Lutetium-177 and iodine-131 loaded chelating polymer microparticles intended for radioembolization of liver malignancies

We describe the synthesis, characterization and radiochemical studies on macroporous chelating polymer beads as carriers of beta-emitters lutetium-177 and iodine-131 intended for radioembolization of liver tumors. The starting poly(glycidyl methacrylate-co-ethylene dimethacrylate) (bead size 20–40 μ) was reacted with ammonia or methylamine to introduce primary and secondary amino groups, respectively. The primary amino groups containing polymer was used for the attachment of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) moieties, while quinoline-8-ol or 8-hydroxyquinoline-5-sulfonic acid moieties, respectively, were introduced onto the secondary amino groups containing polymer. All the polymers were labeled quantitatively by lutetium-177 in ammonium acetate buffer, DOTA containing beads however required heating to 80 °C while the quinoline-8-ol or 8-hydroxyquinoline-5-sulfonic acid moieties containing polymers were quantitatively radiolabeled within 1 h at room temperature. The quinoline-8-ol groups containing polymer was radioiodinated in 95% yield by a chloramine method. Both lutetium-177 and iodine-131 radiolabels were stable in an in vitro study in rat blood plasma. Quinoline-8-ol or 8-hydroxyquinoline-5-sulfonic acid moieties are thus more suitable for the radiolabeling of macroporous beads with lutetium-177 for radioembolization purposes than well-established DOTA moieties and in addition, quinoline-8-ol also allows radiolabeling with iodine-131.     

Water soluble Ir(III) complexes from sulfonate-modified cyclometalating ligand

Five cyclometalated Ir(III) complexes are synthesized from a sulfonate-modified bis-benzimidazole-type organic ligand (3,3′-(2,2′-(1,3-phenylene)bis(1H–benzo [d]imidazole-2,1-diyl))dipropane-1-sulfonic acid, MBS) with different ancillary ligands, and can be classified into two categories. Namely, complexes 1 and 2 (MBS-Ir-ppy and MBS-Ir-Fppy), which are electroneutral, and complexes 3–5 (MBS-Ir-bpy, MBS-Ir-Mebpy, and MBS-Ir-bpyCOOEt), which are cationic and soluble in water. These Ir(III) complexes show tunable luminescence from cyan to orangish red color in solution and yellowish red to pure red color in solid state, with moderately long lifetime (56–528 ns) and high quantum yield (35–71%).     

Highly selective colorimetric detection of cysteine and homocysteine in water through a direct displacement approach

The complex CuQ₂ (HQ = 8-hydroxy-7-(4-tolyldiazenyl)quinoline-5-sulfonic acid) has been synthesized and used as a colorimetric probe for the specific detection of cysteine and homocysteine in water through a displacement reaction. The detection can be performed either by the spectroscopy from the increased UV–vis absorbance at 498 nm or by the change of color from yellow to red upon addition of cysteine or homocysteine to the solution of the complex. The experimental results show no interference by other amino acids to the detection of cysteine and homocysteine.     

不对称金属络合染料C.I.酸性棕355的合成

6-硝基-1,2-重氮氧基萘-4-磺酸与乙萘酚偶合,得偶合物I;2-氨基-4-硝基苯酚-6-磺酸重氮化与1-苯基-3-甲基-5-吡唑啉酮偶合,得到偶合物II;偶合物I与铬明矾在水杨酸存在下络合,得到单络合物III;络合物III再与偶合物II在碱性条件下络合,得到不对称金属络合染料C.I.酸性棕355。     

Synthesis of Ion Imprinted Polymers by Copolymerization of Zn(II) and Al(III)8-hydroxy Quinolone Complexes with Divinylbenzene and Methacryclic Acid

In this research work, Zinc(II) and Aluminum(III)-IIP's were synthesized by optimizing the amount of methacrylic acid as monomer, divinylbenzene as cross-linker. The IIP's were functionalized with 8-hydroxy quinolone complexes of the two metal ions under thermal conditions by copolymerization with monomer and cross-linker. The IIP's and Non-IIP's were characterized using FT-IR, TGA, and SEM analysis. A quite remarkable difference in the size was observed of the polymers (Zn(II) 1.0 µm and Al(III) 0.1 µm). A stronger affinity was observed with IIP in comparison with Non-IIP at pH 3.1 and 4.5 for Zn(II) and Al(III) ions on their respective polymers.     

Heterocyclic compounds. X. Synthesis of some oxazoloquinoline derivatives

A series of 2-aryl-oxazolo[4,5-h]quinoline-5-arylidines (II) was prepared through the reaction of 5,7-diamino-8-hydroxy quinoline with aromatic aldehydes in the presence of a basic catalyst such as piperidine. The reaction also proceeded with aliphatic aldehydes but under slightly different conditions. On the other hand, 2-stilbyl-5-diacetyl-amino-oxazolo[4,5-h]quinolines (V) were prepared by interaction of 2-methyl-5-diacetylamino-oxazolo[4,5-h]quinoline (IV) with aromatic aldehydes. Such compounds possessed structural relationships to some known antibiotics and their chemical constitution was confirmed by spectral studies.     

有机化学综合性实验研究

设计了-个综合性有机化学实验。在该实验中通过重氮化和偶合反应合成无机离子显色剂7-（4-安替吡啉偶氮）-8-羟基喹啉-5-磺酸,阐述了该显色剂在测定金属离子铜含量时的研究方法及内容。新实验在培养学生有机化学实验基本技能的基础上,着重培养了学生的研究探索能力和创新能力。     

Synthesis of polymer-supported metal-ion complexes and evaluation of their catalytic activities

Polymer-supported transition-metal-ion complexes of the N,N′-bis(o-hydroxy acetophenone) propylenediamine (HPPn) Schiff base were prepared by the complexation of iron(III), cobalt(II), and nickel(II) ions on a polymer-anchored N,N′-bis(5-amino-o-hydroxy acetophenone) propylenediamine Schiff base. The complexation of iron(III), cobalt(II), and nickel(II) ions on the polymer-anchored HPPn Schiff base was 83.44, 82.92, and 89.58 wt%, respectively, whereas the unsupported HPPn Schiff base showed 82.29, 81.18, and 87.29 wt % complexation of these metal ions. The iron(III) ion complexes of the HPPn Schiff base showed octahedral geometry, whereas the cobalt(II) and nickel(II) ion complexes were square planar in shape, as suggested by spectral and magnetic measurements. The thermal stability of the HPPn Schiff base increased with the complexation of metal ions, as evidenced by thermogravimetric analysis. The HPPn Schiff base showed a weight loss of 51.0 wt % at 500°C, but its iron(III), cobalt(II), and nickel(II) ion complexes showed weight losses of 27.0, 35.0, and 44.7 wt % at the same temperature. The catalytic activity of the unsupported and supported metal-ion complexes was analyzed by the study of the oxidation of phenol and epoxidation of cyclohexene in the presence of hydrogen peroxide. The supported HPPn Schiff base complexes of iron(III) ions showed a 73.0 wt % maximum conversion of phenol and 90.6 wt % epoxidation of cyclohexene, but unsupported complexes of iron(III) ions showed 63.8 wt % conversion of phenol and 83.2 wt % epoxidation of cyclohexene. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 93.1 wt % and 98.1 wt % with the supported HPPn Schiff base complexes of iron(III) ions, but it was low with the supported Schiff base complexes of cobalt(II) and nickel(II) ions. The selectivity for CTL and ECH varied with the molar ratio of the metal ions but remained unaffected by the molar ratio of hydrogen peroxide to the substrate. The energy of activation for the epoxidation of cyclohexene and oxidation of phenol with the polymer-supported Schiff base complexes of iron(III) ions was 10.0 and 12.7 kJ/mol, respectively, but it was found to be higher with the supported HPPn Schiff base complexes of cobalt(II) and nickel(II) ions and with the unsupported HPPn Schiff base complexes of iron(III), cobalt(II), and nickel(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

一种新偶氮胂酸型试剂及荧光法测定铍的研究

新试剂７－（２＇－胂酸基－５＇－羧基）苯偶氮－８－羟基喹啉－５－磺酸的基本性能。详细研究了此试剂荧光法测定铍的条件，并用于水及铜中铍的测定。     

以弱碱性树脂去除废水中5-氨基-2-氯甲苯-4-磺酸和盐酸：平衡及动力学

考察了废水中5-氨基-2-氯甲苯-4-磺酸（CLT）和盐酸（HCl）在弱碱性离子交换树脂D301R上的吸附。研究了吸附平衡及动力学行为。结果表明两种酸在D301R树脂上的吸附遵循Langmuir吸附平衡模型;CLT吸附动力学过程与二级反应模型相吻合;HCl与一级反应模型吻合得较好;吸附过程为孔扩散控制。CLT在树脂上的吸附度大于HCl。计算了吸附过程热力学参数并进行了讨论。     

以弱碱性树脂去除废水中5-氨基-2-氯苯-4-磺酸和盐酸

This research deals with an investigation of the adsorption of two acids, namely, 5-amino- 2-chlorotoluene-4-sulfonic and chlorhydric acids from their solution onto weakly basic resin. The screening of resins, kinetics, and isotherm were studied. The results indicate that the D301R is more appropriate for the removal of acids from solution. The adsorption of acids obeys Langmuir isotherm and the first-order kinetics model. Sorptive affinity of the two acids on D301R was found to be in the order of 5-amino-2-chlorotoluene-4-sulfonic acid〉 chlorhydric acid. Thermodynamic parameters for the adsorption of acids were calculated and discussed. The maximum removal of acids was observed around 97% and 76% at 25℃ for 5-amino-2-chlorotoluene-4-sulfonic acid and chlorhydric acid, respectively.     

Minor changes in salicylidene/α-hydroxy acid-containing chelates cause major changes in structure and photochemistry of their Fe(III) complexes

The Sal-AHA chelates, which include a salicylidene moiety and an α-hydroxy acid moiety, have been shown to form trinuclear [Fe₃(Sal-AHA)₃(μ₃-OR)]⁻ clusters with Fe(III) that are photochemically active. Several minor modifications have been made to the chelate structure to evaluate the effects of different aspects of the chelate design on both the structure and the photochemistry of their Fe(III) complexes. Small steric changes have little effect on either overall structure or photochemistry. Shifting the position of the hydroxy group (α vs. β to the carboxylate), which bridges the irons in the cluster, also does not disrupt the trinuclear structure. However, shortening the length of the carbon chain between the salicylidene and the carboxylate results in loss of the trinuclear structure, forming FeL₂ complexes instead. Factors that are important to the quantum yield in the photochemical reaction include both the position of the hydroxy group with respect to the carboxylate and the number of Fe(III) ions in the complex.     

A series of lanthanide (III) coordination polymers derived via in situ hydrothermal decarboxylation of quinoline-2,3-dicarboxylic acid

A series of one-dimensional coordination polymers assembled from LnNO₃ · 6H₂O (Ln = Sm(1), Eu(2), Tb(3), La(4), Ce(5), Pr(6), Nd(7), Dy(8)), quinoline-2,3-dicarboxylic acid (2,3-H₂qldc) and 1,10-phenanthroline (phen) formulated as [Ln(2,3-qldc)(3-qlc)(phen)]_n (3-Hqlc = quinoline-3-carboxylic acid) were obtained under hydrothermal conditions. It is remarkable that in situ hydrothermal decarboxylation was observed during preparing these polymers. Complexes 1–8 were characterized by elemental analyses, IR spectroscopy and single crystal X-ray diffraction analyses. The thermal stabilities and photoluminescence properties of these complexes have been investigated.     

Sulfochlorierung von 1,2-Naphthochinondiazid-(2) mit Chlorsulfonsäure

Sulfochlorination of 1,2-Naphthoquinone-(2)-diazide by Chlorosulfonic acid . The sulfochlorination of 1,2-naphthoquinone diazide-(2) ( 1 ) by chlorosulfonic acid was investigated. The yields of the formed products (1,2-naphthoquinone diazide-(2)-4-sulfonic acid ( 4 ), 1,2-naphthoquinone diazide-(2)-5-sulfonic acid ( 5 ), 1,2-naphthoquinone diazide-(2)-4-sulfochloride ( 2 ) and 1,2-naphthoquinone diazide-(2)-5-sulfochloride ( 3 )) depend on the temperature and on the time of reaction. The highest yields of the favoured 1,2-naphthoquinone diazide-(2)-4-sulfochloride ( 2 ) are obtained at 63°C and after a reaction time of 80 minutes (50%).     

A convenient preparaton ofγ-lactones and dialkyltetrahydrofurans from the reaction of fatty acids with epoxides using lithium naphthalenide

Fatty acids reacted with epoxides using lithium naphthalenide in the presence of diethylamine to give corresponding 4-hydroxy acids. These 4-hydroxy acids easily tended to cyclize into their correspondingγ-lactones by refluxing in benzene. Reduction of theseγ-lactones with lithium aluminum hydride followed by intramolecular dehydration with potassium bisulfate afforded corresponding dialkyl tetrahydrofuran derivatives in high yields. For example, 4-methyl-2-(8-nonenyl)γ-butyrolactone (III) was obtained from 10-undecylenic acid and propylene oxide. 2-Methyl-4-(8-nonenyl) tetrahydrofuran (IV) was produced from (III). 2-Methyl-4-(8-nonenyl) and 2-ethyl-4-(8-nonenyl) tetrahydrofurans are woody smelling and may be used as perfumery materials.     

镧、钇掺杂铕-樟脑酸-1,10-菲咯啉三元配合物的合成及荧光性能

实验合成了单核铕-樟脑酸-1,10-菲咯啉三元配合物和La、Y掺杂异核铕-樟脑酸-1,10-菲咯啉三元配合物。通过配位滴定、元素分析和红外光谱等测试,确定其组成为RE2(CA)3(phen)2(RE为Eu、La和Y;CA为樟脑酸;phen为1,10-菲咯啉);通过三维荧光光谱图确定其最佳激发波长为330.0 nm,即在330.0 nm激发光下的发射光谱图中均显示出Eu3+离子5D0→7F0(579nm),5D0→7F1(594 nm)和5D0→7F2(612 nm)等三条特征谱线,其中5D0→7F2(612 nm)为最强跃迁峰。荧光强度变化研究表明,适量镧和钇离子的掺杂并没有降低铕离子的荧光强度,说明镧和钇对铕离子荧光发射有敏化作用。     

两种脱氢松香基喹啉衍生物的合成与表征

以脱氢松香酸为原料,用硫酸二甲酯酯化后,再在苯和无水三氯化铝作用下脱除异丙基,制得顺式脱异丙基化脱氢松香酸甲酯(Ⅲ),Ⅲ再经12位硝化、还原后制得中间体顺式12 氨基脱烷基化脱氢松香酸甲酯(Ⅴ),Ⅴ继续与甘油在浓硫酸作用下缩合得(4R, 4aR, 4bR) 4, 12b 二甲基1, 2, 3, 4, 4a, 5, 6, 12b 八氢化萘并[2, 1 g]喹啉4 羧酸甲酯(Ⅵ)和(8aR, 9R, 12aR) 9, 12a 二甲基7, 8, 8a, 9, 10, 11, 12, 12a 八氢化萘并[1, 2 f]喹啉9 羧酸甲酯(Ⅶ)两种松香基喹啉衍生物,这两种产物的质量分数分别为73 5%和26 5%,产物的结构通过IR,MS,1HNMR进行了表征。     

Comportement électrique des interfaces polyéthylène-métal en liaison avec l'adhésion

Some routes to synthetize covalently bound chelating groups as 8-hydroxyquinoline or 8-hydroxyquinoline-5-sulfonic acid to cellulose are given. The products show a capacity of 500–800 μmol/g, fast kinetics of exchange and good stability against the eluent. The apparent stability constant of the complexes with Zn²⁺ are around 2 · 10⁵ mol^?1 dm³.     

Chitosan gel beads as drug carriers 2. Release of 8-hydroxy-7-iodoquinoline-5-sulfonic acid and 2,5-dihydroxybenzenesulfonic acid

It is shown that chitosan gel beads are suitable carriers of 8-hydroxy-7-iodoquinoline-5-sulfonic acid (SQ) and 2,5-dihydroxybenzenesulfonic acid (DHBSA) - substances applied in medicine. Drug release has been investigated with respect to the nature of the crosslinking agent (epichlorohydrin or glutaraldehyde) and pH of the medium. Considerable differences in the release rate of DHBSA and SQ have been found. The total amount of the desorbed SQ, as well as the release rate of the drug depends on pH of the medium - they decrease from alkaline to acidic medium. The antimicrobial and antimycotic activity of the loaded with SQ beads is demonstrated.     

Metal Complexes of a 5-Nitro-8-Hydroxyquinoline-Proline Hybrid with Enhanced Water Solubility Targeting Multidrug Resistant Cancer Cells

Multidrug resistance (MDR) in cancer is one of the major obstacles of chemotherapy. We have recently identified a series of 8-hydroxyquinoline Mannich base derivatives with MDR-selective toxicity, however with limited solubility. In this work, a novel 5-nitro-8-hydroxyquinoline-proline hybrid and its Rh(η⁵-C₅Me₅) and Ru(η⁶-p-cymene) complexes with excellent aqueous solubility were developed, characterized, and tested against sensitive and MDR cells. Complex formation of the ligand with essential metal ions was also investigated using UV-visible, circular dichroism, ¹H NMR (Zn(II)), and electron paramagnetic resonance (Cu(II)) spectroscopic methods. Formation of mono and bis complexes was found in all cases with versatile coordination modes, while tris complexes were also formed with Fe(II) and Fe(III) ions, revealing the metal binding affinity of the ligand at pH 7.4: Cu(II) > Zn(II) > Fe(II) > Fe(III). The ligand and its Rh(III) complex displayed enhanced cytotoxicity against the resistant MES-SA/Dx5 and Colo320 human cancer cell lines compared to their chemosensitive counterparts. Both organometallic complexes possess high stability in solution, however the Ru(II) complex has lower chloride ion affinity and slower ligand exchange processes, along with the readiness to lose the arene ring that is likely connected to its inactivity.