• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    兩個鑭系金屬配合物的水熱合成、晶體結(jié)構(gòu)、熒光、熱穩(wěn)定性及抑菌活性

    2015-11-30 08:41:16宗廣才任寧張建軍祁曉霞高捷張大海
    無機(jī)化學(xué)學(xué)報 2015年7期
    關(guān)鍵詞:張建軍河北師范大學(xué)晶體結(jié)構(gòu)

    宗廣才 任寧 張建軍*, 祁曉霞 高捷 張大海

    兩個鑭系金屬配合物的水熱合成、晶體結(jié)構(gòu)、熒光、熱穩(wěn)定性及抑菌活性

    宗廣才1,2任寧*,3張建軍*,1,2祁曉霞1,2高捷1,2張大海3

    (1河北師范大學(xué),分析測試中心,石家莊050024)
    (2河北師范大學(xué),化學(xué)與材料科學(xué)學(xué)院,石家莊050024) (3邯鄲學(xué)院,化學(xué)化工與材料學(xué)院,邯鄲056005)

    水熱法合成了2個鑭系配合物[Ln(3,4-DFBA)3(phen)(H2O)]2(H2O)2(Ln=Sm(1),Ho(2);3,4-DFBA=3,4-二氟苯甲酸根,phen=菲咯啉)。利用X-射線單晶衍射儀測定了配合物的晶體結(jié)構(gòu)。配合物1和2結(jié)構(gòu)相同,配位數(shù)為8,屬于三斜晶系,空間群為P1。相鄰的2個雙核分子之間通過分子間相互作用力形成了2D層狀結(jié)構(gòu)。并用元素分析,紅外,紫外,XRD等手段對目標(biāo)配合物進(jìn)行了表征。用TG-DTG技術(shù)測定了配合物的熱穩(wěn)定性,同時對配合物1的熒光性能進(jìn)行了研究。另外,還測定了這兩種配合物對白色念珠菌,革蘭氏陰性菌(大腸桿菌)以及革蘭氏陽性菌(金黃色葡萄球菌)的抑菌活性。

    鑭系元素;3,4-二氟苯甲酸;熱分析;熒光;抑菌活性;晶體結(jié)構(gòu)

    The lanthanide coordination chemistry has become of increasing significance in the last few years[1].Due to the larger radius of lanthanide ions and higher affinity for hard donor centers,lanthanide ions are easily to construct coordination polymers with organic carboxylic acid ligands and neutral ligands using regular methods[2].Lanthanide complexes with fancy chemical and physical characters have potential applications as fluorescence materials and bioprobes and so on[3].Since a lanthanide organic complex of europium emitted brightly photoluminescence was reported firstly by Weissman[4],the fluorescence materials began to be studied and other lanthanide complexes with metal ions Sm(Ⅱ),Tb(Ⅱ),Dy(Ⅱ)had been involved[5-7].In addition,lanthanide complexes have high sterilization ability and wide inhibition zone,hence,the bacteriostatic activity of complexes is a popular topic over the years in the field ofbiological and other aspects[8-11].

    In this paper,two complexes[Ln(3,4-DFBA)3(phen)(H2O)]2(H2O)2(Ln=Sm(1),Ho(2);3,4-DFBA=3, 4-difluorobenzoate,phen=1,10-phenanthroline)have been synthesized by hydrothermal method.Complexes 1 and 2 are binuclear molecules.Two of H2O molecules are coordinated with two metal ions and another two H2O molecules are crystalwater,which are rare in the study of lanthanide carboxylic acid complexes[12-14]. Thermal and luminescent properties,bacteriostatic activities ofthe title complexes are also investigated.

    1 Experimental

    1.1 Materials and measurement

    All reagents and solvents were purchased commercially without further purification.LnCl3·6H2O were prepared by the reaction of Ln2O3and hydrochloric acid in aqueous solution,followed by recrystallization and drying.The obtained complexes were dissolved in DMSO solution with the concentration of 10μmol·L-1and 1 mmol·L-1for the determination of ultraviolet spectra and molar conductivity,respectively.The contents of C,H and N were recorded on FLASH EA 1112 element analyzer (Thermo Fisher).The infrared spectrum were studied with KBr discs technique by using the Bruker TENSOR 27 spectrometer at room temperature over the range of 4 000 to 400 cm-1.Ultraviolet spectra were carried out on a U-3010 Spectrophotometer.The molar conductivity was measured by DDS-307 conductometer(Shanghai Precision&Scientific Instrument CO.LTD)at room temperature.X-ray Diffractions for complexes were tested on X-ray powder(Bruker AXS) diffractometer(Germany,D8 ADVANCE)with a scan speed of 0.1°·s-1,Cu Kαradiation(λ=0.154 18 nm), scan range from 5°to 50°.The thermal stability was investigated by TG/DTG using the NETZSCH STA 449 F3 with a heating rate of 10 K·min-1(Simulated air atmosphere).The fluorescent spectrum of complex 1 was depicted in an F-4500 Hitachispectrophotometer at room temperature.The bacteriostatic activities were investigated by the disk diffusion method using the Mueller-Hinton agar medium.The bacteriostatic effects for escherichia coli and staphylococcus aureus were investigated at the temperature of 310 K,while candida albicans at303 K.

    1.2 Synthesis of the complexes

    3,4-difluorobenzoic acid(3,4-DFHBA,0.3 mmol) and 1,10-phenanthroline(0.1 mmol)were together dissolved in ethanolsolution(95%)and the pH value of the solution was adjusted to 5~7 by adding 1 mol· L-1NaOH solution.LnCl3·6H2O(Ln=Sm(1),Ho(2)) (0.1 mmol)was dissolved in distilled water.The resulting solution of the ligands was then added dropwise into the aqueous solution of lanthanide metal salts under stirring for 40 min.Subsequently,the mixture solution was transferred to the Teflon-lined autoclave and settled in electrothermal constanttemperature dry box at 120℃for 72 h[15-16].Then the transparent crystals suitable for X-ray diffraction analysis were produced.Anal.Calcd.for C66H42F12N4Sm2O16(%):C,47.31;H,2.53;N,3.34.Found(%): C,47.70;H,2.12;N,3.33.Anal.Calcd.for C66H42F12N4Ho2O16(%):C,46.50;H,2.48;N,3.29.Found(%): C,46.74;H,2.35;N,3.29.

    1.3 X-ray crystallography

    A suitable crystal of complex 1 with dimensions of 0.40 mm×0.11 mm×0.06 mm was mounted on aSmart-1000(Bruker AXS)diffractometer with monochromated Mo Kαradiation(λ=0.071 073 nm)at 298 K.A total of 8 023 reflections were collected in the range of2.65°≤θ≤25.02°(-7≤h≤9,-16≤k≤16, -17≤l≤17),and 5 452 reflections were independent with Rint=0.054 9,of which 4 297 reflections were observed with I>2σ(I).

    A suitable crystal of complex 2 with dimensions of 0.40 mm×0.36 mm×0.18mm was mounted on the diffractometer mentioned above.A total of 7 858 reflections were collected in the range of 2.65°≤θ≤25.02°(-9≤h≤7,-15≤k≤16,-17≤l≤17),and 5 316 reflections were independent with Rint=0.054 9, ofwhich 4 497 reflections were observed with I>2σ(I).

    The structures were solved by direct methods using the SHELXS-97 program and refined by fullmatrix least-squares on F2using the SHELXL-97 program[15].The crystal data and structural refinement parameters ofthe complexes are listed in Table 1.

    CCDC:1023982,1;1023981,2.

    Table 1 Crystal data and structural refinement parameters for complexes 1 and 2

    2 Results and discussion

    2.1 Infrared spectra

    The infrared spectra of the complexes and the ligands are displayed in Table S1.The carboxylic acid ligand exhibits an intense C=O stretching vibration band at 1 694 cm-1.While theνC=Odisappears in the IR spectrum of complexes 1 and 2.The two absorbing bands assigned to the asymmetric(νas(COO-))and symmetric(νs(COO-))vibrations are observed at 1 544~1 547 cm-1and 1 431 cm-1,respectively.Besides,the apparent band at 419 cm-1is attributed to theν(Ln-O)of the two complexes.These all indicate that the oxygen atoms of 3,4-DFBA ligand takes part in coordination to the Ln(Ⅱ)ion[18].As shown in Table S1,theνC=N and δC-Hbands in the IR spectra of complexes show a shift to a low frequency as compared with the free 1,10-phenanthroline ligand,indicating that two nitrogenatoms ofthe ligand are coordinated to the Ln(Ⅱ)ion[19].

    2.2 Ultraviolet spectra

    UV spectra of the two ligands and the title complexes are recorded in DMSO solution with DMSO as a reference.The data of UV absorption of the ligands and complexes are listed in Table S2.The intense band(255 nm)of 3,4-DFHBA ligand shifts to 265 nm in complexes.This may be explained by the expansion of theπ-conjugated system due to metal coordination[20].The maximum absorption wavelength (λmax)of 1,10-phenanthroline is similar to that in the complexes,suggesting that the formation of Ln-N has no remarkable influence on ultraviolet absorption of 1,10-phenanthroline.The values of Amaxfor complexes 1 and 2 are stronger than that of two ligands.It can be concluded that a larger chelate ring is constructed after coordination to the Ln(Ⅱ)ions[21].

    2.3 Crystalstructures

    The molecular structures of complexes 1 and 2 with the coordination geometry ofthe Sm(Ⅱ)and Ho(Ⅱ) ions are shown in Fig.1 and Fig.S1.The selected bond lengths of complexes 1 and 2 are listed in Table 2. Because the crystal structures of the two complexes are isostructural,hence complex 1 is taken as an example to discuss in detail.As shown in Fig.1, complex 1 is binuclear and crystallizes in the triclinic P1 space.Each Sm(Ⅱ)ion is eight-coordinated by six O atoms and two N atoms,which resembles a distorted square antiprism geometry.These eight atoms are in three models of bidentate bridging(O5,O6i),bidentate chelating(O3,O4 and N1,N2)and monodentate(O1, O7)to coordinate with the center Sm(Ⅱ)ion.Besides, another two water molecules are not involved in coordination with Sm(Ⅱ)but exist freely in the binuclear crystal structure.It is worth noting that intramolecular hydrogen bond is formed between O7iand O2,O7 and O2i.Further more,the adjacent two binuclear molecules form two-dimensional layered structure by intermolecular forces for complex 1,as shown in Fig.2.The hydrogen bond distances in complexes 1 and 2 are given in Table S3.

    The average distance of Sm(1)-O is 0.243 2(3) nm and thatof Ho(1)-O is 0.234 3(7)nm.The average distance of Sm(1)-N and Ho(1)-N are 0.260 7(0)nm and 0.253 2(5)nm,respectively.The length of Ln-O is always shorter than that of Ln-N,which proves the stronger combination ability of Ln to O than N[22].The result can explain why 1,10-phenanthroline ligand is lostfirstly in the decomposition process.

    Fig.1(a)Molecular structure of complex 1;(b)Coordination geometry of the Sm(Ⅱ)ion

    Table 2 Selected bond lengths of the complexes 1 and 2

    Fig.2 A two-dimensional layered structure of complex 1

    2.4 Thermal analysis

    TG-DTG curves of the title complexes are shown in Fig.3 and 4.For complex 1,the decomposition process can be divided into three steps.The first step begins at 338.15 K and ends at 441.15 K with a weight loss of 2.48%,assigning to the loss of two crystallization water molecules(Calcd.2.15%).The second degradation stage is in the range of 441.15~659.15 K with weight loss of 22.94%,corresponding to the loss of another two coordinated water molecules and two 1,10-phenanthroline molecules(Calcd. 23.67%).The third weight loss of 52.83%between 676.15 K and 1 363.45 K is attributed to the loss of all 3,4-DFBA ligands.In summary,the total loss rate is 78.25%with a theoretical value of 79.20%if Sm2O3was the finalproducts.For complex 2(Fig.4),to begin with,all water molecules are released from 344.15 K to 459.15 K(Found 4.29%,Calcd.4.22%).The following decomposition belongs to the loss of 1,10-phenanthroline molecules with a value of 21.76% (Calcd.21.14%).To the end,the complex 2 is completely degraded into Ho2O3.

    Fig.3 TG-DTG curves of complex 1

    Fig.4 TG-DTG curves of complex 2

    2.5 Powder X-ray diffraction

    The PXRD patterns of the title complexes were checked atroom temperature,as shown in Fig.S2.The peak positions of the simulated and experimental PXRD patterns are in agreement with each other,which demonstrate the good phase purity of the complexes.

    2.6 Fluorescence spectrum

    Because of the orange-red emission of Sm(Ⅱ)ion, the complex 1 has been demonstrated to be potential application in full-color fluorescence materials for applications as full-color fluorescence materials.The emission spectrum of complex 1 under excitation at 335 nm is displayed in Fig.5.The characteristic fluorescence of Sm(Ⅱ)ion(at 601 nm)corresponding to the4G5/2→6F7/2are detected[23],and another two emission peaks at 564 nm and 653 nm are attributed to the transitions of4G5/2→6F5/2,4G5/2→6F9/2,respectively.

    Fig.5 Solid state emission spectra of complex 1 (λex=335 nm)

    Table 3 Bacteriostatic activities of complexes 1 and 2 to escherichia coli(T=310 K)

    Table 4 Bacteriostatic activities of complexes 1 and 2 to staphylococcus aureus(T=310 K)

    2.7 Bacteriostatic activity

    The bacteriostatic circles diameter of the complexes 1 and 2 with different concentrations to escherichia coli,staphylococcus aureus and candida albicans are shown in Table 3~5.The temperature of 310 K is optimum for bacteria(escherichia coli, staphylococcus aureus)growth.While 303 K is optimum for fungus(candida albicans)growth.As can be seen from Table 3 and 4,the bacteriostatic circles diameter is 6 mm with the concentration of 8 mmol·L-1.Then with the increase of solution concen-tration, the bacteriostatic circles diameter increases.In other words,the concentration of the complex is higher,the bacteriostatic effectis more obvious.

    As shown in Table 5,with a concentration of 8 mmol·L-1,average diameter bacteriostatic circles for complexes 1 and 2 are 11.10 and 13.37 mm,respectively,which is larger than 6 mm of filter diameter itself.This confirms that complexes have remarkable bacteriostatic action to candida albicans even at low concentration.Besides,bacteriostatic actions are moreand more obvious with the increase of concentration, which is similar with escherichia coli and staphylococcus aureus.

    Table 5 Bacteriostatic activities of complexes 1 and 2 to candida albicans(T=303 K)

    Lanthanide complexes has certain bacteriostatic actions against microorganism,and it is generally recognized that Ln(Ⅱ)ions are coordinated with the donor atoms of the ligands.This leads to theπelectron delocalization over the chelate ring further to reduces the polarity of the central metal ion.All phenomenon in turn favors permeation to the lipid layer ofthe membrane for lanthanide complexes[24-26].

    3 Conclusions

    In summary,two complexes[Sm(3,4-DFBA)3(phen)(H2O)]2(H2O)2(1)and[Ho(3,4-DFBA)3(phen) (H2O)]2(H2O)2(2)were synthesized and characterized. Both ofthem were binuclear and isostructural with the space group of P1.The intramolecular hydrogen bond is formed in complexes 1 and 2.Thermaldecomposition processes of the two complexes were divided into three steps.The emission spectrum ofcomplex 1 under excitation at 335 nm indicated the characteristic fluorescence of Sm(Ⅱ)ion corresponding to the 4G5/2→6F7/2.Bacteriostatic activities of these complexes to Gram bacteria bacteria(escherichia coli),Gram negative positive(staphylococcus aureus)and candida albicans have obvious effects athigh concentration.

    Supporting Information is available athttp://www.wjhxxb.cn

    [1]Hasegawa Y,Wada Y,Yanagida S.J.Photochem.Photobiol. C,2004,5:183-202

    [2]Yang L R,Liu L,Wu L Z,et al.Dyes Pigm.,2014,111:176-184

    [3]Li W X,Guo F,Zheng Y S,et al.J.Lumin.,2014,153:421-429

    [4]Weissman S I.J.Chem.Phys.,1942,10:214-217

    [5]Ni Y R,Tao J,Jin J Y,et al.J.Alloys Compd.,2014,612: 349-354

    [6]Li L F,Dong D B,Zhang J Y,et al.Mater.Lett.,2014,131: 298-301

    [7]Li W X,Feng S Y,Liu Y,et al.J.Lumin.,2013,143:746-753

    [8]Lekha L,Raja K K,Rajagopal G,et al.J.Mol.Struct.,2014, 1056-1057:307-313

    [9]Kulkarni A,Patil S A,Badami P S.Eur.J.Med.Chem., 2009,44:2904-2912

    [10]Subhan M A,Rahman M S,Alam K,et al.Spectrochim. Acta A,2014,118:944-950

    [11]Lima L M P,Delgado R,Marques F,et al.Eur.J.Med. Chem.,2010,45:5621-5627

    [12]Li X,Zhang Z Y,Zou Y Q.Eur.J.Inorg.Chem.,2005,14: 2909-2918

    [13]Li Y,Zheng F K,Liu X,et al.Inorg.Chem.,2006,45:6308-6316

    [14]Ma D,Li X,Huo R.J.Mater.Chem.C,2014,43:9073-9076 [15]Wang J F,Li H,Zhang J J,et al.Sci.China Ser.B Chem., 2012,55:2161-2175

    [16]Yang Z H,Xu J,Zhang W X,et al.J.Solid State Chem., 2007,180:1390-1396

    [17]Sheldrick G M.SHELXTL-97,Programs for Crystal Structure Refinement,University of G?ttingen,Germany,1997.

    [18]Zhou X J,Zhao X Q,Wang Y J,et al.Inorg.Chem.,2014, 53:12275-12282

    [19]Zheng J R,Ren N,Zhang J J,et al.J.Chem.Thermodyn., 2013,57:169-177

    [20]An B L,Gong M L,Li M X,et al.J.Mol.Struct.,2004,687: 1-6

    [21]ZHANG Ying-Ying(張瑩瑩),REN Shu-Xia(任書霞),ZHANG Jian-Jun(張建軍),et al.Chinese Sci.Bull.(科學(xué)通報),2014,59(27):3398-3405

    [22]?yszczek R,Rzaczyńska Z,Kula A,et al.J.Anal.Appl. Pyrolysis,2011,92:347-354

    [23]Liu D,Yu H,Wang Z G,et al.Polym.Int.,2010,59:937-94

    [24]Hang J,Xu Y H,Chen X K,et al.J.Rare Earths,2012,30: 586-591

    [25]Liu J Y,Ren N,Zhang J J,et al.Thermochim.Acta,2013, 570:51-58

    [26]Zhao Y F,Chu H B,Bai F,et al.J.Organomet.Chem., 2012,716:167-174

    Hydrothermal Syntheses,Crystal Structures,Luminescence, Thermal Stabilities and Bacteriostatic Activities of Two Lanthanide Complexes

    ZONG Guang-Cai1,2REN Ning*,3ZHANG Jian-Jun*,1,2QIXiao-Xia1,2GAO Jie1,2ZHANG Da-Hai3
    (1Testing and Analysis Center,Hebei Normal University,Shijiazhuang 050024,China)
    (2College of Chemistry&Material Science,Hebei Normal University,Shijiazhuang 050024,China)
    (3College of Chemical Engineering&Material,Handan College,Handan,Hebei 056005,China)

    Two lanthanide complexes[Ln(3,4-DFBA)3(phen)(H2O)]2(H2O)2(Ln=Sm(1),Ho(2);3,4-DFBA=3,4-difluorobenzoate,phen=1,10-phenanthroline)were prepared by hydrothermal method.Their structures were determined by single-crystal X-ray diffraction method.The structures of complexes 1 and 2 are isostructural with the coordination number of eight.They crystallized in the triclinic space group P1.The 2D layered structure is formed by intermolecular forces of adjacent two binuclear molecules.The title complexes were characterized by elemental analysis,IR,UV,XRD,and so on.The thermal stability of the complexes was tested using TG-DTG technology.The luminescentproperty ofcomplex 1 had been explored.Besides,the bacteriostatic activities of the two complexes to candida albicans,Gram negative bacteria(escherichia coli)and Gram positive bacteria (staphylococcus aureus)were also studied.CCDC:1023982,1;1023981,2.

    lanthanides;3,4-difluorobenzoic acid;thermal analysis;luminescence;bacteriostatic activity;crystal structure

    O614.33+7;O614.343

    A

    1001-4861(2015)07-1425-08

    10.11862/CJIC.2015.176

    2015-03-13。收修改稿日期:2015-04-20。

    國家自然科學(xué)基金(No.21073053、21473049),河北省自然科學(xué)基金(No.B2012205022)資助項目。

    *通訊聯(lián)系人。E-mail:ningren9@163.com,jjzhang6@126.com;會員登記號:S06N6096M1306(任寧),S06N9443M1404(張建軍)。

    猜你喜歡
    張建軍河北師范大學(xué)晶體結(jié)構(gòu)
    賀河北師范大學(xué)百廿校慶
    河北師范大學(xué)美術(shù)與設(shè)計學(xué)院油畫作品選登
    Classical-field description of Bose-Einstein condensation of parallel light in a nonlinear optical cavity*
    頸椎病患者使用X線平片和CT影像診斷的臨床準(zhǔn)確率比照觀察
    化學(xué)軟件在晶體結(jié)構(gòu)中的應(yīng)用
    A NOTE ON MALMQUIST-YOSIDA TYPE THEOREM OF HIGHER ORDER ALGEBRAIC DIFFERENTIAL EQUATIONS?
    巧用反例在概率論教學(xué)中的作用
    高等學(xué)校書法創(chuàng)作教學(xué)摭談——以河北師范大學(xué)為例
    鎳(II)配合物{[Ni(phen)2(2,4,6-TMBA)(H2O)]·(NO3)·1.5H2O}的合成、晶體結(jié)構(gòu)及量子化學(xué)研究
    含能配合物Zn4(C4N6O5H2)4(DMSO)4的晶體結(jié)構(gòu)及催化性能
    交换朋友夫妻互换小说| 久久午夜亚洲精品久久| 国产97色在线日韩免费| 黄片播放在线免费| 老熟妇乱子伦视频在线观看| 好男人电影高清在线观看| 国产男靠女视频免费网站| 美女扒开内裤让男人捅视频| 久久人人97超碰香蕉20202| 在线观看www视频免费| 国产精品免费视频内射| 侵犯人妻中文字幕一二三四区| 激情视频va一区二区三区| 老熟妇仑乱视频hdxx| 三上悠亚av全集在线观看| ponron亚洲| 国产av在哪里看| 亚洲全国av大片| 久久国产乱子伦精品免费另类| 精品一区二区三卡| 欧美午夜高清在线| 国产欧美日韩精品亚洲av| 国产成人精品在线电影| 一区在线观看完整版| 国产成人啪精品午夜网站| 午夜福利影视在线免费观看| 91成人精品电影| 成人亚洲精品一区在线观看| 满18在线观看网站| 可以免费在线观看a视频的电影网站| 亚洲片人在线观看| 狠狠狠狠99中文字幕| 很黄的视频免费| 高清在线国产一区| 久久久久国产一级毛片高清牌| 国产不卡一卡二| 亚洲美女黄片视频| 97碰自拍视频| 男女午夜视频在线观看| 91成人精品电影| 少妇被粗大的猛进出69影院| 99国产精品免费福利视频| 亚洲人成77777在线视频| 亚洲七黄色美女视频| 久久精品成人免费网站| 欧美色视频一区免费| 99久久精品国产亚洲精品| 高清av免费在线| 50天的宝宝边吃奶边哭怎么回事| 一进一出抽搐gif免费好疼 | 可以免费在线观看a视频的电影网站| 国产激情久久老熟女| 欧美国产精品va在线观看不卡| 亚洲少妇的诱惑av| 久久人妻熟女aⅴ| 99久久精品国产亚洲精品| 在线av久久热| 咕卡用的链子| 国产精品综合久久久久久久免费 | ponron亚洲| 欧美午夜高清在线| 久久久久久大精品| 很黄的视频免费| 美女福利国产在线| 神马国产精品三级电影在线观看 | 国产伦一二天堂av在线观看| 国产成人系列免费观看| av有码第一页| 午夜亚洲福利在线播放| 久热爱精品视频在线9| 一区二区三区激情视频| 12—13女人毛片做爰片一| 啦啦啦免费观看视频1| 久久久国产欧美日韩av| 天天影视国产精品| 亚洲成国产人片在线观看| 免费搜索国产男女视频| 操美女的视频在线观看| 成人影院久久| 中文字幕高清在线视频| 人妻久久中文字幕网| 免费在线观看视频国产中文字幕亚洲| 亚洲成人免费av在线播放| 欧美日韩福利视频一区二区| 成人18禁在线播放| 国产亚洲av高清不卡| 久久天堂一区二区三区四区| 午夜精品久久久久久毛片777| 亚洲精品久久午夜乱码| 日韩免费av在线播放| 女性生殖器流出的白浆| 极品人妻少妇av视频| 欧美乱码精品一区二区三区| 久久狼人影院| 国产精品久久视频播放| 国产av一区在线观看免费| 亚洲欧美精品综合一区二区三区| 91麻豆精品激情在线观看国产 | 日韩国内少妇激情av| 99re在线观看精品视频| 国产成人影院久久av| 搡老乐熟女国产| 亚洲成人免费电影在线观看| 国产午夜精品久久久久久| 国产精品秋霞免费鲁丝片| 丰满人妻熟妇乱又伦精品不卡| 一个人观看的视频www高清免费观看 | 欧美黑人精品巨大| 亚洲一区二区三区欧美精品| 人妻丰满熟妇av一区二区三区| 黄色 视频免费看| 亚洲精品美女久久久久99蜜臀| 在线观看日韩欧美| 一本大道久久a久久精品| 国产在线观看jvid| 久久久久国内视频| 精品日产1卡2卡| 欧美 亚洲 国产 日韩一| 国产又色又爽无遮挡免费看| 91国产中文字幕| 日韩大尺度精品在线看网址 | 欧美日韩中文字幕国产精品一区二区三区 | 成在线人永久免费视频| 中文字幕人妻丝袜制服| 激情在线观看视频在线高清| 99国产精品99久久久久| 亚洲精品av麻豆狂野| 超碰成人久久| 成人黄色视频免费在线看| 久久这里只有精品19| 国产97色在线日韩免费| 少妇的丰满在线观看| 欧美日韩一级在线毛片| 亚洲免费av在线视频| 一区二区三区精品91| 国产成人精品无人区| 色精品久久人妻99蜜桃| 国产成人av教育| 一本大道久久a久久精品| www.自偷自拍.com| 老鸭窝网址在线观看| 大码成人一级视频| 亚洲欧美一区二区三区久久| 欧美黑人精品巨大| 久久中文字幕一级| xxx96com| 精品一区二区三区视频在线观看免费 | 欧美日本亚洲视频在线播放| av在线天堂中文字幕 | 黄色毛片三级朝国网站| 国产视频一区二区在线看| 十八禁网站免费在线| 久久久久九九精品影院| 中文字幕精品免费在线观看视频| 国产在线观看jvid| 在线永久观看黄色视频| 亚洲av熟女| 男人的好看免费观看在线视频 | 免费在线观看视频国产中文字幕亚洲| 久久天堂一区二区三区四区| 超色免费av| 亚洲一区二区三区欧美精品| 男女之事视频高清在线观看| 免费在线观看完整版高清| 亚洲九九香蕉| 中文字幕人妻丝袜制服| av网站免费在线观看视频| 日韩人妻精品一区2区三区| 视频在线观看一区二区三区| 国产单亲对白刺激| 亚洲男人的天堂狠狠| 国产精品一区二区在线不卡| 黄色a级毛片大全视频| 亚洲色图av天堂| 精品国产超薄肉色丝袜足j| 日韩免费av在线播放| 国产三级在线视频| 电影成人av| 人妻久久中文字幕网| 欧美日韩亚洲国产一区二区在线观看| 欧美成人午夜精品| av在线播放免费不卡| 成人黄色视频免费在线看| 精品久久久久久久久久免费视频 | 欧美日本亚洲视频在线播放| 高清黄色对白视频在线免费看| 国产日韩一区二区三区精品不卡| 999久久久精品免费观看国产| 90打野战视频偷拍视频| 老司机靠b影院| 国产精品免费一区二区三区在线| 久久香蕉激情| 激情在线观看视频在线高清| 88av欧美| 狂野欧美激情性xxxx| 黑人操中国人逼视频| 成人特级黄色片久久久久久久| 亚洲av日韩精品久久久久久密| 亚洲一卡2卡3卡4卡5卡精品中文| 亚洲国产中文字幕在线视频| 超碰97精品在线观看| 一级a爱片免费观看的视频| 午夜免费激情av| 成人影院久久| 国产野战对白在线观看| 日日干狠狠操夜夜爽| 精品国产乱子伦一区二区三区| 身体一侧抽搐| 亚洲欧美日韩无卡精品| 日本黄色日本黄色录像| 别揉我奶头~嗯~啊~动态视频| 国产在线精品亚洲第一网站| 色在线成人网| 夜夜爽天天搞| 色综合婷婷激情| 亚洲精品一区av在线观看| 国产精品 国内视频| 午夜久久久在线观看| 热99国产精品久久久久久7| 老熟妇乱子伦视频在线观看| 午夜福利一区二区在线看| 日本wwww免费看| 亚洲精品一卡2卡三卡4卡5卡| 香蕉国产在线看| 成人18禁在线播放| 咕卡用的链子| 在线观看免费视频网站a站| 麻豆国产av国片精品| av网站在线播放免费| 亚洲欧美日韩高清在线视频| 欧洲精品卡2卡3卡4卡5卡区| 欧美黑人精品巨大| 欧美老熟妇乱子伦牲交| 黄色视频不卡| 亚洲精品中文字幕一二三四区| 一区在线观看完整版| 国产精品秋霞免费鲁丝片| 热re99久久国产66热| 日韩免费高清中文字幕av| 亚洲精品国产区一区二| 国产一区在线观看成人免费| 久久人妻熟女aⅴ| tocl精华| 可以免费在线观看a视频的电影网站| 欧美成狂野欧美在线观看| 极品人妻少妇av视频| 久久精品亚洲精品国产色婷小说| 日本免费一区二区三区高清不卡 | 91精品三级在线观看| 黄片大片在线免费观看| 精品福利观看| 欧美激情 高清一区二区三区| 国产精品成人在线| 侵犯人妻中文字幕一二三四区| 日本 av在线| 十八禁人妻一区二区| 亚洲 欧美一区二区三区| 99久久久亚洲精品蜜臀av| cao死你这个sao货| 黄片播放在线免费| 久久国产乱子伦精品免费另类| 日韩人妻精品一区2区三区| 9色porny在线观看| 国产精品国产av在线观看| 欧美色视频一区免费| 日韩精品中文字幕看吧| 88av欧美| 久久精品91无色码中文字幕| 免费日韩欧美在线观看| 99热只有精品国产| 久久伊人香网站| 国产视频一区二区在线看| 一夜夜www| 国产高清videossex| 亚洲自偷自拍图片 自拍| 日韩 欧美 亚洲 中文字幕| 午夜福利一区二区在线看| 两性夫妻黄色片| 欧美日韩av久久| 在线观看一区二区三区激情| 久久九九热精品免费| 免费日韩欧美在线观看| 老汉色av国产亚洲站长工具| 18禁黄网站禁片午夜丰满| 亚洲欧美精品综合一区二区三区| 久久久久久久午夜电影 | 国产精品野战在线观看 | 日韩视频一区二区在线观看| 国产av又大| 亚洲欧美精品综合一区二区三区| 亚洲av片天天在线观看| www日本在线高清视频| 自线自在国产av| 一a级毛片在线观看| 大型av网站在线播放| 99在线视频只有这里精品首页| 亚洲欧美日韩高清在线视频| 国产精品98久久久久久宅男小说| 亚洲少妇的诱惑av| 99国产精品一区二区蜜桃av| 欧美在线一区亚洲| 精品一区二区三区四区五区乱码| 精品久久久久久久久久免费视频 | 中文亚洲av片在线观看爽| 丁香欧美五月| 91成年电影在线观看| www.熟女人妻精品国产| 午夜免费成人在线视频| 亚洲五月天丁香| 中文字幕高清在线视频| 搡老岳熟女国产| 女人精品久久久久毛片| 日韩中文字幕欧美一区二区| 这个男人来自地球电影免费观看| 咕卡用的链子| 琪琪午夜伦伦电影理论片6080| 欧美中文日本在线观看视频| 欧美乱色亚洲激情| 亚洲国产看品久久| 后天国语完整版免费观看| 黄色成人免费大全| 国产av精品麻豆| 国产激情欧美一区二区| 男人舔女人下体高潮全视频| 交换朋友夫妻互换小说| 成年版毛片免费区| 免费在线观看完整版高清| 黑人猛操日本美女一级片| 成人特级黄色片久久久久久久| 亚洲狠狠婷婷综合久久图片| 亚洲九九香蕉| 99国产精品免费福利视频| 另类亚洲欧美激情| 日韩高清综合在线| 久久这里只有精品19| 亚洲色图av天堂| 多毛熟女@视频| 国产成人精品久久二区二区免费| 国产高清视频在线播放一区| 在线免费观看的www视频| av超薄肉色丝袜交足视频| 熟女少妇亚洲综合色aaa.| 日韩国内少妇激情av| 国产成人系列免费观看| 国内毛片毛片毛片毛片毛片| 嫩草影院精品99| 精品熟女少妇八av免费久了| 免费日韩欧美在线观看| 亚洲男人天堂网一区| 在线看a的网站| 黄片播放在线免费| 欧美日韩黄片免| 精品国产乱码久久久久久男人| 国产国语露脸激情在线看| 免费观看精品视频网站| 亚洲国产精品合色在线| 深夜精品福利| 波多野结衣一区麻豆| 91老司机精品| 波多野结衣av一区二区av| 亚洲精品美女久久久久99蜜臀| 亚洲色图 男人天堂 中文字幕| 亚洲av片天天在线观看| 韩国精品一区二区三区| 国产精品日韩av在线免费观看 | 自拍欧美九色日韩亚洲蝌蚪91| 午夜免费鲁丝| 天堂俺去俺来也www色官网| 国产不卡一卡二| 99在线视频只有这里精品首页| 亚洲在线自拍视频| 亚洲熟女毛片儿| 色在线成人网| 黑丝袜美女国产一区| 欧美人与性动交α欧美精品济南到| 国产亚洲欧美精品永久| 悠悠久久av| а√天堂www在线а√下载| 久久精品亚洲精品国产色婷小说| 国产一区二区三区综合在线观看| 丁香六月欧美| 欧美激情 高清一区二区三区| av天堂久久9| 久久久国产欧美日韩av| 嫁个100分男人电影在线观看| 变态另类成人亚洲欧美熟女 | 大型av网站在线播放| 亚洲一区中文字幕在线| 国产一区二区激情短视频| 久久国产亚洲av麻豆专区| 日韩精品免费视频一区二区三区| 免费久久久久久久精品成人欧美视频| 国产精品久久久av美女十八| 免费久久久久久久精品成人欧美视频| 村上凉子中文字幕在线| 婷婷丁香在线五月| 99久久人妻综合| 亚洲成a人片在线一区二区| 欧美成人午夜精品| 这个男人来自地球电影免费观看| 中文字幕精品免费在线观看视频| 精品乱码久久久久久99久播| 欧美一级毛片孕妇| 在线视频色国产色| 18禁黄网站禁片午夜丰满| 久久久久久人人人人人| 一级,二级,三级黄色视频| 最近最新中文字幕大全电影3 | av中文乱码字幕在线| 很黄的视频免费| 午夜两性在线视频| 成人黄色视频免费在线看| 国产精品一区二区精品视频观看| 国产精品成人在线| 亚洲专区中文字幕在线| 久久久国产成人精品二区 | 99riav亚洲国产免费| 男男h啪啪无遮挡| 黄色视频,在线免费观看| 高潮久久久久久久久久久不卡| 亚洲精品美女久久久久99蜜臀| 国产激情久久老熟女| 免费av毛片视频| 婷婷丁香在线五月| 午夜免费观看网址| 老司机福利观看| 国产高清激情床上av| e午夜精品久久久久久久| 国产成人欧美| 国产成人影院久久av| 一区二区三区国产精品乱码| 他把我摸到了高潮在线观看| 高清av免费在线| 欧美午夜高清在线| 久久伊人香网站| 在线免费观看的www视频| 精品午夜福利视频在线观看一区| 男女做爰动态图高潮gif福利片 | 久久中文字幕人妻熟女| 国产99久久九九免费精品| 一本综合久久免费| 欧美性长视频在线观看| 免费看a级黄色片| 国产三级黄色录像| 久久久国产一区二区| 99久久人妻综合| 欧美一级毛片孕妇| 成人三级黄色视频| www.精华液| 国产三级在线视频| 欧美成狂野欧美在线观看| 亚洲精品一卡2卡三卡4卡5卡| 中文字幕人妻丝袜一区二区| 精品国产国语对白av| 人人妻人人爽人人添夜夜欢视频| 久久久久久久久中文| 久久中文看片网| 99精品在免费线老司机午夜| 久久香蕉国产精品| 欧美 亚洲 国产 日韩一| 女性生殖器流出的白浆| 亚洲国产精品合色在线| 中文字幕人妻丝袜制服| 一边摸一边做爽爽视频免费| 亚洲一区二区三区欧美精品| 欧美日韩黄片免| 欧美激情极品国产一区二区三区| 欧美乱色亚洲激情| 国产精品二区激情视频| 色播在线永久视频| 国产亚洲欧美在线一区二区| 中文字幕精品免费在线观看视频| 五月开心婷婷网| 好看av亚洲va欧美ⅴa在| www.999成人在线观看| 日韩大尺度精品在线看网址 | 另类亚洲欧美激情| 午夜精品久久久久久毛片777| 97人妻天天添夜夜摸| 久久精品影院6| 在线观看舔阴道视频| 最近最新中文字幕大全免费视频| 久久人妻av系列| 亚洲精品久久成人aⅴ小说| 午夜影院日韩av| 天天躁狠狠躁夜夜躁狠狠躁| 欧美成人性av电影在线观看| 久久久国产一区二区| 国产精品1区2区在线观看.| 亚洲欧美一区二区三区黑人| 精品国产乱子伦一区二区三区| 国产99白浆流出| 亚洲九九香蕉| 亚洲欧美一区二区三区久久| 国产免费av片在线观看野外av| 欧美日韩一级在线毛片| 久久精品亚洲熟妇少妇任你| 黄色 视频免费看| 亚洲精品久久成人aⅴ小说| 99香蕉大伊视频| 老司机深夜福利视频在线观看| 一进一出好大好爽视频| 国产成人av教育| 日韩精品中文字幕看吧| 露出奶头的视频| 91精品国产国语对白视频| 国产精品久久久人人做人人爽| 波多野结衣一区麻豆| 欧美日本亚洲视频在线播放| 露出奶头的视频| 久久午夜亚洲精品久久| 亚洲欧美日韩高清在线视频| 亚洲欧美日韩无卡精品| 久久久久国内视频| 国产精品电影一区二区三区| 神马国产精品三级电影在线观看 | 久久青草综合色| 久久人人精品亚洲av| 视频在线观看一区二区三区| 久久久久久久久中文| 国产一区在线观看成人免费| 国产精品成人在线| 欧美日韩国产mv在线观看视频| 日韩欧美一区视频在线观看| 国产欧美日韩一区二区精品| 亚洲一区二区三区不卡视频| 午夜a级毛片| 久9热在线精品视频| 国产成人免费无遮挡视频| 亚洲成人精品中文字幕电影 | 人人妻人人添人人爽欧美一区卜| 一级a爱片免费观看的视频| 真人一进一出gif抽搐免费| 亚洲三区欧美一区| 精品一区二区三区四区五区乱码| 欧美人与性动交α欧美软件| 国产精品自产拍在线观看55亚洲| 一级黄色大片毛片| cao死你这个sao货| 国产免费男女视频| 久久中文字幕人妻熟女| 亚洲中文字幕日韩| 国产亚洲欧美98| 精品国产美女av久久久久小说| 欧美一级毛片孕妇| 在线视频色国产色| 国产欧美日韩一区二区精品| 国产又色又爽无遮挡免费看| 国产亚洲欧美98| 亚洲 国产 在线| 欧美中文综合在线视频| 男人舔女人下体高潮全视频| 亚洲男人的天堂狠狠| 国产三级黄色录像| 一级毛片高清免费大全| 女性生殖器流出的白浆| xxxhd国产人妻xxx| 性色av乱码一区二区三区2| 又黄又爽又免费观看的视频| 欧美日韩乱码在线| 亚洲成人免费电影在线观看| 国产成人影院久久av| 一级黄色大片毛片| 性少妇av在线| 神马国产精品三级电影在线观看 | 国产成人一区二区三区免费视频网站| 丁香欧美五月| 麻豆av在线久日| 欧美激情久久久久久爽电影 | 亚洲va日本ⅴa欧美va伊人久久| 免费观看人在逋| 热99国产精品久久久久久7| 日韩欧美免费精品| 精品国产亚洲在线| 亚洲人成电影观看| 国产精品98久久久久久宅男小说| av超薄肉色丝袜交足视频| 男人舔女人的私密视频| 后天国语完整版免费观看| 亚洲一区二区三区色噜噜 | 高清毛片免费观看视频网站 | 手机成人av网站| 久久久久久久精品吃奶| 丝袜美足系列| 极品教师在线免费播放| 自拍欧美九色日韩亚洲蝌蚪91| 国产精品久久久人人做人人爽| 熟女少妇亚洲综合色aaa.| 淫秽高清视频在线观看| 99国产精品99久久久久| 亚洲人成77777在线视频| 中文亚洲av片在线观看爽| www.www免费av| 亚洲欧美精品综合一区二区三区| 国产成人精品无人区| 国产深夜福利视频在线观看| bbb黄色大片| 97碰自拍视频| 成人影院久久| 亚洲激情在线av| 国产片内射在线| 国产伦人伦偷精品视频| 亚洲午夜精品一区,二区,三区| 亚洲aⅴ乱码一区二区在线播放 | 女同久久另类99精品国产91| 这个男人来自地球电影免费观看| 日韩精品中文字幕看吧| x7x7x7水蜜桃| 亚洲av成人不卡在线观看播放网| 久久精品人人爽人人爽视色| 欧美乱色亚洲激情| 欧美成人性av电影在线观看| www.自偷自拍.com| 久久久久久亚洲精品国产蜜桃av| 成人特级黄色片久久久久久久|