There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

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

Hydrogen Storage in Metal–Organic Frameworks

N-Heterocyclic Carbenes in Late Transition Metal Catalysis

17β-Hydroxysteroid dehydrogenase type 3 (17β-HSD3) is expressed at high levels in testes and seminal vesicles; it is also present in prostate tissue and involved in gonadal and non-gonadal testosterone biosynthesis. The enzyme is membrane-bound, and a crystal structure is not yet available. Selective aryl benzylamine-based inhibitors were designed and synthesised as potential agents for prostate cancer therapeutics through structure-based design, using a previously built homology model with docking studies. Potent, selective, low nanomolar IC50 17β-HSD3 inhibitors were discovered using N-(2-([2-(4-chlorophenoxy)phenylamino]methyl)phenyl)acetamide (1). The most potent compounds have IC50 values of approximately 75 nM. Compound 29, N-[2-(1-Acetylpiperidin-4-ylamino)benzyl]-N-[2-(4-chlorophenoxy)phenyl]acetamide, has an IC50 of 76 nM, while compound 30, N-(2-(1-[2-(4-chlorophenoxy)-phenylamino]ethyl)phenyl)acetamide, has an IC50 of 74 nM. Racemic C-allyl derivative 26 (IC50 of 520 nM) was easily formed from 1 in good yield and, to determine binding directionality, its enantiomers were separated by chiral chromatography. Absolute configuration was determined using single crystal X-ray crystallography. Only the S-(+)-enantiomer (32) was active with an IC50 of 370 nM. Binding directionality was predictable through our in silico docking studies, giving confidence to our model. Importantly, all novel inhibitors are selective over the type 2 isozyme of 17β-HSD2 and show <20% inhibition when tested at 10 µM. Lead compounds from this series are worthy of further optimisation and development as inhibitors of testosterone production by 17β-HSD3 and as inhibitors of prostate cancer cell growth.

Substituted Aryl Benzylamines as Potent and Selective Inhibitors of 17β-Hydroxysteroid Dehydrogenase Type 3

Synthesis and reactivity of eta 2(4e)-alkyne and eta 2(3e)-vinyl complexesof rhenium

The homochiral cyclic sulfinamide S(s)R-(+)-1 has been employed for the asymmetric synthesis of α-substituted benzylamines via the benzylidene sulfinamides R(s)R-(–)-4. Following diastereoselective reduction and hydrolysis S(s)R-(+)-1 can be recycled in one step from the sulfinic acid 11. The addition of zinc(II) bromide reverses the diastereoselectivity of the diisobutylaluminium hydride (DIBAL) reduction of the substrates 4. The same reversal is not observed in the reactions of analogues lacking an amide side chain. In one case the required benzylidene sulfinamide exists in the form of an enamine 15, the X-ray crystallographic structure of which is also featured. A second approach to chiral amines, via the addition of Grignard reagents to sulfinylamines derived from S(s)R-(+)-1, is also described.

Asymmetric Synthesis of Amines Using a Chiral, Non-Racemic, Benzylidene Sulfinamide Derived from a Recoverable Precursor.

Sterically Hindered Organometallics. Synthesis of Four-Membered Rings Containing Tin, Oxygen, and Sulfur. The Crystal Structure of 2,2,4,4-Tetrakis(2,4,6-triisopropylphenyl)-1,3,2,4-oxathiadistannetane.

The Au-catalyzed [3,3]-rearrangement of ynamides (I) affords highly reactive α-acyloxyallenamides, which can be trapped through the reaction with nucleophilic indole derivatives (II).

Mary F. Mahon

Papers

Substituted Aryl Benzylamines as Potent and Selective Inhibitors of 17β-Hydroxysteroid Dehydrogenase Type 3

Synthesis and reactivity of eta 2(4e)-alkyne and eta 2(3e)-vinyl complexesof rhenium

Asymmetric Synthesis of Amines Using a Chiral, Non-Racemic, Benzylidene Sulfinamide Derived from a Recoverable Precursor.

Sterically Hindered Organometallics. Synthesis of Four-Membered Rings Containing Tin, Oxygen, and Sulfur. The Crystal Structure of 2,2,4,4-Tetrakis(2,4,6-triisopropylphenyl)-1,3,2,4-oxathiadistannetane.

Gold‐Catalyzed Cascade Rearrangements of Ynamide Propargyl Esters.