Basic concepts of "cation pool" and "cation flow" methods and their applications in conventional and combinatorial organic synthesis

Carbocations have been generally considered to be relatively unstable and transient species. But the "cation pool" method enables the easy accumulation of carbocations in conventional reaction media such as dichloromethane. In the "cation pool" method, carbocations are generated by low-temperature electrochemical oxidation and accumulated in a solution. In the next step, the carbocations thus produced are allowed to react with various nucleophiles. Combinatorial parallel synthesis based upon the "cation pool" method has also been developed. The applicability of the "cation pool" method depends upon the stability of the cation that is accumulated. This problem can be overcome by the "cation flow" method. In the "cation flow" method, carbocations are generated in a microflow electrochemical system. Short residence times and efficient temperature control of the microflow system are advantageous. Combinatorial sequential synthesis has been achieved based on the "cation flow" method.     

Photoassisted "gate-lock" fluorescence "turn-on" in a new Schiff base and coordination ability of E-Z isomers

Rapid photoresponse (1.0-8.0 min) through fluorescence "turn-on" signaling displayed by a novel Schiff base (L) creating "gate lock" via intramolecular C-H···N interaction in photoisomerized product (L') has been described. Coordination chemistry of pre- and postirradiated species demonstrated a drastic change in the reactivity which has been supported by NMR, HRMS, UV-vis, emission, electrochemical, and complexation studies.     

周期律的“不规则性”

本文对周期律的“不规则性”及其理论阐释进行了探讨。     

一款教育类移动应用程序“爱猜元素”的开发

北京大学化学国家级实验教学示范中心开发了一款名为"爱猜元素"的教育类移动应用程序。它是以元素周期表为框架,"猜谜游戏"为逻辑主线,围绕元素知识及相关原理而设计的科普资源平台。本文主要介绍了该化学教育类app的设计理念、产品特点及其应用场景。     

"Click" saccharide/beta-lactam hybrids for lectin inhibition

Hybrid glycopeptide beta-lactam mimetics designed to bind lectins or carbohydrate recognition domains in selectins have been prepared according to a "shape-modulating linker" design. This approach was implemented using the azide-alkyne "click" cycloaddition reaction, and as shown by NMR/MD experiments, binding of the resulting mimetics to Ulex Europaeus Lectin-1 (UEL-1) occurred after a "bent-to-extended" conformational change around a partially rotatable triazolylmethylene moiety.     

Gallium cluster "magic melters"

Calorimetry measurements (using a method based on multicollision induced dissociation) have been performed for unsupported gallium clusters, Gan+ (n = 30-50 and 55). Melting transitions have been identified from spikes in the heat capacities recorded as a function of temperature. There are enormous fluctuations in the melting temperatures and the heats of fusion with cluster size. Clusters with n = 31, 33, 37, and 45-47 are "magic melters" with particularly well-defined melting transitions. There is a strong correlation between the heats of fusion, entropies of fusion, and the stabilities of the clusters. However, these quantities are not strongly correlated with the melting temperatures.     

Resonance CARS study of the structure of "green" and "red" chromophores within the red fluorescent protein DsRed

Vibrational spectra of red fluorescent protein DsRed have been studied for the first time by polarization-sensitive multiplex coherent anti-Stokes Raman scattering at two excitation wavelengths, 545 and 583 nm, in resonance with the absorption bands of the immature "green" and mature "red" protein chromophores. Overall vibrational patterns of both DsRed chromophores were found to be similar to each other and to differ from that of S65T-GFP at pH8. The combined analysis of our CARS data and published structural information suggest that both "green" and "red" DsRed species possess an extended chromophore structure. Consequently, our data suggest that pi-bonding system extension during isomerization around the cis peptide bond between Phe 65 and Gln 66 is a necessary but not sufficient step in DsRed chromophore maturation.     

“课前六备、课中六讲、课后六辅”在线课程混合式教学模式研究与实践——以基于“雨课堂+钉钉直播”的中等无机化学课程为例

Taking the online teaching of "inorganic chemistry" course at Dezhou University as an example, the "six steps before class, six steps in class, six steps after class" online course teaching model based on "Rain Class + Dingding Live" and an online "short class" were constructed. The main content and implementation methods of teaching design, teaching process, teaching effect, teaching reflection, teaching evaluation in online course teaching were discussed. It has been proved in practice that this model can effectively improve students' learning interest and enhance teaching effects.     

"Naked-eye" screening of metal-based chemosensors for biologically important anions

A two-step "naked-eye" screening of selective metal-based chemosensors for biologically important anions such as cyanide, phosphate, and oxalate from commercially available metal indicators and metal ions has been developed. Applications in food safety control have been demonstrated.     

Three-component coupling based on the "cation pool" method

Sequential one-pot three-component coupling reactions have been developed based on the "cation pool" method. An N-acyliminium ion generated by the "cation pool" method adds to an electron-rich carbon-carbon double bond, such as enamine derivatives and vinyl sulfides, to form the second "cation pool". The addition of nucleophiles such as allylsilanes, enol silyl ethers, Grignard reagents, and organoaluminum compounds led to the formation of the corresponding three-component coupling products.     

陶寺、尉迟寺白灰面的测试研究

在XRD和拉曼光谱分析的基础上,借助XRF、ICP-AES和ICP-MS技术,对取自陶寺、尉迟寺遗址的“白灰面”做了相关测试和研究。结果表明,尉迟寺F85号红烧土房墙体表面白灰面为碳酸钙。陶寺“白灰面”有两种,一种为人工烧制的石灰,系石灰石烧制而成,表面打磨得较为光滑,并且有一块样品分4次加工,分为4层,表层主要为方解石和文石,里层则为石英含量略高的粘土和石灰的混合物,具较高的工艺,另外,有一块“白灰面”经检测为二水硫酸钙,这首次表明我国古代先民在4千年前已经开始开采和使用石膏做为建筑材料。     

A "hidden" co-crystal of caffeine and adipic acid

Co-crystal formation between caffeine and adipic acid has been explored over the years without success; utilizing the newly developed co-crystal screening method, we have finally discovered this "hidden" caffeine and adipic acid co-crystal.     

Amphiphilic Janus gold nanoparticles via combining "solid-state grafting-to" and "grafting-from" methods

Despite the great efforts that have been made toward obtaining Janus architectures, synthesizing sub-10 nanometer Janus nanoparticles (NPs) modified with different types of polymers remains a challenging task. In this Communication, "solid-state grafting-to" and "grafting-from" methods were combined to obtain Janus gold NPs (AuNPs) modified with two types of polymer chains on the opposite sides of the NP. We used functionalized polymer single crystals as the solid substrates to immobilize AuNPs. We then used atom transfer radical polymerization to grow polymer chains on the "free" side of the AuNPs. Amphiphilic polyethylene oxide (PEO)-Au-poly(methyl methacrylate), PEO-Au-poly(tert-butyl acrylate) and hydrophilic PEO-Au-poly(acrylic acid) were synthesized. The Janus nature was demonstrated using a platinum-nanoparticle-decoration method. Using polymer single crystals as the reaction substrates is advantageous because they afford higher throughput compared with self-assembled monolayers. Dissolution of the single crystal also leads to NPs with defined polymer patches. We anticipate that our approach could serve as a generic method for synthesizing polymer-functionalized, sub-10 nm Janus NPs. This unique system holds promises for achieving controlled assembly and tunable optic and electronic properties of NPs.     

Small organic molecule in enantioselective, direct aldol reaction "in water"

A small organic molecule, Pro-NH(2), catalyzing the enantioselective aldol reaction "in water" not merely "in the presence of water" with good enantioselectivity has been discovered for the first time.     

Graphitic molecules with partial "zig/zag" periphery

A new synthetic protocol that affords novel hexa-peri-hexabenzocoronene (HBC) derivatives with partial "zig/zag" periphery and dramatically different electronic properties has been developed, which represents an important step toward understanding structure-property relationships of graphitic materials. The scope of this methodology was broadened by application to a much larger polycyclic aromatic hydrocarbon (PAH) with a more extended "zig/zag" character.     

Self-assembly of rectangles and prisms via a molecular "clip"

Aromatic molecular "clips" bearing two symmetrically bound platinum moieties have been prepared. The molecular "clip" 4 readily self-assembled with linear linkers such as 4,4'-bipyridyl, 1,4-bis[2-(4-isocyano-3,5-diisopropylphenyl)ethynyl]benzene, and nicotinic acid to form molecular rectangles. The overall dimensions of the rectangle 7 were 7.3 Angstroms x 15.3 Angstroms. The molecular "clip" also self-assembled with tritopic pyridyl and isocyanide ligands to form trigonal prismatic frameworks. The characterization of the supramolecules by multinuclear NMR, electrospray mass spectrometry, and X-ray crystal structures is also reported.     

某些新型冠醚-卟啉化合物的合成

本文以内消旋不对称单羟基-卟啉化合物1a～d合成了七种新型的冠醚-卟啉化合物3a～g和它们的中间体2a～g.这些化合物中的某些金属络合物对链烯的环氧化作用起催化作用, 它们的结构经元素分析,IR, UV和^1H NMR波谱证实.     

Microwave observation of the "recently found" polar OCS dimer

Recently Afshari et al. reported on the detection of a new infrared band which was assigned to the "long-anticipated polar isomer of the OCS dimer" [J. Chem. Phys. 126, 071102 (2007)]. The authors report here the microwave confirmation of their results. The lowest energy, nonpolar isomer of (OCS)2 has long been known from IR spectroscopy, while the polar form has only been deduced from qualitative beam refocusing experiments. The higher energy, polar isomer of (OCS)2 has been produced by high pressure expansion of dilute OCS in helium. A surprisingly strong microwave spectrum of Cs (OCS)2 has been observed and assigned.     

A novel "double-coupling" strategy for iterative oligothiophene synthesis using orthogonal Si/Ge protection

[reaction: see text] A new iterative synthesis of regioregular oligothiophenes has been developed in which "double-coupling" after each iteration minimizes deletion sequences. The method exploits the susceptibility of alpha-silyl- but not alpha-germyl-substituted thiophene derivatives toward nucleophilic ipso-protodemetalation and features an unusual "base-free" Suzuki-type cross-coupling protocol. The strategy has been designed for the solid-phase synthesis of high purity oligothiophenes using a germanium-based linker.