6-氟-3-(4-哌啶基)-1,2-苯并异噁唑盐酸盐的合成

4-哌啶甲酸(2)与乙酐反应制得N-乙酰基-4-哌啶甲酸(3),3经历酰氯化、与间二氟苯Friedel-Crafts反应得到N-乙酰基-4-(2,4-二氟苯甲酰基)哌啶(4).4脱保护产物5与盐酸羟胺进行缩合反应生成(2,4-二氟苯基)-(4-哌啶基)甲酮肟盐酸盐(6).最后,6经分子内环合、成盐反应得精神病治疗药的中...     

4-(2-溴乙酰基)甲磺酰苯胺的合成工艺研究

以4-乙酰基甲磺酰苯胺与液溴为原料 ,以二氯乙烷为溶剂通过取代反应制备4-(2-溴 乙酰基)甲磺酰苯胺,探讨了合成反应的工艺条件 ,在最佳工艺条件下 ,产品的收率为 93%。     

4-烯丙氧基-6-乙酰基-2-乙酯基吡啶和4-烯丙氧基-2,6-二乙酰基吡啶的合成

乙酰基吡啶是一种重要的希夫碱前驱体。以白屈氨酸为原料,经酯化反应,合成了4-羟基-2,6-二乙酯基吡啶,再与3-溴丙烯反应,得到4-烯丙氧基-2,6-二乙酯基吡啶。此产物与乙酸乙酯在乙醇纳催化下C lais-en酯缩合反应,当控制乙醇钠与4-烯丙氧基-2,6-二乙酯基吡啶的摩尔比为0.9∶1时,得4-烯丙氧基-6-乙酰基-2-乙酯基吡啶,而摩尔比为5∶1时,得4-烯丙氧基-2,6-二乙酰基吡啶。其中4-烯丙氧基-6-乙酰基-2-乙酯基吡啶为首次报道合成。产物通过核磁共振和红外分析确认结构。     

N-{5-[1-(2′,4′-二氯苯氧)乙基]-1,3,4-噻二唑-2-基}-N′-芳氧乙酰基硫脲的合成与生物活性

通过2-氨基-5-[1-(2′,4′-二氯苯氧)乙基]-1,3,4-噻二唑与芳氧乙酰基异硫氰酸酯反应,合成了9种新的芳氧乙酰基硫脲,初步的生物活性测定试验表明,部分化合物具有良好的植物生长调节活性。     

N-乙酰基哌啶-4-甲酰氯的合成

以4-哌啶甲酸为原料、醋酸为酰化剂，后期加入少量醋酸酐反应得到中间体N-乙酰基哌啶-4-甲酸，收率92％；在甲苯溶剂中进行酰氯化得目标产物N-乙酰基哌啶-4-甲酰氯，收率97％。试验结果表明，合成N-乙酰基哌啶-4-甲酸反应后期，温度控制在145℃左右为最好；酰氯化时选用甲苯作为溶剂，可以缩短反应时间。反应减少了氯化亚砜的使用量，操作及处理简单，且三废排放量减少，对环境相对友好。     

中间体3,5-二氯-2-戊酮的绿色合成工艺开发

α-乙酰基-γ-丁内酯与氯气在无溶剂条件下发生氯化反应,得到α-氯-α-乙酰基-γ-丁内酯和副产氯化氢,α-氯-α-乙酰基-γ-丁内酯在少量水和氯化氢的存在下进行开环、氯代和脱羧反应得到3,5-二氯-2-戊酮.对氯气投料比、反应温度、氯化氢用量等因素进行优化.优化工艺条件为,第一步反应:氯化温度为0～5℃、n(氯气)∶n(α--乙酰基-γ-丁内酯)=1.07∶1.00;第二步反应:水解、脱羧及氯化温度为90℃、n(氯化氢)∶n(α-氯-α-乙酰基-γ-丁内酯)=0.7∶1.0,n(水)∶n(α-氯-α-乙酰基-γ-丁内酯)=0.8∶1.0,通入氯化氢4h,此条件下,收率达95.2％.     

中间体3,5-二氯-2-戊酮的绿色合成工艺开发

α-乙酰基-γ-丁内酯与氯气在无溶剂条件下发生氯化反应,得到α-氯-α-乙酰基-γ-丁内酯和副产氯化氢,α-氯-α-乙酰基-γ-丁内酯在少量水和氯化氢的存在下进行开环、氯代和脱羧反应得到3,5-二氯-2-戊酮.对氯气投料比、反应温度、氯化氢用量等因素进行优化.优化工艺条件为,第一步反应:氯化温度为0～5℃、n(氯气)∶n(α--乙酰基-γ-丁内酯)=1.07∶1.00;第二步反应:水解、脱羧及氯化温度为90℃、n(氯化氢)∶n(α-氯-α-乙酰基-γ-丁内酯)=0.7∶1.0,n(水)∶n(α-氯-α-乙酰基-γ-丁内酯)=0.8∶1.0,通入氯化氢4h,此条件下,收率达95.2％.     

2-氯-4-硝基苯基-β-D-吡喃岩藻糖苷的合成

2-氯-4-硝基苯基糖苷是一类重要的糖基酶底物试剂,在相关酶抑制剂制备、酶生物活性研究中有着广泛的应用.以D-半乳糖为原料,通过4步反应得到中间体D-岩藻糖;再经乙酰化制备1,2,3,4-三-O-乙酰基-α,β-D-吡喃岩藻糖,溴代反应获得1-溴-2,3,4-三-O-乙酰基-α-D-吡喃岩藻糖,通过溴代糖与2-氯4-硝基苯酚偶联,立体选择性获得2-氯-4-硝基苯-2,3,4-三-O-乙酰基-β-D-吡喃岩藻糖基糖苷,最后脱除乙酰基保护得标题化合物.该化合物可以作为一种新型的β-D-岩藻糖苷酶底物试剂,用于酶活性测试,其合成方法未见文献报道.     

光催化合成2,3-二(4-吡啶基)-2,3-丁二醇的新方法

研究了2,3-二(4-吡啶基)-2,3-丁二醇的合成,以及Ti O2等催化剂在乙醇体系中和光催化条件下催化4-乙酰基吡啶合成2,3-二(4-吡啶基)-2,3-丁二醇的快慢。结果表明,在以乙醇为溶剂,Ti O2等催化剂存在下的氙光环境中,4-乙酰基吡啶能够在较短时间内偶联成2,3-二(4-吡啶基)-2,3-丁二醇。     

4′-羟基-4-联苯甲酸的合成

以4-羟基联苯为原料,经酯化、傅-克酰基化、相转移催化下的苄基化、氯仿反应、催化氢解等反应,合成了标题化合物,总收率57.8%。化合物4′-苄氧基-4-乙酰基联苯、4′-苄氧基-4-联苯甲酸的结构经1HNMR、IR、MS及元素分析确证。与文献比较,该路线选择性好、产率较高。     

CO2/CH4 and CH4/N2 separation on isomeric metal organic frameworks☆

Two isomeric metal-organic frameworks(MOFs) with 2-dimensional(2D) and 3-dimensional(3D) topologies both comprised of Cu(Ⅱ) and OTf(OTf = trifluoromethanesulfonate) ions were synthesized and characterized.The CO_2,CH_4 and N_2 adsorption properties of the two isomeric MOFs were investigated from 263 K to 298 K at0.1 MPa.The results showed that the 2D MOF exhibited a higher selectivity for CO_2 from CO_2/CH_4 and CH_4from CH_4/N_2 compared to the 3D MOF,even though it possessed a lower surface area and pore volume.The higher adsorption heats of gases on the 2D MOF inferred the strong adsorption potential energy in the layered MOFs.Dynamic separation experiments using CO_2/CH_4 and CH_4/N_2 mixtures on the two MOFs proved that the2 D MOF had a longer elution time than the 3D MOF as well as better separation abilities.     

三维开放框架结构的无机-有机杂化材料[Cu4(SiW12O40)（pyz）4]的合成与晶体结构

以α-Keggin型硅钨酸、碳酸铜和2-乙基-3-甲基吡嗪(pyz)为原料,通过水热方法合成了标题化合物。采用元素分析、红外光谱和单晶X-射线衍射法表征了该化合物的结构。晶体结构分析表明,该化合物属于正交晶系,Pna21空间群,晶胞参数a=2.238 38(4)nm,b=1.386 87(3)nm,c=2.151 07(3)nm,α=β=γ=90°,V=6.677 7(2)nm3,Z=4,F(000)=6 408,Dc=3.598 g/cm3。该化合物中一价铜离子首先被pyz配体连接成波浪型的一维链状结构,而(SiW12O40)4-阴离子作为三齿配体进一步连接这些链形成一个三维的框架结构。     

2-[4-(4-氟苄基)哌嗪-1-基甲基]吡唑并[1,5-a]吡啶的合成及其体外受体结合分析

以吡唑并[1,5-a]吡啶-2-甲醛和N-甲酰基哌嗪为原料,经过还原胺化反应、水解反应、N-烷基化反应,合成了2-[4-(4-氟苄基)哌嗪-1-基甲基]吡唑并[1,5-a]吡啶,总收率29.5%,用1HNMR、19FNMR、ESI-MS对中间体及目标化合物进行了结构表征,并通过体外受体结合实验,测定目标化合物对多巴胺D4受体的亲和常数为1.2nmol/L,对D2、D3受体的亲和常数分别为3 900、1 890 nmol/L,显示对多巴胺D4受体具有较高的亲和性与选择性,是一种潜在的多巴胺D4受体配基。     

(AB)n Segmented Copolyetherimides for 4D Printing

The fourth dimension in 4D printing comprises the ability of materials to recover their shape with time by utilizing 3D printing in combination with shape memory polymers. The focus of this work is on 3D printing of physically crosslinked thermoplastic polymers, which allow a reversible transformation from a temporary to an original shape by an external stimulus temperature, thus realize 4D printing. In this context, (AB)_n segmented copolyetherimides consisting of perylene and poly(ethylene glycol) (PEG) segments are synthesized and characterized regarding their thermal and rheological properties in view of 3D printing. The perylene imide segments act as reversible physical crosslinks which disassemble between 100 and 200 °C. The PEG segments exhibit a low melting temperature around 40 to 60 °C and are semi-crystalline at room temperature. The results show that this type of (AB)_n segmented copolyetherimide combines reliable 3D printing performance, which is indicated by low warp deformation and excellent interlayer bonding. With a blend of two copolymers, it is able to realize 4D printing.     

Cancer Cell Cytotoxicities of 1-(4-Substitutedbenzoyl)-4-(4-chlorobenzhydryl)piperazine Derivatives

A series of novel 1-(4-substitutedbenzoyl)-4-(4-chlorobenzhydryl)piperazine derivatives 5a-g was designed by a nucleophilic substitution reaction of 1-(4-chlorobenzhydryl)piperazine with various benzoyl chlorides and characterized by elemental analyses, IR and (1)H nuclear magnetic resonance spectra. Cytotoxicity of the compounds was demonstrated on cancer cell lines from liver (HUH7, FOCUS, MAHLAVU, HEPG2, HEP3B), breast (MCF7, BT20, T47D, CAMA-1), colon (HCT-116), gastric (KATO-3) and endometrial (MFE-296) cancer cell lines. Time-dependent cytotoxicity analysis of compound 5a indicated the long-term in situ stability of this compound. All compounds showed significant cell growth inhibitory activity on the selected cancer cell lines.     

Enhanced interfacial electronic transfer of BiVO4 coupled with 2D g-C3N4 for visible-light photocatalytic performance

A BiVO₄/2D g-C₃N₄ direct dual semiconductor photocatalytic system has been fabricated via electrostatic self-assembly method of BiVO₄ microparticle and g-C₃N₄ nanosheet. According to experimental measurements and first-principle calculations, the formation of built-in electric field and the opposite band bending around the interface region in BiVO₄/2D g-C₃N₄ as well as the intimate contact between BiVO₄ and 2D g-C₃N₄ will lead to high separation efficiency of charge carriers. More importantly, the intensity of bulid-in electric field is greatly enhanced due to the ultrathin nanosheet structure of 2D g-C₃N₄. As a result, BiVO₄/2D g-C₃N₄ exhibits excellent photocatalytic performance with the 93.0% Rhodamine B (RhB) removal after 40 min visible light irradiation, and the photocatalytic reaction rate is about 22.7 and 10.3 times as high as that of BiVO₄ and 2D g-C₃N₄, respectively. In addition, BiVO₄/2D g-C₃N₄ also displays enhanced photocatalytic performance in the degradation of tetracycline (TC). It is expected that this work may provide insights into the understanding the significant role of built-in electric field in heterostructure and fabricating highly efficient direct dual semiconductor systems.     

Modified commercial UV curable elastomers for passive 4D printing

ABSTRACT

Conventional 4D printing technologies are realized by combining 3D printing with soft active materials such as shape memory polymers (SMPs) and hydrogels. However, the intrinsic material property limitations make the SMP or hydrogel-based 4D printing unsuitable to fabricate the actuators that need to exhibit fast-response, reversible actuations. Instead, pneumatic actuations have been widely adopted by the soft robotics community to achieve fast-response, reversible actuations, and many efforts have been made to apply the pneumatic actuation to 3D printed structures to realize passive 4D printing with fast-response, reversible actuation. However, the 3D printing of soft actuators/robots heavily relies on the commercially available UV curable elastomers the break strains of which are not suf?cient for certain applications which require larger elastic deformation. In this paper, we present two simple approaches to tune the mechanical properties such as stretchability, stiffness, and durability of the commercially available UV curable elastomers by adding: (i) mono-acrylate based linear chain builder; (ii) urethane diacrylate-based crosslinker. Material property characterizations have been performed to investigate the effects of adding the two additives on the stretchability, stiffness, mechanical repeatability as well as viscosity. Demonstrations of fully printed robotic finger, grippers, and highly deformable 3D lattice structure are also presented.     

The Effect of Selected Monoterpenoids on the Cellular Slime Mold, Dictyostelium discoideum NC4

We tested the activity of 11 main compounds identified from Pinus plants on the growth of Dictyostelium discoideum NC4. Four concentrations (1, 0.1, 0.01, 0.001 microg/microl) of each compound were tested using a disk volatilization technique following germination of D. discoideum NC4 spores. Photographs of D. discoideum NC4 fruiting bodies were taken 2 days after treatment. Fenchone (at 0.1, 0.01, and 0.001 microg/microl) and camphene (at 0.01 microg/microl) stimulated growth of D. discoideum NC4. (1S)-(-)-verbenone, (1S)-(-)-alpha-pinene, (+)-beta-pinene, myrcene, (-)-menthone, (-)-bornyl acetate, (S)-(+)-carvone, (-)-camphene, and (R)-(+)-limonene inhibit its growth. All of the compounds at 1 microg/microl had a strong inhibitory effect on cell growth of D. discoideum NC4. Microscopic observation of the fruiting bodies matched the results of growth rate analysis. Most of the inhibitory effects were represented by changes in the shapes of the fruiting bodies. These changes include short sorophores, smaller sized sori, and sori without spores. Our results suggest that inhibition of growth is the most common effect of monoterpenoids on D. discoideum NC4. Nevertheless, some of them, like fenchone and camphene, seem to enhance its growth.     

Formation of a 1D water chain into the channel of a unique 3D hydrogen-bound coordination polymer {[Cd(μ-Cl)(4-pya)(H2O)]2 · 4H2O}∞ (4-pya = trans-4-pyridylacrylate)

A novel Cd(II)/4-pya coordination polymer {[Cd(μ-Cl)(4-pya)(H₂O)]₂ · 4H₂O}_∞ (1) (4-pya = trans-4-pyridylacrylate) was synthesized and structurally characterized. Single-crystal X-ray diffraction revealed that 1 consists of a 2D (4, 4) network constructed from the 4-pya bridging ligand and the dimeric [Cd(μ-Cl)]₂ cores, in which each six-coordinated Cd(II) ion adopts an octahedral coordination geometry. Each 2D layer is further stacked along the a axis through hydrogen bonding interactions to afford a 3D hydrogen-bound network. An infinite water chain is generated via hydrogen bonds into each resulting 1D channel. The luminescent properties of 1 in the solid state were investigated.     

用NaBH4-I2还原合成D-(—)-苯甘氨醇

用NaBH4-I2还原D－（－）－苯甘氨酸得到D－（－）－苯甘氨醇，在最佳条件下，产率达到94．0％。