NHC-Activations on α-, β-, γ-, and Beyond

Over the recent decades, due to the special electronic characteristics and diverse reactivities, N-heterocyclic carbene (NHC) has received significant interest in organocatalyzed reactions. The formation of Breslow intermediates by NHC can convert into acyl anion equivalent, enolates, homoenolate, acyl azolium, and vinyl enolate etc., and the cycloaddition reactions of these species has attracted lots of attention. In this review, we focus on the summry of the development of NHC-activation of carbonyl carbon (or imine carbon) in situ, α-, β-, γ-, and beyond, and the cycloaddition reaction of these species.     

Relative copure injective and copure flat modules

Let R be a ring, n a fixed nonnegative integer and I_n (F_n) the class of all left (right) R-modules of injective (flat) dimension at most n. A left R-module M (resp., right R-module F) is called n-copure injective (resp., n-copure flat) if (resp., ) for any N∈I_n. It is shown that a left R-module M over any ring R is n-copure injective if and only if M is a kernel of an I_n-precover f:A→B of a left R-module B with A injective. For a left coherent ring R, it is proven that every right R-module has an F_n-preenvelope, and a finitely presented right R-module M is n-copure flat if and only if M is a cokernel of an F_n-preenvelope K→F of a right R-module K with F flat. These classes of modules are also used to construct cotorsion theories and to characterize the global dimension of a ring under suitable conditions.     

Synthesis, structure, and magnetic behavior of bis(2-amino-5-fluoropyridinium) tetrachlorocuprate(II)

Reaction of CuCl2 with 2-amino-5-fluoropyridine and HCl in aqueous solution yields bis(2-amino-5-fluoropyridinium) tetrachlorocuprate(II), (5FAP)2CuCl4, (1). The complex crystallizes in the monoclinic space group P21/c with cell dimensions a = 6.926(7) A, b = 21.73(2) A, c = 10.911(10) A, beta = 100.19(2) degrees , V = 1616(3) A3, and R1 = 0.0424 based on 2640 independent reflections. The crystal packing shows that each tetrachlorocuprate ion has four nearest-neighbor Cu(II) ions through three types of Cu-Cl...Cl-Cu potential magnetic interactions: one short Cl...Cl distance (d1 = 3.657 A) and two longer Cl...Cl distances (d2 = 4.073 A) that form a layered distorted honeycomb structure. The third nearest neighbor (d3 = 4.239 A) links these layers into a three-dimensional structure. Both powder and single-crystal magnetic susceptibility measurements on 1, over the temperature range of 1.8-325 K, show significant antiferromagnetic interactions. Attempts to analyze the data using a variety of models showed a best fit to the strong-rung ladder model, with 2Jrung = -17.170(14) and 2Jrail = -5.94(5) K [-11.92(1) and -4.13(3) cm(-1), respectively] for the powder, although a comparable result is obtained using an alternate chain model. However, neither of these two models is compatible with a layered distorted honeycomb crystal packing structure. A first-principles bottom-up theoretical study using the 165 K crystallographic data reproduces the macroscopic properties and reveals that at low temperature the crystal has a 3D magnetic topology (all three magnetic pathways are significant) and a singlet ground state.     

Monolayer behavior of a pyridyl head-group-containing amphiphile and its miscibility with poly(D,L-lactide-co-glycolide) on different pH subphase

In this paper, we investigated the Langmuir film and Langmuir-Blodgett (LB) monolayer film of a nonionic amphiphilic molecule, 4-(6-p-pyridyloxyl)hexyloxyl-4'-dodecyloxylazobenzene (C(12)AzoC(6)Py) and its mixture with poly(D,L-lactide-co-glycolide) (PLG) at different subphase pH values (2.0, 2.6, 3.3, 4.4, and 6.5, respectively) by surface pressure-area (pi-A) isotherms, in situ interface Brewster angle microscopy (BAM), and ex situ atomic force microscopy (AFM). For pure C(12)AzoC(6)Py, its pi-A isotherms display a plateau when the subphase pH value is lower than 3.0. The pressure of the plateau increases with the decrease of pH until 2.0. Over the plateau, the pi-A isotherms become almost identical to the one under neutral conditions. The appearance of such a plateau can be explained as the coexistence of protonation and unprotonation of pyridyl head groups of the employed amphiphile. In contrast to the homogeneous surface morphology of pure C(12)AzoC(6)Py near the plateau by BAM observation, the surface in the case of its mixing with PLG exhibits a dendritic crystalline state under low surface pressure at subphase pH lower than 3.0. The crystalline state becomes soft and gradually melts into homogeneous aggregates with surface pressure increasing to a higher value than that of the plateau. Meanwhile, the hydrolysis of PLG in the mixture system at the interface has been affirmed to be restrained to a very large extent. And the PLG was believed to be compelled to the up layer of the LB film due to the phase separation, which is examined by AFM. Based on the experimental results, the corresponding discussion was also performed.     

Structural characterization and chemical response of a Ag-coordinated supramolecular gel

Supramolecular gels exhibit potential applications in the areas of sensors, nanodevices, drug and catalyst carriers, and so on. To develop a novel organogel with a multiresponse, we designed a component molecule bearing a pyridyl group for metal coordination and an amide group for the formation of intermolecular hydrogen bonding. A complex building block with a symmetrical structure was selectively constructed by the coordination of a silver cation to the organic component. The coordination existing in the complex and the hydrogen bonding existing between complexes were examined by IR, Raman, and 1H NMR spectroscopy. The gel formation and phase transition were examined by viscosity and differential scanning calorimetry measurements. The selection of metal ions for the formation of a gel has proved to be crucial as only the complex of a binary coordinated metal ion, Ag+, was found to form a gel structure. From the band shift of the L1 solution with different amounts of silver ion, the binding ratio of silver ion to L1 was estimated to be 1:2 and the calculated stability constant was 3.6 x 10(8) M(-2). On the basis of the analysis of X-ray diffraction and transmission electron microscopy results, we proposed a possible stacking structure of the complex in the fibrous aggregates. Of interest is that the organogel exhibits a 3-D network structure of a beltlike fiber composed of ordered lamellar arrangements of the coordinated complex and shows a rapid response to wide chemical stimulations such as anions I-, Br-, and Cl-, gases such as H(2)S and NH(3), and a change of pH.     

A novel method to fabricate patterned bilayer lipid membranes

We introduce a new method for forming tethered bilayer lipid membranes on surfaces patterned using a photocleavable self-assembled monolayer (SAM). A SAM terminated with a hydrophobic fluorocarbon residue was bound to a gold surface through a link containing a photocleavable ortho-nitrobenzyl moiety. Hydrophilic regions were produced by irradiation with soft UV (365 nm) through a photomask. The patterned surface was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. Tethered bilayer lipid membranes with well-defined bilayer and monolayer regions were then formed by exposure to egg PC vesicles. The membranes had resistance and capacitance values of 0.52 MOmega.cm2 and 0.83 microF.cm-2, respectively.     

Old and New Morrey Spaces with Heat Kernel Bounds

Given p ∈ [1,∞) and λ ∈ (0, n), we study Morrey space of all locally integrable complex-valued functions f on such that for every open Euclidean ball B ⊂ with radius r_B there are numbers C = C(f ) (depending on f ) and c = c(f,B) (relying upon f and B) satisfying

扁平水槽的应用

无色透明的有机玻璃扁平水槽,它的特点是可见度好,不易碎,易加工维修,绝缘性好,适宜做电化学实验。一、实验装置1.扁平水槽的制作(见图1)     

Wavelet basis analysis in perturbed periodic KdV equation

I.IntroductionandSignsThephenomenaofnaturealwaysoccursatacertaintimeandacertainspace.Thecomplexityoftimeandspaceisduetodescribingtherelationbetweentimeandspaceandthelongtimebehaviorofsystembyusingthepartialdifferentialequation.Traditionally,thestatefunctionisexpandedinFotlrierseries,andthepartialdifferentialequationistransformedintotheordinarydifIYrentialequationwiththeevolutionofFouriercoefficientastimegoeson.ButitisverydifficulttoknowwelltheFouriercoefficientwhichplaysanimportantroleasthe…