Cascade One‐Pot Synthesis of Orange‐Red‐Fluorescent Polycyclic Cinnolino[2,3‐f]phenanthridin‐9‐ium Salts by Palladium(II)‐Catalyzed C−H Bond Activation of 2‐Azobiaryl Compounds and Alkenes

Quaternary ammonium salts were synthesized in moderate to good yields through double oxidative C?H bond activation on azobenzenes. The mechanism of the highly regioselective reaction of 2‐azobiaryls with alkenes to give orange‐red‐fluorescent cinnolino[2,3‐f]phenanthridin‐9‐ium salts and 15H‐cinnolino[2,3‐f]phenanthridin‐9‐ium‐10‐ide is proposed to involve ortho C?H olefination of the 2‐azobiaryl compound with the alkene, intramolecular aza‐Michael addition, concerted metalation–deprotonation (CMD), reductive elimination, and oxidation.     

Structure Determination of Alkynyl‐Protected Gold Nanocluster Au22(tBuC≡C)18 and Its Thermochromic Luminescence

An alkynyl‐protected gold nanocluster, Au₂₂(^tBuC≡C)₁₈ ( 1 ), has been synthesized and its structure has been determined by single‐crystal X‐ray diffraction. The molecular structure consists of a Au₁₃ cuboctahedron kernel and three [Au₃(^tBuC≡C)₄] trimeric staples. The cluster 1 has strong luminescence in the solid state with a 15 % quantum yield, and it displays interesting thermochromic luminescence as revealed by temperature‐dependent emission spectra. The enhanced room‐temperature emission is characterized as thermally activated delayed fluorescence.     

Autocatalytic polymerization of selenium/polypyrrole nanocomposites as functional theranostic agents for multi-spectral photoacoustic imaging and photothermal therapy of tumor

The synchronization of diagnosis and treatment is a new trend in cancer treatment. Photoacoustic imaging (PAI) and photothermal therapy (PTT) are recognized as one of the perfect combinations. The autocatalytic polymerization of selenium/polypyrrole (Se@PPy) nanocomposites with a wide-absorption band at near-infrared region (NIR, 800 nm) has been developed in this paper. The wide optical absorption characteristics enable Se@PPy nanocomposites to achieve multi-spectral PAI. Ex vivo experiments show desirable photoacoustic ability of the Se@PPy nanocomposites at wavelengths ranging from 700 nm to 900 nm, which is better than that of commercial indocyanine green (ICG). Se@PPy nanocomposites have high photothermal conversion efficiency up to 36.3% as well as excellent photo-thermal stability. In vitro cytotoxicity test demonstrates that the Se@PPy nanocomposites have good bio-safety. Furthermore, the feasibility of Se@PPy nanocomposites for enhancing multi-spectral PAI guided PTT was verified on 4T1 tumor-bearing nude mice. Our results indicate that Se@PPy nanocomposites could be used as an effective theranostic agent for near-infrared light-mediated PAI and PTT of tumor.     

单分散磁性Fe3O4纳米粒子修饰石墨烯的制备及应用

通过油相热分解法在石墨烯(Gr)的表面修饰单分散的Fe3O4纳米颗粒,然后将二亚乙基三胺五乙酸(DTPA)通过多巴胺(DPA)化学键合到到Gr复合物表面,制备了新型磁性纳米复合材料Gr@Fe3O4-DPA-DTPA,采用X射线衍射、透射电镜、振动样品磁强计、傅里叶红外、拉曼和紫外光谱等技术对该材料进行了表征。结果表明,材料对水中的芳香族化合物和重金属离子具有很强的吸附能力,对水中的萘和Cu2+的吸附容量分别达到207.9和72.2mg/g。     

New Insights into Keggin‐Type 12‐Tungstophosphoric Acid from 31P MAS NMR Analysis of Absorbed Trimethylphosphine Oxide and DFT Calculations

The acid and transport properties of the anhydrous Keggin‐type 12‐tungstophosphoric acid (H₃PW₁₂O₄₀; HPW) have been studied by solid‐state ³¹P magic‐angle spinning NMR of absorbed trimethylphosphine oxide (TMPO) in conjunction with DFT calculations. Accordingly, ³¹P NMR resonances arising from various protonated complexes, such as TMPOH⁺ and (TMPO)₂H⁺ adducts, could be unambiguously identified. It was found that thermal pretreatment of the sample at elevated temperatures (≥423 K) is a prerequisite for ensuring complete penetration of the TMPO guest probe molecule into HPW particles. Transport of the TMPO absorbate into the matrix of the HPW adsorbent was found to invoke a desorption/absorption process associated with the (TMPO)₂H⁺ adducts. Consequently, three types of protonic acid sites with distinct superacid strengths, which correspond to ³¹P chemical shifts of 92.1, 89.4, and 87.7 ppm, were observed for HPW samples loaded with less than three molecules of TMPO per Keggin unit. Together with detailed DFT calculations, these results support the scenario that the TMPOH⁺ complexes are associated with protons located at three different terminal oxygen (O_d) sites of the PW₁₂O₄₀³⁻ polyanions. Upon increasing the TMPO loading to >3.0 molecules per Keggin unit, abrupt decreases in acid strength and the corresponding structural variations were attributed to the change in secondary structure of the pseudoliquid phase of HPW in the presence of excessive guest absorbate.     

Synthetic Transformations of Sulfur‐Substituted 4‐Quinolizidinones

Sulfur‐substituted 4‐quinolizidinones, previously prepared by aza‐Diels‐Alder reactions and ring‐closing metathesis, are now subjected to further synthetic transformations. Formal synthesis of cermizine C and 5‐epi‐cermizine C, and some other useful reactions have been achieved.     

Understanding the Effect of Solvent Environment on the Interaction of Hydronium Ion with Biomass Derived Species: A Molecular Dynamics and Metadynamics Investigation

The addition of aprotic solvents results in higher reactivities and selectivities in many key aqueous phase biomass reactions, including the acid-catalyzed conversion of fructose to 5-hydroxyl methyl furfural (HMF). The addition of certain co-solvents inhibits the formation of humins via preferential solvation of key functional groups and can alter reaction kinetics. An important factor in this context is the relative stability of the hydronium ion (the catalyst) in the vicinity of the biomass moiety as compared to that in bulk, as it could determine its efficacy in the protonation step. Hence, in the present work, molecular dynamics (MD) simulations of HMF (the model product) and fructose (the model reactant) in acidic water and water-DMSO mixtures are performed to analyze their interaction with the hydronium ions. We show that the presence of DMSO favors the interaction of the hydronium ion with fructose, whereas it has a detrimental effect on the interaction of hydronium ion with HMF. Well-tempered metadynamics (WT-MTD) simulations are performed to determine the relative stability of the hydronium ion in the immediate vicinity of fructose and HMF, as compared to that in the bulk solvent phase, as a function of solvent composition. We find that DMSO improves the stabilization of the hydronium ions in the first solvation shell of fructose compared to that in the bulk solvent. On the other hand, hydronium ions become less stable in the immediate vicinity of HMF, as the concentration of DMSO increases.     

Further studies of M3(μ3-O)(μ-X)3(μ-O2CCH3)3L3 (M=Mo,W) type clusters with nine core electrons

Four new compounds having nine cluster electrons and cores of the types Mo₃OCl₃, Mo₃OBr₃, and W₃OCl₃ are reported. Compound (1) prepared by reduction of [Bu₄N][Mo₃OCl₆(OAc)₃] in THF with metallic zinc, was shown by X-ray crystallography to be Mo₃OCl₄(OAc)₃ (THF)₂ (1). It forms crystals in space groupP2₁ with unit cell dimensionsa=9.472(2) Å,b=13.546(4) Å,c=9.652(2) Å, =101.70(2)°,V=1201(1) Å₃,Z=2. The [Mo₃(₃-O)(-Cl)₃]⁴⁺ core is surrounded by three -O₂CCH₃ anions, one Cl^–, and two THF and has Mo-Mo distances of 2.620(1) Å, 2.613(1) Å, and 2.530(1) Å, with the shortest bond between the two Mo atoms to which the THF molecules are coordinated. Compounds [Bu₄N]₂ [Mo₃OBr₆(O₂CCH₃)₃] · Me₂CO, (2) and [Mo₃OBr₃(O₂CCH₃)₃(PMe₃)₃]₃ · BF₄, (3) are the first two nine-electron Mo₃ species with a [Mo₃(₃-O) Br₃]⁴⁺ core. Both were obtained by zinc reduction of [Mo₃OBr₆(O₂CCH₃)₃]^– in the presence of (NBu₄) Br (2) or PMe₃ and NaBF₄ (3), and each was characterized crystallographically. Compound (2) crystallized in space group Cc with unit cell dimensionsa=25.037(5) Å,b=12.827(2) Å,c=21.484(4) Å, =122.96(1)⁰,V=5790(3) ų,Z=4. While the anion has no crystallographically required symmetry, its virtual symmetry is C_3v . The Mo-Mo distances are 2.619(2) Å, 2.610(3) Å, 2.644(2) Å, with a mean value of 2.624[14] Å. Compound (3) crystallized in space groupP2₁/c with unit cell dimensionsa=10.846(2) Å,b=25.033(5) Å,c=12.641(5) Å, =94.74(2)⁰,V=3420(2) ų,Z=4. The cation occupies a general position but has virtual C_3v symmetry, with Mo-Mo distances of 2.601(2) Å, 2.610(2) Å, 2.627(2) Å, with a mean value of 2.613[14] Å. Thus the anionic and cationic Mo₃ clusters in (2) and (3), respectively, have average Mo-Mo distances that are equal within experimental error. Compound (4), [NEt₄]₂ [W₃OCl₆(O₂CCH₃)₃] is the first 9-electron compound of this type containing tungsten. It was prepared by reduction of [Et₄N][W₃OCl₆(OAc)₃] in benzene with Na/Hg. It crystallized in space groupP2₁2₁2₁ with unit cell dimensionsa=11.076(2) Å,b=14.345(2) Å,c=21.026(3) Å,V=3574(1) ų,Z=4. The anion resides on a general position but has virtual C_3v symmetry, with W-W distances of 2.577(1) Å, 2.612(1) Å, 2.584(1) Å and a mean value of 2.591[15] Å.     

与时俱进，不断开创物理化学课程建设新局面

As a necessary basic theory course for undergraduates majoring in chemistry, materials, pharmacy, chemical engineering, and biology, physical chemistry plays an important role in cultivating talents to meet the needs of social and economic development. Over the years, the teaching team of physical chemistry of East China University of Science and Technology has carried out the curriculum reform and innovation persistently based on "Team building as the foundation, resource building as the root, mode innovation as the soul, ability training as the origin". This paper will summarize our thinking and experience in striving for the first-class course from the aspects of first-class team construction, first-class resource construction, teaching connotation innovation, teaching mode exploration, and extract the experience that can be used as reference by teaching peers.     

à 3E态CH3N自由基的稳定性

观察到了CH_3N自由基Ã ~3E←X~3A_2体系317-272 nm的荧光激发谱, 特别讨论了振动激发的Ã 态的稳定性. 报导了v_3~′=6态的色散荧光和荧光时间谱, 该态在240 Pa下的寿命大约是80 ns. 实验表明Ã ~3E 态CH_3N自由基是稳定的, 势能面至少距振动基态4800 cm~(-1)内是束缚的, 异构化或预离解作用并不重要.