DDHI-DIPP二元体系固液平衡数据的测定和关联

测定了DDHI－DIPP体系的固液平衡相图，用理想溶液模型和UNIQUAC活度系数模型进行了关联；其中用UNIQUAC活度系数模型所获得的结果较满意。     

水—1，2－丙二醇二元体系在101．325kPa下的汽液平衡

用自制的汽液平衡釜测定了水—１，２－丙二醇二元体系在１０１．３２５ｋＰａ下全浓度范围的汽液平衡数据。所测数据通过了热力学一致性校验；并用最小二乘法回归Ｗｉｌｓｏｎ和ＮＲＴＬ方程参数，由于所测温度范围较宽，参数表示为温度的线性关系进行拟合，所得计算值与实验值符合良好。     

5-氯-2，3-二氢-2-羟基-1-氧代-1H-茚-2-羧酸甲酯合成研究进展

综述了5-氯-2,3-二氢-2-羟基-1-氧代-1H-茚-2-羧酸甲酯的各种合成方法。认为研究开发基于手性配体的金属催化剂是提高产品ee值和产率的重要发展途径。     

6-氟-4-氧代-3,4-二氢-2H-1-苯并吡喃-2-甲酸的合成

以对氟苯酚为原料,经酚羟基甲基化、与顺丁烯二酸酐发生傅-克酰基化反应、在碱性条件下迈克尔加成环合,合成6-氟-4-氧代-3,4-二氢-2H-1-苯并吡喃-2-甲酸.研究了环合反应条件,得到了最佳反应条件:以10%NaHCO3为催化剂,回流温度下,反应时间15min环合为最佳.总产率78%.     

3-(2-氧代-1,2-二氢喹啉-4-基)丙氨酸的合成研究

以丙二酸二乙酯为原料,经亚硝化、还原、乙酰化、缩合、水解、脱羧反应制得3-（2-氧代-1,2-二氢喹啉-4-基）丙氨酸,总收率为41.5%,含量为98.7%.合成工艺简单易操作,适合工业化生产.     

在氢环境中2(1/4)Cr-1Mo材料的断裂特性的研究

本文以某大型石化厂的加氢反应器壁材料为原材料,分别测定了原始状态、原始+电化学渗氢、步冷状态、步冷+热充氢试样的断裂韧性。甩金相法考察了各相应条件下的组织变化。用扫描电镜研究了断裂特性。     

在氢环境中2(1/4)Cr-1Mo钢的断裂特性

研究了在模拟加氢反应器工况条件下,国产加氢反应器壁材料2(1/4)Cr-1Mo钢的断裂特性。应用断裂力学方法,分别测定了原始状态、原始＋电化学渗氢、步冷状态、步冷＋热渗氢试样的断裂韧性K_IC;计算了埋入裂纹和表面裂纹的裂纹尖端的应力强度因子K_I。结果表明：步冷处理提高了2(1/4)Cr-1Mo钢的断裂韧性,氢降低了2(1/4)Cr-1Mo钢的断裂韧性;只要反应器内壁无表面裂纹,设备运行是安全的。     

2-氟-5-[(4-氧代-3,4-二氢二氮杂萘-1-基)甲基]苯甲酸的合成新方法

2-氟-5-[(4-氧代-3,4-二氢二氮杂萘-1-基)甲基]苯甲酸是合成奥拉帕尼的关键中间体。以邻羧基苯甲醛为原料,与亚磷酸二甲酯反应得到磷叶立德,再与2-氟-5-甲酰基苯甲酸进行WittigHorner反应、环合反应得到目标化合物,并对各步反应条件进行了优化,三步反应总收率70.9%。目标化合物经(1 H NMR)和(MS)确证结构。     

1-(5,5-二甲基-2-环己烯-1-酮-3-基)-戊-2-酮的合成

以α-异佛尔酮为原料,在氯化锌和己二酸存在下,尝试合成氧代二氢大马酮香料,却意外得到了氧代二氢大马酮的一个异构体,即标题化合物,用气相色谱-质谱和核磁共振谱进行了结构表征,并研究优化了合成此化合物的工艺条件,即使用无水氯化锌、最佳反应温度为145 ℃、最佳反应时间为8 h.     

Changes in the Ratio of Tc1/Tc2 and Th1/Th2 Cells but Not in Subtypes of NK-Cells in Preeclampsia

It has been suggested that natural killer (NK) cell activity and Th1 immunity may be involved in the pathogenesis of preeclampsia. This study aimed to investigate the immunophenotypes of NK cells and type 1/type 2 immunity in both decidua and maternal peripheral blood between normal (n=11) and preeclamptic pregnant women (n=20) by flow cytometry. The results showed that no significant difference was observed between patients and controls by detecting CD56⁺CD69⁺ and CD56⁺CD94⁺ NK cells in both peripheral blood and decidua. Moreover, in preeclamptic patients, decreased percentages of Tc2 and Th2 cells and the increased ratios of Tc1/Tc2 were determined in both decidua and maternal peripheral blood. In addition, the ratio of Th1/Th2 in peripheral blood also increased. There was no significant difference of immunophenotypes of uNK cells between preeclampsia and normal pregnancy. Local decidua and systematic immunity did not correlate with each other. These results suggest that the type 1/type 2 immunity shifted to type 1 immunity including Th1 and Tc1 cells may contribute to the patho-genesis of preeclampsia.     

Mycobacterium tuberculosis RpfE-Induced Prostaglandin E2 in Dendritic Cells Induces Th1/Th17 Cell Differentiation

Prostaglandin E2 (PGE2) is an important biological mediator involved in the defense against Mycobacterium tuberculosis (Mtb) infection. Currently, there are no reports on the mycobacterial components that regulate PGE2 production. Previously, we have reported that RpfE-treated dendritic cells (DCs) effectively expanded the Th1 and Th17 cell responses simultaneously; however, the mechanism underlying Th1 and Th17 cell differentiation is unclear. Here, we show that PGE2 produced by RpfE-activated DCs via the MAPK and cyclooxygenase 2 signaling pathways induces Th1 and Th17 cell responses mainly via the EP4 receptor. Furthermore, mice administered intranasally with PGE2 displayed RpfE-induced antigen-specific Th1 and Th17 responses with a significant reduction in bacterial load in the lungs. Furthermore, the addition of optimal PGE2 amount to IL-2-IL-6-IL-23p19-IL-1β was essential for promoting differentiation into Th1/Th17 cells with strong bactericidal activity. These results suggest that RpfE-matured DCs produce PGE2 that induces Th1 and Th17 cell differentiation with potent anti-mycobacterial activity.     

Sex-Based Selectivity of PPARγ Regulation in Th1, Th2, and Th17 Differentiation

Peroxisome proliferator-activated receptor gamma (PPARγ) has recently been recognized to regulate adaptive immunity through Th17 differentiation, Treg functions, and T_FH responses. However, its role in adaptive immunity and autoimmune disease is still not clear, possibly due to sexual differences. Here, we investigated in vitro treatment study with the PPARγ agonist pioglitazone to compare Th1, Th2, and Th17 differentiation in male and female mouse splenic T cells. Pioglitazone treatment significantly inhibited various effector T cell differentiations including Th1, Th2, and Th17 cells from female naïve T cells, but it selectively reduced IL-17 production in male Th17 differentiation. Interestingly, pioglitazone and estradiol (E2) co-treatment of T cells in males inhibited differentiation of Th1, Th2, and Th17 cells, suggesting a mechanism for the greater sensitivity of PPARγ to ligand treatment in the regulation of effector T cell differentiation in females. Collectively, these results demonstrate that PPARγ selectively inhibits Th17 differentiation only in male T cells and modulates Th1, Th2, and Th17 differentiation in female T cells based on different level of estrogen exposure. Accordingly, PPARγ could be an important immune regulator of sexual differences in adaptive immunity.     

Kurarinone Attenuates Collagen-Induced Arthritis in Mice by Inhibiting Th1/Th17 Cell Responses and Oxidative Stress

Kurarinone is a flavanone, extracted from Sophora flavescens Aiton, with multiple biological effects. Here, we determine the therapeutic potential of kurarinone and elucidate the interplay between kurarinone and the autoimmune disease rheumatoid arthritis (RA). Arthritis was recapitulated by induction of bovine collagen II (CII) in DBA/1 mice as a collagen-induced arthritis (CIA) model. After the establishment of the CIA, kurarinone was given orally from day 21 to 42 (100 mg/kg/day) followed by determination of the severity based on a symptom scoring scale and with histopathology. Levels of cytokines, anti-CII antibodies, and the proliferation and lineages of T cells from the draining lymph nodes were measured using ELISA and flow cytometry, respectively. The expressional changes, including STAT1, STAT3, Nrf2, KEAP-1, and heme oxygenase-1 (HO-1) changes in the paw tissues, were evaluated by Western blot assay. Oxidative stress featured with malondiadehyde (MDA) and hydrogen peroxide (H₂O₂) activities in paw tissues were also evaluated. Results showed that kurarinone treatment reduced arthritis severity of CIA mice, as well as their levels of proinflammatory cytokines, TNF-α, IL-6, IFN-γ, and IL-17A, in the serum and paw tissues. T cell proliferation was also reduced by kurarinone even under the stimulation of CII and anti-CD3 antibody. In addition, kurarinone reduced STAT1 and STAT3 phosphorylation and the proportions of Th1 and Th17 cells in lymph nodes. Moreover, kurarinone suppressed the production of MDA and H₂O_2. All while promoting enzymatic activities of key antioxidant enzymes, SOD and GSH-Px. In the paw tissues, upregulation of Nrf-2 and HO-1, and downregulation of KEAP-1 were observed. Overall, kurarinone showed an anti-inflammatory effect by inhibiting Th1 and Th17 cell differentiation and an antioxidant effect exerted in part through activating the Nrf-2/KEAP-1 pathway. These beneficial effects in CIA mice contributed to the amelioration of their arthritis, indicating that kurarinone might be an adjunct treatment option for rheumatoid arthritis.     

Fish oil supplementation of lactating mothers affects cytokine production in 2 1/2-year-old children

n−3 PUFA influence immune functioning and may affect the cytokine phenotype during development. To examine whether maternal fish oil supplementation during lactation could modify later immune responses in children, 122 lactating Danish mothers with a fish intake below the population median were randomized to groups supplemented for the first 4 mon of lactation with 4.5 g/d of fish oil (equivalent to 1.5 g/d of n−3 long-chain PUFA) or olive oil. Fifty-three mothers with a fish intake in the highest quartile of the population were also included. The FA composition of erythrocyte membranes was measured at 4 mon and at 2 1/2 yr. Plasma immunoglobulin E (IgE) levels and cytokine production in lipopolysaccharide-stimulated whole-blood cultures were determined at 2 1/2 yr. Erythrocyte n−3 PUFA at 4 mon were higher in infants from the fish oil group compared with the olive oil group (P<0.001) but were no longer different at 2 1/2 yr. The median production of lipopolysaccharide-induced interferon γ(IFN-γ) in the fish oil group was fourfold higher than that in the olive oil group (P=0.034), whereas interleukin-10 (IL-10) production was similar. The IFN-γ/IL-10 ratio was twofold higher in the fish oil group (P=0.019) and was positively correlated with 20∶5n−3/20∶4n−6 in erythrocytes at 4 mon (P=0.050). The percentages of atopic children and plasma IgE were not different in the two groups, but the study was not designed to look at atopy. Cytokine responses and erythrocyte FA composition in children of mothers with a high fish intake were intermediate in comparison with those in the randomized groups. Fish oil supplementation during lactation resulted in increased in vitro IFN-γ production in the children 2 yr after the supplementation was given, which may reflect a faster maturation of the immune system.     

超临界干燥法制备TiO2/凹凸棒复合光催化剂

以凹凸棒为载体,四氯化钛为钛源,通过溶胶-凝胶法结合超临界干燥法制备TiO₂/凹凸棒复合光催化材料。采用XRD、SEM、TEM、BET、XPS等方法对材料的结构、形貌及催化性能进行表征。研究结果表明：超临界干燥可增大复合材料的比表面积,抑制TiO₂发生晶型转变。凹凸棒吸附特性良好,增加了材料表面的活性位点,显著提高催化剂的光催化活性。不同煅烧温度下的TiO₂均为锐钛矿型,粒径约为20 nm,呈不规则短棒状,成功负载于凹凸棒上。在400℃煅烧2 h条件下,催化剂3 h后对亚甲基蓝的降解率可达98.4%。     

Reactivation of spent Pd/AC catalyst by supercritical CO2 fluid extraction

In this article, we reported a nondestructive and environmentally friendly method for the reactivation of a spent Pd/AC catalyst for the hydrogenation of benzoic acid by using supercritical CO₂ (scCO₂) fluid extraction. The effects of reactivation conditions, such as extraction temperature, pressure, CO₂ flow rate, and time, on the activity of the reactivated Pd/AC catalyst, were presented. The catalyst was characterized by N₂ physisorption, laser particle size analysis, and transmission electron spectroscopy, and the liquid extract was analyzed by GC-MS. It is found that scCO₂ fluid extraction was very efficient in eliminating organic substances blocking the pores of the catalyst, while did not affect noticeably the granule size of the catalyst and the particle size of Pd. The reactivated Pd/AC catalyst regained more than 70% of the activity of the fresh 5.0 wt % Pd/AC catalyst, and has been successfully used in an industrial unit for the hydrogenation of benzoic acid. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Preparation of V2O3 nanopowders by supercritical fluid reduction

V₂O₃ nanoparticles, with diameters of 30-60 nm, have been synthesized by supercritical ethanol fluid reduction of VOC₂O₄. It was found that the reaction time has little influence on the purity and morphology of as-prepared products. And carbon oxides decomposed from C₂O₄²⁻ were conducive to the formation of the uniform sphere-like nanoparticles. The reaction mechanism of synthesizing uniform V₂O₃ nanoparticles is believed to be the redox reaction between VOC₂O₄ and ethanol in the supercritical condition. The crystal growth mechanism was proposed on the basis of the discussion about the formation process of the uniform sphere-like nanoparticles.     

Origin of Relaxor Behavior in K1/2Bi1/2TiO3–Bi(Mg1/2Ti1/2)O3 Investigated by Electrical Impedance Spectroscopy

Lead‐free binary K_1/2Bi_1/2TiO₃‐Bi(Mg_1/2Ti_1/2)O₃ (KBT‐BMT) ferroelectric ceramics with a morphology of dense and evenly sized grains have been prepared by conventional solid oxide reaction route. X‐ray diffraction analysis indicates that all the samples possess pure perovskite structure, and undergo a phase transformation from tetragonal to pseudocubic phase as BMT adds into KBT. Meanwhile, BMT addition brings in the enhancement of the relaxor behavior as revealed by temperature‐dependent dielectric profiles and the P–E loops. The impedance analysis reveals that the relaxation process existing in the ceramics belongs to a localized species. Further, in the frequency‐dependent M″(f) spectra, a shoulder response emerges accompanied by a bulk response as suitable amount of BMT is added, and its frequency dependence obeys Vogel–Fulcher relation f = f₀ exp[ ‐ E_b/k_B(T ‐ T_VF)]. The shoulder response is believed to be the evidence of the existence of the polar nanoregions, which dominate the relaxor behavior of KBT‐BMT ceramics.     

Negative thermal expansion of (Al1/3Fe1/3Cr1/3)2(Mo1/2W1/2)3O12 (AFCMW) and low thermal expansion of AFCMW-(Co1/2Ni1/2)(Mo1/2W1/2)O4 with high entropy

A₂Mo₃O₁₂ (A-Al, Fe, Cr) have large negative thermal expansion (NTE) coefficients and structural stability but high phase-transition temperatures (PTTs). Herein, we prepared (Al_1/3Fe_1/3Cr_1/3)₂(Mo_1/2W_1/2)₃O₁₂ (AFCMW), and found it to have a low NTE coefficient and a low PTT. Furthermore, combination of AFCMW with (Co_1/2Ni_1/2)(Mo_1/2W_1/2)O₄ (CNMW) afforded an AFCMW–CNMW composite with a low thermal expansion (LTE). We determined that the PTT reductions in A₂Mo₃O₁₂ are largely due to the high-entropy effect resulting from the introduction of different ions into its A and M sites. Moreover, we found that the low LTE of the AFCMW–CNMW composite is attributable to the opposite thermal expansion behaviours of AFCMW and CNMW. We suggest that the suppressed thermal expansion during the phase transition process of the AFCMW–CNMW composite could be derived from the high-entropy effect resulting from its increased diversity of polyhedra, the influence of Co²⁺ and Ni²⁺ dopants, and CNMW-induced lattice distortion.