Synthesis of Biaryls via Pd-Catalyzed Decarboxylative Coupling of Substituted Benzoic Acids with Phenylboronic Acids

A Pd-catalyzed decarboxylative coupling of substituted benzoic acids with phenylboronic acid has been developed. Under the optimized conditions, a variety of substituted benzoic acids were found to undergo decarboxylative coupling with various phenylboronic acids to give the desired unsymmetrical biaryls in good yields.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Excellent Capacitive Performance of a Three‐Dimensional Hierarchical Porous Graphene/Carbon Composite with a Superhigh Surface Area

Three‐dimensional hierarchical porous graphene/carbon composite was successfully synthesized from a solution of graphene oxide and a phenolic resin by using a facile and efficient method. The morphology, structure, and surface property of the composite were investigated intensively by a variety of means such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption, Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). It is found that graphene serves as a scaffold to form a hierarchical pore texture in the composite, resulting in its superhigh surface area of 2034 m²g^?1, thin macropore wall, and high conductivity (152 S m^?1). As evidenced by electrochemical measurements in both EMImBF₄ ionic liquid and KOH electrolyte, the composite exhibits ideal capacitive behavior, high capacitance, and excellent rate performance due to its unique structure. In EMImBF₄, the composite has a high energy density of up to 50.1 Wh kg^?1 and also possesses quite stable cycling stability at 100 °C, suggesting its promising application in high‐temperature supercapacitors. In KOH electrolyte, the specific capacitance of this composite can reach up to an unprecedented value of 186.5 F g^?1, even at a very high current density of 50 A g^?1, suggesting its prosperous application in high‐power applications.     

A New Approach to Prepare Efficient Blue AIE Emitters for Undoped OLEDs

Two aggregation‐induced emission active luminogens (TPE–pTPA and TPE–mTPA) were successfully synthesized. For comparison, another six similar compounds were prepared. Because of the introduced hole‐dominated triphenylamine (TPA), fluorene groups with high luminous efficiency, and unconjugated linkages, the π conjugation length of the obtained luminogens is effectively restricted to ensure their blue emission. The undoped organic light‐emitting diodes based on TPE–pTPA and TPE–mTPA exhibited blue or deep‐blue emissions, low turn‐on voltages (3 V), and high electroluminescence efficiencies with L_max, η_C,max, and η_P,max values of up to 26 697 cd m^?2, 3.37 cd A^?1, and 2.40 Lm W^?1.     

Studying the fine microstructure of the passive film on nanocrystalline 304 stainless steel by EIS,XPS, and AFM

The fine microstructure of the passive films on nanocrystalline (NC) and coarse crystalline (CC) 304 stainless steels (SSs) in 0.5 M H₂SO₄ were investigated by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The results indicate that the passive film on both CC and NC SSs exhibits a two-layer microstructure consisting of a compact inner layer and a porous outer layer. Some hydrated compounds (HC) were present in the porous outer layer of NC SS but not CC SS in 0.5 M H₂SO₄ solution. The pores in the outer layer of the NC SS were observed to be in the nanoscale by AFM. HC filling of the pores in the passive film on NC SS may occur due to capillary forces endowed by the nanosize pores. XPS analysis of the passive films on both CC and NC SSs, however, does not show such a composition difference which is attributed to dehydration occurring in the XPS vacuum chamber. Both the inner and outer layers of the NC SS were determined by EIS analysis to be more compact and protective than the corresponding films on CC SS as evidenced by the lower Q value, higher n, and much higher R value in the corresponding layer.     

三次采油耐温抗盐聚合物的合成与评价

以丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和氢氧化钠(Na OH)为原料,采用过硫酸铵[(NH4)2S2O8]、亚硫酸钠(Na2SO3)和四甲基脲[N(CH3)2CON(CH3)2]作为新型复合引发体系,通过共聚后水解工艺,合成了高分子量三元共聚物(AM-AANa-AMPSNa).考察了引发剂用量、单体浓度、p H和引发温度对共聚物黏均分子量的影响.确定最优条件为:引发剂用量0.035%,单体质量浓度为25%,介质p H 7,引发温度0℃.通过红外光谱和核磁碳谱表征了其结构,并系统评价了其理化性能指标、黏弹性、注入性和驱油性能.结果表明,该共聚物较高分子量部分水解聚丙烯酰胺(HPAM)具有更优异的耐温抗盐性能.其黏均相对分子量达到3000万以上,在胜利油田III型盐水中,浓度1500 mg/L,温度85℃条件下,溶液表观黏度达到17.7 m Pa s,岩心驱油实验在水驱采收率51.8%基础上,可再提高15.8%.上述性能表明,该高分子量三元共聚物有望应用在高温高盐油藏三次采油技术中.     

Model Equations and Traveling Wave Solutions for Shallow-Water Waves with the Coriolis Effect

In the present study, we start by formally deriving the simplified phenomenological models of long-crested shallow-water waves propagating in the equatorial ocean regions with the Coriolis effect due to the Earth’s rotation. These new model equations are analogous to the Green–Naghdi equations, the first-order approximations of the KdV-, or BBM type, respectively. We then justify rigorously that in the long-wave limit, unidirectional solutions of a class of KdV- or BBM type are well approximated by the solutions of the Camassa–Holm equation in a rotating setting. The modeling and analysis of those mathematical models then illustrate that the Coriolis forcing in the propagation of shallow-water waves can not be neglected. Indeed, the CH-approximation with the Coriolis effect captures stronger nonlinear effects than the nonlinear dispersive rotational KdV type. Furthermore, we demonstrate nonexistence of the Camassa–Holm-type peaked solution and classify various localized traveling wave solutions to the Camassa–Holm equation with the Coriolis effect depending on the range of the rotation parameter.

     

Synthesis,Magnetism, and Thermostability of a Series of Two‐Dimensional Lanthanide–Nickel Heterometallic Coordination Polymers

A series of Ln–Ni heterometallic coordination polymers, {[Ln₂Ni(MIDA)₄(H₂O)₆](H₂O)₄} (Ln = La ( 1 ), Ce ( 2 ), Pr ( 3 ), and Nd ( 4 ); H₂MIDA = N‐methyl‐iminodiacetic acid), were obtained under hydrothermal conditions. Single crystal X‐ray diffraction revealed that they feature two‐dimensional isomorphic frameworks, which could be viewed as the construction by one‐dimensional {Ln}_n chain connecting by bridges of [Ni(MIDA)₂]². The magnetic measurements reveal that compounds 2 – 4 exhibit antiferromagnetic properties. TGA results indicate compounds 1 and 4 have good thermostability with the critical temperature of 375 °C.     

A 3D Hybrid Praseodymium–Antimony–Oxochloride Compound: Single‐Crystal‐to‐Single‐Crystal Transformation and Photocatalytic Properties

A 3D organic–inorganic hybrid compound, (2‐MepyH)₃ [{Fe(1,10‐phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH) Cl_11.5}(TDC)_4.5({Pr₄Sb₁₂O₁₈(OH)Cl_9.5} Cl)] ? 3 (2‐Mepy) ? 28 H₂O ( 1 ; 2‐Mepy=2‐methylpyridine, 1,10‐phen=1,10‐phenanthroline, H₂TDC=thiophene‐2,5‐dicarboxylic acid), was hydrothermally synthesized and structurally characterized. Unusually, two kinds of high‐nuclearity clusters, namely [(Pr₄Sb₁₂O₁₈ (OH)Cl₁₁)(COO)₅]^5? and [(Pr₄Sb₁₂O₁₈ (OH)Cl₉)Cl(COO)₅]^4?, coexist in the structure of compound 1 ; two of the latter clusters are doubly bridged by two μ₂‐Cl^? moieties to form a new centrosymmetric dimeric cluster. An unprecedented spontaneous and reversible single‐crystal‐to‐single‐crystal transformation was observed, which simultaneously involved a notable organic‐ligand movement between the metal ions and an alteration of the bridging ion in the dimeric cluster, induced by guest‐release/re‐adsorption, thereby giving rise to the interconversion between compound 1 and the compound (2‐MepyH)₃[{Fe(1,10‐phen)₃}₃][{Pr₄Sb₁₂O₁₈(OH)Cl_11.5}(TDC)₄({Pr₄Sb₁₂O₁₈Cl_10.5(TDC)_0.5(H₂O)_1.5}O_0.5)] ? 25 H₂O ( 1′ ). The mechanism of this transformation has also been discussed in great detail. Photocatalytic H₂‐evolution activity was observed for compound 1′ under UV light with Pt as a co‐catalyst and MeOH as a sacrificial electron donor.     

Phthalocyanine‐Sensitized Graphene–CdS Nanocomposites: An Enhanced Photoelectrochemical Immunosensing Platform

A novel strategy is developed for the fabrication of graphene–CdS (G–CdS) nanocomposites by in situ growth of CdS nanoparticles onto simultaneously reduced graphite oxide, which is noncovalently functionalized by sodium 1‐pyrene sulfonate through strong π–π stacking interactions. Subsequently, cobalt 2,9,16,23‐tetraaminophthalocyanine (CoTAPc) is self‐assembled on the G–CdS nanocomposites through electrostatic interactions to produce phthalocyanine‐sensitized G–CdS nanocomposites. The photoactive superstructure enhances the photocurrent generation capability, and presents an efficient photoelectrochemical immunosensing platform for the ultrasensitive detection of the prostate‐specific antigen (PSA). The quantitative measurement of PSA is based on the decrease in the photocurrent intensity of the phthalocyanine‐sensitized G–CdS nanocomposites, which results from an increase in the steric hindrance due to the formation of the immunocomplex. A linear relationship between the photocurrent decrease and the PSA concentration is obtained in the wide range from 1 pg mL^?1 to 5 μg mL^?1 with a detection limit of 0.63 pg mL^?1. The proposed sensor shows high sensitivity, stability, reproducibility, and can become a promising platform for other biomolecular detection.     

Biodegradable Nanocomposites Based on the Polyester Poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) and Layered Silicate or Expanded Graphite

Novel nanocomposites based on the biodegradable polymer poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHx) and layered fillers, specifically layered silicate (clay25A) and expanded graphite (EG), were prepared by melt intercalation. The dispersion of the fillers in the PHBHx was characterized by wide‐angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM). The effects of the fillers on the polymer structure, thermal stability and mechanical properties of the nanocomposites were also studied, by differential scanning calorimetry, thermogravimetric analysis, and strain‐stress measurements in elongation, respectively. The WAXD and TEM results showed that the clay25A and EG was exfoliated into well‐dispersed sheets in the polymer matrix, especially when the filler concentration were relatively low. This gave rise to considerable improvements in Young's modulus, and resulted in increases in the thermal degradation. It should be possible to convert the EG dispersions obtained thus far to ones yielding filler‐filler networks that show electrical conductivity.