Synthesis of New Schiff Bases Containing Thiophene Moiety

Seven new Schiff bases, which are 4,4,4-trifluo-ro-1-(2-thienyl)-1-butanone-3-Z, Z =-thioseraicarbazone (a); -thiocarbohydrazone (b),-benzoic hydrazone (c), -( o-hydroxyphenyl) imine (d) ,-nicotinic hydrazone (e),-salicylic hydrazone (f), and -(p-fluoro-m-chlorophenyl) imine (g), have been synthesized by reaction of 4, 4, 4-trifluoro-1-(2-thienyl)-1,3-butanedione (TFTBD) with corresponding hy-drazides or anilines, acetic acid or p-toluence sulfonic acid as catalyst, and characterized by Elemental analysis, IR, UV-Vis,1H NMR and MS. The MS spectra confirmed that the -C3=O condensed with primary amino group. Tauto-merism of the compounds is discussed.

Nucleoside diphosphate-linked moiety X-type motif 15 R139C genotypes impact 6-thioguanine nucleotide cut-off levels to predict thiopurine-induced leukopenia in Crohn’s disease patients

BACKGROUND Thiopurine-induced leukopenia(TIL)is a life-threatening toxicity and occurs with a high frequency in the Asian population.Although nucleoside diphosphate-linked moiety X-type motif 15(NUDT15)variants significantly improve the predictive sensitivity of TIL,more than 50%of cases of this toxicity cannot be predicted by this mutation.The potential use of the 6-thioguanine nucleotide(6TGN)level to predict TIL has been explored,but no decisive conclusion has been reached.Can we increase the predictive sensitivity based on 6TGN by subgrouping patients according to their NUDT15 R139C genotypes?AIM To determine the 6TGN cut-off levels after dividing patients into subgroups according to their NUDT15 R139C genotypes.METHODS Patients’clinical and epidemiological characteristics were collected from medical records from July 2014 to February 2017.NUDT15 R139C,thiopurine S methyltransferase,and 6TGN concentrations were measured.RESULTS A total of 411 Crohn’s disease patients were included.TIL was observed in 72 individuals with a median 6TGN level of 323.4 pmol/8×10^8 red blood cells(RBC),which was not different from that of patients without TIL(P=0.071).Then,we compared the 6TGN levels based on NUDT15 R139C.For CC(n=342)and CT(n=65)genotypes,the median 6TGN level in patients with TIL was significantly higher than that in patients without(474.8 vs 306.0 pmol/8×10^8 RBC,P=9.4×10-^5;291.7 vs 217.6 pmol/8×10^8 RBC,P=0.039,respectively).The four TT carriers developed TIL,with a median 6TGN concentration of 135.8 pmol/8×10^8 RBC.The 6TGN cut-off levels were 411.5 and 319.2 pmol/8×108 RBC for the CC and CT groups,respectively.CONCLUSION The predictive sensitivity of TIL based on 6TGN is dramatically increased after subgrouping according to NUDT15 R139C genotypes.Applying 6TGN cut-off levels to adjust thiopurine therapies based on NUDT15 is strongly recommended.

SYNTHESIS AND CHARACTERIZATION OF NOVEL MULTIFUNCTIONAL HOST COMPOUNDS.1.β-CYCLODEXTRIN DERIVATIVE BEARING DIETHANOLAMINE MOIETY

A novel β-cyclodextrin(β-CD)derivative bearing diethanolamine moiety was synthesized by a convenient method with 63% yield,and the new host compound was characterized by (13)~C-NMR,FT-IR spectra etc,

Ion shielding functional separator using halloysite containing a negative functional moiety for stability improvement of Li–S batteries

Lithium–sulfur batteries are one of the attractive next-generation energy storage systems owing to theienvironmental friendliness,low cost,and high specific energy densities.However,the low electrical conductivity of sulfur,shuttling of soluble intermediate polysulfides between electrodes,and low capacitretention have hampered their commercial use.To address these issues,we use a halloysitemodulated(H-M)separator in a lithium–sulfur battery to mitigate the shuttling problem.The H-M separator acts as a mutual Coulombic repulsion in lithium-sulfur batteries,thereby selectively permitting Lions and efficiently suppressing the transfer of undesired lithium polysulfides to the Li anode sideMoreover,the use of halloysite switches the surface of the separator from hydrophobic to hydrophilicconsequently improving the electrolyte wettability and adhesion between the separator and cathodeWhen sulfur-multi-walled carbon nanotube(S-MWCNT)composites are used as cathode active materialsa lithium–sulfur battery with an H-M separator exhibits first discharge and charge capacities of 1587 an1527 m Ah g-1,respectively.Moreover,there is a consistent capacity retention up to 100 cyclesAccordingly,our approach demonstrates an economical and easily accessible strategy for commercialization of lithium–sulfur batteries.

STUDIES ON STEROIDAL PLANT GROWTH REGULATOR 24. STEREOCONTROLLED CONSTRUCTION OF THE SIDE CHAIN OF BRASSINOLIDE AND HOMOBRASSINOLIDE VIA A TANDEM VICINAL DIALKYLATION OF PYRANONE MOIETY

A stereocontrolled construction of the side chain of brassinclide and homobrassinolide has been achieved via the tandem vicinal dialkylation of the pyranone moiety as a key step.

Synthesis and Characterization of a New Bifunctional Dye Containing Spirobenzopyran and Cinnamoyl Moiety

A novel bifunctional dye containing spirobenzopyran and cinnamoyl moiety has been prepared and its photochromic behavior following irradiation at different wavelengths of monochrome UV light was investigated. The colourless bifunctional dye in film or solution exhibits unusual photochromism through structural and geometrical transformation from spirobenzopyran to merocyanine accompanying with photocrosslinking reaction in cinnamoyl moieties. Two kinds of photochemical reaction were achieved by irradiation at the different wavelengths of monochrome UV light (275 nm, 365 nm) selectively. The photochromic process of the bifunctional dye was discussed and the dynamic behaviors of the decolorization process were investigated.

SYNTHESIS OF FUNCTIONALIZED CALIX[4]ARENE BEARING [M]DAZOLE MOIETY TO SERVE AS CATALYTIC FUNCTION

Synthesis of catix[4]arene with one imidazolyl group on the upper rim is presented.

A NEW SYNTHETIC APPROACH TO PHOSPHONOPEPTIDE WITH PHOSPHONAMIDE MOIETY

A novel tricomponental condensation leading to p-nitrophenyl- ethyl hydrogen substituted benzylphosphonates was described.The use of these compounds for the synthesis of phosphonopeptide with phosphonamide moiety was demonstrated.

The origin and biosynthesis of the naphthalenoid moiety of juglone in black walnut

Several members of the Juglandaceae family produce juglone,a specialized 1,4-naphthoquinone(1,4-NQ)natural product that is responsible for the notorious allelopathic effects of black walnut(Juglans nigra).Despite its documented ecological roles and potential for being developed as a novel natural product-based herbicide,none of the genes involved in synthesizing juglone have been identified.Based on classical labeling studies,we hypothesized that biosynthesis of juglone’s naphthalenoid moiety is shared with biochemical steps of the phylloquinone pathway.Here,using comparative transcriptomics in combination with targeted metabolic profiling of 1,4-NQs in various black walnut organs,we provide evidence that phylloquinone pathway genes involved in 1,4-dihydroxynaphthoic acid(DHNA)formation are expressed in roots for synthesis of a compound other than phylloquinone.Feeding experiments using axenic black walnut root cultures revealed that stable isotopically labeled L-glutamate incorporates into juglone resulting in the same mass shift as that expected for labeling of the quinone ring in phylloquinone.Taken together,these results indicate that in planta,an intermediate from the phylloquinone pathway provides the naphthalenoid moiety of juglone.Moreover,this work shows that juglone can be de novo synthesized in roots without the contribution of immediate precursors translocated from aerial tissues.The present study illuminates all genes involved in synthesizing the juglone naphthoquinone ring and provides RNA-sequencing datasets that can be used with functional screening studies to elucidate the remaining juglone pathway genes.Translation of the generated knowledge is expected to inform future metabolic engineering strategies for harnessing juglone as a novel natural product-based herbicide.

Effect of Silyl Moiety on the Reaction of O,O'-Phenylenephosphoryl Chloride with N-Silylvaline Silyl Ester

N-Trimethylsilylvaline trimethylsilyl ester IIa, N-triethylsilylvaline triethylsilyl ester IIb and N-tert-butyldimethylsilylvaline tert-butyldimethylester IIc showed evidently different reactivities with O,O'-phenylenephosphorylchloride The formation speed of the fmal spiro-bicyclic pentacoordinated phosphorus compounds IV depends on the intramolecular transfer ability of the silyl moiety crucially

Synthetic Approach for Novel Fluorine Substituted <i>α</i>-Aminophosphonic Acids Containing 1,2,4-Triazin-5-One Moiety as Antioxidant Agents

Novel fluorine substituted α-amino phosphonic acids containing 1,2,4-triazin- 5-one (6a-f) have been obtained from fluoroacylation of 6-(2&prime;-amino-5&prime;-nitrophenyl)-3-thioxo-1,2,4-triazin-5(4H)-one (1) followed by ammonilysis to give the corresponding 3-amino-derivative 3. Condensation of compound 3 with nitro/halogenated aromatic aldehydes yielded the Schiff bases 4. The simple addition of diethyl phosphonate to compound 4 produced the α-amino phosphonates 5. Acidic hydrolysis of compound 5 produced the fluorine substituted α-amino acids derivatives 6. Structures of the new compounds have been established with the help of elemental analysis and spectral measurements. Also, the products evaluated as antioxidants, where the fluorinated α-amino phosphonic acids 6 are more active than the other synthesized systems.

Non-fullerene acceptors with heteroatom substitution on the core moiety for efficient organic photovoltaics

Organic photovoltaics(OPVs)represent one of the most promising photovoltaic technologies owing to their high capacity to convert solar energy to electricity.With the continuous structure upgradation of photovoltaic materials,especially that of non-fullerene acceptors(NFAs),the OPV field has witnessed rapid progress with power conversion efficiency(PCE)exceeding 19%.However,it remains challenging to overcome the intrinsic trade-off between the photocurrent and photovoltage,restricting the further promotion of the OPV efficiency.In this regard,it is urgent to further tailor the structure of NFAs to broaden their absorption spectra while mitigating the energy loss of relevant devices concomitantly.Heteroatom substitution on the fused-ringπ-core of NFAs is an efficient way to achieve this goal.In addition to improve the nearinfrared light harvest by strengthening the intramolecular charge transfer,it can also enhance the molecular stacking via forming multiple noncovalent interactions,which is favorable for reducing the energetic disorder.Therefore,in this review we focus on the design rules of NFAs,including the polymerized NFAs,of which the core moiety is substituted by various kinds of heteroatoms.We also afford a comprehensive understanding on the structure–propertyperformance relationships of these NFAs.Finally,we anticipate the challenges restricting the efficiency promotion and industrial utilization of OPV,and provide potential solutions based on the further heteroatom optimization on NFA core-moiety.

Modularly engineered prodrug-nanoassemblies for cancer therapy:Nonpharmacological moiety dominating delivery fates

Self-engineered small-molecule prodrug-nanoassemblies have emerged as promising nanomedicines for cancer treatment.Modular design of prodrug molecules is crucial to guarantee the favorable assembly stability,tumor-specific prodrug activation,and satisfactory antitumor effect.However,too much attention has been paid to the pharmacophores and chemical linkages in prodrug molecules while neglects the vital roles of nonpharmacological moieties.Herein,we found that iso-carbon fatty acids with different number,position,and cis-trans configuration of double bonds dramatically affect the nanoassembly feature and drug delivery fates of thioether-linked paclitaxel prodrug-nanoassemblies.Particularly,the number and cis-trans configuration of double bonds in fatty acid moieties not only dominate the self-assembly ability and colloidal stability of prodrugs,but also exert significant influences on the pharmacokinetics,prodrug activation,and antitumor activity of prodrug-nanoassemblies.Finally,oleic acid with one cis double bond stands out as the optimal nonpharmacological moiety for thioether-linked paclitaxel prodrugnanoassemblies.This study elucidates the crucial roles of nonpharmacological moieties in prodrugs,and provides new insights into the modular design of prodrug-based nanomedicines for cancer therapy.

Tuning Structural and Electronic Configuration of FeN_(4) via External S for Enhanced Oxygen Reduction Reaction

The Fe-N-C material represents an attractive oxygen reduction reaction electrocatalyst,and the FeN_(4)moiety has been identified as a very competitive catalytic active site.Fine tuning of the coordination structure of FeN_(4)has an essential impact on the catalytic performance.Herein,we construct a sulfur-modified Fe-N-C catalyst with controllable local coordination environment,where the Fe is coordinated with four in-plane N and an axial external S.The external S atom affects not only the electron distribution but also the spin state of Fe in the FeN_(4)active site.The appearance of higher valence states and spin states for Fe demonstrates the increase in unpaired electrons.With the above characteristics,the adsorption and desorption of the reactants at FeN_(4)active sites are optimized,thus promoting the oxygen reduction reaction activity.This work explores the key point in electronic configuration and coordination environment tuning of FeN_(4)through S doping and provides new insight into the construction of M-N-C-based oxygen reduction reaction catalysts.

Synthesis and antiviral bioactivities of novel chiral bis-thiourea-type derivatives containing α-aminophosphonate moiety

Starting from 1-((1R,2R)-2-aminocyclohexyl)-3-substituted thioureas (3a–c) and substituted isothiocyanates (9a–d),chiral bis-thiourea derivatives containing α-aminophosphonate moiety 10a–l were prepared and completely characterized by elemental analysis,physical and spectral (IR,1H NMR,13C NMR,31P NMR) data.The results of bioassay revealed that compounds 10a and 10e possessed appreciable curative bioactivities on cucumber mosaic virus (CMV) at 0.5 mg/mL in vivo (inhibitory rate = 60.3%,64.8% respectively) and tobacco mosaic virus (TMV) at 0.5 mg/mL in vivo (inhibitory rate = 50.3%,50.8% respectively),which were comparable to the values shown by standard reference (58.7%) and commercial product Ningnanmycin (56.3%),respectively.Chiral compound 10e displayed more potent antiviral activity (EC50 = 0.149 mg/mL) than Ningnanmycin (EC50 = 0.201mg/mL) against CMV.

Synthesis and Antifungal Activity of Novel Chiral α-Aminophosphonates Containing Fluorine Moiety

Chiral α-aminophosphonates were synthesized using （R） or （S）-1-phenylethylamine in the presence of BF3·Et2O under microwave irradiation in moderate to good yields. The new compounds were identified by ^1H NMR, ^19F NMR, IR and elemental analysis. Their antifungal activities were evaluated and some compounds were found to exhibit excellent antifungal activities. To the best of our knowledge, this is the first report on antifungal activity of chiral α-aminophosphonates containing fluorine moiety.

Syntheses and Insecticidal Activity of Spirocyclic Tetronic Acid Derivatives Containing Oxime Ether Moiety

In order to develop novel spirocyclic tetronic acid lead compounds,a series of new spirocyclic tetronic acid derivatives containing oxime ether moiety was synthesized and bioassayed.The stmctures of 16 target compounds were characterized by lH NMR spectra,13C NMR spectra and high-resolution mass spectrometer(HRMS).Preliminary bioassays indicated that most of the title compounds displayed excellent insecticidal activity against Aphis fabae and Nilapmyata lugens at 100 mg/L.In particular,compound 6k showed the similar activity(LC50=6.87 mg/L)against A.fabae as the spirotetramat(LC50=4.56 mg/L)and had better efIects(LC50=l.64 mg/L)against N.lugens in comparison with spirotetramat(LC5o=7.90 mg/L).The study showed that compound 6k exhibited more promising and broad-spectrum insecticide activity and may serve as a new insecticidal agent for sucking pests.

Regioselective oxidation of tetracycline by permanganate through alternating susceptible moiety and increasing electron donating ability

Permanganate has attracted much attention in wide range of chemistry and particularly in degradation of environmental pollutants.However,few studies have discussed the feature of regioselective reactivity of permanganate with specific moiety of the target compound.Herein,we studied the reaction between permanganate and tetracycline that is an emerging micropollutant with different species containing several electron-rich groups.The second-order rate constants increased from 6.0 to 9.0 and could be quantitatively modeled by considering the speciation of both reactants,yielding kTC0=11.7(mol/L)^-1 sec^-1,kTC-=35.7(mol/L)^-1 sec^-1,kTC2-=43.1(mol/L)^-1 sec^-1 for individual reaction channels.Degradation products were then identified as the hydroxylated and demethylated compounds.The result suggested a rate-limiting step of simple hydroxylation at the phenolic and/or alkene moieties,while the demethylation should be caused by the unavoidably formed manganese oxide via single electron oxidation.This is supported by the DFT calculation,indicating the primary oxidation of phenolic group of TC0 with activation barrier of 44.5 kcal/mol and of alkene group of TC-and TC2-with activation barriers of 44.0 and 43.4 kcal/mol,respectively.This is in agreement with the experimental results,implying the alternation of regioselectivity associated with the deprotonation process.The result was further supported by performing the Fukui function and electrostatic potential analysis,reflecting the more probable site and better electron donating tendency beneficial to the permanganate oxidation.

Study of the synthesis,antiviral bioactivity and interaction mechanisms of novel chalcone derivatives that contain the 1,1-dichloropropene moiety

A series of novel chalcone derivatives that contain the 1,1-dichloropropene moiety was designed and synthesized. Bioactivity assays showed that most of the target compounds exhibited moderate to good antiviral activity against tobacco mosaic virus（TMV） at 500 mg/m L. Among the target compounds,compound 7h showed the highest in vivo inactivation activity against TMV with the EC50 and EC90value of 45.6 and 327.5 mg/m L, respectively, which was similar to that of Ningnanmycin（46.9 and 329.4 mg/m L）and superior to that of Ribavirin（145.1 and 793.1 mg/m L）. Meanwhile, the microscale thermophoresis and fluorescence spectroscopy experiments showed that the compound 7h had a strong interaction with the tobacco mosaic virus coat protein.