三個新的鋅的幾何異構物
在本實驗中,我們合成了三個新的鋅的幾何異構物:trans-facial-[Zn(dipica)₂]Cl2.CH3OH(dipica=dipicolylamine,C12H13N3,雙(2吡啶甲基)胺)trans-facial-[Zn(dien)2]Cl2(dien=diethylenetriamine,C4H14N3,二乙基三胺)及反式-[Zn(demn)2Cl2](demn=N,N’-dimethylethylenediamineC4H12N2,N,N'-二甲基乙二胺)。本實驗的特色皆在室溫下反應,採用擴散法培養晶體。trans-facial-[Zn(dipica)22]Cl2.CH3OH晶體為三斜晶系,晶格常數a=8.8269(6)Å, b=8.9908(6)Å, c=10.0292(6)Å,α=76.715(1)。,β=81.232(1)。,γ=67.753(1)。;其空間群為P1,可信度R=0.025,Rw=0.0697。六配位的陽離子,其結構為扭曲八面體,兩個含氮三牙基(dipica)trans-facial配位,赤道面(ZnN(1)N(2)N(1A)N(2A))由兩個含吡啶環之氮(N(1)、N(1A))及兩個飽和胺之氮(N(2)、N(2A))所組成。主軸為兩個吡啶環之氮所組成。兩個含氮三牙基(dipica)與鋅的咬合角皆為84.5。。trans-facial-[Zn(dien)2]Cl2晶體為單斜晶系,晶格常數為a=11.3050(3)Å,b=10.9264(3)Å, c=12.6147(3)Å,β=92.884(1)。;其空間群為P21/c,可信度R=0.0191,Rw=0.0484。六配位的離子,其結構為扭曲八面體,兩個含氮三牙基(dien)與鋅的咬合角為156°、157°。反式-[Zn(dmen)2Cl2]晶體為單斜晶系,晶格常數 a=10.3397(4)Å,b=8.5916(4)Å,c=7.9774(3)Å,β=100.520(1)°;其空間群為C2/m,可信度R=0.0266,Rw=0.0686。其結構為八面體,鋅原子四個氮原子組成赤道面(ZnN(1)N(1A)N(1B)N(1C)),兩個氯原子位於此平面的兩側。兩個含氮雙牙基(dmen)與鋅的咬合角皆為83.0(1)Å。
In this study, we have synthesized three new geometrical isomers of zinc(II)complexes: trans-facial-bis(dipicolylamine)zinc(II)chloride-mathanol(1/2)(trans-fac-[Zn(dipica)2]Cl2.2CH3OH), trans-facial-bis(ethylenetriamine)zinc(II)chloride(trans-fac[Zn(dien)2]Cl2)and trans-bis(N, N'-dimethylethylenetriamine)zinc(II)chloride(trans-[Zn(dmen)2]Cl2). The crystals suitable for X-ray diffraction were obtained by slow diffusion of ether to solution of the products. There molecular strctures determined by X-ray diffraction. The complex trans-fac-[Zn(dipica)2]Cl2.2CH3OH crystallizes in the triclinic space group P 1 with a=8.8269(6)Å, b=8.9908(6)Å, c=10.0292(6)Å,α=76.715(1)。,β=81.232(1)。,γ= 67.753(1)。, for Z=1. The R value is 0.0259 for 3286 significant reflections. In the hexacoordinate cation, the two tridentate dipicolylamine ligands are trans-facially coordinated with two pyridine nitrogens and two secondary amine nitrogens situated on four positions in a basal plane(ZnN(1)N(2)N(1A)N(2A)). The remaining two pyridine nitrogens constitute the axis in a distorted octahedra structure. Colorless trans-fac-[Zn(dien)2]Cl2 crystallizes the monoclinic space group P21/c with a=11.3050(3)Å, b=10.9264(3)Å, c =12.6147(3)Å,β=92.884(1)。,and Z=1. The R value is 0.0191 for 3285 significant reflections. The zinc(II) atom has distorted octahedra coordination, in which the ligands are bound in a trans-facial configuration. Colorless trans-[Zn(dmen)2Cl2] crystallizes the monoclinic space group C2/m with a=10.3397(4)Å, b= 8.5916(4)Å, c=7.9774(3)Å,β=100.520(1)。, and Z=2. The R value is 0.0266 for 856 significant reflections. The zinc(II)atom of trans-[Zn(dmen)2Cl2]is six coordinate with 4 nitrogens of bidentate dmen forming a basal plane(ZnN(1)N(1B)N(1A)N(1C)),and two chlorines on the axial sites completing an octahedra structure.
你喝下了多少?-台灣市售優酪乳乳酸菌生長力及抗酸性之探討
現今乳酸菌飲料風行,但是乳酸菌是否真能通過胃酸的考驗,到達腸道進行複製,利益人體?我們首先以市售乳酸菌粉(加拿大Rosell 公司,含二種菌,暫時命名為"小毛"及"小白")為預測菌種,利用分光光度計測定乳酸菌於Thioglycollate 培養基中的生長能力(OD600)。小毛在pH 值 1、 3 、5、 7 時之生長力分別為0、 0.008 、0.682 、0.847 ,小白為 0、 0.015 、0.973、 0.636。若於培養基中添加不同濃度的螺旋藻熱分解物,如加入0.01%的添加物後,小毛在以上各種pH 值生長力分別為0.042、1.291, 、1.447, 、1.213 ,小白為 0.053、1.392、 1.531、 0.988,意外發現可大幅提升菌的生長力及抗酸力。再取台灣市售4 種廠牌優酪乳(以甲、乙、丙、丁代表之),分離乳酸菌,再於各種pH 值中培養。結果在pH 3 時,螺旋藻熱分解物僅對丙廠牌有效, 乙廠牌無效, 甲與丙則有無填加生長力都很差。在pH 1 時, 則對乙、丙、丁皆有效,故建議廠商慎選菌種,並於製程及成品中添加螺旋藻熱分解物。The yogurt is a popular drink. But whether the lactobacilli inside can resist the destruction of gastric acid and grow well in the intestinal tract is still questionable. We used pure lactobacilli powder (Rosell Company, Canada, containing two bacteria named in this report as "Little Hair" and "Small White") for pre-test. The growth ability in thioglycollate medium was determined by spectrophotometer (OD600). The results of bacterial growth at pH 1, 3, 5, and 7 for "Little Hair" were 0, 0.008, 0.682, and 0.847, respectively. Those for "Small White" were 0, 0.015, 0.973, and 0.636, respectively. After supplement with 0.01% of the boiled lysate of Spirulina algae (ProBio Biotech, Taiwan), growth abilities at pH 1, 3, 5, and 7 for "Little Hair" were 0.042, 1.292, 1.447, and 1.213, respectively. Those for "Small White" were 0.053, 1.392, 1.531, and 0.988, respectively. The algae extract amply promotes the growth and acid-resistance, especially at pH 3, of these bacteria. The lactobacilli isolated from four different products of yogurt in Taiwan, named as A, B, C, and D, were then tested as above. Results showed the supplement with the boiled lysate of Spirulina algae was very effective, at pH 3, for promoting growth of C, but not effective for B. Growth abilities of both A and D were very unsatisfactory with or without this supplement. At pH 1, algae lysate supplement significantly improved the growths of B, C, and D. Therefore, this supplement in culture and product for yogurt preparation was suggested.
重金屬錯影響細胞生理功能的研究
儘管鍺在電子工業上被廣泛運用,但對於暴露在鍺化合物所產生的毒害則尚未被詳細的探討。在探討鍺對細胞所產生的生理影響中,我們使用了二氧化鍺 ( GeO2)和有機鍺( Ge-132 )。由實驗結果顯示, GeO2,會造成人類子宮上皮癌細胞( A 431 ) 及巨噬細胞株( Raw264.7 )死亡,而 Ge -132 對細胞生長則不造成任何影響,為了進一步了解鍺引起細胞死亡是否是經過細胞凋亡(apoptosis ) ,我們將鍺處理過的細胞進行染色體 D NA 的分析,結果發現細胞中 DNA 染色體沒有斷裂。由先前 Huang 等人於 1999 年的研究結果顯示,砷對細胞所造成的毒性是經由有絲分裂活化酵素( MAPK )傳導路徑,所以為了解鍺誘導細胞死亡的路徑,我們亦分析 MAPK 傳導路徑是否亦參與其中,我們發現 GeO2加入 A431 細胞後,會活化有絲分裂活化酵素中的 ERK ,但對JNK 及 p38 皆無影響,在對蛋白質表現方面,轉錄因子 c-Jun 的蛋白質表現也是隨著GeO2加入的時間增加而上升。 GeO2加入 Raw 264 . 7cell 後,會造成 JNK 、 ERK 的活化,同樣的轉錄因子 c- Jun 也會增加,由此一結果得知鍺對細胞的影響會因細胞的不同而有所差異,為了分析自由基是否參與砷及鍺所造成細胞死亡的過程,我們分析在 A431 細胞中可產生的 NO 的可誘導性 nitric oxide synthase ( iNOS )的表現,我們發現氧化鍺及砷都會誘導 iNOS 的表現量增加。綜合以上結果,可能顯示氧化錯可能會經由 M A PK 訊息傳遞路徑來促使細胞的死亡,並且 iNOS 亦可能參與此過程。就我們所知,這是第一個提出重金屬所造成的毒害可能會經由 iNOS 來誘導產生的研究。
Despite the extensive use of germanium (Ge) in the electronic industry and optical devices, the potential risks of exposure to germanium compounds have not been evaluated. The effects of germanium on cell physiological functions were studied. We first asked if germanium oxide (GeO2) or carboxyethylgermanium (Ge-l32) could affect cell viability. We found that GeO2, but not Ge-l32, reduced cell viability in a dose-dependent manner in epidermoid carcinoma A43 I and macrophage Raw 264.7 cells. In order to test whether apoptosis contributes to germanium cytotoxicity, DNA fragmentation was evaluated in A43 1 and Raw 264.7 cells treated with GeO2 or Ge-132, respectively. We found that neither GeO2 nor Ge- 132 had effect on chromosomal DNA fragmentation. Previous studies by Huang (1999) et al indicated that sodium arsenite (NaAsO2) cytotoxicity is mediated through mitogen-activated protein kinase (MAPK) pathways. In order to study the mechanism(s) by which GeO2 mediates cell death, we analyzed the signal transduction pathways triggered by GeO2 We found that GeO2 stimulated the extracellular signal-regulated kinase (ERK) activity and transcription factor c-Jun in a time-dependent manner, but not c-Jun amino-terminal kinasc (JNK), or p38 MAPK in A431 cells. Treatment of the Raw 264.7 cells with GeO2, induced activities of ERK, JNK and c-Jun in a time-dependent manner. Collectively, these results suggested that GeO2 effects might be cell type specific. To test whether free radicals were involved in NaAsO2 or GeO2 mediated cell death, the expression of inducible nitric oxide synthase (iNOS), which produced the NO free radical, was determined in A431 cells treated with NaAsO2 or GeO2. We found that expression of iNOS was induced in a time-dependent manner in NaAsO2 or GeO2-treted A431 cells. Taken together, our results indicated that GeO2-induccd cell death may be mediated through MAPK signal pathways and that iNOS may contribute to NaAsO2 or GeO2 mediated cell death. To our knowledge, this is the first report that iNOS may contribute to heavy metal mediated cytotoxicity.
“碘化鋅”產率變變變---溶劑對產率的影響
The research mainly discuss the influence on the rate of zinc iodine with different solution as catalytic agent. We use water, acid water, ethanol methanol acid ethanol, and acid methanol and so on as different solution to participate in the process of an equation: Zn+I2 → ZnI2 to work out the variation of the product's amount. Besides, we also change the proportion of Zinc and Iodine to discuss the difference between the proportion of reactant and the product's amount. The result shows that the product of this equation is ZnI2 not Zn(I3)2. Ethanol and methanol have the same effect as water to accelerate the process of the equation. We find out that this reaction get higher product's amount in acid condition. Also, put the mass Zinc with the mass iodine can get higher product's amount, Furthermore, acid in specific range (0.01M—1.00M), the denser the acid is, the higher product's amount we get. But how the water as catalytic agent work in the reaction is the direction we can research deeply in the days to come.
鋅和碘作用生成碘化鋅的反應,是用水作為催化劑,然而一小滴水卻使這個反應劇烈進 行,我們嘗試了多種和水具有相同作用的催化劑,由於反應時間極短不易測量,我們考慮由 產率部分著手,讓原本只需一小滴的水〈催化劑〉改為此反應的溶劑,計算其產率的變化。
實驗分為三部分,第一部份先是改變不同的溶劑,讓鋅和碘在不同溶劑〈水、酸化水、乙醇、酸化乙醇、甲醇、酸化甲醇〉下反應,計算出產率的變化,我們發現在酸中的產率的確較不加酸者來得高。第二部分我們改變加入鋅和碘的量,改變鋅和碘的比例,讓鋅由過量到成為此反應的限量試劑,觀察其產率的變化,我們發現碘作為限量試劑較鋅作為限量試劑的產率高。由於此反應在酸中產率較高,但酸的濃度高低是否又會影響產率呢?我們繼續第三部分的實驗,改變酸的濃度,讓此反應在不同的酸化水濃度的溶劑下反應,討論產率和酸濃度的關係,我們發現在一定範圍內〈0.01M~0.5M〉,酸的濃度越高,產率亦越高。
實驗方法是將鋅和碘置入同一試管中反應,並使其在不同溶劑中反應,接著離心,將碘化鋅水溶液與未反應完的反應物分離,將所得的碘化鋅水溶液使用結晶法得到碘化鋅晶體,秤重並計算其產率。