New software, OLEX2, has been developed for the determination, visualization and analysis of molecular crystal structures. The software has a portable mouse-driven workflow-oriented and fully comprehensive graphical user interface for structure solution, refinement and report generation, as well as novel tools for structure analysis. OLEX2 seamlessly links all aspects of the structure solution, refinement and publication process and presents them in a single workflow-driven package, with the ultimate goal of producing an application which will be useful to both chemists and crystallographers.

OLEX2: a complete structure solution, refinement and analysis program

Chromium is introduced into the environment by effluents in several industries. It is important to control this element since it is both toxic and carcinogenic. As its toxicity depends on its state of oxidation, it is especially interesting to determine its most abundant species, Cr(III) and Cr(VI). In this overview, we describe the requirements for chromium determination and speciation and review the analytical methods that have been used in these studies. Focusing in particular on developments since 2000, we examine the features of detection techniques, pre-treatments and applications of the various methods.

Chromium determination and speciation since 2000

Speciation and determination of ultra trace amounts of chromium by solidified floating organic drop microextraction (SFODME) and graphite furnace atomic absorption spectrometry.

Element speciation analysis using capillary electrophoresis: twenty years of development and applications.

This review as a sequel of three earlier similar reports gives a summary of the progress and significant methodological developments, starting from 2002, in the use of capillary electrophoresis (CE) for inorganic ion analysis. As substantiated by the illustrative number of relevant references, improvements in sensitivity achieved both in and outside a CE system, advances in manipulating the separation selectivity, novel hardware configurations, and system performance innovations are continually being reported over the review period. Specifically viewed are the recent advancements in elemental (bio)speciation analysis, which remains one of the most fertile areas of CE research, as well as in three recently booming research topics: contactless conductivity detection, separations on microchips, and transient isotachophoretic preconcentration. A state-of-the-art picture of technique's potentialities within the field of interest presented here demonstrates that CE has become recognized and is growing in acceptance as a reliable alternative to traditional analytical methods such as high-performance liquid chromatography (HPLC).

Capillary electrophoresis of inorganic ions: An update

The sixteen neutral ML2 complexes of Co, Ni, Cu and Zn(II) with the p-toluenesulfonamide and trifluoromethylsulfonamide derivatives of 2-aminomethylpyridine (L1, L2) and its 6-Me homologue (L3, L4) have been characterised by low temperature X-ray crystallography (100–120 K). Complexes of Co and Zn invariantly adopted a distorted tetrahedral geometry and whilst Cu(II) complexes of L2, L3 and L4 also took up a distorted tetrahedral geometry, that with L1 was square planar. A database survey of the distortion from limiting tetrahedral/square planar geometry has been carried out, aided by a simple geometric analysis. The trifluoromethylsulfonamide ligands (L2 and L3) were less basic, e.g. log K1 7.51(3) for L2vs. 12.23(6) for L1
(80% MeOH/H2O) and afforded a weaker ligand field, exemplified by the position of the visible d–d transition in Cu(II) complexes and the ease of reduction of the Cu(II) centre: E1//2 values (MeCN vs. Ag/AgCl) are −430, −137, +55 and −240 mV for Cu(L1)2, Cu(L2)2, Cu(L3)2 and Cu(L4)2. Ligand protonation and stepwise formation constants have been measured for L1–L3 and derived species distribution diagrams reveal that for complexes with L2 and L3, the predominant species present at pH 7.4 when zinc was in the nanomolar range was ZnL2.

Examination of cobalt, nickel, copper and zinc( ii ) complex geometry and binding affinity in aqueous media using simple pyridylsulfonamide ligands

We present a method for the speciation of chromium by capillary electrophoresis. Cr(III) was complexed with diethylenetriaminepentaacetic acid (DTPA) to form a negatively charged complex. Using 20 mM phosphate buffer of pH 8 containing 0.5 mM tetradecyltrimethylammonium hydroxide (TTAOH) at a separation voltage of -15 kV, both forms of chromium CrDTPA(2-) and CrO(4) (2-) were separated in less than 6 min. Direct UV detection at 214 nm was used. The effect of the presence of interfering ions was investigated. The application of the developed method to speciation of chromium in tanning liquor is demonstrated. The obtained results have shown a good correlation with those of flame atomic absorbance spectrometry (FAAS), inductively coupled plasma-mass spectrometry (ICP-MS) and UV/VIS spectrophotometry.

Capillary electrophoresis speciation of chromium in leather tanning liquor

Ligand protonation and stepwise dissociation constants, formation constants and speciation of four pyridyl sulfonamide ligands (Congreeve et al., New J. Chem. 27:98–106, 2003) were assessed, using potentiometric and UV/Visible spectrophotometric pH titrations (in 80% MeOH − 20% H2O). The suitability of these ligands as Cu(II) and Zn(II) sensors for physiological applications was assessed. Two ligands L1 and L4 were p-toluenesulfonamide derivatives while L2 and L3 were triflurosulfonamide derivatives. Additionally L3 and L4 were appended with α-methyl groups. The most stable complex was formed by L1 with Cu(II) owing to the fact that this complex was square planar (log 10 K1=12.15±0.004 and log 10 β2=15.42±0.006). The rest of the complexes invariably formed distorted tetrahedron geometry and complexation was weaker. Speciation diagrams show the effect of ligand to metal concentration, revealing that the L2 and L3 ligands are the most suitable for forming ML2 complexes at physiological pH.

Mark Knell

Papers

Examination of cobalt, nickel, copper and zinc( ii ) complex geometry and binding affinity in aqueous media using simple pyridylsulfonamide ligands

Capillary electrophoresis speciation of chromium in leather tanning liquor

Complexation Studies of Pyridyl Sulfonamide Ligands for Sensing Zinc and Copper Ions