-MS, TG-DTA analysis, and IR spectra. In addition, relaxivity (R1) of complexes are determined. The relaxivity of LaL, EuL, GdL, TbL, and Gd(DTPA)2- used as a control are 0.94, 2.79, 6.39, 1.59, and 4.34 L·mmol-1·s-1, respectively. The spin-lattice relaxivity of GdL is larger than that of Gd(DTPA)2-. The results showed that complex of GdL may be a potential magnetic resonance imaging contrast agent.
- Zhang, Ding-Wa,Yang, Ya-Jun,Ying, Shao-Ming,Liu, Yin-Qiu
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p. 217 - 220
(2013/04/10)
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- EDTA and DTPA modified ligands as sequestering agents for uranyl decorporation
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Synthesis of modified EDTA and DTPA ligands and determination of their binding affinities for the uranyl cation are described. Thanks to a screening method, based on a chromophoric complex displacement procedure, chelating properties were studied in aqueous media under various pH conditions for evaluation of their in vivo uranyl-removal efficacy. Each ligand showed a more or less pronounced affinity for uranium. Specific ligands based on EDTA or DTPA analogues containing sulfocatecholamide (CAMS) were found to exhibit a significant affinity towards uranyl ion in acidic, neutral or basic conditions.
- Leydier, Antoine,Lin, Yi,Arrachart, Guilhem,Turgis, Rapha?l,Lecerclé, Delphine,Favre-Reguillon, Alain,Taran, Frédéric,Lemaire, Marc,Pellet-Rostaing, Stéphane
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body text
p. 1163 - 1170
(2012/02/15)
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- Purely heterometallic lanthanide(III) macrocycles through controlled assembly of disulfide bonds for dual color emission
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Lanthanide complexes based on bis(amides) of die thy lenetria minepentaace tic acid with thiol functionalities are modified with 2,2′-dipyridyl disulfide to give activated complexes that can selectively react with thiol-functionalized complexes to form heterometallic lanthanide macrocycles. The preparation and full characterization of the polyaminocarboxylate ligands N,N″-bis-[p-thiophenyl(aminocarbonyl)]diethylenetriamine-N, N′, N″-triacetic acid (H3LX) and the activated N, NPrime;-bis[p-(pyridyldithio)-[phenyl(aminocarbonyl)]]diethylenetriamine-N, N′, N″-triacetic acid (H3Ly) and the complexes LaLx, NdLx, SmLx, EuLx, GdL x, DyLx, TbLx, ErLx, and YbL x are reported. The luminescence properties of the LnLx complexes emitting in the visible (where Ln = Dy3+, Tb3+, Eu3+, and Sm3+) are examined by steady-state and time-resolved photoluminescence, and the triplet state energy level of GdL x was estimated to be 24 100 cm-1 from the 0-0 band of the 77 K phosphorescence spectrum. Near-infrared emission was detected for the NdLx, YbLx, and ErLx complexes, demonstrating the versatility of the thiophenol chromophore. The assembly of purely heterometallic EuTbLx2 macrocycles by reaction of EuL x with TbIy was followed by UV-vis absorption spectroscopy, monitoring the characteristic absorption peak of pyridyl-2-thione at 353 nm. Analysis of the solution by mass spectrometry reveals the formation of purely heterometallic macrocycle EuTbLx2. This is in contrast with the results obtained by dynamic self-assembly under oxidative conditions, where we observe a statistical mixture of macrocyclic complexes of Eu2Lx2, Tb2Lx 2, and EuTbLx2. The EuTbLx 2 macrocycle displays dual color emission, incorporating the characteristicf-ftransitions of Eu3+ and Tb3+. Investigation into the time-resolved photophysical properties of EuTbL x2 reveals energy transfer from Tb3+ to Eu 3+, facilitated by the different conformations of the macrocycle in solution.
- Lewis, David J.,Glover, Peter B.,Solomons, Melissa C.,Pikramenou, Zoe
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experimental part
p. 1033 - 1043
(2011/03/22)
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- Sensitization of Eu(III) luminescence by donor-phenylethynylfunctionalized DTPA and DO3A macrocycles
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The synthesis and complexation to Eu(III) of two macrocyclic ligands functionalized donor-phenylethynyl-moieties as sensitizer is presented. The two ligands based on DTPA bis-amide ([Eu(L1)]) and DO3A ([Na][Eu(L 2)]) have been chosen because of their increased stability in water for potential applications as luminescent bioprobes for one-or twophoton excited scanning microscopy. The DTPA and DO3A ligands possess oxygen or sulfur donor atoms, respectively, connected to a triethyleneglycol (PEG) chain to ensure the water solubility. The optical properties were studied and reveal that ([Eu(L1)]) present a lower brightness than the ([Na][Eu(L 2)]) counterpart because of its inner sphere water molecule coordination that quenches the emission. On the other hand, [Na][Eu(L 2)] exhibits excellent spectroscopic properties with high quantum yield φ = 0.284, and brightness B = 10,220M-1cm -1(defined as e.φ). Unfortunately, the two-photon crosssection of this last complex was measured to be only 4 GM limiting its potential applications to linear microscopy.
- D'Aléo, Anthony,Allali, Mustapha,Picot, Alexandre,Baldeck, Patrice L.,Toupet, Lo?c,Andraud, Chantal,Maury, Olivier
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experimental part
p. 681 - 690
(2011/11/06)
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- PREPARATION OF COMPLEXING AGENTS AND METAL ION COMPLEXES IN AQUEOUS MEDIA
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The invention relates to methods of preparation for bis-amide complexing agents, as well as paramagnetic metal ion complexes that include such agents. To prepare these complexing agents, a reaction mixture is formed that includes a bis-anhydride, a nitrogen-containing compound, and an aqueous solvent system. The nitrogen-containing compound reacts with the bis-anhydride in the reaction mixture to form the bis-amide complexing agent. The molar ratio of water to the nitrogen containing compound in the reaction mixture is greater than 3:1, respectively. In addition, the molar ratio of the nitrogen-containing compound to the bis-anhydride in the reaction mixture is no greater than 2.5:1, respectively. In some embodiments, a base other than the nitrogen-containing compound may be included in the reaction mixture (e.g., to buffer the reaction mixture). In some embodiments, the bis-amide complexing agent may be contacted with a paramagnetic metal ion salt to form a paramagnetic metal ion complex of the invention.
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Page/Page column 17
(2010/11/29)
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- DTPA derivatives and metal complexes therof, and radiation source and contrast agent including the metal complexes
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The present invention relates to diethylenetriamine pentaacetic acid (DTPA) derivates and metal complexes thereof, and radiation sources and contrast agents including the metal complexes. More particularly, the present invention relates to DTPA derivatives, which contain iodine and are useful as contrast agents for diagnosing renal function, metal complexes of the DTPA derivatives with 99mTc, 166Ho, 111In, 90Y, 153Sm, 186Re, 188Re, 68Ga, or 177Lu, which are useful as liquid radiation sources for treating vascular stenosis and contrast agents for diagnosing renal function, and radiation sources and contrast agents including the metal complexes. The DTPA derivatives and metal complexes thereof are safe because the metal complexes are excreted via the kidneys and bladder within several minutes from the time of use as liquid radiation sources for treating vascular stenosis, and are cost-effective because they are potentially useful as contrast agents and as agents for diagnosing renal function.
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(2008/06/13)
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- DTPA derivatives and metal complexes thereof, and radiation source and contrast agent including the metal complexes
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The present invention relates to diethylenetriamine pentaacetic acid (DTPA) derivates and metal complexes thereof, and radiation sources and contrast agents including the metal complexes. More particularly, the present invention relates to DTPA derivatives, which contain iodine and are useful as contrast agents for diagnosing renal function, metal complexes of the DTPA derivatives with 99mTc, 166Ho, 111In, 90Y, 153Sm, 186Re, 188Re, 68Ga, or 177Lu, which are useful as liquid radiation sources for treating vascular stenosis and contrast agents for diagnosing renal function, and radiation sources and contrast agents including the metal complexes. The DTPA derivatives and metal complexes thereof are safe because the metal complexes are excreted via the kidneys and bladder within several minutes from the time of use as liquid radiation sources for treating vascular stenosis, and are cost-effective because they are potentially useful as contrast agents and as agents for diagnosing renal function.
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- LANTHANIDE CHELATES AND USE THEREOF IN BIOANALYSIS
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The invention relates to novel chemical compounds, of application in fluorometric analytical methods, for qualitative and quantitative determination of biomolecules. The aim of the invention is to identify and prove the suitability of such compounds. Said aim is achieved with compounds of formula (I), where R1 is an antenna function, R2 is a chelate forming agent, containing a coordinated lanthanide (III) ion, X is -OH or a group with affinity for the biomolecule, bonded to a carboxyl group of the chelate forming agent by means of an amide bond and Y is -H or a group with affinity for the biomolecule, coupled to the antenna function.
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- New agents for magnetic imaging method
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The invention provides MRI detectable species of formula (I)Dp-Sn-Nm wherein D is a MRI detectable moiety ???S is a spacer ???N is a molecule of a nutrient or pseudo-nutrient ???n is 0 or an integer ???m is an integer and ???p is an integer. These compounds are useful for internalising into tumor cells an amount of the MRI detectable moiety that is distinguishably higher than the amount internalised in normal healthy cells thus allowing the diagnosis of tumors. Preferred compounds of formula (I) are those wherein D is the chelated complex of a paramagnetic metal ion. In this case when the paramagnetic metal ion is a neutron capture isotope, e.g. 157Gd, the new compounds can also be used for the treatment of the tumor, by selective irradiation of the tumor mass.
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- Synthesis of a Sialyl LewisX mimetic conjugated with DTPA, potential ligand of new contrast agents for medical imaging
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The structure of a mimetic of sialyl LewisX, namely 3-[2-(α-D-mannopyranosyloxy)phenyl]phenylacetic acid, was coupled to diethylenetriaminepentaacetic acid (DTPA) via a flexible alkyl spacer and the amide linkage. The overall yield of the eleven-step synthesis starting from 3-bromophenylacetic acid was 4-8%. This new ligand is expected to target inflammation sites through specific interactions with selectins, the adhesion molecules expressed on the vascular endothelium in pathological conditions. In particular, complexation of the DTPA moiety with gadolinium or radionuclides could produce contrast agents for medical imaging. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
- Fu, Yanjun,Laurent, Sophie,Muller, Robert N.
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p. 3966 - 3973
(2007/10/03)
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