Crystallography in Turkey

This Special Report was published in the IUCr Newsletter, Vol. 19, No. 3 (2011).

Crystallography in Turkey

Crystallography became an independent scientific discipline in Turkey in the 1960's. Crystal geometry and optics were taught in the Geology and Mineralogy Depts. to prepare students for microscopic investigation of crystalline materials. In some departments, including the Mineral Research and Exploration Inst. of Turkey (MTA), X-ray powder diffractometers were used for materials identification. In physics and chemistry departments, crystal symmetry, physical and chemical properties of crystals were taught without structure analysis.

Left: Some of the older equipment used for crystallography research in Turkey. Right: The participants of the 2nd National Meeting in Kayseri.

In the mid 1960's A. F. Cesur of Ankara U. started an X-ray crystallography laboratory which used photographic single crystal data collection techniques. In 1970, D. Ulku established a laboratory at Hacettepe U. in Ankara equipped with a 5 kW X-ray generator, a GE-SPG2 Spectrogoniometer with a quarter circle single crystal orienter, proportional and scintillation counters, and Wiessenberg, Buerger Precession and powder cameras. This laboratory has become the leading centre of X-ray crystallography in the country. The purchase of a CAD-4 diffractometer in 1992 attracted young scientists to do graduate work in X-ray crystallography. In 1999, a rotating anode X-ray generator was put in operation in the same department. Crystallography laboratories at Gazi, Erciyes, Ondokuz Mayıs and Atatürk U. were established by these young crystallographers who are very active in chemical crystallography today. Several X-ray single crystal and powder diffraction units are currently scattered across the country. University X-ray diffraction laboratories, dedicated to materials science research, also utilize crystallographic methods.

The SESAME (Synchrotron Light for Experimental Science and Applications in the Middle East) Project, developed by UNESCO, will further expand crystallographic research in Turkey. SESAME, based in Jordan, will provide opportunities for research in structural molecular biology, environmental, surface and interface science, microelectromechanical devices, X-ray imaging, archaeological microanalysis, and materials characterization. The founding members of the project are Bahrain, Cyprus, Egypt, Iran, Israel, Jordan, Pakistan, the Palestine Authority and Turkey. Turkey will be involved in building the protein crystallography and powder diffraction beamlines. Young Turkish scientists have benefited from extensive training in accelerator technology and applications at different European, US and Taiwanese Light Source laboratories (for more information, see: www.sesame.org.jo).

Photos from the ECM25 Istanbul Meeting.

The Turkish Crystallographic Association (TCA; www.tucr.org), formed in 2001, presently has about 140 registered members, one fourth of whom are senior scientists. The TCA was accepted in the European Crystallographic Association at its General Assembly in Cracow in August 2001. TCA organizes biannual National Meetings and workshops. W. Duax, J. Glusker, G. Cascarano and P. Rizkallah attended the 2006 National Meeting held in Kayseri. The 25th European Crystallographic Meeting was organized in Istanbul in 2009 by TCA (IUCr Newsletter, Volume 18, Number 1, 2010).

The Crystallography group and laboratory at Hacettepe University in Ankara.

The Crystallography Laboratory of Hacettepe U. in Ankara (contact: [email protected]) specializes in organic and inorganic compounds such as polynuclear coordination complexes of transition metals with unusual magnetic properties, inclusion compounds such as Hoffmann clathrates and crown ethers, phosphazene derivatives, intermetallic compounds, synthetic metallic materials, and pharmaceutical compounds (flavones, oxime ether derivatives, indoles, benzimidazoles, triazole and thiosemicarbazones). Protein crystallography has also begun in the lab (contact: [email protected]). The plant lectins have been studied at Daresbury Laboratory, UK in collaboration with P. Rizkallah. The structures of neurotoxic peptides extracted from Turkish scorpions have been studied in collaboration with J. R. Helliwell from Manchester U. The first Turkish small and wide angle X-ray scattering system (Hecus SWAXS) was installed in the laboratory in 2009. SWAXS analysis of multicompartment micelles, lamellar liquid crystals, hydrogels, polymer coated magnetic nanoparticles, stimuli-responsive block copolymers, marble dust, nanocomposites, membrane interactions, teeth and spider silks are in progress (contact: [email protected]).

The Advanced Materials Research Group, Hacettepe University.

The scientific activities of the Advanced Materials Research Group (AMRG, www.imal.hacettepe.edu.tr; contact: [email protected]) include the following four major research areas: intercalation compounds, graphite-like compounds, nanocarbon, and high-pressure and superconducting materials. Materials science research at AMRG addresses understanding the relationships between structural and material properties using powder, high-pressure and electron crystallography, and developing new synthesis and characterization techniques for advanced materials. The group is also in charge of the powder diffraction beamline at SESAME.

Left: The Material Research Laboratory, Ankara. Right: The Nonlinear Optics Laboratory, Ankara University.

The Material Research Laboratory at Ankara U., Ankara (contact: [email protected]) collaborates with research centers in Germany on single and powder crystal diffraction analysis of electrical, magnetic and specific heat properties of mono- and hetero-crystals and rare earth alloys. They also perform research related to the production and characterization of rare earth-intermetallic magnetic compounds between 2 K and 350 K, magnetocaloric materials, hard and soft magnetic materials, magnetic sensor materials and nanomagnetism.

The Nonlinear Optics Laboratory (contact: [email protected]) established in 2005 is equipped with a Spectra Physics femtosecond laser system, a Light Conversion Topas-C optic parametric amplifier, a Newport Helios spectroscopy system, a Quantel Briallant Nanosaniye laser system and a J. A. Woolaam M2000V spectroscopic ellipsometer for measurements of the second and third-order NLO properties and optical limiting behavior of organic thin films, carbon nanotubes, polymers, organic and organometallic compounds.

The Molecular Biology Research Laboratory at Sabancı University.

Studies in the Molecular Biology Research Laboratory at Sabancı U., İstanbul (contact: [email protected]) are focused on determining mechanisms of fundamental processes in living organisms, prediction of function from the 3D structure, and for engineering new systems via cloning, purification, characterization, and 3D structure determination using synchrotron X-ray solution scattering and diffraction techniques. The current applications include environmental pollution remediation and pathogen resistance in plants.

X-ray crystallography research at Ondokuz Mayis University, Samsun.

The introduction of the IPDS II diffractometer with a low temperature apparatus in the Physics Dept. at Ondokuz Mayıs U. (OMU), Samsun, (contact: [email protected]) has allowed fourteen researchers from the academic staff as well as a number of MSc and PhD students to study organic crystals with non-linear optical properties, the biological activities of novel saccharin and acesulfame metal complexes, structural and magnetic properties of dimeric cyano complexes, supramolecular structures and crystal engineering. The academic staff in the Department cooperates with researchers from different areas of science.

Left: The Advanced Thin Film Research Group at Anadolu University, Eskişehir. Right: Research facilities at the Anadolu University, Eskişehir.

The Advanced Thin Film Research Group at Anadolu U., Eskişehir (contact: [email protected]) was established in 2008 at the Dept. of Material Sciences and Engineering to study spintronics (spin valves and tunnel magnetoresistance) and photovoltaics (wide band gap semiconductors, complex metal oxide thin films). A self-designed multi-chamber sputtering tool with magnetic annealing oven is used for production of nanoscale/ultra thin film systems containing metal, semiconductor and insulator materials. Facilities for structural characterization of thin films include instruments for grazing incidence X-ray diffraction, X-ray reflectivity and rocking curve measurements and a scanning probe microscopy (AFM, STM, LFM).

The Chemistry Dept. of Middle East Technical U., Ankara is involved in chiral synthesis of amino acids, drugs, biologically active compounds, biodegradable polymers, and natural products, the application of quantum chemical methods to spectroscopic studies, metal clusters and colloids, measurement and control of hazardous substances, and application and development of nuclear analytical, atomic spectroscopic and chromatographic techniques for pollution studies and for analysis of trace elements in biological materials. In addition, low energy atom diffraction (LEAD), X-ray photoelectron diffraction, scanning probe microscopy and quartz crystal microbalance studies of self-assembled monolayers (SAMs) and organic semiconductor thin films are performed. The Central Laboratory is equipped with Rigaku Ultima IV X-ray diffraction system and provides services for the university.

The X-ray Research Laboratory at Erciyes U., Kayseri (contact: [email protected]) operates an Enraf-Nonius Diffractis 583 X-ray generator, Weissenberg and Buerger Precession cameras, and one microdensitometer. The U. of Technology Research Center has a Bruker AXS D8 Advance X-ray powder diffractometer and a LEO 440 scanning electron microscope. The group members work on structures of organic and metal-organic compounds with medical and pharmacological properties, and quantum mechanical calculations of crystal phase identification and analysis.

In the X-ray Crystallography Laboratory at Kırıkkale U., Kırıkkale a full circle single crystal X-ray diffractometer Rigaku MSC/AFC-7s and a TEM were purchased in 1998 for studies including boron complexes obtained from acidic amines, amides and organics, Al and Cu based microstructures, and metallic borons.

Members of the X-ray Crystallography Laboratory, Dokuz Eylül University.

M. Aygün and his coworkers from the X-ray Crystallography Laboratory at Dokuz Eylül U., İzmir (contact: [email protected]) are interested in intermolecular interactions of N-Heterocyclic Carbene (NHC) complexes with transition metals and the theoretical foundations of classical crystallography (CCr) and quantum crystallography (QCr).

Researchers at Dokuz Eylül U. have improved the solution of the phase problem with a new methodology called Generalized Classical Crystallography (GCCr) in which the tangent formula was recast in terms of perturbative contributions from various orders with the aid of information theory and a generalized polynomial equation satisfied by electron density in the unit cell. From a generalized point of view, conventional crystallography, zeroth order crystallography and higher order crystallographic studies are possible. In addition, a novel iterative scheme was developed for the application of Generalized Quantum Classical Crystallography (GQCr).

Left: The research group at the Laboratory for Advanced Analysis, İstanbul University. Right: İstanbul University, İstanbul, Turkey.

Crystallographic work in İstanbul started in 2003 when the Advanced Analysis Laboratory was established at İstanbul U. (contact: [email protected]) with single crystal (Rigaku R-AXIS Rapid-S) and powder diffraction (Rigaku D-Max family) studies of natural and synthetic organic and inorganic molecules, and phase analysis of functional materials and clays.

A crystallography laboratory in Atatürk U., Erzurum was established in the Organic Chemistry Dept. in 2005, where the synthesis of natural products, synthetic organic chemistry studies, asymmetric synthesis and mechanistic studies are conducted. Together with organic and inorganic compounds from other working groups, an average of 40-50 structures are determined per year.

The X-ray research group at Balıkesir University.

A research group at Balıkesir U., Balıkesir (contact: [email protected]) works on the structures and magnetic properties of novel polynuclear Schiff base transition metal complexes that have potential applications for storage of information at the molecular and nanoscale level. The group plans to develop new materials with novel magnetic properties, such as single molecule magnets, for technological applications.

Other institutions in Turkey that operate diffraction facilities

Some laboratories running X-ray diffraction facilities exist as research infrastructure of the Applied Physics and Material Science Depts. located at the Middle East Technical U. (Metallurgical & Materials Dept. and Central Research Laboratory), Anadolu U. (AUBIBAM, Eskişehir), Gazi U. (Semiconductor Tech. Adv. Research Laboratory), Harran U. (Urfa) and İzmir Inst. of Technology (Materials Research Centre, İzmir). In addition to these, there are many industrial institutions in Turkey including labs that perform powder diffraction for materials characterization and quality control, such as the Turkish Atomic Energy Agency, the General Directorate of Mineral Research and Exploration, the General Directorate of Highways and the General Directorate of State Hydraulic Works.

Engin Kendi ([email protected])