Crystallography in China (mainland) — past, present, and future

Song Gao

Chinese Crystallographic Society (CCrS)

Peking University, Beijing 100871, China

E-mail: gaosong@pku.edu.cn

IYCr2014 Opening Ceremony, Paris, Jan. 20, 2014

Outline 1. Before 1980

2. Last 20 years in 20th century

3. Since 2000, and future

4. CCrS and its activity

Before 1980

(since the foundation of P. R. China)

Difficult years,

Environment

Poor and limited available facilities for crystallographic researches.

However, several diffraction laboratories found by pioneers.

In north China: Peking Univ., and Inst. Chem. CAS, by Prof. Youqi

Tang (唐有祺)

Inst. Biophys. CAS, by Prof. Shizhang Bei and Prof.

Dongcai Liang (贝时璋，梁栋材)

Inst. Phys. CAS, by Prof. Xueshan Lu (陆学善) and

Prof. Qianzhang Wu (吴乾章)

Inst. Metal Res. CAS, by Prof. Kehin Guo (郭可信)

Jilin University, by Prof. Ruihuang Yu (余瑞璜)

In south China: Xiamen Univ., Fuzhou Univ., and Fujian Inst. of

Research on the Structure of Matter (FIRSM), CAS,

by Prof. Jiaxi Lu (卢嘉锡)

And: in Shanghai Inst. Ceramics, Shanghai Inst.

Biochem., etc..

胡刚复1918 叶企孙1924 吴有训1926

The oldest physicists related to X-ray, Prof. Gangfu Hu (left), Prof. Qisun Ye (middle), and Prof. Youxun Wu (right), returned from USA, in very earlier days (before 1949).

W. L. Bragg

Ruihuang Yu 余瑞璜 Xueshan Lu 陆学善

Youqi Tang

Jiaxi Lu

Linus Pauling

Jingkui Liang Xintao Wu

Chuangtian Chen Maochun Hong

Haifu Fan Chunli Bai

Ze Zhang Hengqiang Ye

Prof. Kehin Guo had worked in Sweden.

Prof. Dongcai Liang Prof. Jinling Huang

returned from USSR

Determination of insulin structure in 1960s~70s by Peking Insulin Structure Research Group (PISRG)

Scientists were preparing insulin derivatives (left) and examining electron density maps (right)

at 4.0Å (1970) at 1.8Å (1974)

Scientia Sinica (test issue) 1972; Scientia Sinica 1973, 1, 93; Scientia Sinica 1973, 16, 136; and Scientia Sinica 1974, 17, 51; published the research results on crystal structure analysis of the rhombohedral 2-zinc pork insulin molecule at resolutions of 4.0 Å, 2.50 Å and 1.80 Å. The structure was studied at resolution 1.20 Å in 1980s.

Comments by Nobel Laureate Dorothy Hodgkin, after her visiting Peking Insulin Structure Research Group (PISRG): “Standards there as high as achieved elsewhere” at the 9th International Conference of Crystallography (Kyoto), and “the present Peking map at 1.80 Å resolution is the most accurate map available of the insulin electron density defined by experimental, isomorphous phase angles… and may well remain so” in “News and Views” article in Nature (Nature, 1975, 255, 103)

Prof. D. Hodgkin (at right middle) visited PISRG at Beijing.

N2

N2

N2 Rhizobia

Protein

Bio-nitrogen-fixing process

Active center by American scientists in 1992

Fuzhou Model By Jiaxi. Lu in 1973

Similar to the coupled structure

Artificial nitrogen-fixing research

Structural Chemistry in 1970s

Last 20 years in 20th century

Rapid development of crystallography in China, and its

covering wide research fields.

Diffractometers, electron microscopes, and so on,

gradually available in Chinese universities and institutes.

Researchers returned from USA, Japan, Europe, etc.

Facilities of synchrotron radiation and neutron sources

in construction.

FJIRSM has carried out long-term first class research on NLO crystals

“Nature lies on structure” —Prof. Jiaxi Lu’s academic thought

Prof. Jiaxi Lu and Prof. Linus Pauling

β-BaB2O4 (BBO, left) and LiB3O5 (LBO, right) Non-linear optical crystals, by Prof. Jiaxi Lu, Prof. Chuangtian Chen, et al., in FJIRSM

Top 10 Laser Product in 1987 (BBO), 1989 (LBO),

by Laser and Photonics

The theory and applications of dielectric superlattices (a ca 20 years research project), by Prof. Naiben Min (闵乃本), et al., in Nanjing University For multi-color laser, etc.

Contribution of China to the Study of Quasicrystals (QCs) Top 3 in publications for more than 10 years; Opened the research line from TCP phases to QCs, and discovered a lot of QCs of icosahedral, 10-fold and 12-fold symmetry; Discovered two-dimensional 8-fold QCs; Provided important evidences for the debate of “QCs of multiple twins”; Proved experimentally that the necessary condition for QCs is quasi-periodicity, instead of non-crystallographic rotational symmetry ……

Prof. K.-H. Guo

8-fold QC

12-fold QC

Developing methods in solving protein structures, incommensurate structures, and so on. Published “Physical and Non-physical Methods of Solving Crystal Structures”, with M. M. Woolfson Cambridge University Press, 1995

Contribution to structure determination, by Prof. Haifu Fan, Inst. of Physics, CAS

Synchrotron radiation Facilities in China

Mainland: Beijing Synchrotron Radiation facility (BSRF) 2.5 GeV, light out in 1989 14 experimental stations Hefei Synchrotron Radiation Laboratory (HFSRL) 800MeV, light out, old ring 1989, new ring 2013 14 experimental stations Shanghai Synchrotron Radiation Facility (SSRF) 3.5 GeV, light out 2007 7 experimental stations

SRRC in Taiwan

BSRF HFSRL

Synchrotron radiation Facilities in China

SSRF SRRC 1.5 Gev 1994 A new 3 GeV ring

Since 2000, the development and improvement of laboratory instrumentations and the availability of domestic synchrotron radiation facilities (Beijing, BSRF and Shanghai, SSRF) have allowed Chinese crystallographers (many returned from USA, Europe, etc.) to study various systems from macromolecules to superconductors.

2007–2009, ca. 40 protein structures were solved on BSRF

Prof. W.-R. Chang

Crystal structure of spinach

major light-harvesting

complex at 2.72 Å resolution

Nature 2004, 428, 287-292

Substrate-analog : Cbz－Val－Asn－Ser－Thr－Leu－Gln－CMK Soaking Time : 18 hours

First Crystal Structures of SARS Virus Proteins — the main proteinase M pro Complex with Inhibitor （ SARS-CoV Mpro）PNAS, 2003, 100, 13190 by Prof. Z.-H. Rao

Electron density for the inhibitor and its binding to the enzyme

programmed cell death membrane protein structure and function protein degradation and quality control ……

Great contributions from Prof. Y.-G. Shi’s team, in Tsinghua University

Characterization of two distinct neuraminidases from avian-origin human-infecting H7N9 influenza viruses, Cell Research (2013) 23:1347-1355, by Prof. George F. Gao Structure of the CCR5 Chemokine Receptor–

HIV Entry Inhibitor Maraviroc Complex, Science 341, 1387 (2013); by Prof. Beili Wu

University 144 Institute 103 Hospital 18 Company 32

User Visits 16184 Users 6485

海南1

黑龙江4

吉林5

辽宁5

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福建4

湖北11

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内蒙古1 甘肃3

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四川9

云南2

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江苏22

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Singapore 3 Australia 2 South Korea 16 Japan 5 Sweden 1 Denmark 1 Canada 1 USA 3 Portugal 1 Thailand 1

⊙重庆2

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SSRF Users (until Jul 31, 2013 )

西藏1

Publications (until Jul 31, 2013 ) Papers published by users 1183 Nature and Science 23

The quality and quantity of publications both are increasing rapidly

Numbers of Publications

Impact factor ≥ 5

In Shandong University, Technical Institute of Physics and Chemistry, and Fujian Institute of Research on the Structure of Matter

KBe2BO3F2, KBBF, is the only practical crystal for deep ultra-violet (DUV) and it has been successfully used to manufacture all solid state lasers in DUV region by prism technology.

Diffractometers (CCD, IP, and PXRD) now are popular in Chinese universities and institutes. Therefore Chinese crystallographers working on small molecules are able to investigate the very wide physical and chemical systems and materials, such as MOFs, molecular materials, and so on. Chinese crystallographers thus have had significant contribution to CSD and ICDD.

Angew. Chem. Int. Ed. 2009, 48, 5287 Nature Commun. 2012, 3, 642 Hierarchical pore

M

M

MOO

O

O

O

OO

O O

O

O

OO

By Geometry Analysis

Metal Cluster-Based Strategy, by Prof. Xiaoming Chen et al., in Sun Yat-Sen University

Prediction: Synthetic Possibility, Yield, Stability

× OO

O O

5.9 Ao

OO

8.1 Ao

OO OO

O O

10.3 Ao

O O

OO

12.5 Ao

OO

O O

14.7 Ao

NO

O

4.4 Ao

N

O

O

6.6 Ao

NO

O

8.8 Ao

N

O

O

11.0 Ao

NO

O

13.2 Ao

× × × × × ×

× ×

× ×

×

Single-ion Magnets

[Dy(acac)3(H2O)2] (~D4d) (COT)ErCp* (~C∞v)

[CoIICoIII3] (~D3)

J. Am. Chem. Soc. 2011, 133, 4730

Angew.Chem.Int.Ed. 2010, 49, 7448

Chem. Sci. 2013, 4, 1802

Ueff = 323 / 197 K

“The discovery of a bona fide organometallic SMM brings the topic of magnetic bistability to a whole new synthetic audience. The field is now absolutely wide open for new developments.” (C&EN, March 28, 2011 89(13), 8).

Molecular Nanomagnets

Certainly one of the most remarkable findings in organolanthanide chemistry in 2011 is the identification of two lanthanide-COT complexes as single-ion magnets. (Coord. Chem. Rev. 2013, 257, 1122)

Coexistence of Magnetic and Electric Orderings in the Metal–Formate Frameworks of [NH4][M(HCOO)3]

P6322 (293K) P63 (90K)

Point group D6 to C6

Magnetism-Ferroelectricity

J. Am. Chem. Soc. 2010, 132, 9588；2011, 133, 14948. Adv. Mater. 2010, 22, 1526 Chemistry, a European Journal 2013, DOI: 10.1002/chem.201303425 Inorganic Chemistry Frontiers, 2013, DOI: 10.1039/c3qi00034f

Multifunctional molecular magnets

Molecular ferroelectrics with ferroelectric properties of large PS, high TC, large ε’, and low ε’’ or tanδ, comparable to the pure inorganic ferroelectric oxides. Science 2013, 339, 425.

39

400

h

k

[100]

Sun, Corma, Zou et al. Nature 2009, 458, 1154

ITQ-37 by combining ED and PXRD

Use ED intensities to pre-partition overlapped peaks in PXRD

Cubic

20 21 22 23

Future Facilities of synchrotron radiation and neutron sources

SSRF: building more beam lines and stations, and

developing X-ray FEL (free electron laser)

New BSRF: in plan

CARR: China Advanced Research Reactor, in

Beijing, started to run 2012

CAEPR: A new Reactor in Sichuan

CSNS: China Spallation Neutron Source, in

construction, in Guangdong

Development plan of SSRF

2010 2015 2020

III (18 stations)

II (22 stations)

now (7 stations)

Soft X-FEL

Hard X-FEL 1

Hard X-FEL 2

SSRF

FEL

I

用户线

公共线

III II SSRF

Future

The crystallographic researches

in China are going and

developing smoothly, and we

expect its prosperity in future.

CCrS: Chinese committee of IUCr, founded 1978, became CCrS 1994

At present, ca. 1500 members, 89 council members, 7 commissions

Youqi Tang

Naiben Min

Zihe Rao

Jianhua Lin Song Gao

Commissions The 5th CCrS

Chairs Vice-Chairs Small Molecular Structure (CSC/CIMS)

Xiaoming Chen Chengyong Su, Zheming Wang

Macro-molecular Structure (CBM) Xiaodong Su Jianping Ding Powder Diffraction (CPD) Zhenhong Mai Ming Li，Libing Liao

Crystal Growth & Characterization (CCGCM)

Jiyang Wang Mu Wang, Shifu Zhu

Electron Diffraction (CEC) Lianmao Peng Rong Yu Crystallography Education & Popular Science (CCT)

Liwen Niu Shixiong Liu

Drug Crystallography Yang Lv Pingbao Wang

CCrS organization: President: Prof. Song Gao, College of Chemistry and Molecular Engineering (CCME), Peking University, Vice-president of Peking University Secretary-general: Prof. Zheming Wang, CCME, Peking University

1986, 1st IUCr conference on small molecules

1993, IUCr 16th Congress

2009, National summer school on crystallography and crystal engineering

Some CCrS activities:

Prof. S. Larsen gave lecture in CCME. Prof. S. Larsen met Prof. Song Gao and Prof. Zheming Wang. Prof. Gautam R. Desiraju visited Sun Yat-Sen University and met Prof. Xiao-Ming Chen et al..

In IYCr 2014, we will conduct series activities in China, such as, Organizing “IYCr2014 Beijing International Conference on Crystallography”, October, 2014, and you are welcome, Composing book “History and Development of Crystallography in China”, and so on.

Thank you for your attention