Synthesis of novel tetrazole C5-linked C0- and C2-ribonucleoside phosphoramidites using MePOM and POM groups for probing RNA catalysis

Novel C5-linked C₀- and C₂-tetrazole ribonucleoside phosphoramidites were designed and synthesized via tetrazole C-nucleosides. Pivaloyloxymethyl (POM) and methyl-substituted POM (MePOM) groups were introduced as N-protecting groups in the tetrazole ring that can be readily removed under mild basic conditions. The phosphoramidites were successfully incorporated into the VS ribozyme substrate and hence providing a chemogenetic approach to determine which nucleobases of ribozymes function as the acid or base, in the studies of ribozyme general acid and base catalysis.     

Synthesis of C4-linked imidazole ribonucleoside phosphoramidite with pivaloyloxymethyl (POM) group

A novel C4-linked imidazole ribonucleoside phosphoramidite was designed and successfully synthesized starting from tribenzylribofuranosylimidazole. This phosphoramidite product enables incorporation of the imidazole moiety into an RNA sequence and hence allows study of its role in the general acid and base catalysis of ribozymes. Pivaloyloxymethyl (POM) was first introduced as an N-protecting group for the imidazole ribonucleoside that can be readily removed under mild basic condition.     

Synthesis and characterization of a novel imidazole cyclic trimer

A novel cyclic trimer of imidazole 1, in which imidazole rings are connected by amide bonds, has been synthesized with the help of LiCl as a template for the cyclization. The absorption spectra of 1 indicate the extension of conjugation between imidazole rings and amide bonds. The addition of 3 M equiv of MgCl₂ solubilizes 1 in polar organic solvent, suggesting the chelating ability of 1 to Mg cation.     

Unexpected formation of novel two-component gels comprising of glycoluril carboxylic acid amides and imidazole: Synthesis and morphology

New gelling agents have been discovered: glycoluril carboxylic acid amides, giving two-component gels with imidazole. First, the one-pot, two step reaction of glycoluril carboxylic acids, CDI and various amines was investigated for the preparation of gels and it was found that the reaction mixtures were gelled in dry DMF during the preparation of some amides. The conditions of the gel-sol-gel transitions were found. The morphology of the xerogels was studied by SEM. The structure of the xerogels is constructed from interlocked rods or from interlaced curved fibres. Self-organization in the co-crystals of amides with H₂O or imidazole was detected. The molecules of the co-crystals of amides with H₂O are self-assembled into homochiral tapes.     

Isomer transformation and photoluminescence in novel coordination polymers constructed from 1,4-cyclohexanedicarboxylic acid and imidazole

Three novel coordination polymers [M(chdc)(imi)]_n (chdc=1,4-cyclohexanedicarboxylic dianion, imi=imidazole, M=Ni 1, Co 2 and Zn 3) have been synthesized by solvothermal technique and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The trans-chdc have been partially transformed into cis-chdc and the cis-chdc have been separated from the mixture of cis- and trans-chdc in the synthetic reactions of the three compounds. The three compounds exhibit similar one dimension chain-like architecture constructed by their M(II) dimers interconnected via double strands of cis-chdc-bridge. M(II) atom of the dimer exhibits a square-pyramidal geometry and interaction happens within two metal centers. Both compounds 1 and 2 do not exhibit emission spectra whereas compound 3 shows intense photoluminescence property at room temperature.     

Synthesis and application of a novel 9,9-diethyl-1,2-diaryl-1,9-dihydrofluoreno[2,3-d]imidazole for blue organic light emitting diode

Two novel 2-(4-(9,9-disubstitued-9 H-fluoren-2-yl)phenyl)-9,9-diethyl-l-phenyl-1,9-dihydrofluoreno-[2,3-d]imidazole derivatives 2 a and 2 b were synthesized and characterized.Their photophysical and electrochemical properties,thermal stability property,and electroluminescence(EL)performance of 2 b were investigated.The fabricated device based on 2 b doping into 4,4’-N,N’-dicarbazole-biphenyl(5%)as an emitter present a maximum brightness of 1272 cd/m^2 at 4 V with the CIE coordinate of(0.1590,0.0465).     

Reversed-phase high-performance liquid chromatographic/mass spectrometric method for separation of 4-methylimidazole and 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl)imidazole at pg levels

A high-performance liquid chromatographic/mass spectrometric method (HPLC/MS) has been developed to determine both 4-methylimidazole (4MeI) and 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl)imidazole (THI) in one run. Among three sorbents tested, the best peak shape of 4MeI was achieved on a reversed-phase MetaChem Polaris C18-A at pH 9.5. The sensitivity and the range of UV detection at 215 and 290 nm for 4MeI and THI, respectively, were compared to the parameters achieved by the electrospray ionization mass spectrometric (ESI/MS) detection in the presence of 5 mmol l⁻¹ ammonium hydroxide using selected ion-monitoring (SIM) mode. The on-column limits of detection were 0.147 ng of 4MeI and 0.084 ng of THI using UV detection and 1 pg of 4MeI and 3 pg of THI using ESI/MS detection, respectively. The effect of both ammonium ion concentration and energy of fragmentation on 4MeI and THI ionization is discussed. The method could be applied for a fast and sensitive determination of 4MeI and THI in different biological materials as well as in Class III Caramels.     

Synthesis and Structure of a Chiral Copper(II) Sulfate (C3N2H4)3CuSO4 from Achiral Materials

A novel chiral compound (C₃N₂H₄)₃CuSO₄ ( 1 ) was synthesized at room temperature by using achiral organic amine imidazole as the structure‐directing agent, crystallizing in the chiral space group P2₁2₁2₁. Single‐crystal structural analysis reveals that compound 1 consists of alternating CuO₂N₃ and SO₄ units exhibiting a neutral one‐dimensional helical chain.     

配合物Cu(C14H9NO3)(C3H4N2)的合成、晶体结构及性质研究

合成了配合物Cu(C₁₄H₉NO₃)(C₃H₄N₂)[C₁₄H₉NO₃^2- 为N-(2-羧基苯基)-水杨醛亚胺,C₃H₄N₂为咪唑].晶体属正交晶系,空间群Pca2₁,晶胞参数a=0.94453(12)nm,b=1.12278(9)nm,c=2.9123(4)nm,V=3.0885(6)nm³,Mr=370.84,Z=8,最终的偏离因子R=0.036,wR=0.087,GOF=0.975.三齿Schiff碱配体中的二个氧原子、一个氮原子和咪唑的一个氮原子与铜原子配位,形成扭曲的平面正方形结构.通过元素分析,IR,UV,CV和TG表征了配合物的结构.     

Synthesis and application of novel imidazole and 1H-tetrazolic acid containing catalysts in enantioselective organocatalyzed Diels–Alder reactions

Herein we report studies on the organocatalytic Diels–Alder reaction using a variety of catalysts capable of activating α,β-unsaturated carbonyl compounds for reactions with dienes. The structurally attractive catalysts 4 and 14 were utilized in the enantioselective organocatalytic Diels–Alder reactions. Catalyst 4 provided the products in fair yields and more importantly in good enantioselectivities of up to 83% ee. Catalyst 14 was synthesized in high yield and was assessed in the enantioselective organocatalytic Diels–Alder reaction. Catalyst 14 proved to be a highly active and selective catalyst providing the products in high yield and high enantioselectivities up to 95% ee.     

Synthesis,cytotoxicity and apoptosis-inducing activity of novel 1H-benzo[d]imidazole derivatives of dehydroabietic acid

With the expectation of finding new and effective antitumor drugs, a series of novel N-(1H-benzo[d]imidazole-2-yl)-benzamide/benzenesulfonamide derivatives of dehydroabietic acid were synthesized and evaluated for cytotoxic activity against three human cancer cell lines (MCF-7, HeLa, and HepG2 cells) and one human normal hepatocyte cell line (LO2). As a result, a number of derivatives showed moderate to good antitumor activities. Among them, compound 8h exhibited the most potent activities against three cancer cell lines with IC₅₀ values of 0.87 ± 0.18, 9.39 ± 0.72, and 8.31 ± 0.64 μM, respectively, and was less active to normal hepatocyte LO2 cells. Further mechanism studies revealed that compound 8h could arrest the cell cycle of MCF-7 cells at S phase and induce the apoptosis of MCF-7 cells in ROS-mediated mitochondrial pathway.     

Synthesis,structural and spectroscopic characterization of a new cadmium(II) complex containing imidazole (Im) as ligand, [Cd(Im)6](ClO4)2

Reaction between the 1,1′-carbonyldiimidazole ligand and mixtures of cadmium(II) acetate with sodium perchlorate provided the unusual crystalline material [Cd(Im)₆](ClO₄)_2, (Im?=?imidazole). This new Cd^II complex, has been characterized by elemental analysis, IR-, ¹H NMR-, ¹³C NMR and ¹¹³Cd NMR spectroscopy. The coordination number in this complex is six, CdN₆ and coordination environment around the Cd(II) may be described as distorted octahedral with a D_2h point group. There are both edge-to-face π–π stacking and C–H(Im)?···?π interactions between aromatic “Im” rings belonging to adjacent chains in this network.     

5-甲基水杨醛缩对氨基水杨酸席夫碱的合成、表征及性质

用5-甲基水杨醛和对氨基水杨酸为原料,合成了一种新型席夫碱,用元素分析、IR、1 H NMR、MS验证其结构.采用荧光光谱法研究该化合物与牛血清白蛋白(BSA)的相互作用机制,采用位点结合模型公式、热力学公式求解出不同温度下的结合常数、结合位点数、热力学参数,得出其淬灭机制为静态淬灭,结合位点数为1,作用力类型为氢键和范德华力.     

Synthesis of polymer-supported Fe3O4 nanoparticles and their application as a novel route for the synthesis of imidazole derivatives

Research on Chemical Intermediates - Cross-linked poly(4-vinylpyridine) supported Fe3O4 nanoparticles, abbreviated as [P4-VP]-Fe3O4NPs, were easily prepared as a new magnetic polymeric catalyst and...     

Synthesis, crystal structure and spectroscopy studies of a novel five-coordinated Zn(II) ion complex with l-tyrosine and imidazole

The new five-coordination zinc(II) complex of formula [Zn(Im)(l-tyr)₂]₂·5H₂O consisting of l-tyrosine (l-tyr) and imidazole (Im) molecules as ligands was prepared as crystals and characterized by X-ray diffraction, IR-FIR vibrational and UV-Vis electronic spectroscopy. The [Zn(Im)(l-tyr)₂]₂·5H₂O complex crystallizes in the orthorhombic crystal system and P2₁2₁2 space group. The [ZnN₂N′O₂] chromophore has distorted bipiramidal geometry with value of τ parameter 0.7. The sensitive intra and inter-molecular hydrogen bonds created the layers arrangement and the “pseudo-baskets” fashion. The intraligand charge transfer (ILCT) π-π^∗ and π-π^∗ transitions in the ligands molecule are corresponded to the intensity bands in the UV-Vis region.     

Synthesis and nucleic acid binding studies of novel pyrrolidinyl PNA carrying an N-amino-N-methylglycine spacer

Two novel pyrrolidinyl peptide nucleic acids comprising alternating sequences of thymine-modified d- or l-proline and an N-amino-N-methylglycine spacer were synthesized using solid-phase methodology. UV and CD titrations together with a gel-binding shift assay revealed that neither of the homothymine PNA decamers bind to their complementary DNA or RNA. This was considered to be due to an unfavorable secondary structure which could not be alleviated by the presence of the positively charged protonated amine in the PNA backbone.     

Synthesis and biological activities of novel 2-amino-1,3-thiazole-4-carboxylic acid derivatives

A series of novel 2-amino-1, 3-thiazole-4-carboxylic acid derivatives were designed and synthesized. Their structures were confirmed by melting points, IR, ¹H NMR, ¹³C NMR, and HRMS or elemental analysis. Biological activities of all title compounds including fungicidal activity and antivirus activity were evaluated systematically. Preliminary bioassays indicated that these compounds exhibited good fungicidal activity at 50 μg/mL, compounds 4b and 4i exhibited over 50% activity against six fungi tested. Most compounds showed good activity against TMV with different models in vivo at 100 μg/mL. Compounds 4c and 4e stood out with high effects against TMV in vivo in all models tested, including protective, inactivative, curative, and inductive activities. These data demonstrate a new strategy for fungi and virus control.     

Thio effects on the departure of the 3'-linked ribonucleoside from diribonucleoside 3',3'-phosphorodithioate diesters and triribonucleoside 3',3',5'-phosphoromonothioate triesters: implications for ribozyme catalysis

To provide a solid chemical basis for the mechanistic interpretations of the thio effects observed for large ribozymes, the cleavage of triribonucleoside 3',3',5'-phosphoromonothioate triesters and diribonucleoside 3',3'-phosphorodithioate diesters has been studied. To elucidate the role of the neighboring hydroxy group of the departing 3'-linked nucleoside, hydrolysis of 2',3'-O-methyleneadenosin-5'-yl bis[5'-O-methyluridin-3'-yl] phosphoromonothioate (1 a) has been compared to the hydrolysis of 2',3'-O-methyleneadenosin-5'-yl 5'-O-methyluridin-3'-yl 2',5'-di-O-methyluridin-3'-yl phosphoromonothioate (1 b) and the hydrolysis of bis[uridin-3'-yl] phosphorodithioate (2 a) to the hydrolysis of uridin-3'-yl 2',5'-di-O-methyluridin-3'-yl phosphorodithioate (2 b). The reactions have been followed by RP HPLC over a wide pH range. The phosphoromonothioate triesters 1 a,b undergo two competing reactions: the starting material is cleaved to a mixture of 3',3'- and 3',5'-diesters, and isomerized to 2',3',5'- and 2',2',5'-triesters. With phosphorodithioate diesters 2 a,b, hydroxide-ion-catalyzed cleavage of the P--O3' bond is the only reaction detected at pH >6, but under more acidic conditions desulfurization starts to compete with the cleavage. The 3',3'-diesters do not undergo isomerization. The hydroxide-ion-catalyzed cleavage reaction with both 1 a and 2 a is 27 times as fast as that compared with their 2'-O-methylated counterparts 1 b and 2 b. The hydroxide-ion-catalyzed isomerization of the 3',3',5'-triester to 2',3',5'- and 2',2',5'-triesters with 1 a is 11 times as fast as that compared with 1 b. These accelerations have been accounted for by stabilization of the anionic phosphorane intermediate by hydrogen bonding with the 2'-hydroxy function. Thio substitution of the nonbridging oxygens has an almost negligible influence on the cleavage of 3',3'-diesters 2 a,b, but the hydrolysis of phosphoromonothioate triesters 1 a,b exhibits a sizable thio effect, k(PO)/k(PS)=19. The effects of metal ions on the rate of the cleavage of diesters and triesters have been studied and discussed in terms of the suggested hydrogen-bond stabilization of the thiophosphorane intermediates derived from 1 a and 2 a.     

Synthesis and characterization of sulfonated-mercaptopropanoic acid coated Fe3O4 nanoparticles as a novel acid magnetic catalyst for Biginelli reaction

In this paper, Fe₃O₄ nanoparticles were coated with 3-mercaptopropanoic acid (MPA) through a simple in-situ method and subsequently oxidized by H₂O₂/H₂SO₄ to obtain a novel acid magnetic catalyst (Fe₃O₄/SMPA). This catalyst exhibited high catalytic activity in the one-pot synthesis of different 3,4-dihydropyrimidin-2(1H)-ones under mild and solvent-free conditions, along with excellent level of reusability.     

Determination Co2+ in vitamin B12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H2O2 chemiluminescence reaction

In this paper, three kinds of imidazole derivatives, 2-(4-methylphenyl)-4,5-di(2-furyl) imidazole (MDFI), 2-(4-nitrophenyl)-4,5-di(2-furyl) imidazole (NDFI), and 2-(4-tert-butylphenyl)-4,5-di(2-furyl) imidazole (t-BDFI) were synthesized. In an alkaline medium, the chemiluminescence (CL) reaction of imidazole derivatives with H₂O₂ has been investigated. It was also found that MDFI/H₂O₂ and t-BDFI/H₂O₂ systems gave strong CL. When Co²⁺ was added into the two CL systems, the CL intensity was remarkably enhanced. In the optimum conditions, the CL intensity is linearly related to the logarithm of concentration of Co²⁺. The linear ranges are 5 × 10⁻⁹–2.5 × 10⁻⁷ mol/L for MDFI/H₂O₂ system and 5 × 10⁻⁹–2.5 × 10⁻⁷ mol/L for t-BDFI/H₂O₂ system, and the corresponding detection limits are 1.2 × 10⁻⁹ mol/L and 1.1 × 10⁻⁹ mol/L, respectively. The method was applied to the determination of Co²⁺ in vitamin B₁₂ injection. Furthermore, the CL mechanism was also discussed.