一种荷叶效应涂层的制备

Composite coatings with lotus effect were fabricated via imbedding micro-silica and then nano-silica. The micro-silica and nano-silica was subsquently fixed on the surface to form hierarchical micro- and nano-structures, and at the same time, the epoxy resin modified by low surface free energy material was coated on the coatings. The staic contact angle of the coatings is as high as 165° and the tilt angle for 6.5 μL water droplet is as low as 2.5°. The coatings show the similar hydrophobic capability and structure to lotus leaves.     

铝表面ZnO/Zn-Al LDH微米-纳米结构及其超级疏水性能

A multi-dimension bionic-like super-hydrophobic material， ZnO/Zn-Al LDH， was fabricated by modifying the Al surface in alkaline conditions at room temperature. After coated by ZnO/Zn-Al LDH， the aluminum surface shows both micro- and nano-bionic-like structures of lotus leaves.     

具有米状纳微阶层结构的仿生超疏水十二硫醇铅表面的简单制备

A superhydrophobic surface of lead dodecanethiolate with the water contact angle(CA) of 152.2°±1.2° and the sliding angle(SA) of 3.8°±1.0° was fabricated using a simple and relative inexpensive route based on our previous reported method. The procedure employed a one-pot reaction between lead salt and alkanethiolate to form a thermal stable superhydrophobic coating under mild conditions. SEM images revealed the lead dodecanethiolate surface morphology with packed aggregate “rice-like” particles of micrometer scale in length and nanometer scale in thickness. Also, Lead dodecanethiolate powder was investigated by TGA and XRD.     

SURFACE REARRANGEMENTS OF OXYGEN PLASMA TREATED POLYSTYRENE： SURFACE DYNAMICS AND HUMIDITY EFFECT

The time evolution of oxygen plasma treated polystyrene(PS)surfaces was investigated upon storing them in theair under controlled humidity conditions.The methods of water contact angle,X-ray photoelectron spectroscopy(XPS),sumfrequency generation(SFG)vibrational spectroscopy,and atomic force microscopy(AFM)were used to infer the surfaceproperties and structure.Chemical groups containing oxygen were formed on the PS surface with the plasma treatment,demonstrated by water contact angle and XPS.The surface polarity decayed markedly on time,as assessed by steady increasein the water contact angle as a function of storage time,from zero to around 60°.The observed decay is interpreted as arisingfrom surface rearrangement processes to burying polar groups away from the uppermost layer of the surfaces,which is incontact with air.On the other hand,XPS results show that the chemical composition in the first 3 nm surface layer isunaffected by the surface aging,and the depth profile of oxygen is essentially the same with time.A possible change of PSsurface roughness was examined by AFM,and it showed that the increase of water contact angle during surface aging couldnot be attributed to surface roughness.Thus,it is concluded that surface aging is attributable to surface reorganization andthe motion of oxygen containing groups is confined within the XPS probing depth.SFG spectroscopy,which is intrinsicallyinterface-specific,was used to detect the chemical structure of PS surface at the molecular level after various aging times.The results are interpreted as follows.During the aging of the plasma treated PS surfaces,the oxygen containing groupsundergo reorientation processes toward the polymer bulk and/or parallel to the surface,while the CH_2 moiety stands up onthe PS surface.Our results indicate that the surface configuration changes do not require large length scale segmentalmotions or migration of macromolecules.Motions that are responsible for surface configuration changes could be relativelysmall rotational motions.The aging behaviors under different relative humidity conditions were shown to be similar from18% to 91%,whereas the kinetics of surface polarity decays were faster in higher relative humidity.Here,the surfacerearrangement of polystyrene films that were previously treated by oxygen plasma and aged,and was investigated in terms ofcontact angle after the water immersion.The contact angles of the water-immersed samples were found to change andapproach the initial values before the immersion asymptotically.     

Reason for the loss of hydrophilicity of TiO_2 film and its photocatalytic regeneration

TiO2 film was prepared on soda-lime glass by sol-gel method. The water contact angle (θ) of the fresh TiO2 film is 0°. During storage in air, the surface of TiO2 film is gradually converted to the hydrophobic state. XPS and ITD results reveal that it is due to the adsorption of organic contaminants on TiO2 surface in air ambience. The lost hydrophilicity of TiO2 film can be regenerated by UV illumination.     

EFFECTS OF SOLVENT TREATMENT ON SURFACE MORPHOLOGY AND COMPOSITION OF POLY(METHYL METHACRYLATE)-g-POLY(ETHYLENE OXIDE)

Surface morphology and composition of solution-cast films of poly(methyl methacrylate)-g-poly(ethylene oxide)(PMMA-g-PEO) were investigated by using XPS, DSC, SEM and contact angle measurement. The microphase separatedstructure of the copolymers was studied by TEM. Generally, for the same graft copolymer, the surface content of PEO orhydrophilicity can be as follows: Surface treated with petroleum ether or cyclohexane>surface untreated with solvent>surface treated with water or ethyl alcohol. Graft copolymer having longer PEO side chains and higher PEO content shows aseparated PEO phase with even a certain degree of crystallinity on the surface. PEO crystallinity was destroyed by water orethyl alcohol treatment, however, surface treatment with petroleum ether or cyclohexane favors the growth of PEO crystal.TEM shows that graft copolymers with longer PEO side chains (M_n of PEO, 3200) may readily undergo microphase separation and the shape and size of domains depend on the copolymer's composition.     

STUDY ON FACTORS AFFECTING ROOM TEMPERATURE TRANSITION OF POLYTETRAFLUOROETHYLENE

In the X-ray diffiaction intensity distribution diagram of PTFE, three diffraction peaks exist inthe range of Bragg angle 30--45°, which are very sensitive to the Crystal trausition at room temperature.At 15℃, the crystal is triclinic and the "small spikes" along with the main peaks appear on the dif-fraction scans due to the distortion of the unit cell, while at 23℃, distortion no longer exists, "smallspikes" disappear completely. When the temperature is raised to 34℃, the hexagonal crystal fur-ther randomizes and the peak at Bragg angle 42°vanishes. We assigned correctly Miller index (108) tothis peak and used 2θ=30--45°region ("sensitive region") as a criterion to characterize qualita-tively the crystal transition. It has been found that some factors such as γ-irradiation, cold press-ing, drawing, calendering and copolymerization which are usually encountered in the fabrication orapplication of PTFE articles have profound effect on the crystal transition as evidenced by X-raydiffraction patterns and DSC thermograms. The information obtained in the present work isbeneficial to the use of PTFE articles.     

MODIFICATION OF EPOXY RESIN WITH POLYSILOXANE BEARING PENDANT QUATERNARY AMMONIUM GROUPS

Polysiloxane bearing pendant quaternary ammonium groups (PSI) was used to modify the surface properties ofepoxy resins. In the cured resin, PSI formed the dispersed phase. Remarkable enrichment and gradient distribution ofpolysiloxane on the surface region of the epoxy resins were demonstrated by XPS analysis. The composition and propertiesof the surface of PSI-modified epoxy resin, which is in contact with the mold, are dependent on the material of the mold.Through the incorporation of PSI, epoxy resins with low surface energy and low friction coefficient were obtained.Polysiloxane with lower ionic group content shows a higher degree of enrichment on the resin surface and leads to a highercontact angle against water, while the polysiloxane having optimum compatibility with the epoxy resin shows a greater effectin reducing the static friction coefficient of the resin against glass.     

Flame-retardant Coating by Alternate Assembly of Poly（vinylphosphonic acid） and Polyethylenimine for Ramie Fabrics

A novel intumescent flame retardant coating,consisting of poly(vinylphosphonic acid)(PVPA) as the acid source and branched polyethylenimine(BPEI) as the blowing agent,was constructed on the surface of ramie fabrics by alternate assembly to remarkably improve the flame retardancy of ramie.The PVPA/BPEI coating on the surface of individual fibers of ramie fabric pyrolyzes to form protective char layer upon heating/burning and improves the flame retardancy of ramie.Thermogravimetric analysis reveals that the PVPA/BPEI-coated ramie fabrics left as much as 25.8 wt% residue at 600 °C,while the control(uncoated) fabric left less than 1.4 wt% residue.Vertical flame test shows that all PVPA/BPEI-coated fabrics have shorter after-flame time,and the residues well preserved the original weave structure and fiber morphology,whereas,the uncoated fabric left only ashes.Microscale combustion calorimetry shows that the PVPA/BPEI coatings greatly reduce the total heat release by as much as 66% and the heat release capacity by 76%,relative to those of the uncoated fabric.     

MISCIBILITY AND MORPHOLOGY OF THIN FILMS OF BLENDS OF POLYSTYRENE WITH BROMINATED POLYSTYRENES： EFFECTS OF VARYING THE MOLECULAR WEIGHT, BROMINATION DEGREE AND ANNEALING

Thin films of incompatible polymer blends can form a variety of structures during preparation and subsequent annealing process. For the polymer blend system consisting of polystyrene and poIy(styrene-co-p-bromo-styrene), i.e., PS/PBrxS, its compatibility could be adjusted by varying the degree of bromination and the molecular weight of both components comprised, in this paper, surface chemical compositions of the cast and the annealing films were investigated by X-ray photoelectron spectroscopy (XPS) and contact angle measurement; meanwhile, surface topographical changes are followed by atomic force microscopy (AFM). In addition, substantial attention was paid to the effect of annealing on the morphologic variations induced by phase separation and/or dewetting of the thin film. Moreover, the influences of the molecular weight, Aw, as well as the brominated degree, x%, on the sample surface are explored systematically, and the corresponding observations are explained in virtue of the Flory-Huggins theory, along with the dewetting of the polymer thin film.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.