Synthesis and Structural Characterization of 2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol

2,3-Bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（C6H12N2O8） was synthesized by condensation,cyclization,oxidative dimerization and deketalization of nitromethane with a total yield of 42.4%.The structure of the title compound was characterized by 1H NMR,13C NMR,FT-IR,elementary analysis,and X-ray single-crystal diffraction analysis,which reveals that the title compound crystallizes in triclinic,space group P with a = 0.6324（2）,b = 0.6454（3）,c = 0.7062（3） nm,α= 111.550（4）,β= 95.505（4）,γ= 113.395（4）°,V = 0.23595（16） nm3,Z = 1,Mr = 240.18,Dc = 1.690 g·cm-3,μ = 0.159 mm-1,F（000） = 126,R = 0.0304 and wR = 0.0907.

1,3-Bis(2-chloroethyl)-1-nitrosourea enhances the inhibitory effect of Resveratrol on 5-fluorouracil sensitive/resistant colon cancer cells

AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resistance(5-FU-R)cell line derived from continuous exposure(25μmol/L)to 5-FU for 20 wk in 5-FU sensitive HCT-116 cells.The proliferation and expression of different representative apoptosis and anti-apoptosis markers in 5-FU sensitive and 5-FU resistance cells were measured by the MTT assay and by Western blotting,respectively,after treatment with Resveratrol(Res)and/or 1,3-Bis(2-chloroethyl)-1-nitrosourea(BCNU).Apoptosis and cell cycle arrest was measured by 4',6'-diamidino-2-phenylindole hydrochloride staining and fluorescence-activated cell sorting analysis,respectively.The extent of DNA damage was measured by the Comet assay.We measured the visible changes in the DNA damage/repair cascade by Western blotting.RESULTS:The widely used chemotherapeutic agents BCNU and Res decreased the growth of 5-FU sensitive HCT-116 cells in a dose dependent manner.Combined application of BCNU and Res caused more apoptosis in5-FU sensitive cells in comparison to individual treatment.In addition,the combined application of BCNU and Res caused a significant decrease of major DNA base excision repair components in 5-FU sensitive cells.We established a 5-FU resistance cell line(5-FU-R)from 5-FU-sensitive HCT-116(mismatch repair deficient)cells that was not resistant to other chemotherapeutic agents(e.g.,BCNU,Res)except 5-FU.The 5-FU resistance of 5-FU-R cells was assessed by exposure to increasing concentrations of 5-FU followed by the MTT assay.There was no significant cell death noted in5-FU-R cells in comparison to 5-FU sensitive cells after5-FU treatment.This resistant cell line overexpressed anti-apoptotic[e.g.,AKT,nuclear factorκB,FLICE-like inhibitory protein),DNA repair(e.g.,DNA polymerase beta(POL-β),DNA polymerase eta(POLH),protein Flap endonuclease 1(FEN1),DNA damage-binding protein 2(DDB2)]and 5-FU-resistance proteins(thymidylate synthase)but under expressed pro-apoptotic proteins(e.g.,DAB2,CK1)in comparison to the parental cells.Increased genotoxicity and apoptosis were observed in resistant cells after combined application of BCNU and Res in comparison to untreated or parental cells.BCNU increased the sensitivity to Res of 5-FU resistant cells compared with parental cells.Fifty percent cell death were noted in parental cells when 18μmol/L of Res was associated with fixed concentration(20μmol/L)of BCNU,but a much lower concentration of Res(8μmol/L)was needed to achieve the same effect in 5-FU resistant cells.Interestingly,increased levels of adenomatous polyposis coli and decreased levels POL-β,POLH,FEN1 and DDB2 were noted after the same combined treatment in resistant cells.CONCLUSION:BCNU combined with Res exerts a synergistic effect that may prove useful for the treatment of colon cancer and to overcome drug resistance.

An efficient synthesis of 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one catalyzed by recyclable solid superacid SO_4^(2-)/TiO_2 under grinding condition

An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.

Synthesis and Crystal Structure of 3,9-Bis(pyridin-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecane

The title compound 3,9-bis（pyridin-2-yl）-2,4,8,10-tetraoxaspiro[5.5]undecane 4（C17H18N2O4） has been synthesized by the reaction of 2,2-bis（hydroxymethyl）propane-1,3-diol with pyridine-2-carbaldehyde in the presence of p-toluenesulfonic acid,and characterized by IR,1H-NMR and X-ray single-crystal diffraction.The crystal belongs to monoclinic system,space group C2/c with a = 25.133（2）,b = 5.7219（5）,c = 21.942（2）（A°） ,β = 99.145（2）°,V = 3115.3（5）（A°）^3,Z = 8,Dc = 1.340 g/cm^3,Mr = 314.33,F（000） = 1328,μ = 0.097 mm-1,MoKa radiation（λ = 0.71073）,R = 0.0352 and wR = 0.1022 for 2486 observed reflections with I 〉 2σ（I）.X-ray analysis reveals that the two 1,3-dioxane rings passing through the central spiro-C atom both adopt chair conformation.Intermolecular C-H…π,C-H…O and C-H…N weak interactions link the molecules to form a three-dimensional samdwich,which are effective in the stabilization of the crystal structure.

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 508.31,F（000） = 518,the final R = 0.0523 and wR = 0.0935 with I 〉 2σ（I）. In the title complex,Co（Ⅱ） ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3？-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate（AP） with complex 1 was explored by differential scanning calorimetry（DSC）. AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g^（-1）,significantly higher than that of pure AP. By Kissinger＇s method,the ratio of Ea/ln（A） is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.

Synthesis,Crystal Structure,and Magnetic Property of One 3D Nickel Coordination Polymer Based on 2-Hydroxy-5-(3',5'-terephthalic acid)Pyridine and 1,4-Bis(1-imdazoly)benzene

One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.

Synthesis and Crystal Structure of (1S)-1,1'-Bis{[N-ethyl-N-(1-methylethyl)-amino]-carbonyl}-2-(hydroxydiphenylmethyl)-ferrocene

The title complex, （1S）-1,1＇-bis{[N-ethyl-N-（1-methylethyl）-amino]carbonyl}-2- （hydroxyldiphenylmethyl）-ferrocene （[Fe（C24H22NO2）（C11H16NO）]2·H2O, Mr = 1207.13）, was synthesized via （-）-Sparteine-mediated enantioselective directed ortho-lithiation of 1,1‘-bis{[N- ethyl-N-（1-methylethyl）-amino]carbonyl}-2-（hydroxydiphenylmethyl）-ferrocene. The structure of the rifle compound was determined by X-ray single-crystal diffraction. The crystal belongs to the orthorhombic system, space group P212121, with a = 10.266（2）, b = 17.676（4）, c = 34.097（7）A, V = 6187（2）A3, Z = 4, C70H86Fe2N4O7, Dc = 1.296 g/cm^3,μ = 0.527 mm^-1, T= 113（2） K, F（000） = 2568, the final R = 0.0469 and wR = 0.0984 for 13940 observed reflections with I 〉 2σ（I）. The neighboring ferrocene derivatives are joined into dimers via O-H…O=C intermolecular hydrogen bonding by a water molecule. Besides, the dimers form neat rows along the a axis.

The Intramolecular Coupling Reaction of 1,6-Bis(1-Alky1-2-Methylindol-3-yl)hexane-1,6-dione Induced by Low-valent Titanium

The intramolecular reductive coupling reaction of 1,6-bis(subshtuted indolyl)hexane-1,6-dione using zero-valent titanium reagent as catalyst proderes the novel photochromic 1,2-diheterocyclic cyclohexenes 2, together with unexpected compounds 3

Crystal and Molecular Structure, and Spectral Characteristics of Sodium 3,5-Bis(Hydroxyimino)-1-Methyl-2,4,6-Trioxocyclohexanide

Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3);b(?) 12.446(3);c(?) 13.716(3);(o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2)?? and from 1.292(2) to 1.293?? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.

Synthesis of a New Ligand Containing 1, 7-Diaza-12-crown-4 and the Application in Asymmetric Cyclopropanation Reaction

A new chiral multidenate ligand (S, S)-1,7-bis(4-benzyloxazolin-2-yl-methyl)-1, 7-diaza- 12-crown-4 1 has been synthesized and used as ligand in the copper catalyzed asymmetric cyclopropanation of 1, 1-diphenylethylene.

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Polycarboxylate Ligand 5-(4-Hydroxypyridinium-1-ylmethyl)-isophthalic Acid: Synthesis, Structure, and Property

A Zn（Ⅱ） supramolecular coordination polymer, {[Zn2（L）2（m-bix）（H20）]6H2O}n（1）, with an interesting 1D→2D polythreading array from a flexible and angular organic aromaticpolycarboxylate ligand 5-（4-hydroxypyridinium-l-ylmethyl）isophthalic acid （H2L）, and N-donorligand 1,3-bis（imidazol-l-ylmethyl）benzene （m-bix）, has been obtained under hydrothermalconditions and characterized by elemental analysis, powder X-ray diffraction （PXRD）, IR, thermalgravimetric analyses （TGA） and single-crystal X-ray diffraction. In 1, the Zn（Ⅱ） center has twocoordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other isa tetrahedral geometry; L2- has two different coordination modes, with one connecting three Zn（Ⅱ）ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and theother bridging two Zn（Ⅱ） ions through two carboxylate groups. The L2- anions connect the Zn（Ⅱ）centers forming an infinite 1D tubular structure. These 1D tubes are interconnected by the m-bixspacers to form a 2D framework. Such 2D layers are further assembled into a 3D supramolecularnetwork via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigatedin detail.

Antiviral stereoisomers of 3,5-bis(2-hydroxybut-3-en-1-yl)-1,2,4-thiadiazole from the roots of Isatis indigotica

Four stereoisomers of 3,5-bis（2-hydroxybut-3-en-1-yl）-l,2,4-thiadiazole, named insatindigothiadia- zoles A-D （1a-1d）, were isolated from the roots oflsatis indigotica. Their structures were determined by spectroscopic analysis; specifically, the absolute configurations were assigned by using the MPA determination rule based on △δrs values of MPA esters, and supported by electronic CD （ECD） calculations. Proposed biosynthetic pathways and preliminary investigations of the biological activities of la-1d against influenza virus A （H3N2）, Coxsackie virus B3, and/or HSV-1 are also discussed.

Electronic spectroscopy and photochromic mechanism of bis-Schiff bases, N, N'-bis(2-hydroxy-1-naphthylidene)-1,4-phenyldiamine

The steady state and transient state absorption spectra and fluorescence spectra of N,N’-bis(2-hy-droxy-1-napbthylidcne)-1,4-phenyldiamme ( BNP ) in cyclohexane and acetonitrile were determined.The pho-tochromic mechanism was discussed In nonpolar solvents,BNP exists mainly in the enol form and has the absorption maximum in the UV region In polar solvents,however,both the enol and proton transfer tautomer are formed,but the farmer is the main one Fluorescence emissions result from the excited state of proton transfer product.

Synthesis and Crystal Structure of a Two-hydroxyphenyl Adamantane-type Epoxy Resin

A two-hydroxyphenyl adamantane-type epoxy resin oligomer,namely 1,3-bis（4-（2,3-epoxpropyloxy）phenyl） adamantine （BEPAD）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The unit cell of C28H32O4：Mr =432.5,monoclinic,space group P21/n,with a =10.510（6）,b =16.972（9）,c =13.374（7） （A）,β =109.356（6）°,V=2251（2） （A）3,Z =4,Dc =1.277 Mg·m^-3 and μ（MoKa） =0.084 mm^-1.In BEPAD,the methylene and epoxide rings on two ends are statistically disordered.The intermolecular interactions are also discussed,suggesting that the intermolecular interactions in BEPAD are stronger than that in the crystals of similar compounds due to the large adamantine group between the two benzene rings.

A New Co(Ⅱ)Coordination Compound Constructed by Tripyridyltriazole and Pyromellitic Acid:Synthesis,Crystal Structure and Antifungal Activity

A new coordination compound, [Co（L223）2（H2O）2]·H2pm（1, L223 = 3,4-bis（2-pyridyl）-5-（3-pyridyl）-1,2,4-triazole and H4 pm = pyromellitic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the triclinic system, space group P1 with a = 10.2470（8）, b = 10.2879（9）, c = 10.2951（11） ？, α = 109.398（2）, β = 97.6590（10）, γ = 95.3260（10）°, V = 1003.60（16） ？3, Z = 1, Dc = 1.565 g/cm^3, μ = 0.508 mm%^-1, Mr = 945.73, F（000） = 485, the final R = 0.0562 and w R = 0.0783 with I 〉 2σ（I）. Two L223 as chelating ligands link one Co（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 2D coordination pattern with hydrogen bonds. In addition, the antifungal effects of the ligand and the complex were evaluated by the disc diffusion method against Colletotrichum gloeosporioides Penz. 1 represents antifungal activity with high levels of inhibitory potency which is larger than the corresponding ligand.

Improved stability of blue TADF organic electroluminescent diodes via OXD-7 based mixed host

Thermally activated delayed fluorescence(TADF)organic light-emitting diodes(OLEDs)have been demonstrated in applications such as displays and solid-state lightings.However,weak stability and ineffi-cient emission of blue TADF OLEDs are two key bottlenecks limiting the development of solution processable displays and white light sources.This work presents a solution-processed OLED using a blue-emitting TADF small molecule bis[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]sulfone(DMAC-DPS)as an emitter.We comparatively investigated the effects of single host poly(Nvinylcarbazole)(PVK)and a co-host of 60%PVK and 30%2,2′-(1,3-phenylene)-bis[5-(4-tert-butylphenyl)-1,3,4-oxadiazole](OXD-7)on the device performance(the last 10%is emitter DMAC-DPS).The co-host device shows lower turn-on voltage,similar maximum luminance,and much slower external quantum efficiency(EQE)rolloff.In other words,device stability improved by doping OXD-7 into PVK,and the device impedance simultaneously and significantly reduced from 8.6103 to 4.2103 W at 1000 Hz.Finally,the electroluminescent stability of the co-host device was significantly enhanced by adjusting the annealing temperature.

A novel and efficient synthesis of alkyl thiocyanates from alkyl halides in water using phase transfer catalysts

1,4-Bis（triphenylphosphonium）-2-butene dichloride（BTPBDC） and 1,4-bis（triphenyl phosphonium）-2-butene dithiocyanate （BTPBDT） were prepared and used as phase-transfer catalysts.Alkyl halides were converted efficiently to the corresponding alkyl thiocyanates under mild reaction conditions in water.No evidence for the formation of isothiocyanates as by-product of the reaction was observed.