全 文 :广 西 植 物 Guihaia 32(2):257-260 2012年3月
DOI:10.3969/j.issn.1000-3142.2012.02.022
Isolation and crystal ctructure of sulfur
fromCapparis spinosafruits
LI Hai-Jun1,2,BAI Hong-Jin1,2*,ZHANG Ji-Wen3,WANG An-Yin1,2
(1.Key Laboratory of Protection and Utilization of Biological Resources in Tarim Basin,Xinjiang Prodution and
Construction Corps,Alar 843300,China;2.College of Life Sciences,Tarim University,Alar 843300,
China;3.College of Sciences,Northwest A &F University,Yangling 712100,China)
Abstract:The purpose of this paper studied single crystal structure of S8isolated firstly fromCapparis spinosa
fruits.The S8crystal structure was investigated by single-crystal X-ray crystalographic analysis crystalizes in
the monoclinic system,M=256.48.space group Fddd.Unit cel parameters a=10.456(7),b=12.908(9),
c=24.483(17),V=3305(4)3,Z=16,F(000)=2048.The final R1=0.0915,wR2=0.1820.
Key words:Capparis spinosal;element sulfur;single-crystal X-ray diffraction;crystal structure
CLC Number:R284.2;O723 Document Code:A Article ID:1000-3142(2012)02-0257-04
①
刺山柑果实中硫单质的分离与晶体结构
李海军1,2,白红进1,2*,张继文3,王安银1,2
(1.新疆生产建设兵团塔里木盆地生物资源保护利用重点实验室,新疆 阿拉尔843300;2.塔里木大学
生命科学学院,新疆 阿拉尔843300;3.西北农林科技大学 理学院,陕西 杨凌712100)
摘 要:从刺山柑果实中首次分离纯化得到S8单质。经X-射线单晶衍射分析,确认该化合物为S8晶体,M=
256.48。晶体属斜方晶系,空间群Fddd。晶胞参数a=10.456(7),b=12.908(9),c=24.483(17),V=
3305(4)3,Z=16,F(000)=2048,R1=0.0915,wR2=0.1820。
关键词:刺山柑;硫单质;X-射线单晶衍射;晶体结构
Capparis spinosa is a vine that belongs to
family Capparaceae,genus Capparis,mainly dis-
tributed in Xinjiang,Tibet and other places in Chi-
na,lives on extremely arid Gobi desert or arid ston-
y mountain(Liu et al.,2011).As the Uyghur folk
medicine,the root bark,leaf,fruit of C.spinosa
were widely used for treatment of gout,rheumatoid
arthritis(Chinese medicine dictionary,1977).
Chemical studies on C.spinosahave reported many
beneficial chemical compounds(Ao,et al.,2007).
Including volatile oil,mustard oil glycoside,alka-
loid,terpenes,flavonoids and other ingredients;mo-
reover,laboratory studies have shown that the ex-
tract of the plant has pharmacological effects such
as liver protection,antinflammatory,antiviral,an-
tioxidant,immune regulation,hypoglycemic,reduc-
① Received date:2012-01-05 Accepted date:2012-02-21
Foundation items:Supported by Policy Guiding Project of Science and Technology Bureau of Xinjiang Production and Construction Corps(2006YD29);Open
Project of Xinjiang Prodution and Constrction Key Laboratory of Protection and Utilization of Biological Resources in Tarim Basin(BR0609)
Biography:LI Hai-Jun(1984-),male,Datong of Shanxi Province,graduate student for a Master’s degree,research fields:Natural Product
Chemistry,(E-mail)lihaijun1030@163.com.
*Author for correspondence(E-mail:bhj67@163.com)
ing blood lipid and other biological activity(Chen,
et al.,2010;Li,et al.,2007;Nizar et al.,2010;
Yang,et al.,2008,2010;Gagdoli C,1999).This
paper reports the single-crystal structure of S8iso-
lated firstly from the fruit parts of C.spinosa,
which wil facilitate the study of this plant and lay
a foundation for its exploitation and utilization.
1 Experimental
1.1General experimental procedures
The melting point was performed on X-4mi-
cro melting point apparatus(uncorrected).The IR
spectra was recorded on a Fourier transform infra-
red spectrometer with KBr pelets.Single-crystal
structure of S8 was measured on an X-ray diffrac-
tion surface detector Bruker SMART CCDⅡ dif-
fractometer.
1.2Plant material
The fruit parts of C.spinosal were colected
from South Xinjiang in July 2008.It was identified
by Professor Li Zhi-Jun Colege of Plant Science,
Tarim University.
1.3Extraction and isolation
The air-dried and finely powdered fruit parts
of C.spinosa were extracted with petroleum ether
for three times at room temperature,every time for
48h,then filtrated.The filtrate was evaporated
under reduced pressure to gain crude petroleum e-
ther extraction.Firstly,the extraction was separa-
ted by silica gel column chromatography,further
purified by repeated silica gel column Chromatog-
raphy,finaly using crystalization to get a light
yelow compound.
1.4Preparation of the single crystal
The light yelow compound was recrystalized
in the mixture solution of petroleum ether and eth-
yl acetate,and the single crystal was obtained at
the constant temperature(20℃).
1.5Crystalographic data colection and structure de-
termination
A yelow single crystal with dimensions 0.34mm
×0.27mm×0.19mm was put on a Bruker SMART
CCD Ⅱdiffractometer equipped with a graphite-
monochromatic Moka radiation(0.71073)by u-
singφ-ωscan mode.Out of the total 3 813reflec-
tions colected in the range of 2.64°to 25.09°.739
were unique(Rint=0.0338).An absorption correc-
tion by using SADABS software was applied.A-
tomic coordinates of atoms were dissolved with
SHELXS-97program firstly,and then atomic coor-
dinates and anisotropic thermal parameters of al
atoms were determined from difference Fourier
map.The crystal structure was solved by direct
methods using SHELXS-97program.Al atoms
were refined by ful-matrix least-squares tech-
niques on F2with SHELXTL-97.The final R indi-
ces(I>2σ(I))were R1=0.0915,wR2=0.1820.The
largest peak and hole on final difference Fourier
map were 1.298and-2.367e.-3,respectively.
2 Results and Analysis
The single crystal of S8was recrystalized un-
der the mixture solution of petroleum ether and
ethyl acetate at the constant temperature and isola-
ted from C.spinosa fruits for the first time.The
composition and configuration of S8have been in-
vestigated by single-crystal X-ray crystalographic
analysis crystalizes in the monoclinic system.The
crystal data and structure refinement are given in
Table 1.The atomic coordinates and equivalent iso-
tropic displacement parameters are given in Table
2.Bond lengths and bond angles are listed in Table
3.Anisotropic displacement parameters(2×103)
for title compound are listed in Table 4.Torsion
angles for title compound are listed in Table 5and
Figure 1shows the drawing of the molecule config-
uration and Figure 2shows the packing diagram of
the unit cel of compound.We obtained S8fromC.
spinosafruits through separation and purification,
but how it formed was stil not clear,maybe as the
report went the biochemical pathway leading to the
accumulation of elemental sulphur remained unex-
plained(Lognay,et al.,1993),maybe other reasons
need to be futher investigation.
852 广 西 植 物 32卷
Table 1 Crystal data and structure refinement
for title compound
Item Parameter
Empirical formula S8
Formula weight 256.48
Temperature 296(2)K
Wavelength 0.71073
Crystal system,space group Orthorhombic,Fddd
Unit cel dimensions a=10.456(7),α=90deg
b=12.908(9),β=90deg
c=24.483(17),γ=90deg
Volume 3305(4)3
Z,Calculated density 16,2.062Mg/m3
Absorption coefficient 2.061mm-1
F(000) 2 048
Crystal size 0.34mm×0.27mm×0.
19mm
Theta range for data colection 2.64to 25.09deg
Limiting indices -5≤h≤12,-15≤k≤15,
-29≤l≤29
Reflections colected/unique 3813/739(Rint=0.0338)
Completeness to theta=25.09 100.0%
Absorption correction None
Max.and Min.transmission 0.7017and 0.5400
Refinement method Ful-matrix least-squares
on F2
Data/restraints/parameters 739/0/37
Goodness-of-fit on F2 1.046
Final R indices[I>2σ(I)] R1=0.0915,wR2=0.1820
R indices(al data) R1=0.0939,wR2=0.1846
Largest diff.peak and hole 1.298and-2.367e.-3
Table 2 Atomic coordinates(×104)and equivalent
isotropic displacement parameters
(2×103)for title compound
Atom x y z Ueq
S(2) 341(1) 7803(1) 4238(1) 39(1)
S(3) -428(1) 7298(1) 4959(1) 37(1)
S(4) 1056(1) 7027(1) 5486(1) 37(1)
S(1) 359(1) 6578(1) 3705(1) 36(1)
U(eq)is defined as one third of the trace of the orthogonalized Uij
tensor
Table 3 Bond lengths[]and angles
[°]for title compound
Bond lengths Bond angles
S(2)-S(3) 2.0464(19)
S(3)-S(2)-S(1) 107.90(8)
S(2)-S(1) 2.049(2)
S(2)-S(3)-S(4) 107.45(9)
S(3)-S(4) 2.048(2)
S(4)#1-S(4)-S(3) 108.52(8)
S(4)-S(4)#1 2.046(3)
S(1)#1-S(1)-S(2) 109.15(8)
S(1)-S(1)#1 2.046(3)
Symmetry transformations used to generate equivalent atoms:
#1-x+1/4,-y+5/4
Table 4 Anisotropic displacement parameters
(2×103)for title compound
U11 U22 U33 U23 U13 U12
S(2) 50(1) 30(1) 35(1) 9(1) -4(1) 1(1)
S(3) 36(1) 42(1) 34(1) -2(1) 5(1) 10(1)
S(4) 53(1) 32(1) 27(1) -8(1) -5(1) 3(1)
S(1) 27(1) 55(1) 27(1) -3(1) -6(1) -2(1)
The anisotropic displacement factor exponent takes the form:-2
pi 2[h2 a*2 U11+...+2hk a*b* U12]
Table 5 Torsion angles[°]for title compound
S(1)-S(2)-S(3)-S(4) 100.75(8)
S(2)-S(3)-S(4)-S(4)#1 -98.84(9)
S(3)-S(2)-S(1)-S(1)#1 -97.98(9)
Symmetry transformations used to generate equivalent atoms:#1
-x+1/4,-y+5/4
Fig.1 The molecular structure of the title compound
Fig.2Packing diagram of the unit cel of title compound
References
Ao MZ(敖明章),Gao YY(高莹莹),Yu LJ(余龙江).2007.Ad-
9522期 李海军等:刺山柑果实中硫单质的分离与晶体结构
vances in studies on constituents and their pharmacological ac-
tivities of Capparis spinosa[J].Chin Trad Herb Drug(中草
药),38(3):464-467
Chen YL(陈义磊),Ma GC(马国才),Bai HJ(白红进).2010.
Study on antiexidative activities in vitro of total flavonoids ex-
tracted solution from Capparis spinosa[J].Xinjiang Agric
Sci(新疆农业科学),47(12):2 489-2 495
Li YQ(李云秋),Feng YL(冯育林),Yang SL(杨世林),et al.
2007.The chemical constituents of Capparis spinosa[J].Chin
Trad Herb Drug(中草药),38(4):510-512
Liu J(刘静),Zhao HY(赵红艳),Ma M(马淼).2011.Anatomy
of stem and leaf in different populations of Capparis spinosain
China[J].Guihaia(广西植物),31(6):735-740
Jiangsu Medical Colege.1977.Chinese Medicine Dictionary(Ru-
din)[M].Shanghai:Shanghai People’s Publishing House:843
Yang T(杨涛),Liu YQ(刘玉琴),Wang CH(王长虹),et al.
2008.Chemical composition,pharmacological activities and clin-
ical application of Capparis spinosa[J].Chin J Chin Mat Med
(中国中药杂志).33(21):2 453-2 458
Yang T(杨涛),Cheng XM(程雪梅),Yu FS(于富生),et al.
2010.The chemical constituents of Capparis spinosafruit[J].
Northwest Pharm J(西北药学杂志),25(4):260-263
Nizar T,Walid E,Ezzeddine S,et al.2010.The caper(Capparis):
Ethnopharmacology,phytochemical and pharmacological proper-
ties[J].Fitoterapia:1-9
Gagdoli C,Mishra SH.1999.Antihepatotoxic activity of p-me-
thoxybenzoic acid from Capparis spinosa[J].Ethnopharma-
col,66:187-92
Germano MP,DePasquale R,D'Angelo V,et al.2002.Evaluation
of extracts and isolated fraction fromCapparis spinosa buds as
an antioxidant source[J].Agr Food Chem,50:1168-7
Lognay G,Seck D,Maklier M,et al.1993.Identification of ele-
mental sulphur(S8)in Boscia senegalensis(Pers.)LAM ex Poir.
leaves[J].Bull Rech Agron Gembloux,28(4):
櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘櫘
501-505
(上接第184页Continue from page 184)
在群落及生境的保护。
参考文献:
马克平.1994.生物多样性的测度方法Ⅰɑ多样性的测度方法
(上)[J].生物多样性,2(3):162-168
王伯荪,余世孝,彭少麟.1996.植物群落学实验手册[M].广
州:广东高等教育出版社
刘玉壶,等.1996.中国植物志[M].北京:科学出版社
陈卫娟.2006.中亚热带常绿阔叶林区系分析[M].华东师范
大学硕士论文
杨纪.2003.史前遗老观光木[J].国土绿化,(8):9
吴征镒.1980.中国植被[M].北京:科学出版社
张金屯.2004.数量生态学[M].北京:科学出版社
林英.1990.井冈山自然保护区考察研究[M].北京:新华出版
社:140-198
傅立国,金鉴明.1992.中国植物红皮书:稀有濒危植物(第1
册)[M].北京:科学出版社
潘文钻.2002.福建牛姆林自然保护区观光木群落特征的初步
研究[J].林业勘探设计,1:13-15
Deng LX(邓贤兰),Liu YC(刘玉成),Wu Y(吴杨).2003.Stud-
ies on species diversity of Castanopsis community in Jinggang
Mountain Nature Reserve(井冈山自然保护区栲属群落物种多
样性的研究)[J].Guihaia(广西植物),21(1):61-65
Fu L(付琳),Xu FX(徐风霞),Zeng QW(曾庆文).2009.Studies
on Microsporogenesis and development of male gametophyte in
Tsoongiodendron odorumChun(观光木的小孢子发生与雄配
子体发育的研究)[J].J Trop and Subtrop Bot(热带亚热带植
物学报),17(5):419-426
He KY(何开跃),Li XC(李晓储),Zhang SQ(张双全),et al.
2007.Study on volatile oil components and activities of restrai-
ning and eliminating supper oxygen anion(观光木叶片挥发油成
分及其对超氧阴离子抑制与清除活性研究)[J].Fore Res(林
业科学研究),20(1):58-62
Ma KP(马克平),Huang JH(黄建辉),Yu SL(于顺利),et al.
1995.Plant community diversity in Dongling Mountain,Beijing,
China:Ⅱ.Species richness,eveness and species diversities(北京
东灵山地区植物群落多样性的研究,Ⅱ丰富度、均匀度和物种
多样性指数)[J].Acta Ecol Sin(生态学报),15(3):268-277
Wu WS(吴文珊),Liu JQ(刘剑秋),Zhang QQ(张清其),et al.
1997.Karyotype studies of Tsoong iodendronodorum(观光木染
色体核型的研究)[J].J Fujian Teach Univ:Nat Sci Edi(福
建师范大学·自然科学版),14(1):90-92
Wu ZY(吴征镒).1991.The areal-types of Chinese cenera of seed
plants(中国种子植物属的分布区类型)[J].Acta Bot Yunnan
(云南植物研究),Suppl.Ⅳ:1-139
Xia NH,Liu YH,Nooteboom HP.2009.Flora of China[M].Bei-
jing:Science Press
Xu H(许涵),Zhuang XY(庄雪影),Huang JX(黄久香),et al.
2007.Population Structure and Distribution Pattern of Tsoon-
giodendron odorumon Nankunshan,Guangdong Province(南昆
山观光木种群结构及分布格局)[J].J South China Agric
Univ(华南农业大学学报),28(2):73-77
Xu H(许涵),Zhuang XY(庄雪影),Huang JX(黄久香),et al.
2008.Population structure and distribution pattern of Tsoongio-
dendron odorumon Nankunshan,Guangdong Province(南昆山
观光木所在群落优势树种的种间联结性)[J].J South China
Agric Univ(华南农业大学学报),29(1):57-62
Zeng XF(曾宪锋),Qiu HY(邱贺媛),Qian HL(钱会莲),et al.
2009.Preliminary study on the pteridophyte flora of east
Guangdong,China(粤东蕨类植物区系初步研究)[J].Guihaia
(广西植物),29(4):466-470
062 广 西 植 物 32卷