- Synthesis of heterobinuclear Cu(Ⅱ)-Ni(Ⅱ) complex: Structure, CT-DNA interaction, hydrolytic function and antibacterial studies
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A new benzyls pendant-armed macrobicyclic heterbinuclear Cu(Ⅱ)-Ni(Ⅱ) complex has been obtained by template-directed synthesis and characterized by elemental analysis, IR spectra, electrospray mass spectra, and single crystal X-ray diffraction. The complex was bridged by two phenolic oxygens and an acetate radical, with the Cu(Ⅱ)-Ni(Ⅱ) distance of 2.9292(8) ?. The hydrolytic function, CT-DNA binding and antibacterial properties were also studied. The initial rate values for the hydrolysis of 4-nitophenylphosphate to 4-nitrophenolate by the Cu(Ⅱ)-Ni(Ⅱ) complex was 1.33 × 10?5 s?1, and 104 times faster than that the spontaneous hydrolysis of the phosphate monoester. The complex shows a better binding property to CT-DNA and the intrinsic binding constant is 1.29 × 105 M?1. The Stern-Volmer constant is 1.25 × 105 M?1. The viscosity increased obviously with the increase of complex concentration, the results showed that the complex bind to DNA through intercalation mode, which was in accordance with the absorption and emission spectral studies. The antibacterial activities against E.coli was also investigated using the Gentamycinas reference system.
- Ding, Peipei,Wang, Yang,Kou, Huizhi,Li, Jianfen,Shi, Baoxian
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- Brightly Luminescent and Kinetically Inert Lanthanide Bioprobes Based on Linear and Preorganized Chelators
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The synthesis, photophysical properties, and kinetic stability of a series of water-soluble, highly emissive Tb(III) and Eu(III) complexes featuring triethylenetetraamine hexaacetic acid (TTHA) and cyclohexyl triethylenetetraamine hexaacetic acid (cyTTHA) chelator scaffolds and carbostyril sensitizers are reported. The unique and modular design of the chelators gives rise to striking quantum yields of emission in aqueous solutions (up to 54%) as well as the characteristic lanthanides' photophysical properties (long excited-state lifetimes, large effective Stokes shifts, and narrow emission peaks). Furthermore, the preorganized chelators (L3, L4, and L6) bind metal within minutes at ambient temperature yet exhibit substantial resistance to transchelation in the presence of a challenge solution (EDTA, 1 mM). Moreover, the Eu(III) complex of L4 remains stably luminescent in HeLa cells over hours, demonstrating the suitability of these compounds for live-cell imaging applications. Representative chelators suitable for derivatization and protein bioconjugation were also prepared that were functionalized with clickable azide and alkyne moieties, biotin, and trimethoprim (TMP). With exceptional long-wavelength brightness, enhanced kinetic inertness, and an adaptable synthetic route, the reported lanthanide complexes are promising probes and labels for time-gated bioanalysis, biosensing, and optical microscopy.
- Mohamadi, Ali,Miller, Lawrence W.
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- A combination risk assessment of paracetamol: Electrochemical oxidation behavior and cytotoxic effect evaluation of paracetamol in the presence of: N 1, N 2-dibenzylethane-1,2-diamine
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The cytotoxic effect of paracetamol in the presence of a diamine derivative was evaluated in liver cells. In this study, hydropyrazinoquinoxalinylidene-acetamide (HPQA), as an agent that is toxic to the liver, was synthesized in an electrochemical cell as a simulated body environment by an electrooxidation reaction. A direct electron transfer (DET) mechanism occurred during the process on the surface of the carbon anode. The electrochemical oxidation of paracetamol was studied using cyclic voltammetry and controlled-potential coulometry (CPC) techniques. The product was characterized by FT-IR, 1H NMR, 13C NMR and ESI-MS2 after purification. The cytotoxicity of the final compound was evaluated using an MTT assay on the CCL-13 liver cell line. The results indicate that the presence of amine derivatives leads to an increase in the toxic effects of paracetamol in the human body. The cell viability at a concentration of 500 μg mL-1 was 78% for paracetamol, whereas the viability of liver cells in the presence of the product was 18% at 168 μg mL-1. A cycloaddition mechanism was suggested according to the overall results that were obtained.
- Dowlati, Bahram,Othman, Mohamed Rozali,Ahmad, Azizan,Safaei, Elham
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- Synthesis and antimycobacterial activity of ferrocenyl ethambutol analogues and ferrocenyl diamines
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A new series of ferrocenyl diamino alcohols and diamines were synthesized and their inhibitory potencies were probed with Mycobacterium tuberculosis. Interestingly, ferrocenyl diamines 6a and b display significant activities against M. tuberculosis H37Rv.
- Razafimahefa, Dorothee,Ralambomanana, Dimby Andrianina,Hammouche, Lies,Pelinski, Lydie,Lauvagie, Sylvia,Bebear, Christiane,Brocard, Jacques,Maugein, Jeanne
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- Platinum Assisted Tandem P–C Bond Cleavage and P–N Bond Formation in Amide Functionalized Bisphosphine o-Ph2PC6H4C(O)N(H)C6H4PPh2-o: Synthesis, Mechanistic, and Catalytic Studies
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The reactions of amide functionalized bisphosphine o-Ph2PC6H4C(O)N(H)C6H4PPh2-o (1) with platinum salts are described. Treatment of 1 with [Pt(COD)Cl2] yielded a chelate complex, [PtCl2{o-Ph2PC6H4C(O)N(H)C6H4PPh2-o}κ2-P,P] (2), which on subsequent treatment with LiHMDS formed a novel 1,2-azaphospholene-phosphine complex [Pt(C6H5)Cl{o-C6H4{C(O)N(o-PPh2(C6H4))P(Ph)}}κ2-P,P] (3) involving a tandem P–C bond cleavage and P–N bond formation. The same complex 3 on passing dry HCl gas afforded the dichloro complex [PtCl2{o-C6H4{C(O)N(o-PPh2(C6H4))P(Ph)}}κ2-P,P] (5). Complex 2 upon refluxing in toluene or treatment of 1 with [Pt(COD)Cl2] in the presence of a base at room temperature resulted in the pincer complex [PtCl{o-Ph2PC6H4C(O)N(C6H4PPh2-o)}κ3-P,N,P] (4). Reaction of 1 with [Pt(COD)ClMe] at room temperature also afforded the pincer complex [PtMe{o-Ph2PC6H4C(O)N(C6H4PPh2-o)}κ3-P,N,P] (6). Mechanistic studies on 1,2-azaphospholene formation showed the reductive elimination of LiCl to form a phosphonium salt that readily adds one of the P–C bonds oxidatively to the in situ generated Pt0 species to form a chelate complex 3. The analogous palladium complex [PdCl2{o-C6H4{C(O)N(o-PPh2(C6H4))P(Ph)}}κ2-P,P] (7) showed excellent catalytic activity toward N-alkylation of amines with alcohols with a very low catalyst loading (0.05 mol %), and the methodology is very efficient toward the gram-scale synthesis of many N-alkylated amines.
- Balakrishna, Maravanji S.,Kunchur, Harish S.
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supporting information
(2022/01/19)
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- Systematic research of H2dedpa derivatives as potent inhibitors of New Delhi Metallo-β-lactamase-1
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New Delhi Metallo-β-lactamase-1 (NDM-1), a Zn (II)-dependent enzyme, can catalyze the hydrolysis of almost all β-lactam antibiotics including carbapenems, resulting in bacterial antibiotic resistance, which threatens public health globally. Based on our finding that H2dedpa is as an efficient NDM-1 inhibitor, a series of H2dedpa derivatives was systematically prepared. These compounds exhibited significant activity against NDM-1, with IC50 values 0.06–0.94 μM. In vitro, compounds 6k and 6n could restore the activity of meropenem against Klebsiella pneumoniae, Escherichia coli and Proteus mirabilis possessing either NDM or IMP. In particular, the activity of meropenem against E. coli producing NDM-4 could be improved up to 5333 times when these two compounds were used. Time–kill cell-based assays showed that 99.9% of P. mirabilis were killed when treated with meropenem in combination with compound 6k or 6n. Furthermore, compounds 6k and 6n were nonhemolytic (HC50 > 1280 μg/mL) and showed low toxicity toward mammalian (HeLa) cells. Mechanistic studies indicated that compounds 6k and 6n inhibit NDM-1 by chelating the Zn2+ ion of the enzyme.
- Bai, Meng-Meng,Cui, De-Yun,Han, Jiang-Xue,Kong, Hong-Tao,Liu, Yi-Shuang,Shen, Bo-Yuan,Wang, Cong-Cong,Xiao, Chun-Ling,Yan, Da-Chao,Yang, Yi,Zhang, En
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- A new macrocyclic heterobinuclear Cu(II)-Zn(II) complex: synthesis, crystal structure, phosphate hydrolysis, and DNA binding studies
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A new macrocyclic heterobinuclear Cu(II)-Zn(II) complex was synthesized and characterized by elemental analysis, FT-IR, ES-MS, and single-crystal X-ray diffraction. Five-coordinate geometry for the new complex is proposed. The copper…zinc distance bridged by two phenolic oxygens and a acetate ligand is 2.9508 ?. The phosphate ester hydrolysis activity and the DNA binding ability of the complex were studied. The results showed that the present complex has an efficient catalytic activity of phosphoester bond cleavage. The catalytic rate constant kcat for the hydrolysis of 4-nitrophenyl phosphate disodium salt hexahydrate (pNPP) by the synthesized complex is 2.69 × 10?4 s?1 and 105 times faster than the spontaneous hydrolysis of the phosphate monoester. The complex shows a good binding ability to calf thymus (CT-DNA) and the corresponding binding constant is 1.9 × 105 M?1. The linear Stern-Volmer quenching constant obtained by the fluorescent spectroscopic is 6.3 × 104 M?1.
- Kou, Huizhi,Wang, Yang,Ding, Peipei,Li, Jianfen,Shi, Baoxian
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p. 1683 - 1696
(2019/05/22)
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- Manganese-Catalyzed Transfer Hydrogenation of Aldimines
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The reduction of imines to amines via transfer hydrogenation was achieved promoted by phosphine-free manganese(I) catalyst. Using isopropanol as reductant, in the presence of tBuOK (4 mol %) and manganese complex [Mn(CO)3Br(κ2N,N-PyCH2NH2)] (2 mol %), a large variety of aldimines (30 examples) were typically reduced in 3 hours at 80 °C with good to excellent yield.
- Wei, Duo,Bruneau-Voisine, Antoine,Dubois, Maxime,Bastin, Stéphanie,Sortais, Jean-Baptiste
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p. 5256 - 5259
(2019/04/17)
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- METAL CHELATORS FOR IMAGING, THERAPEUTICS, AND BIOANALYSIS
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A variety of compounds are provided capable of chelating a metal, in particular a lanthanide such as Eu(III) and Tb(III). Luminescent complexes of the compound and a metal ion are also provided, in particular luminescent metal complexes are provided containing a lanthanide such as Eu(III) or Tb(III) and a compound described herein. In some aspects, the luminescent complexes are capable of exhibiting bright emissions with high quantum yields. Methods of making the compound are provided. Methods of using the compounds and luminescent complexes are also provided, for example for imaging and therapeutic applications.
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Paragraph 0154
(2018/09/26)
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- Design, synthesis and evaluation against Mycobacterium tuberculosis of azole piperazine derivatives as dicyclotyrosine (cYY) mimics
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Three series of azole piperazine derivatives that mimic dicyclotyrosine (cYY), the natural substrate of the essential Mycobacterium tuberculosis cytochrome P450 CYP121A1, were prepared and evaluated for binding affinity and inhibitory activity (MIC) against M. tuberculosis. Series A replaces one phenol group of cYY with a C3-imidazole moiety, series B includes a keto group on the hydrocarbon chain preceding the series A imidazole, whilst series C explores replacing the keto group of the piperidone ring of cYY with a CH2-imidazole or CH2-triazole moiety to enhance binding interaction with the heme of CYP121A1. The series displayed moderate to weak type II binding affinity for CYP121A1, with the exception of series B 10a, which displayed mixed type I binding. Of the three series, series C imidazole derivatives showed the best, although modest, inhibitory activity against M. tuberculosis (17d MIC = 12.5 μg/mL, 17a 50 μg/mL). Crystal structures were determined for CYP121A1 bound to series A compounds 6a and 6b that show the imidazole groups positioned directly above the haem iron with binding between the haem iron and imidazole nitrogen of both compounds at a distance of 2.2 ?. A model generated from a 1.5 ? crystal structure of CYP121A1 in complex with compound 10a showed different binding modes in agreement with the heterogeneous binding observed. Although the crystal structures of 6a and 6b would indicate binding with CYP121A1, the binding assays themselves did not allow confirmation of CYP121A1 as the target.
- El-wahab, Hend A.A. Abd,Accietto, Mauro,Marino, Leonardo B.,McLean, Kirsty J.,Levy, Colin W.,Abdel-Rahman, Hamdy M.,El-Gendy, Mahmoud A.,Munro, Andrew W.,Aboraia, Ahmed S.,Simons, Claire
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p. 161 - 176
(2017/11/29)
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- Manganese catalyzed reductive amination of aldehydes using hydrogen as a reductant
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A one-pot two-step procedure was developed for the alkylation of amines via reductive amination of aldehydes using molecular dihydrogen as a reductant in the presence of a manganese pyridinyl-phosphine complex as a pre-catalyst. After the initial condensation step, the reduction of imines formed in situ is performed under mild conditions (50-100 °C) with 2 mol% of catalyst and 5 mol% of tBuOK under 50 bar of hydrogen. Excellent yields (>90%) were obtained for a large combination of aldehydes and amines (40 examples), including aliphatic aldehydes and amino-alcohols.
- Wei, Duo,Bruneau-Voisine, Antoine,Valyaev, Dmitry A.,Lugan, No?l,Sortais, Jean-Baptiste
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supporting information
p. 4302 - 4305
(2018/05/03)
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- Preparation method of N,N-dibenzyl ethylenediamine diacetate
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The invention discloses a preparation method of N,N-dibenzyl ethylenediamine diacetate. The method comprises the following steps: S1, adding 50 parts by weight of diacetyl dibenzyl ethylenediamine material into a three-necked bottle, and adding 80-120 parts by weight of concentrated hydrochloric acid into the three-necked bottle to obtain 36.0-37.5 parts by weight of a compound B; S2, adding 200 parts by weight of water into the compound B obtained in the step S1 for fully dissolving, and dropwise adding a sodium hydroxide solution to adjust the pH value to 8-9; then, adding toluene for extracting for a plurality of times, and carrying out layered treatment to obtain an organic phase of a mixture of a compound C and the toluene; S3, adding the organic phase of the mixture of the compound Cand toluene into the three-necked bottle and distilling under the reduced pressure until no fraction is obtained, then adding ethyl acetate for dissolving, heating up to 60 DEG C, then dropwise adding 20 parts by weight of glacial acetic acid, and drying to obtain 47.0-49.0 parts by weight of dibenzyl ethylenediamine diacetate finally. The preparation method provided by the invention improves thereaction safety and reduces the reaction cost; furthermore, the yield of the dibenzyl ethylenediamine diacetate is also increased to 93% or above.
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Page/Page column 8-10
(2018/10/19)
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- One-pot synthesis of imidazolinium salts via the ring opening of tetrahydrofuran
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A new one-pot synthesis of C2-hydroxypropyl-substituted imidazolinium salts via the ring opening of tetrahydrofuran (THF) with N,N′-disubstituted diamines has been developed. Preliminary studies of the reaction mechanism suggest the CO2-promoted oxidative ring opening of THF followed by Hg(ii)-mediated oxidation of an imidazolidine intermediate. These novel C2-substituted imidazolinium salts have shown to be active catalysts for the aza-Diels-Alder reactions.
- Huang, Yong-Qing,Zhao, Yue,Wang, Peng,Okamura, Taka-Aki,Laforteza, Brian N.,Lu, Yi,Sun, Wei-Yin,Yu, Jin-Quan
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supporting information
p. 12430 - 12433
(2017/10/06)
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- Efficient route to pre-organized and linear polyaminopolycarboxylates: Cy-TTHA, Cy-DTPA and mono/di- reactive, tert-butyl protected TTHA/Cy-TTHA
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Pre-organized polyaminopolycarboxylate chelators Cy-TTHA and Cy-DTPA were synthesized via modular five-step syntheses from commercially available starting materials in ~62% and 47% overall yields, respectively. Furthermore, strategies are reported for the efficient preparation of mono- and di-reactive, tert-butyl-protected TTHA/Cy-TTHA to selectively functionalize central chelators’ carboxylic acids.
- Mohamadi, Ali,Miller, Lawrence W.
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supporting information
p. 1441 - 1444
(2017/03/23)
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- Synthesis and supramolecular features of hybrid POM/onium solid-state assemblies
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Polyoxomolybdate-based organic-inorganic hybrid architectures were synthesised and characterised by X-ray crystallography. The supramolecular assemblies present rows of metallic clusters H-bonded by ammonium cations, with a 1:2 molybdate/ammonium ratio. The organic moieties of the ammonium cations establish hydrophobic contact among them such as van der Waals, C-Hπ and ππ interactions that stabilise the supramolecular architectures. In particular, for compound 5 the n-alkyl tails pack closely together giving a lipid-like bilayer. In compound 6, the aromatic phenyl rings of the organic cation allow the stabilisation of the supramolecular architecture by C-Hπ and ππ interactions. Regarding the X-ray structure of the compound 11, the tetraanionic octa-molybdate [Mo8O26]4- cluster is surrounded by four ethyl-triphenyl-phosphonium cations. Running along the b-axis open channels are occupied by DMF solvent molecules. Interestingly, a soaking experiment in n-pentane with the corresponding crystals of compound 11 afforded to a crystal structure very different from the native one. Van der Waals, C-Hπ and ππ interactions between large organic moieties are fundamental in the stabilization of hybrid organic-inorganic POM architectures.
- Talotta, Carmen,Rubino, Luca,Gaeta, Carmine,Capitelli, Francesco,Saviano, Michele,Brancatelli, Giovanna,Geremia, Silvano,Vasca, Ermanno,Neri, Placido
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p. 403 - 417
(2016/04/19)
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- Experimental and Theoretical Study of an Intramolecular CF3-Group Shift in the Reactions of α-Bromoenones with 1,2-Diamines
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The reactions of trifluoromethylated 2-bromoenones and N,N′-dialkyl-1,2-diamines have been studied. Depending on the structures of the starting compounds, the formation of 2-trifluoroacetylpiperazine or 3-trifluoromethylpiperazine-2-ones was observed. The mechanism of the reaction is discussed in terms of multistep processes involving sequential substitution of bromine in the starting α-bromoenones and intramolecular cyclization of the captodative aminoenones as key intermediates to form the target heterocycles. The results of theoretical calculations are in perfect agreement with the experimental data. The unique role of the trifluoromethyl group in this reaction is demonstrated.
- Muzalevskiy, Vasily M.,Ustynyuk, Yury A.,Gloriozov, Igor P.,Chertkov, Vyacheslav A.,Rulev, Alexander Yu.,Kondrashov, Evgeniy V.,Ushakov, Igor A.,Romanov, Alexey R.,Nenajdenko, Valentine G.
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p. 16982 - 16989
(2015/11/16)
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- Comparative study of ring-opening polymerization of L-lactide and ε-caprolactone using zirconium hexadentate bis(aminophenolate) complexes as catalysts
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A series of zirconium bis(aminophenolate) complexes as catalysts for the ring opening polymerization of l-lactide (LA) and ε-caprolactone (CL) were investigated. Ligands bearing various chelating groups have a profound influence on the catalysis results. Among them, the thiophen-2-yl methyl group showed the greatest activity while the pyridine-2-yl methyl group showed the worst performance with regard to the rate of CL polymerization. However, the trend was reversed for the rate of LA polymerization. The kinetic results indicated a first-order dependency on [CL] and [LA]. However, the order of the catalyst concentration was different. Polymerization proceeded with second-order dependence on [LOMeZr(OBn)2] for CL but with first-order dependence on [LOMeZr(OBn)2] for LA.
- Ou, Hsiu-Wei,Chiang, Michael Y.,Vandavasi, Jaya Kishore,Lu, Wei-Yi,Chen, Yen-Jen,Tseng, Hsi-Ching,Lai, Yi-Chun,Chen, Hsuan-Ying
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p. 477 - 484
(2015/02/19)
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- N-heterocyclic carbene-catalyzed α-alkylation of ketones with primary alcohols
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Several N-heterocyclic carbene precursors are synthesized and used in the α-alkylations of ketones with primary alcohols. With the assistance of a base, these N-heterocyclic carbenes can catalyze the reaction smoothly to furnish dialkylated ketones in good-to-excellent yields.
- Zhu, Yanfang,Cai, Chun,Lu, Guoping
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p. 1666 - 1671
(2015/01/09)
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- Determination of cysteine and glutathione based on the inhibition of the dinuclear Cu(II)-catalyzed luminol-H2O2 chemiluminescence reaction
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The catalyzed luminol chemiluminescent reaction has received a great amount of attention because of its high sensitivity and low background signal which make the reaction an attractive analytical chemistry tool. The present study, introduces the beneficial catalytic effects of dinuclear Cu(II) complex [Cu 2L2(TAE)]X2, where TAE = tetraacetylethane; L = N,N'-dibenzylethylenediamine and X = ClO4 on the luminol chemiluminescent reaction as a novel probe for the determination of glutathione (GSH) and L-cysteine (CySH) in human serum and urine. The [Cu2L 2(TAE)]X2 has exhibited highly efficient catalytic activity of luminol CL as an artificial peroxidase model at pH as low as 7.5 in water in the presence of H2O2×GSH and CySH can induce a sharp decrease in CL intensity from the [Cu2L 2(TAE)]X2-catalyzed luminol system. Under the selected experimental conditions, a linear relationship was obtained between the CL intensity and the concentrations of GSH and CySH in the range of 1.0 × 10-7-1.0 × 10-4 M, with detection limits (S/N = 3) of 2.7 × 10-8 and 6.8 × 10-8 M and RSD 4.2% (n = 7) for GSH and CySH, respectively.
- Chaichi, Mohammad Javad,Ehsani, Mahjoobeh,Khajvand, Tahereh,Golchoubian, Hamid,Rezaee, Ehsan
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p. 405 - 410
(2014/01/06)
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- Synthesis and evaluation of hexahydropyrimidines and diamines as novel hepatitis C virus inhibitors
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In order to identify novel anti-hepatitis C virus (HCV) agents we devised cell-based strategies and screened phenotypically small molecule chemical libraries with infectious HCV particles, and identified a hit compound (1) containing a hexahydropyrimidine (HHP) core. During our cell-based SAR study, we observed a conversion of HHP 1 into a linear diamine (6), which is the active component in inhibiting HCV and exhibited comparable antiviral activity to the cyclic HHP 1. In addition, we engaged into the biological characterization of HHP and demonstrated that HHP does not interfere with HCV RNA replication, but with entry and release of viral particles. Here we report the results of the preliminary SAR and mechanism of action studies with HHP.
- Hwang, Jong Yeon,Kim, Hee-Young,Jo, Suyeon,Park, Eunjung,Choi, Jihyun,Kong, Sunju,Park, Dong-Sik,Heo, Ja Myung,Lee, Jong Seok,Ko, Yoonae,Choi, Inhee,Cechetto, Jonathan,Kim, Jaeseung,Lee, Jinhwa,No, Zaesung,Windisch, Marc Peter
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p. 315 - 325
(2013/11/19)
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- An efficient electrochemical method for the synthesis of quinoxaline-dione derivatives from oxidation of catechols in the presence of N1, N 2-dibenzylethane-1,2-diamine
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A series of 1,4-dibenzyl-1,2,3,4-tetrahydroquinoxaline-6,7-dione derivatives (6a-6c) were electrosynthesized. In the present work, electrochemical oxidation of catechols 1a-1d in the presence of the N 1,N2-dibenzylethane-1,2-diamine (3) as a nucleophile, has been studied in aqueous solutions using cyclic voltammetry and controlled-potential coulometry (CPC) methods. Various parameters such as the applied potential, pH of the electrolytic solution, cell configuration and also purification techniques, were carried out to optimize the yields of corresponding products. New quinoxaline-6,7-dione derivatives were synthesized in excellent yield using an electrochemical procedure coupled with a Schiff base as a facile, efficient and practical method.
- Dowlati, Bahram,Nematollahi, Davood,Othman, Mohamed Rozali
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- H4octapa: An acyclic chelator for 111In radiopharmaceuticals
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This preliminary investigation of the octadentate acyclic chelator H 4octapa (N4O4) with 111In/ 115In3+ has demonstrated it to be an improvement on the shortcomings of the current industry "gold standards" DOTA (N 4O4) and DTPA (N3O5). The ability of H4octapa to radiolabel quantitatively 111InCl3 at ambient temperature in 10 min with specific activities as high as 2.3 mCi/nmol (97.5% radiochemical yield) is presented. In vitro mouse serum stability assays have demonstrated the 111In complex of H 4octapa to have improved stability when compared to DOTA and DTPA over 24 h. Mouse biodistribution studies have shown that the radiometal complex [111In(octapa)]- has exceptionally high in vivo stability over 24 h with improved clearance and stability compared to [ 111In(DOTA)]-, demonstrated by lower uptake in the kidneys, liver, and spleen at 24 h. 1H/13C NMR studies of the [In(octapa)]- complex revealed a 7-coordinate solution structure, which forms a single isomer and exhibits no observable fluxional behavior at ambient temperature, an improvement to the multiple isomers formed by [In(DTPA)]2- and [In(DOTA)]- under the same conditions. Potentiometric titrations have determined the thermodynamic formation constant of the [In(octapa)]- complex to be log KML = 26.8(1). Through the same set of analyses, the [111/115In(decapa)] 2- complex was found to have nonoptimal stability, with H 5decapa (N5O5) being more suitable for larger metal ions due to its higher potential denticity (e.g., lanthanides and actinides). Our initial investigations have revealed the acyclic chelator H 4octapa to be a valuable alternative to the macrocycle DOTA for use with 111In, and a significant improvement to the acyclic chelator DTPA.
- Price, Eric W.,Cawthray, Jacqueline F.,Bailey, Gwendolyn A.,Ferreira, Cara L.,Boros, Eszter,Adam, Michael J.,Orvig, Chris
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experimental part
p. 8670 - 8683
(2012/06/29)
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- Design, synthesis and biological activity of peptidomimetic analogs of insect allatostatins
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Allatostatins (ASTs) comprise a family of insect neuropeptides isolated from cockroaches and found to inhibit the production of juvenile hormone (JH) by the corpora allata (CA). For this reason, the ASTs can be regarded as possible IGR candidates for pest control. Six peptidomimetic analogs according to the C-terminal pentapeptide of ASTs were prepared by solid-phase organic synthetic methods in an attempt to obtain new simple substitution agents. Assays of inhibition of JH biosynthesis in vitro by corpora allata from the cockroach Diploptera punctata showed that the activity of analog I (IC50: 0.09 μM) was more active than that of the C-terminal pentapeptide (Tyr-Xaa-Phe-Gly-Leu-NH2, IC50: 0.13 μM) it mimicked and the activity of the analog II (IC50: 0.13 μM) proved roughly equivalent to the C-terminal pentapeptide. The results indicate that a new simple mimicry for Tyr-Xaa-Phe-Gly has been discovered; analog I may be a novel compound candidate for potential IGRs. This study will be useful for the design of new AST analogs for insect management.
- Xie, Yong,Kai, Zhen Peng,Tobe, Stephen S.,Deng, Xi Le,Ling, Yun,Wu, Xiao Qin,Huang, Juan,Zhang, Li,Yang, Xin Ling
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experimental part
p. 581 - 586
(2012/01/13)
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- Reversible aminal formation: Controlling the evaporation of bioactive volatiles by dynamic combinatorial/covalent chemistry
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Dynamic mixtures generated by reversible aminal formation efficiently prolong the duration of evaporation of bioactive volatile aldehydes. Secondary diamines used for the generation of dynamic mixtures are obtained by treatment of primary diamines with carbonyl compounds and reduction of the diimines with NaBH4. The reversibilities of the reactions were demonstrated by NMR measurements in buffered aqueous solutions. Kinetic rate constants and equilibrium constants for the formation and hydrolysis of aminals were determined. The performance of dynamic mixtures as delivery systems for perfumery ingredients was tested after deposition onto cotton, and the long-lastingness of fragrance evaporation was investigated by dynamic headspace analysis against a reference sample. The simplicity of the concept together with its excellent performance makes this delivery system highly interesting for applied perfumery. Reversible aminal formation might also be successfully applicable to dynamic combinatorial/covalent chemistry for screening of pharmaceutically or catalytically active ligands and receptors. The evaporation of bioactive volatiles that are emitted from flowers to attract insects and that are used as fragrances in our everyday life is limited in time. Dynamic mixtures obtained by reversible aminal formation of suitably designed diamines with volatile aldehydes prolong the perception of these compounds in functional perfumery.
- Buchsnee Levrand, Barbara,Godin, Guillaume,Trachsel, Alain,De Saint Laumer, Jean-Yves,Lehn, Jean-Marie,Herrmann, Andreas
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experimental part
p. 681 - 695
(2011/03/22)
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- Effects of tethered ligands and of metal oxidation state on the interactions of cobalt complexes with the 26S proteasome
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In this paper we report on the synthesis and characterization of three cobalt complexes described as [CoII(L1)2] (1), [CoII(L2)] (2), and [CoIII(L1) 2]ClO4 (3). These complexes contain the deprotonated forms of the [NN′O] tridentate ligand HL1 and its newly synthesized [N2N′2O2] hexadentate counterpart H 2L2, namely, 2,4-diiodo-6-((pyridine-2-ylmethylamino) methyl)phenol and 6,6′-((ethane-1,2-diylbis((pyridin-2-ylmethyl) azanediyl))bis(methylene))bis(2,4-diiodophenol). Characterizations for 1-3 include electrospray ionization (ESI) spectrometry, infrared, and UV-visible spectroscopies, and elemental analyses. A detailed 1H-NMR study was conducted for 3 and X-ray structural data was obtained for 2. The viability of this series as potential agents for proteasome inhibition and cell apoptotic induction involving PC-3 cancer cells is presented comparing the behavior of the untethered [NN′O]2 six-coordinate 1 and 3 and the tethered counterpart 2 with a 1:1 metal-to-ligand ratio. It is observed that the tethering in 2 decreases inhibition activity. When 1 and 3 are compared, the most inert, but redox-active, cobalt(III) species shows the highest chymotrypsin-like activity inhibition on purified proteasome and PC-3 cancer cells. A hypothesis based on the role of oxidation states for proteasome inhibition is offered.
- Tomco, Dajena,Schmitt, Sara,Ksebati, Bashar,Heeg, Mary Jane,Dou, Q. Ping,Verani, Cláudio N.
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experimental part
p. 1759 - 1766
(2012/04/17)
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- Fluorescent sensors based on 2-substituted imidazolidines
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A number of 2-substituted imidazolidines were synthesized from N,N'-dibenzylethane-1,2-diamine derivatives and benzaldehyde, naphthalene-1-carbaldehyde, 2-hydroxynaphthalene-1-carbaldehyde, and anthra-cene-9-carbaldehyde. Examination of the obtained compounds by spectral methods revealed selective sensor properties of 2-(anthracen-9-yl)-1,3- dibenzylimidazolidine and 2-(anthracen-9-yl)-1,3-bis(2-hydroxybenzyl)- imidazolidine for Hg2+ and Cu2+ ions. Pleiades Publishing, Ltd., 2010.
- Tolpygin,Shepelenko,Revinskii,Tsukanov,Dubonosov,Bren,Minkin
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scheme or table
p. 1181 - 1184
(2011/01/04)
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- Copper-catalyzed amidation of aryl iodides in the presence of various chelating ligands
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N,N′-Dibenzylethylenediamine is presented as a new, efficient, and versatile bidentate ligand suitable for the copper catalyzed formation of the C-N bond. This bidentate ligand has been demonstrated to facilitate the copper catalyzed cross-coupling reactions of aryl iodides with amides to afford the desired products in good to excellent yields.
- Hosseinzadeh, Rahman,Golchoubian, Hamid,Masoudi, Mahtab
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body text
p. 649 - 653
(2009/05/11)
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- Synthesis and antitubercular activity of ferrocenyl diaminoalcohols and diamines
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A total of 21 ferrocenyl and benzyl diaminoalcohols and diamines were synthesized and evaluated against Mycobacterium tuberculosis H37Rv. Interestingly, ferrocenyl diamines exhibit better activities than ferrocenyl diaminoalcohols.
- Andrianina Ralambomanana, Dimby,Razafimahefa-Ramilison, Dorothee,Rakotohova, Andry Clement,Maugein, Jeanne,Pelinski, Lydie
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experimental part
p. 9546 - 9553
(2009/04/06)
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- Synthesis of [N, N'-Bis(5-benzoyl-4-phenylthiazol-2-yl)-N, N-bisbenzyl]ethane-1, 2-diamines
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Synthesis of [N,N'-bis(N-benzoylthiocarbamoyl)-N,N'-bis(benzyl)]ethane-1,2- diamines 4a-h, their cyclization to [N,N'-bis(5-benzoyl-4-phenylthiazol-2-yl)-N, N'-bisbenzyl]ethane-1,2-diamines 5a-h by reaction with phenacyl bromide and the results of antibacterial activity assay of 4a-h and 5a-h are reported.
- Asha,Manju,Pradeep,George,Rajasekharan
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scheme or table
p. 1726 - 1730
(2009/05/30)
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- CONTROLLED RELEASE OF ACTIVE ALDEHYDES AND KETONES FROM EQUILIBRATED DYNAMIC MIXTURES
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The present invention concerns a dynamic mixture obtained by combining, in the presence of water, at least one diamine derivative, comprising at least one benzylamine moiety, with at least one active aldehyde or ketone. The invention's mixture is capable of releasing in a controlled and prolonged manner said active compound, in particular perfuming ingredients, in the surrounding environment.
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Page/Page column 31-33
(2008/12/07)
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- Electroorganic synthesis of benzathine
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Benzathine is prepared in good yields from cyanobenzene by a combination of electrochemical hydrogenation and Kolbe electrolysis using nickel and platinum electrodes in the presence of methanolic sodium methoxide in an undivided cell.
- Lateef, Shaik,Reddy Krishna Mohan, Srinivasulu,Reddy Jayarama Reddy, Srinivasulu
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- METHOD FOR PRODUCING N-MONOALKYL-SUBSTITUTED ALKYLENE AMINE
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PROBLEM TO BE SOLVED: To provide a method for producing an N-monoalkyl-substituted alkylene amine especially useful for uses such as medicine intermediates, agrochemical intermediates, urethane resin-foaming catalysts, surfactants and the like among alkyl-substituted alkylene amine compounds from an alcohol and an alkylene amine as raw materials. SOLUTION: This method for producing the N-monoalkyl-substituted alkylene amine is characterized by reacting the alkylene amine with a ≥2C alkyl alcohol in the presence of a copper-containing oxide catalyst system. The N-monoalkyl-substituted alkylenamine is produced in high conversion and in N-monoalkylation selectivity.
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Page/Page column 7
(2010/02/11)
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- Synthesis, structural and solvent influence studies on solvatochromic of acetylacetonatocopper(II) with N,N′-dibenzylic or thiophene derivatives of ethylenediamine complexes
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Five mixed-chelate copper(II) complexes with the general formula [Cu(acac)(diam)]ClO4, where acac is acetylacetonate ion and diam is N,N′-dibenzylic or thiophene derivatives of ethylenediamine were prepared and characterized by elemental analysis, spectroscopic and conductance measurements. The X-ray crystal analysis of these complexes demonstrated that ClO4- ions are bound weakly above and below of the chelate plane. In solution, the perchlorate ions are driven out by solvent molecules leading to their solvatochromism.
- Asadi, Hamid,Golchoubia, Hamid,Welter, Richard
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- Novel cationic amphiphiles
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A cationic amphiphile for facilitating transport of a biologically active molecule into a cell has the structure A-F-D, in which A is a lipid anchor, D is a head group, and F is a spacer group having the structure described herein. A method for facilitating transport of a biologically active molecule into a cell comprises preparing a lipid mixture comprising a cationic amphiphile having structure A-F-D, preparing a lipoplex by contacting the lipid mixture with a biologically active molecule; and contacting the lipoplex with a cell, thereby facilitating transport of the biologically active molecule into the cell.
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Page/Page column 42, 15
(2010/02/06)
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- A convenient "one-pot" reaction for selective monoalkylation of N,N′-disubstituted ethylenediamines
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A study on the scope of the method to obtain N,N,N′-trisubstituted ethylenediamines III by monoalkylation of N,N′-disubstituted ethylenediamines I through a "one-pot" reaction is presented. It involves condensation of compounds I with aldehydes followed by reduction of the formed imidazolidines II without previous isolation.
- Salerno, Alejandra,Figueroa, Maria Amalia,Perillo, Isabel A.
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p. 3193 - 3204
(2007/10/03)
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- Synthesis of novel tetrahydroimidazole derivatives and studies for their biological properties
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Ethylenediamine was reacted with suitable aromatic aldehydes in order to prepare their respective diSchiff bases. These compounds were then reduced to give the corresponding tetrahydrodiSchiff bases, which were low melting in nature. Finally, these derivatives were condensed with different aromatic aldehydes to give the desired tetrahydroimidazoles. The structures of all these compounds were established on the basis of spectral data. These novel tetrahydroimidazoles showed promising anti-inflammatory and analgesic activity. The compounds were also screened for their anti-bacterial property against Staphylococcus aureus and Escherichia coli.
- Sharma, Vibha,Khan
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p. 651 - 658
(2007/10/03)
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- Synthesis of a new type of N2S2 tetradentate ligand
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Synthesis of a new type of N2S2 tetradentate ligand 3 possessing the bis-(hydrazonothioamide) structure based on condensation of the dihydrazines 8 with an α-ketoester is described.
- Charrier, Jean-Damien,Reliquet, Alain,Meslin, Jean-Claude
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p. 8645 - 8646
(2007/10/03)
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- O2 activation and aromatic hydroxylation performed by diiron complexes
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Chemical models of active sites of diiron oxo proteins have been synthesized. The polydendate ligands are EDTA derivatives which provide a balanced supply of nitrogen atoms and carboxylate groups together with an oxidizable phenyl moiety, thus mimicking both the iron coordination in methane monooxygenase and a nearby substrate site. All the diferric complexes have been characterized in solution by ESI-MS, optical absorption, and in some cases by 1H NMR. In the case of the ligand L1 [L1 = (N,N'-bis(3,4,5- trimethoxybenzyl)ethylenediamine N,N'-diacetic acid)], the X-ray structure of the corresponding iron complex has been determined, revealing an original tetranuclear unit, Fe4O2(L1)4·10H2O, issued from the dimerization of two [Fe2O(L1)2] units linked by carboxylate bridges. In a solution containing water or acetate, the tetranuclear complex decomposed into dinuclear complexes, which proved to be able to react with hydrogen peroxide or dioxygen in the presence of ascorbate. The final product was a mononuclear complex identified as [Fe(III)L'1(H2O)] with L'1 resulting from the quantitative hydroxylation of L1. The complex and the oxidized ligand were characterized by EPR, NMR, and UV-vis spectroscopies and by mass spectrometry. Labeling experiments showed that with both H2O2 or O2 and ascorbate, the incorporated oxygen came from the oxidant exclusively. This reaction mimicks the transformation of a tyrosine residue, brought into proximity of the active center of Ribonucleotide reductase of Escherichia coli by site-directed mutagenesis, into 3,4-dihydroxyphenylalanine.
- Ménage, Stéphane,Galey, Jean-Baptiste,Dumats, Jacqueline,Hussler, Georges,Seité, Michel,Luneau, Isabelle Gautier,Chottard, Geneviève,Fontecave, Marc
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p. 13370 - 13382
(2007/10/03)
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- Method and apparatus for sunless tanning
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Apparatus for simulating skin tanning comprises a receptacle containing a fluid comprising dihydroxyacetone, a receptacle containing a fluid comprising a secondary polyamine, and dispensing means for simultaneously or sequentially providing desired amounts of dihydroxyacetone and polyamine.
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- Synthesis of N,N'-Dibenzylethylenediamine via Palladium-Carbon-catalysed Reductive Alkylation
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Reductive alkylation of ethylenediamine with benzaldehyde and hydrogen in the presence of Pd-C has been investigated in order to optimize the synthesis of N,N'-dibenzylethylenediamine; the efficiency of the procedure has been improved by minimizing undesired competing reactions of cyclization and hydrogenolysis.
- Pallavicini, Marco,Valoti, Ermanno,Piccolo, Oreste
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p. 472 - 473
(2007/10/03)
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- Synthesis of chiral and C2-symmetric iron(II) and cobalt(II) complexes bearing a new tetradentate amine ligand system
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A synthesis for the new tetrapodal ligands -1,2-ethylene diamine (L1) (3a) and -1,2-ethylene diamine (L2) (3b) and for the related octahedral complexes (L1,2)FeCl2 (6a and 6b) and (L1,2)CoCl2 (7a and 7b) is given.The solid state structures of 3b and 6a have been determined.Three different modes are possible for a tetradentane coordination of L1,2 to FeCl2 or CoCl2.In 6a the ligand adopts a single chiral geometry around the Cl-Fe-Cl plane.Keywords: Iron; Cobalt; Tetradentane amine ligand; Solid state structures; Chirality
- Rieger, Bernhard,Abu-Surrah, Adnan S.,Fawzi, Riad,Steiman, Manfred
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- Homochiral lithium amides: Enantioselective deprotonation of cyclohexene oxide
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Reaction of cyclohexene oxide with chiral lithium amides has been studied and (S)-2-cyclohexen-1-ol was prepared in 20-82% ee. The optical purity was determined by proton NMR measurement of α-methoxy-α- (trifluoromethyl)phenylacetic acid (MTPA) derivative of the corresponding alcohol.
- Bhuniya,Singh
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p. 375 - 385
(2007/10/02)
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- Stereochemistry of N,N'-Bis--ethylenediamine
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N,N'-Bis--ethylene diamine (5), synthesized from racemic 1,2-anhydro-3-O-(o-ethoxyphenyl)-glycerol (1) and ethylene diamine (2) or N,N'-dibenzyl ethylene diamine (3) crystallized in two fractions with different melting points.Both of these analytically pure products gave identical two spot tl-chromatograms on achiral phases.Attempts were made to resolve the mixtures which proved to consist of configurative but not constitutive isomers.Optically pure products were synthesized from chiral precursors.
- Kristen, H.,Wrubel, F.,Widuwild, H.,Luecke, L.
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p. 545 - 554
(2007/10/02)
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- Synthesis of 1,2-Diazetidinones (Aza-β-lactams) by Photochemical Ring Contraction
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Irradiation of 4-diazopyrazolidine-3,5-diones (11) in the presence of alcohols, diethylamine, or water gives 1,2-diazetidinones (12) formed by photochemical Wolff rearrangement with ring contraction followed by reaction of the resulting ketene with the nucleophile.In the case of the bicyclic diazo compound (11d) a fragmentation reaction competes with ring contraction.The aza-β-lactams (12) show the expected high frequency carbonyl stretch in their i.r. spectra.The acid (12e) readily decarboxylates to give the 4-unsubstituted 1,2-dibenzyldiazetidinone (28), the four-membered ring of which is cleaved by alkaline hydrolysis, lithium aluminium hydride or diborane to give (29), (30), and (31), respectively (Scheme 9).Attempts to modify the carboxy substituent of (12e) into an acylamino group were unsuccessful.
- Lawton, Geoffrey,Moody, Christopher J.,Pearson, Christopher J.
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p. 877 - 884
(2007/10/02)
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- Synthesis of 1,3-Disubstituted Diazolidines
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Symmetrical and unsymmetrical 1,3-diaminoethanes 1 are obtained by the reduction of N,N'-disubstituted oxamides 4 with lithium aluminum hydride.The oxamides 4 are readily produced by treatment of diethyl oxalate with primary amines.The 1,3-diaminoethanes 1 lead to 1,3-diazolidines 2 on treatment with formaldehyde.
- Lambert, Joseph B.,Huseland, Dave E.,Wang, Gen-tai
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p. 657 - 658
(2007/10/02)
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- Reduction of Imines Using NADH Models
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Reduction of substituted N-arylideneanilines (3) and NN'-bisarylidene-ethylenediamines (10) in glacial acetic acid takes place smoothly with 3,5-bis(eyhoxycarbonyl)-2,6-dimethyl-1,4-dihydropyridine (Hantzsch ester) (2) at room temperature in the dark.One-pot reductive amination of aromatic aldehydes in glacial acetic acid using (2) was equally efficient.Enamines (6)-(8) underwent reduction on protonation with trifluoroacetic acid in dichloromethane, but not in acetic acid.These reductions are analogous to NADH-mediated biochemical reductive aminations of carbonyl compounds.Imines (3) are also reduced to the corresponding amines (4) when irradiated with Pyrex-filtered light in the presence of (2) in benzene under nitrogen.This photoreduction also proceeds in the solid state and a two-phase system was successfully tested for recycling an NADH model for photoreduction of (3) using sunlight.
- Singh, Serjinder,Sharma, Vijay K.,Gill, Sarbjeet,Sahota, Ravjit Inder K.
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p. 437 - 440
(2007/10/02)
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- Synthesis of Aza-β-lactams by Photochemical Ring Contraction
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Photochemical decomposition of 4-diazopyrazolidine-3,5-diones (3) in the presence of nucleophiles, XH, leads to the aza-β-lactams (4); decarboxylation of (4e) gives the aza-β-lactam (7), which undergoes reductive ring cleavage to (8), and ring expansion to (9) on treatment with base.
- Lawton, Geoffrey,Moody, Christopher J.,Pearson, Christopher J.
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p. 754 - 756
(2007/10/02)
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- Electrochemical Reduction of Di-Schiff Bases. Synthesis of Piperazines, Indoloindoles, Diazepines, and Diazocines
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The electrochemical reduction of a series of di-Schiff bases had led to examples where products representing reduction, cyclization, and transannular cyclization are found.Useful synthetic pathways for piperazines, indoloindoles, diazepines, and diazocines are described.
- Koch, Russell W.,Dessy, Raymond E.
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p. 4452 - 4459
(2007/10/02)
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