From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids.

This critical review will be of interest to the experts in porous solids (including catalysis), but also solid state chemists and physicists. It presents the state-of-the-art on hybrid porous solids, their advantages, their new routes of synthesis, the structural concepts useful for their ‘design’, aiming at reaching very large pores. Their dynamic properties and the possibility of predicting their structure are described. The large tunability of the pore size leads to unprecedented properties and applications. They concern adsorption of species, storage and delivery and the physical properties of the dense phases. (323 references)

Hybrid porous solids: past, present, future

Although zeolites and related materials combine nanoporosity with high thermal stability, they are difficult to modify or derivatize in a systematic way. A highly porous metal coordination polymer [Cu3(TMA)2(H2O)3]n (where TMA is benzene-1,3,5-tricarboxylate) was formed in 80 percent yield. It has interconnected [Cu2(O2CR)4] units (where R is an aromatic ring), which create a three-dimensional system of channels with a pore size of 1 nanometer and an accessible porosity of about 40 percent in the solid. Unlike zeolites, the channel linings can be chemically functionalized; for example, the aqua ligands can be replaced by pyridines. Thermal gravimetric analysis and high-temperature single-crystal diffractometry indicate that the framework is stable up to 240 degreesC.

http://science.sciencemag.org/content/sci/283/5405/1148.full.pdf

A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n

Allergic rhinitis is a symptomatic disorder of the nose induced after allergen exposure by an IgE-mediated inflammation of the membranes lining the nose. It is a global health problem that causes major illness and disability worldwide. Over 600 million patients from all countries, all ethnic groups and of all ages suffer from allergic rhinitis. It affects social life, sleep, school and work and its economic impact is substantial. Risk factors for allergic rhinitis are well identified. Indoor and outdoor allergens as well as occupational agents cause rhinitis and other allergic diseases. The role of indoor and outdoor pollution is probably very important, but has yet to be fully understood both for the occurrence of the disease and its manifestations.

In 1999, during the Allergic Rhinitis and its Impact on Asthma (ARIA) WHO workshop, the expert panel proposed a new classification for allergic rhinitis which was subdivided into 'intermittent' or 'persistent' disease.

This classification is now validated. The diagnosis of allergic rhinitis is often quite easy, but in some cases it may cause problems and many patients are still under-diagnosed, often because they do not perceive the symptoms of rhinitis as a disease impairing their social life, school and work.

The management of allergic rhinitis is well established and the ARIA expert panel based its recommendations on evidence using an extensive review of the literature available up to December 1999. The statements of evidence for the development of these guidelines followed WHO rules and were based on those of Shekelle et al. A large number of papers have been published since 2000 and are extensively reviewed in the 2008 Update using the same evidence-based system. Recommendations for the management of allergic rhinitis are similar in both the ARIA workshop report and the 2008 Update. In the future, the GRADE approach will be used, but is not yet available.

Another important aspect of the ARIA guidelines was to consider co-morbidities. Both allergic rhinitis and asthma are systemic inflammatory conditions and often co-exist in the same patients. In the 2008 Update, these links have been confirmed.

The ARIA document is not intended to be a standard-of-care document for individual countries. It is provided as a basis for physicians, health care professionals and organizations involved in the treatment of allergic rhinitis and asthma in various countries to facilitate the development of relevant local standard-of-care documents for patients.

/pdf/allergic-rhinitis-and-its-impact-on-asthma-aria-2008-update-13eqfzaw4u.pdf

Allergic rhinitis and its impact on asthma (ARIA) 2008 update (in collaboration with the World Health Organization, GA(2)LEN and AllerGen)

1. Advantages of Chemical Redox Agents 878 2. Disadvantages of Chemical Redox Agents 879 C. Potentials in Nonaqueous Solvents 879 D. Reversible vs Irreversible ET Reagents 879 E. Categorization of Reagent Strength 881 II. Oxidants 881 A. Inorganic 881 1. Metal and Metal Complex Oxidants 881 2. Main Group Oxidants 887 B. Organic 891 1. Radical Cations 891 2. Carbocations 893 3. Cyanocarbons and Related Electron-Rich Compounds 894

/pdf/chemical-redox-agents-for-organometallic-chemistry-4fs84ntwp8.pdf

Chemical Redox Agents for Organometallic Chemistry

An oxalate-linked copper(II) coordination polymer, [Cu2(oxalate)2(pyrazine)3]n, constructed with two different copper units: x-ray crystallographic and electronic structures

New copper(II) intercalation compounds, {[Cu(CA)(H2O)2](G)}n (H2CA = chloranilic acid; G = 2,5-dimethylpyrazine (dmpyz) (1a and 1b) and phenazine (phz) (2)) have been synthesized and characterized. 1a crystallizes in the triclinic space group P1, with a = 8.028(2) A, b = 10.269(1) A, c = 4.780(2) A, α = 93.85(3)°, β = 101.01(2)°, γ = 90.04(3)°, and Z = 1. 1b crystallizes in the triclinic space group P1, with a = 8.010(1) A, b = 10.117(1) A, c = 5.162(1) A, α = 94.40(1)°, β = 97.49(1)°, γ = 112.64(1)°, and Z = 1. 2 crystallizes in the triclinic space group P1, with a = 8.071(1) A, b = 11.266(1) A, c = 4.991(1) A, α = 97.80(1)°, β = 99.58(1)°, γ = 83.02(1)°, and Z = 1. For all the compounds, the crystal structures consist of one dimensional [Cu(CA)(H2O)2]m chains and uncoordinated guest molecules (G). Each copper atom for 1a, 1b, and 2 displays a six-coordinate geometry with the two bis-chelating CA2- anions and water molecules, providing an infinite, nearly coplanar linear chains running along the a-dir...

Rational Design of a Novel Intercalation System. Layer-Gap Control of Crystalline Coordination Polymers, {[Cu(CA)(H2O)m](G)}n (m = 2, G = 2,5-Dimethylpyrazine and Phenazine; m = 1, G = 1,2,3,4,6,7,8,9-Octahydrophenazine)

Palladium-catalyzed polycondensation between diiodoferrocenes (1,1‘-diiodoferrocene and 1,6-diiodo-1‘,6‘-biferrocene) and diethynyl aromatic compounds HC⋮CArC⋮CH (e.g., 2,5-diethynylpyridine and 2,5-diethynyl-3-hexylthiophene) gives poly(aryleneethynylene) (PAE) type polymers containing the ferrocene unit in the π-conjugated main chain. The prepared polymers include (FcC⋮CPhC⋮C)n, PAE-Fc-1, (FcC⋮CPyC⋮C)n, PAE-Fc-2, and (FcC⋮ChexThC ⋮C)n, PAE-Fc-3 (Fc = 1,1‘-ferrocenylene; Ph = p-phenylene; Py = pyridine-2,5-diyl; hexTh = 3-hexylthiophene-2,5-diyl). 1H-NMR and IR spectra of the polymers are reasonable for their structures. The PAE type polymer containing the pyridine unit (PAE-Fc-2) is soluble in formic acid, and the polymer containing the hexylthiophene unit (PAE-Fc-3) is soluble in common organic solvents such as CHCl3, THF, and benzene. UV−visible spectra of the polymers exhibit a main π−π* absorption peak at about 330 nm and a d−d absorption peak at about 450 nm. The cyclic voltammogram of the polymers...

Poly(aryleneethynylene) Type Polymers Containing a Ferrocene Unit in the π-Conjugated Main Chain. Preparation, Optical Properties, Redox Behavior, and Mössbauer Spectroscopic Analysis

The [8Fe−7S] core of the P-clusters in nitrogenases is unique among the known [Fe−S] clusters which are essential to electron-transfer processes in nature. The [8Fe−7S] cluster has been thought unstable and to exist only in protein environments. We found that this unusual [8Fe−7S] structure can be self-assembled from the reaction of Fe(II) bis-amide, tetramethylthiourea, 2,4,6-triisopropylbenzenethiol, and elemental sulfur in a specific mole ratio. The structure of the complex isolated therefrom closely resembles that of the reduced form (PN) of the P-clusters, while the 6Fe(II)2Fe(III) oxidation state was manifested by the Mossbauer study.

Synthesis of the P-cluster inorganic core of nitrogenases.

We demonstrate a novel form of metallofullerenes, namely, those with radioactive atoms encapsulated in the C[sub 82]cage. The metal atoms were made radioactive by a neutron capture reaction or through a nuclear decay process. The most important and intriguing finding of the present study is that the endohedral form of metallofullerenes is not affected by the recoil energy of the metal atom resulting from emission of electrons in the [beta] decay. Such a stability of the cage against the recoil energy of the encapsulated atom was confirmed by the elution behavior of the metallofullerene in liquid chromatography. Successful encapsulation of radioactive atoms inside the fullerene cage will greatly widen the potential use of endohedral metallofullerenes not only in basic science and technology but also in other areas, such as medicine. 14 refs., 3 figs.

Motomi Katada

Papers

An oxalate-linked copper(II) coordination polymer, [Cu2(oxalate)2(pyrazine)3]n, constructed with two different copper units: x-ray crystallographic and electronic structures

Rational Design of a Novel Intercalation System. Layer-Gap Control of Crystalline Coordination Polymers, {[Cu(CA)(H2O)m](G)}n (m = 2, G = 2,5-Dimethylpyrazine and Phenazine; m = 1, G = 1,2,3,4,6,7,8,9-Octahydrophenazine)

Poly(aryleneethynylene) Type Polymers Containing a Ferrocene Unit in the π-Conjugated Main Chain. Preparation, Optical Properties, Redox Behavior, and Mössbauer Spectroscopic Analysis

Synthesis of the P-cluster inorganic core of nitrogenases.

Encapsulation of radioactive 159gd and 161tb atoms in fullerene cages