Conventionally, an experimentally determined phase diagram requires studies of phase formation at a range of temperatures for each composition, which takes years of effort from multiple research groups. Combinatorial ...Conventionally, an experimentally determined phase diagram requires studies of phase formation at a range of temperatures for each composition, which takes years of effort from multiple research groups. Combinatorial materials chip technology, featuring high-throughput synthesis and characterization, is able to determine the phase diagram of an entire composition spread of a binary or ternary system at a single temperature on one materials library, which, though significantly increasing efficiency, still requires many libraries processed at a series of temperatures in order to complete a phase diagram. In this paper, we propose a "one-chip method" to construct a complete phase diagram by individually synthesizing each pixel step by step with a progressive pulse of energy to heat at different temperatures while monitoring the phase evolution on the pixel in situ in real time. Repeating this process pixel by pixel throughout the whole chip allows the entire binary or ternary phase diagram to be mapped on one chip in a single experiment. The feasibility of this methodology is demonstrated in a study of a Ge-Sb-Te ternary alloy system, on which the amorphouscrystalline phase boundary is determined.展开更多
An efficient poly(ethylene glycol) (PEG)-supported liquid-phase parallel approach to di(aryloxyacetyl)thiosemicarbazides is described. PEG-bound phenol reacted with chloroacetic acid to afford PEG-bound phenyloxyaceti...An efficient poly(ethylene glycol) (PEG)-supported liquid-phase parallel approach to di(aryloxyacetyl)thiosemicarbazides is described. PEG-bound phenol reacted with chloroacetic acid to afford PEG-bound phenyloxyacetic acid, which was readily converted into corresponding phenyloxyacetyl chloride. Subsequent nucleophilic substitution with ammonium thiocyanate followed by addition of aryloxyacetic acid hydrazides gave PEG-bound di(aryloxyacetyl)thiosemi-carbazides, which were easily cleaved to give the resulting library of 1-aryloxyacetyl-4-(4'-methoxylcarbonylphenyloxyacetyl)thiosemicarbazides in good to high yield and high purity.展开更多
This paper describes a combinatorial Synthesis of the Mannich Bases in Solution through the Mannich reaction using 3 ketones, 5 amines and formaldehyde in solution and hydrochloride as a catalyst and then using a macr...This paper describes a combinatorial Synthesis of the Mannich Bases in Solution through the Mannich reaction using 3 ketones, 5 amines and formaldehyde in solution and hydrochloride as a catalyst and then using a macroporous quarterized ammonium resin (CO32- form) as a scavenge agent to remove the acid catalyst when the Mannich reaction is completed. It was found by GC/MS analysis that the symmetrical ketone, such as acetone, in the Mannich reaction mainly produces one Mannich base; while the asymmetrical ketone, such as 2-pentanone, gives two Mannich bases. The reactivity depends on the tereo-hinder of both ketones and amines.展开更多
Excellent yields and purity were obtained in the aqueous medium Suzuki, Sonogashira, Stille and Heck reactions using palladium (II) as catalyst in liquid phase synthesis. Polyethylene glycol (PEG) acted as soluble pol...Excellent yields and purity were obtained in the aqueous medium Suzuki, Sonogashira, Stille and Heck reactions using palladium (II) as catalyst in liquid phase synthesis. Polyethylene glycol (PEG) acted as soluble polymeric support and phase transfer catalyst as well.展开更多
An efficient and rapid parallel liquid-phase synthesis of isoxazolines has been reported. The one-pot three-component reaction of polyethylene glycol-supported acrylates, aldehydes and hydroxylamine hydrochloride in...An efficient and rapid parallel liquid-phase synthesis of isoxazolines has been reported. The one-pot three-component reaction of polyethylene glycol-supported acrylates, aldehydes and hydroxylamine hydrochloride in the presence of chloramine-T in methanol gave the corresponding PEG-supported isoxazolines, which can be cleaved from the support under mild condition to afford isoxazolines in good yields (>80%) and high purities (>86%).展开更多
Based on the binding mode for hydrouracil in photosystem II (PS II) Dl protein, a general method for the solid phase combinatorial synthesis of hydrouracil library was developed. The acryloyl chloride or acid were cou...Based on the binding mode for hydrouracil in photosystem II (PS II) Dl protein, a general method for the solid phase combinatorial synthesis of hydrouracil library was developed. The acryloyl chloride or acid were coupled to Wang resin1 to afford the acryloyl ester2. Resin bound ester2 reacted with various primary amines to give secondary amines3, which were converted to the resin bound ureas4 by treatment with isocyanates. Preparation of the hydrouracils5 was achieved by the acidic cyclization-cleavage from the resin. For characterization purposes,8 hydrouracil analogues were synthesized in parallel, following which a small library of9 hydrouracil derivatives was prepared after cleavage from Wang resin. All the9 bydrouracil derivatives desired were identified by GCMS.展开更多
Treatment of lithio derivative of novel PEG-supported a-phenylselenopropionate with aldehydes, followed by oxidation-elimination with 30% hydrogen peroxide, formed Baylis-Hillman products, which were then reacted with...Treatment of lithio derivative of novel PEG-supported a-phenylselenopropionate with aldehydes, followed by oxidation-elimination with 30% hydrogen peroxide, formed Baylis-Hillman products, which were then reacted with sodium arylsulfinate. The resulting sulfonylated products were cleaved from the PEG efficiently affording methyl （2Z）-2-arylsulfonylmethyl-2-alkenoates in good yields and high purities.展开更多
基金supported in part by National High Technology Research and Development Program (2015AA034204)the National Natural Science Foundation of China (51472044)
文摘Conventionally, an experimentally determined phase diagram requires studies of phase formation at a range of temperatures for each composition, which takes years of effort from multiple research groups. Combinatorial materials chip technology, featuring high-throughput synthesis and characterization, is able to determine the phase diagram of an entire composition spread of a binary or ternary system at a single temperature on one materials library, which, though significantly increasing efficiency, still requires many libraries processed at a series of temperatures in order to complete a phase diagram. In this paper, we propose a "one-chip method" to construct a complete phase diagram by individually synthesizing each pixel step by step with a progressive pulse of energy to heat at different temperatures while monitoring the phase evolution on the pixel in situ in real time. Repeating this process pixel by pixel throughout the whole chip allows the entire binary or ternary phase diagram to be mapped on one chip in a single experiment. The feasibility of this methodology is demonstrated in a study of a Ge-Sb-Te ternary alloy system, on which the amorphouscrystalline phase boundary is determined.
文摘An efficient poly(ethylene glycol) (PEG)-supported liquid-phase parallel approach to di(aryloxyacetyl)thiosemicarbazides is described. PEG-bound phenol reacted with chloroacetic acid to afford PEG-bound phenyloxyacetic acid, which was readily converted into corresponding phenyloxyacetyl chloride. Subsequent nucleophilic substitution with ammonium thiocyanate followed by addition of aryloxyacetic acid hydrazides gave PEG-bound di(aryloxyacetyl)thiosemi-carbazides, which were easily cleaved to give the resulting library of 1-aryloxyacetyl-4-(4'-methoxylcarbonylphenyloxyacetyl)thiosemicarbazides in good to high yield and high purity.
基金National Natural Science Foundation of China (29674915, 29844001).
文摘This paper describes a combinatorial Synthesis of the Mannich Bases in Solution through the Mannich reaction using 3 ketones, 5 amines and formaldehyde in solution and hydrochloride as a catalyst and then using a macroporous quarterized ammonium resin (CO32- form) as a scavenge agent to remove the acid catalyst when the Mannich reaction is completed. It was found by GC/MS analysis that the symmetrical ketone, such as acetone, in the Mannich reaction mainly produces one Mannich base; while the asymmetrical ketone, such as 2-pentanone, gives two Mannich bases. The reactivity depends on the tereo-hinder of both ketones and amines.
文摘Excellent yields and purity were obtained in the aqueous medium Suzuki, Sonogashira, Stille and Heck reactions using palladium (II) as catalyst in liquid phase synthesis. Polyethylene glycol (PEG) acted as soluble polymeric support and phase transfer catalyst as well.
文摘An efficient and rapid parallel liquid-phase synthesis of isoxazolines has been reported. The one-pot three-component reaction of polyethylene glycol-supported acrylates, aldehydes and hydroxylamine hydrochloride in the presence of chloramine-T in methanol gave the corresponding PEG-supported isoxazolines, which can be cleaved from the support under mild condition to afford isoxazolines in good yields (>80%) and high purities (>86%).
文摘Based on the binding mode for hydrouracil in photosystem II (PS II) Dl protein, a general method for the solid phase combinatorial synthesis of hydrouracil library was developed. The acryloyl chloride or acid were coupled to Wang resin1 to afford the acryloyl ester2. Resin bound ester2 reacted with various primary amines to give secondary amines3, which were converted to the resin bound ureas4 by treatment with isocyanates. Preparation of the hydrouracils5 was achieved by the acidic cyclization-cleavage from the resin. For characterization purposes,8 hydrouracil analogues were synthesized in parallel, following which a small library of9 hydrouracil derivatives was prepared after cleavage from Wang resin. All the9 bydrouracil derivatives desired were identified by GCMS.
基金Project supported by the National Natural Science Foundation of China （No. 20562005） and the Natural Science Foundation of Jiangxi Province （No 0620021 ）.
文摘Treatment of lithio derivative of novel PEG-supported a-phenylselenopropionate with aldehydes, followed by oxidation-elimination with 30% hydrogen peroxide, formed Baylis-Hillman products, which were then reacted with sodium arylsulfinate. The resulting sulfonylated products were cleaved from the PEG efficiently affording methyl （2Z）-2-arylsulfonylmethyl-2-alkenoates in good yields and high purities.
