Single-atom Pd catalyst anchored on Zr-based metal-organic polyhedra for Suzuki-Miyaura cross coupling reactions in aqueous media

The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to anchor a single-atom catalyst and provide high degree of dispersion and substrate access in aqueous media.Here,we prepared discrete cages of metal-organic polyhedra anchoring single Pd atom(MOP-BPY(Pd))and successfully performed a Suzuki-Miyaura cross coupling reaction with various substrates in aqueous media.It was revealed that each tetrahedral cage of MOP-BPY(Pd)has 4.5 Pd atoms on average and retained its high degree of dispersion up to 3 months in water.The coupling efficiencies of the Suzuki-Miyaura cross coupling reaction exhibited more than 90.0%for various substrates we have tested in the aqueous media,which is superior to those of the molecular Pd complex and metal-organic framework(MOF)anchoring Pd atoms.Moreover,MOP-BPY(Pd)was successfully recovered and recycled without performance degradation.

Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction of organoboronic acids with N-protected 4-iodophenyl alanine linked isoxazoles

Suzuki-Miyaura coupling reaction of N-protected 4-iodopheyl alanine isoxazoles with arylboronic acids,catalyzed by palladium,efficiently produce benzyl-N-（4-bipheyl）-2-（3-methyl-5（E）-2-aryl-1-ethenyl-4-isoxazolyl）-amino-2-oxoethyl）carba- mates in good yields.This process is first of its kind to construct carbon-carbon bond formation having biaryl motif on amino acid linked isoxazole moiety.

Ligand assisted copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines

Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.

Application of CFD and FEA Coupling to Predict Structural Dynamic Responses of A Trimaran in Uni-and Bi-Directional Waves

To predict the wave loads of a flexible trimaran in different wave fields,a one-way interaction numerical simulation method is proposed by integrating the fluid solver(Star-CCM+)and structural solver(Abaqus).Differing from the existing coupled CFD-FEA method for monohull ships in head waves,the presented method equates the mass and stiffness of the whole ship to the hull shell so that any transverse and longitudinal section stress of the hull in oblique waves can be obtained.Firstly,verification study and sensitivity analysis are carried out by comparing the trimaran motions using different mesh sizes and time step schemes.Discussion on the wave elevation of uni-and bi-directional waves is also carried out.Then a comprehensive analysis on the structural responses of the trimaran in different uni-directional regular wave and bi-directional cross sea conditions is carried out,respectively.Finally,the differences in structural response characteristics of trimaran in different wave fields are studied.The results show that the present method can reduce the computational burden of the two-way fluid-structure interaction simulations.

Double Position Servo Synchronous Drive System Based on Cross-Coupling Integrated Feedforward Control for Broacher

Synchronization errors directly deteriorate the machining accuracy of metal parts and the existed method cannot keep high synchronization precision because of external disturbances. A new double position servo synchronous driving scheme based on semi-closed-loop cross- coupling integrated feedforward control is proposed. The scheme comprises a position error cross-coupling feedfor-ward control and a load torque identification with feed- forward control. A digital integrated simulation system for the dual servo synchronous drive system is established. Using a 20 t servo broacher, performance analysis of the scheme is conducted based on this simulation system and the simulation results show that systems with traditional parallel or single control have problems when the work- table works with an unbalanced load. However, the system with proposed scheme shows good synchronous perfor- mance and positional accuracy. Broaching tests are performed and the experimental results show that the maximum dual axis synchronization error of the system is only 8μm during acceleration and deceleration processes and the error between the actual running position and the given position is almost zero. A double position servo synchronous driving scheme is presented based on crosscoupled integrated feedforward compensation control, which can improve the synchronization precision.

ANALYSIS OF COUPLING INFLUENCES OF LABYRINTH SEAL PARAMETERS ON CROSS COUPLED STIFFNESS AND DIRECT DAMPING COEFFICIENT

Labyrinth seal can cause steam-exciting, the structural and operating parameters of labyrinth seal have effect on stability of rotor-system. For investigating the coupling influences of the structure and operating parameters of labyrinth seals on dynamic coefficients, a model of calculating dynamic coefficients of labyrinth seals is presented using a two control volume model. The coupling influences of parameters on cross-coupled stiffness and direct damping of labyrinth seal are discussed. In the conclusion, a reference of preventing steam-exciting vibration and optimum determination of design parameters of labyrinth seals are provided.

Sustainable electrochemical cross‐dehydrogenative coupling of4‐quinolones and diorganyl diselenides

An environmentally friendly method for the synthesis of 3‐organylselenyl quinolones through theelectrochemical cross‐dehydrogenative coupling of 4‐quinolones and diorganyl diselenides wasdeveloped.As a green,atom economic and self‐separating process,the present reaction requiresneither external oxidants nor electrolytes,forming a recyclable catalytic system.

Cross-coupling integral adaptive robust posture control of a pneumatic parallel platform

A pneumatic parallel platform driven by an air cylinder and three circumambient pneumatic muscles was considered. Firstly, a mathematical model of the pneumatic servo system was developed for the MIMO nonlinear model-based controller designed. The pneumatic muscles were controlled by three proportional position valves, and the air cylinder was controlled by a proportional pressure valve. As the forward kinematics of this structure had no analytical solution, the control strategy should be designed in joint space. A cross-coupling integral adaptive robust controller(CCIARC) which combined cross-coupling control strategy and traditional adaptive robust control(ARC) theory was developed by back-stepping method to accomplish trajectory tracking control of the parallel platform. The cross-coupling part of the controller stabilized the length error in joint space as well as the synchronization error, and the adaptive robust control part attenuated the adverse effects of modelling error and disturbance. The force character of the pneumatic muscles was difficult to model precisely, so the on-line recursive least square estimation(RLSE) method was employed to modify the model compensation. The projector mapping method was used to condition the RLSE algorithm to bound the parameters estimated. An integral feedback part was added to the traditional robust function to reduce the negative influence of the slow time-varying characteristic of pneumatic muscles and enhance the ability of trajectory tracking. The stability of the controller designed was proved through Laypunov's theory. Various contrast controllers were designed to testify the newly designed components of the CCIARC. Extensive experiments were conducted to illustrate the performance of the controller.

Photo-induced reductive cross-coupling of aldehydes, ketones and imines with electron-deficient arenes to construct aryl substituted alcohols and amines

Umpolung reactions of C=X bonds(X=O,N)are valuable ways of constructing new C–C bonds,which are sometimes difficult to be constructed using traditional synthetic pathways.Classical polarity inversion of C=X bonds(X=O,N)usually requires air or moisture‐sensitive and strong reducing agents,which limit the feasibility of substrate scope.Herein we describe a photo‐induced reductive cross‐coupling reaction of aldehydes,ketones and imines with electron‐deficient arenes(aromatic nitriles)using fac‐Ir(ppy)3as a photocatalyst and diisopropylethylamine(DIPEA)as a terminal reductant under visible light irradiation.Mild conditions and high yields mean that this new polarity inversion strategy can be used with aryl‐substituted alcohols and amines.Spectroscopic studies and control experiments have demonstrated the oxidative quenching of Ir(ppy)3*by electron‐deficient arenes involved in the key step for the C–C bond formation.

Cu(OAc)_2 catalyzed Sonogashira cross-coupling reaction in amines

A simple Cu（OAc）2 catalyzed Sonogashira coupling protocol is presented. It was found that the couplings of a variety of aryl halides with terminal alkynes were conducted smoothly to afford the corresponding desired products in moderate to excellent yields, using Cu（OAc）2 as the catalyst and Et3N as the solvent.

Synthesis of Enamines via the Cross-coupling of Thioamides and Diarylketones Promoted by the Sm/SmI_(2)Mixed Reagent

Enamines, promoted by the samarium/samarium diiodide mixed reagent, were synthesized via the cross-coupling of thioamides and diarylketones in good yields.

Microwave-assisted Palladium Catalyzed Cross-coupling Reaction of Sodium Tetraphenylborate with Carboxylic Anhydrides

A rapid and efficient method for synthesis of unsymmetrical ketones under microwave irradiation is reported.

Polybinaphthyls of (R)-3,3′-Diiodo-2,2′-binaphtho-20-crown-6 with p-Divinylbenzene via Heck Cross-coupling Reaction

The present paper deals with the polymerization of ( R ) 3,3′ diiodo 2,2′ binaphtho 20 crown 6 with \{ p divinylbenzene\} under Heck coupling reaction condition. Both the monomers and the polymer were analyzed by NMR, FTIR, UV, CD, fluorescent spectroscopy, polarimetry, GPC and elemental analysis. The polymer can emit a strong blue fluorescence and is expected to have the potential application in the polarized blue light emitting sensors. The chiral conjugated polymer exhibits a strong Cotton effect in its Circular Dichroism(CD ) spectrum, indicating the high rigidity of the polymer backbone.

Highly active and stable supported Pd catalysts on ionic liquidfunctionalized SBA-15 for Suzuki–Miyaura cross-coupling and transfer hydrogenation reactions

Highly dispersed palladium nanoparticles were synthesized in the presence of immobilized ionic liquid on mesoporous silica SBA-15.PdNPs(2.4 nm)_me-Im@SBA-15 catalyst was prepared by the reduction using NaBH_4 as the reducing agent with controlled feed rate and has been investigated as ligand-free catalyst for Suzuki–Miyaura cross-coupling reaction at room temperature in aqueous solution under air.PdNPs catalyst was also prepared in situ from PdCl4_me-Im@SBA-15 during the reaction and demonstrated high activity and stability towards nitrobenzene hydrogenation at high temperature. Both catalysts were reusable at least for four recycle processes without significant loss in activity with simple procedure. The catalysts were characterized by TEM, EXAFS, FTIR and XPS.

Close coupling calculations for excitation partial cross sections in Ne-HF collisions

This paper reports that an exact quantum close coupling calculation is carried out for rotational excitation in Ne HF collisions on the available anisotropic potential. Partial cross sections are obtained separately at the incident energies of 48.35, 75, 120 and 150meV. The reliability of the results is demonstrated by comparison with previously published theoretical findings. Based on the calculations, the effect of the potential energy surface on the excitation partial cross sections is discussed in detail.

Microwave Irradiated Cross Coupling of Carboxylic Acids and Crotyl Bromides: Efficient Application to Make Arachidonic Acid Esters

A microwave irradiated palladium-catalyzed reaction of carboxylic acids and crotyl type bromides creates series of esters in good to high yields. This facile ester synthesis then is applied to make esters from arachidonic acid, salicylic acid, folic acid, and aspirin efficiently.

Improvement of Water Sensitivity of Macro-defect-free Cement Based Composites with Cross Coupling Agent

The enhancement of interface bonding between cement and polymerand the structural reticula- tion of the water-soluble polymer areproposed to minimize the shortening of the mechanical properties ofmacro-de- fect-free(MDF)cement based composites at high relativehumidity. The MDF composites incorporated with vari- ouscross-coupling agents studied experimentally. The results show thatthe MDF composites modified with small amounts of cross-couplingagent had raised mechanical properties, but it is more important thatthe modified MDF composites had a significant increase in waterresistance compared to the original one.

Microwave Irradiated Palladium-Catalyzed Cascade Type Cross Coupling of Phenols and Halides for the Synthesis of Polyphenolic Ethers

A mild, cascade type methodology was developed for the synthesis of polyphenolic ethers by the palladium-catalyzed cross coupling of phenols and halo compounds under microwave heating. In most cases, reactions run in neat conditions and in some cases, IPA/water mixture, and 1,4-dioxane were employed as solvents to furnish the products. By applying this new method, we were able to synthesize and purify a good number of polyether compounds with complete spectral data.

Cu-catalyzed cross-couplings under ligandless conditions

The possibility to carry out Cu-catalyzed cross-couplings under ligandless conditions was studied. It was found that by using K3PO4 as the base, the cross-coupling could proceed successfully between aryl iodides and several types of nucleophiles. Aryl bromides were completely inactive under the same reaction conditions.

Stereoselective Synthesis of (E)-1,3-Enynyl Bromides via Pd/Cu-cata-lyzed Cross-coupling Reaction of (Z)-α-Bromovinylstannanes

Z)-á-Bromovinylstannanes undergo the cross-coupling reaction with alkynyl iodides in the presence of Pd(PPh3)4 and CuI in THF at room temperature to afford stereoselectively (E)-1, 3- enynyl bromides in good yields.