Transient‐Ligand‐Enabled ortho‐Arylation of Five‐Membered Heterocycles: Facile Access to Mechanochromic Materials

Reported herein is the first example of a direct arylation of heteroarenes by a transient‐ligand‐directed strategy without the need to construct and deconstruct the directing group. A wide range of heteroarenes undergoes the coupling with diverse aryl iodides to assemble a large library of highly selective and functionalized 3‐arylthiophene‐2‐carbaldehydes. This route provides an opportunity to rapidly access new mechanofluorochromic materials. Moreover, a novel strategy for mechanochromic luminogens with chromism trends of red‐ and blue‐shifts has been disclosed for the first time by facile functional‐group modifications to a common structural core.     

An Assembled Nanocomplex for Improving both Therapeutic Efficiency and Treatment Depth in Photodynamic Therapy

Photodynamic therapy (PDT) shows unique selectivity and irreversible destruction toward treated tissues or cells, but still has several problems in clinical practice. One is limited therapeutic efficiency, which is attributed to hypoxia in tumor sites. Another is the limited treatment depth because traditional photosensitizes are excited by short wavelength light (<700 nm). An assembled nano‐complex system composed of oxygen donor, two‐photon absorption (TPA) species, and photosensitizer (PS) was synthesized to address both problems. The photosensitizer is excited indirectly by two‐photon laser through intraparticle FRET mechanism for improving treatment depth. The oxygen donor, hemoglobin, can supply extra oxygen into tumor location through targeting effect for enhanced PDT efficiency. The mechanism and PDT effect were verified through both in vitro and in vivo experiments. The simple system is promising to promote two‐photon PDT for clinical applications.     

Smart DNA Hydrogel Integrated Nanochannels with High Ion Flux and Adjustable Selective Ionic Transport

Nanochannels based on smart DNA hydrogels as stimulus‐responsive architecture are presented for the first time. In contrast to other responsive molecules existing in the nanochannel in monolayer configurations, the DNA hydrogels are three‐dimensional networks with space negative charges, the ion flux and rectification ratio are significantly enhanced. Upon cyclic treatment with K⁺ ions and crown ether, the DNA hydrogel states could be reversibly switched between less stiff and stiff networks, providing the gating mechanism of the nanochannel. Based on the architecture of DNA hydrogels and pH stimulus, cation or anion transport direction could be precisely controlled and multiple gating features are achieved. Meanwhile, G‐quadruplex DNA in the hydrogels might be replaced by other stimulus‐responsive DNA molecules, peptides, or proteins, and thus this work opens a new route for improving the functionalities of nanochannel by intelligent hydrogels.     

肉桂酰酪胺类似物的合成与抗血小板聚集评价

为了探究肉桂酰酪胺的苯环上甲氧基取代、酪胺上羟基和酰胺上胺基被甲基化对衍生物抗血小板聚集活性的影响,以8种苯甲醛衍生物为原料,经过缩合反应及甲基化等反应制得肉桂酰酪胺类似物,经核磁共振波谱仪(NMR)、质谱(MS)、单晶衍射等技术手段表征了目标化合物结构。 基于变温核磁,探讨了化合物4a~4h中旋转异构及酰胺C-N键双键性质对氢核磁谱的影响。 采用Born比浊法对目标化合物进行活性筛选,9个类似物的活性均强于柄果花椒酰胺,特别是化合物2c、4c、4f在200 μmol/L时显示出强的抑制率,分别为50.03%、60.87%、53.33%。 该类化合物的构效关系是4位甲氧基取代对化合物的抗ADP(二磷酸腺苷)诱导血小板聚集活性最为有利,甲基化B环中的羟基和结构中的酰胺氮原子时,在某种程度上可增强化合物活性。     

基于核酸和蛋白的生物大分子热致液晶研究进展

生物固体大分子诸如核酸、蛋白和病毒颗粒,因其尺寸超出了分子间作用力的范围,升温之后会导致它们降解而无法形成生物大分子的液体形态。 因此,发展新型的合成和制备策略,实现无溶剂包覆的生物大分子的流体态及其应用,是一个崭新的研究领域。 结合我们前期工作,简要介绍了核酸、蛋白流体(液晶态和液体态)材料的制备及性质。 借助静电力自组装,上述生物大分子能够与带有相反电荷的表面活性剂结合,形成热致液晶材料,其热致液晶性质使得生物分子具有长程有序性和流动性,在此基础上,可以探索生物大分子在无水环境下的技术应用。     

Two new hirsutane-type sesquiterpenoids chondrosterins N and O from the marine fungus Chondrostereum sp.

The marine fungus Chondrostereum sp. was collected from a soft coral Sarcophyton tortuosum from the South China Sea. This fungus was cultured in glucose-peptone-yeast (GPY) medium and the culture broth was extracted with EtOAc. By the method of ¹H NMR pre-screening and tracing the diagnostic proton signals of the methyl groups, two new hirsutane-type sesquiterpenoids, chondrosterins N and O (1 and 2) were isolated from the metabolite extracts. Their structures were elucidated on the basis of MS, 1D and 2D NMR data.     

草药中 11种元素的聚焦微波辅助萃取-等离子体质谱法测定

利用ICP－MS对青钱柳叶、龙胆草以及秦皮中的11种金属元素进行测定。应用CEM Star-Ⅱ聚焦微波萃取系统,采用正交设计实验研究了温度、时间、料液质量体积比对浸取效率的影响。结果表明,温度是影响提取效率的主要因素,提取时间对某些元素影响也比较明显,但料液比对几乎所有元素的影响都很小。钒元素在微波萃取条件下溶出率很低。     

Mg-Al-CO3水分散液的稳定性及流变性

水滑石;水分散体系;层状结构;Mg-Al-CO3水分散液的稳定性及流变性     

Study on new typical ionic clusters K+ (KNO3)n and NO3‐(KNO3)m

The sample solution of KNO₃ is ejected into the gas phase and the ionic dusters of K⁺(KNO₃)_n and NO₃ (KNO₃)_m are formed and observed by electrospray ionization mass spectrometry (ESIMS). Hie full mass spectra of both the positive ion and the negative ion show that the differences between each peak nearby are all about 101 (m/z), which correspond to the molecular weight of KNO₃. The general formula of the ionic clusters can be assigned as K⁺(KNO₃)_n and NO₃′‐(KNO₃)_m..     

Crystal Structure,Magnetic Exchange Interaction,and DFT Study of 2,2′‐(1‐Oxidopyridine‐2,6‐diyl)bis[4,5‐dihydro‐4,4,5,5‐tetramethyl‐3‐oxido‐1H‐imidazol‐1‐oxyl] Hydrate

The structure of a novel oxido‐aminoxyl (=`nitronyl nitroxide') biradical, 2,2′‐(1‐oxidopyridine‐2,6‐diyl)bis[4,5‐dihydro‐4,4,5,5‐tetramethyl‐3‐oxido‐1H‐imidazol‐1‐oxyl] hydrate ( 1 ⋅H₂O) was established by X‐ray analysis in the solid state: monoclinic, space group P2₁/c, Z=4 with a=12.621(4), b=15.704(5), and c=13.001(4) Å, and β=115.202(6)°. Variable‐temperature magnetic susceptibilities show a weak antiferromagnetic interaction between the two oxido‐substituted aminoxyl moieties of 1 , indicative of a singlet ground state. AM1 Calculations located minima for the possible structure based on the X‐ray crystal structure. A hybride density‐functional‐theory calculation with the UB3LYP method from the X‐ray crystal structure establishes the same spin sign in the two aminoxyl moieties and shows that a small spin density is localized at the C‐atoms of the pyridine moiety. These theoretic results are in good agreement with the determined weak antiferromagnetic interaction of 1 .