MoO_3、NiO、ZnO在小表面金红石上的分散行为

氧化物、盐类在氧化物载体表面的自发分散是一种广泛存在的现象，文献中已报导过大量氧化物和盐类在高比表面载体上分散的研究结果［'－3］TIO。作为一种较新型的载体，与Y－AI。O。、硅胶等传统载体相比，有许多不同特性．活性组分在TIO。表面的分散状态及所得催化剂的性能已有不少报导［'－'］，但所用的TIOZ主要是较高比表面的锐钛矿型TIOZ（刘金红石型TIO。（r）和锐钛矿型TIOZ（a）的结构不同，它是高温生成相，比表面较小［'］．氧化物在金红石上的分散行为仍未见报导．我们制备了三种具有不同比表面的TIO水），系统地研…     

含吡啶环系西佛碱大环配合物和氮杂大环自由配体的合成

2,6-二羟甲基吡啶(1)经活性MnO_2氧化得到2,6-二甲酰基吡啶(2)。邻硝基苯酚与N-取代的二(氯乙基)胺在DMF溶液中反应,得到N-取代的1,5-二(邻硝基苯氧基)-3-氮杂戊烷(3a～3c),再经水合肼/Raney Ni还原,获得N-取代的1,5-二(邻氨基苯氧基)-3-氮杂戊烷(4a～4c)。利用Ba~(2 )作为模板离子,(2)分别与(4a～4c)反应,合成了一类新的含吡啶环系西佛碱大环配合物Ⅰ～Ⅲ,配合物Ⅰ、Ⅲ经与NaBH_4的乙醇溶液还原解络,得到氮杂大环自由配体Ⅳ和Ⅴ。所有西佛碱大环配合物和氮杂大环自由配体均经元素分析、IR、~1H NMR、MS等证实了它们的结构和组成。     

A novel small-molecule near-infrared II fluorescence probe for orthotopic osteosarcoma imaging

Osteosarcoma is the most common primary malignant tumor of bone, particularly among children and adolescents. Advances in imaging, surgical techniques, and implants have dramatically reduced the need for amputation in the past three decades.Recently, in vivo fluorescence imaging in the second near-infrared window(NIR-II, 1,000–1,700 nm) shows impressive advantages of deeper tissue penetration and higher spatial resolution, which makes it a promising tool for the early diagnosis and post-operative observation of Osteosarcoma. To the best of our knowledge, this paper is the first time to develop a novel NIR-II fluorescence probe conjugated with an osteosarcoma targeted oligopeptide for molecular tumor imaging in a xenograft orthotopic osteosarcoma mouse model.     

An unusual mixed-valence Cu(I)-Cu(II) 3-D framework

The reaction of Cu(CH(3)CN)(4)ClO(4) with 2-pyridylacrylic acid (2-HPYA) affords an unusual mixed-valence Cu(I)-Cu(II) 3-D framework ([Cu(II)(2-PYA)(2)](3).[Cu(I)(2-PYA)](2).(H2O)(2))n (1) with a novel topology which features Cu(II) dimeric units (or paddle-wheel unit). The almost perpendicular coordinating direction between the N atom of pyridyl and the O atom of carboxylate groups may be responsible for the formation of such a novel network.     

Gas Phase Catalysis by Metal Nanoparticles in Nanoporous Alumina Membranes

Nanoporous alumina membranes, loaded with palladium and ruthenium nanoparticles of various size, were used for gas phase hydrogenation of 1, 3‐butadiene and for oxidation of carbon monoxide, respectively. Those membranes contain 10⁹ ‐ 10¹¹ pores per cm², all running perpendicular to the surface. Membrane discs of 20 mm in diameter and only 60 μm thick, incorporated in a reactor in which the reactants can be pumped in a closed circuit through the pores, turned out to very actively catalyze hydrogenation of butadiene (Pd) and oxidation of CO (Ru). The activity of the Pd catalysts depends characteristically on the particles size, the gas flow, and of the educts ratio. As could be expected, larger particles are less active than smaller ones, whereas increasing gas flows in case of hydrogenation accelerates the reactions. Excessive hydrogen reduces selectivity with respect to the various butenes, but favours formation of butane.     

Three tetrahydroisoquinolinedione derivatives

N‐(2‐Chloro­benzyl)‐1,2,3,4‐tetra­hydro­iso­quinoline‐1,3‐dione, C₁₆H₁₂ClNO₂, crystallizes in P2₁/n with three crystallographically independent mol­ecules in the asymmetric unit, which differ slightly in conformation, N‐(2‐bromo‐4‐methyl­phenyl)‐1,2,3,4‐tetra­hydro­iso­quinoline‐1,3‐dione, C₁₆H₁₂BrNO₂, crystallizes in P2₁/n with one mol­ecule in the asymmetric unit andN‐(2,3‐di­chloro­phenyl)‐1,2,3,4‐tetra­hydro­iso­quinoline‐1,3‐dione, C₁₅H₉Cl₂NO₂, crystallizes in P2₁/c with one mol­ecule in the asymmetric unit. In all three structures, the heterocyclic rings adopt approximately planar conformations. The pyridine rings are orthogonal to the substituted phenyl rings. In all three structures, the crystal packing is stabilized by intermolecular C—H?O hydrogen bonds.     

Cover Picture: Highly Regioselective Sequential 1,1‐Dihydrosilylation of Terminal Aliphatic Alkynes with Primary Silanes (Chin. J. Chem. 5/2019)

The cover picture shows that sequential 1,1‐dihydrosilylation of terminal aliphatic alkynes with primary silanes enabled by one earth‐abundant cobalt catalyst has been developed. This protocol is operationally simple using readily available aliphatic alkynes, including simple acetylene and complex drug derivative, for efficient access to valuable gem‐bis(dihydrosilyl)alkanes in highly regioselective and atom‐economic manners. Corresponding asymmetric transformations are achieved with excellent enantioselectivities. More details are discussed in the article by Lu et al. on page 457–461.

     

Indirect Determination of Captopril with Sodium Nitrate and Thiocyanate by Floatation Separation of Copper

A new method for indirect determination of captopril (CPT) with NaNO₃ and NH₄SCN by floatation and separation of copper has been studied. In the weak acid, a small amount of Cu(II) can be reduced to Cu(I) by CPT, then Cu(I) reacted with the SCN, which can float on the surface of the liquid phase with NaNO₃. A good linear relationship is observed between the floatation yield (E%) of Cu(II) and the amount of captopril. The linear range is 2?32 mg/L. On the ground, captopril can be indirectly determined by determining E(%) of Cu(II). The method is simple, rapid, reliable and has good selectivity. The developed method can be applied to indirect determination of captopril with satisfactory results.     

A New Saponin Transformed from Ginsenoside Rh1 by Bacillus subtilis

A novel saponin was isolated from the transformed products of ginsenoside Rh1 by Bacillus subtilis. It‘s structure was determined to be 3-O-β-D-glucopyranosyl-6-O-β-D-glucopyranosyl-20 (S)-protopanaxatriol on the basis of the spectral data.     

DPPH (= 2,2‐Diphenyl‐1‐picrylhydrazyl = 2,2‐Diphenyl‐1‐(2,4,6‐trinitrophenyl)hydrazyl) Radical‐Scavenging Reaction of Protocatechuic Acid Esters (= 3,4‐Dihydroxybenzoates) in Alcohols: Formation of Bis‐alcohol Adduct

Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD₃OD/(D₆)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents.