Immobilization of metal-organic molecular cage on g-C3N4 semiconductor for enhancement of photocatalytic H2 generation

A new compound based on immobilizing of Pd6(RuL3)8(BF4)28 (L=2-(pyridin-3-yl)-1H-imidazo [4,5-f][1,10]-phenanthroline) cage (MOC-16) on g-C3N4 was synthesized. Infrared spectrum and powder X-ray diffraction were used to characterize structure of hybrid MOC-16/g-C3N4, as well as UV-vis absorption spectrum and X-ray photoelectron spectroscopy were carried out to unveil photocatalytic mechanism. With the introduction of MOC-16, the absorption edge of MOC-16/g-C3N4 in UV-vis spectrum extended apparently to long-wavelength region compared with pristine g-C3N4. H2 evolution yielded with MOC-16/g-C3N4 in aqueous solution containing TEOA was much higher than that with RuL3/g-C3N4, Pd/RuL3/g-C3N4 and mixture of MOC-16 and g-C3N4, showing that the octahedral cage structure with high-efficient electron transfer and the interface interaction between MOC-16 and g-C3N4 were significant for improvement of H2 evolution.

Rational Engineering of Secondary Metabolic Pathways in a Heterologous Host to Enable the Biosynthesis of Hibarimicin Derivatives with Enhanced Anti-Melanomic Activity

A 61-kb biosynthetic gene cluster(BGC),which is accountable for the biosynthesis of hibarimicin(HBM)B from Microbispora rosea subsp.hibaria TP-A0121,was heterologously expressed in Streptomyces coelicolor M1154,which generated a trace of the target products but accumulated a large amount of shunt products.Based on rational analysis of the relevant secondary metabolism,directed engineering of the biosynthetic pathways resulted in the high production of HBM B,as well as new HBM derivates with improved antitumor activity.These results not only establish a biosynthetic system to effectively synthesize HBMs-a class of the largest and most complex Type-Ⅱpolyketides,with a unique pseudo-dimeric structure-but also set the stage for further engineering and deep investigation of this complex biosynthetic pathway toward potent anticancer drugs.

Enantiodifferentiation of chiral diols and diphenols via recognition-enabled chromatographic^(19)F NMR

A novel and efficient method for distinguishing between chiral diols and diphenols has been established through the use of^(19)F NMR spectroscopy.Central to this system's efficacy is a chiral amine,strategically modified with a CF_(3)group.This amine reacts in-situ with 2-formylphenylboronic acid to create a chiral^(19)F-labeled probe.This probe demonstrates discriminatory capabilities by interacting with hydroxy-containing analytes to form boronic esters.These esters produce distinct^(19)F NMR signals that vary according to their stereoconfiguration,facilitating accurate chiral differentiation.The method's resolution capacity was demonstrated by successfully identifying 12 distinct chiral analytes(six pairs of enantiomers)in complex mixtures,highlighting its extensive potential in diverse chiral analysis applications.

Synthesis and Crystal Structure of 3,4-Bis(azidoacetamino)furazan

Bis(azidoacetamino)furazan (DAZAF) was synthesized and characterized by elemental analysis, IR, 1H NMR and MS as an energetic compound. The crystal structure of the title compound was determined by single-crystal X-ray diffraction with the following data: C6H6N10O3, monoclinic, P21/n, Z = 4, a = 8.402(3), b = 15.146(3), c = 9.247(3) ? ?= 111.09(2)? V = 1098.0(6) 3, Mr = 266.18, Dc = 1.610 g/cm3, F(000) = 544, ?=1.34 cm-1, R = 0.037 and wR = 0.044 for 2136 observed reflections (I > 2(I)). Intra- and inter-molecular hydrogen bonds were identified between the O and H atoms of two intramolecular acetylamino groups and two intermolecular acetylamino groups, respectively.

Superior performance of iridium supported on rutile titania for the catalytic decomposition of N_2O propellants

N2O is a promising green propellant and exhibits great potential for satellite propulsion systems. It is difficult for catalytic decomposition, which is an important way to initiate the propulsion process, to occur at temperatures below 600 °C due to the high activation energy of N2O. In this work, we report an Ir supported on rutile TiO2（Ir/r-TiO2） catalyst which exhibits a fairly high activity for high-concentration N2O decomposition. HAADF-STEM, H2-TPR, and XPS results indicate that highly dispersed Ir particles and improved oxygen mobility on the Ir/r-TiO2 could facilitate the decompo-sition of N2O and desorption of the adsorbed oxygen. Bridge-bonded peroxide intermediates were observed with in-situ DRIFT and herein, a detailed decomposition route is proposed.

Electron paramagnetic resonance study of amphiphiles partitioning behavior in desiccation-tolerant moss during dehydration

Desiccation tolerance is a crucial characteristic for desert moss surviving in arid regions. Desiccation procedure always induces amphiphiles transferring from the polar cytoplasm into lipid bodies. The behavior of amphiphiles transferring can contribute to the enhancement of desiccation tolerance and the reduction of plasma membrane integrity simultaneously. The effects of amphiphiles partitioning into the lipid phase during water loss has been studied for pollen and seeds using electron paramagnetic resonance （EPR） spectroscopy. However, desiccation-tolerant high plants occur among mosses, several angiosperms and higher plants seeds or pollens. They have different strategies for survival in dehydration and rehydration. A desiccation-tolerant moss Tortula desertorurn was used to investigate the behaviors of amphiphilic molecules during drying by spin label technology. There are small amount of amphiphilic probes partitioning into membrane during moss leaves dehydration, comparing with that in higher plants. Cytoplasm viscosity changed from 1.14 into glass state only dehydration less than 60 min. Moss leaves lost plasma membrane integrity slightly,from 0.115 to 0.237, occurred simultaneously with amphiphiles partition. The results showed the more advantages of mosses than higher plants in adapting fast dehydration. We propose that EPR spin label is feasible for studying the amphiphiles partitioning mechanisms in membrane protection and damage for desiccation-tolerant mosses.

Synthesis of Enamines via the Cross-coupling of Thioamides and Diarylketones Promoted by the Sm/SmI_(2)Mixed Reagent

Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.

Fabrication of a novel poly(dimethylsiloxane) microchips with two sharpened stretching tips

An integrated poly(dimethylsiloxane) (PDMS) microchip with two sharpened stretching has been presented. The sample was directly introduced into the separation channel through the stretching inlet tip without complicated power switching supplies and without injection cross-channel. Operations of running buffer refreshing or channel cleaning also becomes simple by vacuumed in one end and placed another tip into solution vial. The fabrication method can be easily applied in most analytical laboratories at low cost in the absence of soft lithography and plasma bonding equipments. Characteristics of the chips were tested and it can be used to separate fluorescence labeled molecules.

HOW DO THE RATES OF HALOPHILIC ATTACKS COMPARE WITH THE RATES OF PROTOPHILIC ATTACKS?

The measured relative rates of halophilic and protophilic attacks (k_X/k_H) indicate that the rates of halophilic attacks are comparable in magnitude to those of protophilic attacks (deprotonations).

ISOLATION AND STRUCTURES OF FOUR CYCLODIPEPTIDES

Three novel interesting polychlorinated cyclodipeptides,designated dyssmide A(1),B(2),C(3)and a known compound,2,3-dihydrodyeamide C(4)were isolated from the sponge Dysidea sp.Their structures were elucidated by spectroscopic methods.

Recovery of Li_(2)CO_(3)and FePO_(4)from spent LiFePO_(4)by coupling technics of isomorphic substitution leaching and solvent extraction

Efficient and low-cost recycling of spent lithium iron phosphate(LiFePO_(4),LFP)batteries has become an inevitable trend.In this study,an integrated closed-loop recycling strategy including isomorphic substitution leaching and solvent extraction process for spent LFP was proposed.An inexpensive FeCl_(3)was used as leaching agent to directly substitute Fe^(2+)from LFP.99%of Li can be rapidly leached in just 30 min,accompanied by 98%of FePO_(4)precipitated in lixivium.The tri-n-butyl phosphate(TBP)-sulfonated kerosene(SK)system was applied to extract Li from lixivium through a twelve-stage countercurrent process containing synchronous extraction and stepwise stripping of Li^(+)and Fe^(3+).80.81%of Li can be selectively enriched in stripping liquor containing 3.059 mol·L^(-1)of Li^(+)under optimal conditions.And the Fe stripping liquor was recovered for LFP re-leaching,of which,Fe^(2+)was oxidized to Fe^(3+)by appropriate H_(2)O_(2).Raffinate and lixivium were concentrated and entered into extraction process to accomplished closeloop recycling process.Overall,the results suggest that more than 99%of Li was recovered.FeCl_(3)holding in solution was directly regenerated without any pollutant emission.The sustainable mothed would be an alternative candidate for total element recycling of spent LFP batteries with industrial potential.

Synthesis of Mono-esters of Phenyl-and Substituted Phenylphosphonic Acids and Their Performance in Rare Earth Extraction

Methodsfor the synthesis of acidic phenyl-and substituted phenylphosphonates bearing a branched long chain ester alkyl group are described.These synthetic routes are incomparably superior to other methods in vari- ous aspects including better reaction yield and higher purity of the product.The behaviour of the mono(2-butyloctyl)esters and mono(2-methyldodecyl)esters of both phenyl-and o-methylphenylphosphonic acids thus obtained in extraction of lanthanum,praseodymium,neodymium and lutecium as representatives of light and heavy rare earths,is investigated and discussed on the basis of their chemical structure.The dependence of the extraction constants and separation factors accords with the Reactivity-Selectivity Principle in solvent ex- traction proposed by us.The composition and structure of the extracted species have been characterized by infra-red and proton nuclear magnetic resonance spectroscopy in addition to elemental analyses.

Extraction of Lithium from Salt Lake Brine using N523-TBP Mixture System

In this work, problems encountered by tri-butyl phosphate (TBP) in the industrialization of lithium extraction from salt lake brine were discussed in detail. The behavior of N, N-bi-(2-ethylhexyl) acetamide (N523) during lithium extraction was investigated, and its disadvantages were analyzed in the view of practical application. An N523-TBP mixture extraction system was proposed to alleviate or avoid the defects that N523 and TBP met when they were used separately. The optimal composition of this mixture extraction system was determined to be 20%N523-30%TBP-50% kerosene. The effects of brine acidity, Fe/Li molarity ratio, phase ratio and chloride ion concentration on lithium extraction efficiency were discussed. The operation conditions in single-stage extraction were optimized as brine acidity=0.05 mol/L, Fe/Li molarity ratio=1.3, and phase ratio=2. The high concentration of chloride ions in brine was beneficial for the extraction of lithium. The structure of the extracted complex was proposed as (LiFeCl 4 · n N523 · m TBP)·(2- n )N523 ·(2- m )TBP (m+n=2) by chemical analysis and slope-fitting methods. The extraction thermodynamic functions were calculated preliminarily, and the results suggested that the extraction process was an exothermic (ΔH <0) and spontaneous (ΔG <0) reaction, and the degree of disorder increased (ΔS >0) during the extraction process. This work will give some guidance to the lithium industry of Qinghai in both the fundamental theory and practical application.

ENZYME REACTION IN AQUEGUB-ORGANIC BYSTEM —KINETIC RESOLUTION OP RACEMIC OXIRANECARBOXYLIC ESTERS WITH LIPASE

The chiral oxiranecarboxylic acids or esters 2a-e were obtained with lipase (CCL) in aqueous-organic system.The ee and the absolute configurations of the products were determined.

Synthesis, Characterization and Crystal Structure of Neutral Homoleptic Lanthanide Amide Yb(NPh_2)_3(THF)

A neutral homoleptic lanthanide amide Yb(NPh 2) 3(THF) 2 was obtained by reaction of anhydrous YbCl 3 with LiNPh 2 in THF. The product was characterized by elemental analysis, infrared spectrum and X-ray crystallographic analysis. The crystal data are monoclinic, P2 1/n space group, a=1.2052(2) nm, b=1.9369(3) nm, c=1.6523(2) nm, β=92.79(1)°, V=3.8524(9) nm 3, Z=4, D c=1.417 g·cm -3, μ=24.67 cm -1 (Mo Kα), F(000)=1668, R=0.036, R w=0.039. The central metal ytterbium is coordinated by three terminal NPh 2 groups and two THF molecules to form a five-coordinate distorted trigonal bipyramid. The mean Yb-N bond length is 0.2219(6) nm.

Pd-catalyzed sequential reaction for the synthesis of fused tricyclic compounds containing a dihydrofuran or isobenzofuranone unit

A novel Pd-catalyzed sequential reaction for the synthesis of fused tricyclic compounds with a dihydrofuran or isobenzofuranone unit was developed.

Addition of Allyltrimethylsilane to tert-Butanesulfinyl Imines Triggered by Tetra-n-butylammonium Fluoride

The addition of allyltrimethylsilane to tert-butanesulfinyl imines triggered by tetra-n-butylammonium fluoride （TBAF） in the presence of 4A molecular sieves has been studied, and homoallylsulfinamides were obtained in good yields with moderate to high diastereoselectivities.

CONDENSATION OF 1,2-DIAMINES AND CARBOXYLICACIDS UNDER MICROWAVE IRRADIATION

A facile method of preparation of benzimidazoles by microwave irradiation was described. The mixtures of o-phenylenediamine and carboxylic acids were heated by microwave irradiation, to give 2-substituted benzimidazoles with yields of 49%～93%. The reaction time was shortened to 3～6 min. However, the reaction of ethylenediamine with carboxylic acids did not give imidazoles but the N,N-diacyl ethylenediamines. The alphatic diamines lacked the activity to form imidazole ring. With adipic acid, intermolecular acylation took place to afford poly(ethylene adipamide).

Synthesis and Crystal Structure of Tetra(diisopropyl-amido-N)ytterbium Mono(tetrahydrofuran-O)lithium

The reaction of anhydrous YbCl3 with LiNPri2 in 1:3 molar ratio gave the homo- leptic lanthanide amide ate complex Yb(C6H14N)4Li(C4H8O). The crystal structure was determined by X-ray diffraction and the following crystallographic data were obtained: C28H64N4OYbLi, Mg = 652.82, monoclinic, P21/c (#14), a = 15.239(3), b = 21.502(6), c = 21.288(4) ? b = 93.18(2), V = 6964(2) 3, Z = 8, Dc = 1.245 g/cm3, F(000) = 2728 and m(MoKa) = 27.08 cm-1. The final R and Rw are 0.044 and 0.053 for 6765 observed reflections with I > 3.00s(I), respectively. The ytterbium atom is bonded to two terminal amide ligands with the normal YbN distances of 2.171(6) and 2.174(7) ? and two bridging amide ligands with the YbN bonds about 0.1 ?longer than those of the formers, forming a distorted tetrahedral geometry.