Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

J. Appl. Cryst.の発刊に際して

Metal–organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).

Luminescent Metal–Organic Frameworks

The accidental discovery of the anticancer properties of cisplatin and its clinical introduction in the 1970s represent a major landmark in the history of successful anticancer drugs. Although carboplatin--a second-generation analogue that is safer but shows a similar spectrum of activity to cisplatin--was introduced in the 1980s, the pace of further improvements slowed for many years. However, in the past several years interest in platinum drugs has increased. Key developments include the elucidation of mechanisms of tumour resistance to these drugs, the introduction of new platinum-based agents (oxaliplatin, satraplatin and picoplatin), and clinical combination studies using platinum drugs with resistance modulators or new molecularly targeted drugs.

The resurgence of platinum-based cancer chemotherapy

Structure of diaqua[1,6‐bis(4‐imidazolyl)‐2,5‐dithiahexane]nickel(II) dinitrate

Two isostructural mononuclear compounds with formula {[Cd(dipm)(H2O)(ClO4)](dipm)(ClO4)(H2O)} (1) {[Zn(dipm)(H2O)(BF4)](dipm)(BF4)(H2O)} (2) and (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesised and characterised by X-ray crystallography and infrared spectroscopy. The structure of compound 1 has been solved in the space group P21/n with a = 18.860(4), b = 8.579(2), c = 20.917(4) A, β = 101.33(3)°, V = 3318.4(12) A3, Z = 4 with final R = 0.0454. The structure of compound 2 has also been solved in the space group P21/n with a = 19.026(4), b = 8.389(1), c = 20.720(4) A, β = 101.37(3)°, V = 3242.2(10) A3, Z = 4 with final R = 0.0689. The geometry around the metal ions is octahedral, and is constituted by four nitrogen atoms from two dipm molecules, an oxygen atom from a water molecule and a semi-coordinating anion atom (
 $$ O_{{\rm ClO}_{4}} $$
 for compound 1 and $$ F_{{\rm BF}_{4}} $$
 for compound 2). In the lattice are also present: a non-coordinating water molecule, an anion molecule and a dipm molecule. For compound 1, the Cd–N distances are between 2.296 and 2.328 A. The $$ \hbox{Cd}{-}\hbox{O}_{{\rm H}_{2}{\rm O}} $$
 distance is 2.310 A and the $$ \hbox{Cd}{-}\hbox{O}_{{\rm ClO}_{4}} $$
 is 2.477 A. The Zn–N distances in compound 2 are between 2.121 and 2.164 A. The $$ \hbox{Zn}{-}\hbox{O}_{{\rm H}_{2}{\rm O}} $$
 distance is 2.147 A and the $$ \hbox{Zn}{-}\hbox{F}_{{\rm BF}_{4}} $$
 distance is 2.373 A. A hydrogen bond interaction of the Watson–Crick type is observed between the amine N atom of a dipm ligand to a pyrimidyl N atom and a non-coordinating dipm ligand with N···N distances, which vary from 3.066(5) to 3.109(5) A. Furthermore medium to strong hydrogen bond interactions are present between oxygen atoms of the water molecules and the anions of the compounds. Two isostructural mononuclear compounds with formula {[Cd(dipm)(H2O)(ClO4)](dipm)(ClO4)(H2O)} (1) {[Zn(dipm)(H2O)(BF4)](dipm)(BF4)(H2O)} (2) and (in which dipm = bis(pyrimidin-2-yl)amine) have been synthesised and characterised by X-ray crystallography and infrared spectroscopy. .

Two Mononuclear Compounds with bis(Pyrimidin-2-yl)amine as a Ligand and as a Hydrogen-bonded Lattice Molecule. Synthesis, Structure and Spectroscopy of {[M(dipm)(H2O)(A)](dipm)(A)(H2O)} (M = Cd with A = ClO4; and Zn with A = BF4)

Ein strukturmodell fur reine fe-hydrogenasen

The synthesis of three bis[(tert-butoxy)carbonyl]-protected (tetramine)dichloroplatinum complexes 2a – c of formula cis-[PtCl2(LL)] and of their cationic deprotected analogs 3a – c and their evaluation with respect to in vitro cytotoxicity, intramolecular stability, DNA binding, and cellular uptake is reported. The synthesis comprises the complexation of K2[PtCl4] with di-N-protected tetramines 1a – c to give 2a – c and subsequent acidolysis, yielding 3a – c. The cytotoxicity of the complexes is in direct relation to the length of the polyamine. Complexes 3a – c display a significant higher affinity for CT DNA as well as for cellular DNA in A2780 cells than cisplatin.

Mononuclear Tetraamineplatinum(II) Complexes: Synthesis, Anticancer Activity, DNA Binding, and Cellular Uptake

This paper establishes a new and previously unrecognized pathway for the formation of dienes and trienes from model 1,5-polyolefins. It has been found that in the presence of dioxygen and at high temperatures model 1,5-polyolefins are oxidized to yield allylic alcohols or hydroperoxides. These structures subsequently dehydrate to form dienes and trienes, a reaction which was found to be catalyzed by bis(dimethyldithiocarbamato)zinc(II) (ZDMC) and bis(mercaptobenzothiazolato)-zinc(II) (ZMBT), but not by zinc stearate. The observed dehydration reaction has been established to occur exclusively via a 1,2-dehydration pathway; whereas 1,4-dehydration was not observed. In addition, the present paper reports that NBCI, a model compound for the anti-reversion agent 1,3-bis(citraconimidomethyl)benzene (BCIMB), reacts completely within 2 h with squalene at 170 °C in the absence of vulcanization curatives, which can be attributed to this oxidation/dehydration mechanism. The combined results suggest that the...

Jan Reedijk

Papers

Structure of diaqua[1,6‐bis(4‐imidazolyl)‐2,5‐dithiahexane]nickel(II) dinitrate

Two Mononuclear Compounds with bis(Pyrimidin-2-yl)amine as a Ligand and as a Hydrogen-bonded Lattice Molecule. Synthesis, Structure and Spectroscopy of {[M(dipm)(H2O)(A)](dipm)(A)(H2O)} (M = Cd with A = ClO4; and Zn with A = BF4)

Ein strukturmodell fur reine fe-hydrogenasen

Mononuclear Tetraamineplatinum(II) Complexes: Synthesis, Anticancer Activity, DNA Binding, and Cellular Uptake

Homogeneous Zinc(II) Catalysis in Accelerated Vulcanization II. (Poly)Olefin Oxidation, Dehydration, and Reaction with Anti-Reversion Coagents