Carbon chains and the (5,5) single-walled nanotube: structure and energetics versus length

Reliable thermochemistry is computed for infinite stretches of pure-carbon materials including acetylenic and cumulenic carbon chains, graphene sheet, and single-walled carbon nanotubes (SWCNTs) by connection to the properties of finite size molecules that grow into the infinitely long systems. Using ab initio G3 theory, the infinite cumulenic chain (:C[double bond]C[double bond]C[double bond]C:) is found to be 1.9+/-0.4 kcal/mol per carbon less stable in free energy at room temperature than the acetylenic chain (.C[triple bond]C-C[triple bond]C.) which is 24.0 kcal/mol less stable than graphite. The difference between carbon-carbon triple, double, and single bond lengths (1.257, 1.279, and 1.333 A, respectively) in infinite chains is evident but much less than with small hydrocarbon molecules. These results are used to evaluate the efficacy of similar calculations with the less rigorous PM3 semiempirical method on the (5,5) SWCNT, which is too large to be studied with high-level ab initio methods. The equilibrium electronic energy change for C(g)-->C[infinite (5,5) SWCNT] is -166.7 kcal/mol, while the corresponding free energy change at room temperature is -153.3 kcal/mol (6.7 kcal/mol less stable than graphite). A threefold alternation (6.866, 6.866, and 6.823 A) in the ring diameter of the equilibrium structure of infinitely long (5,5) SWCNT is apparent, although the stability of this structure over the constant diameter structure is small compared to the zero point energy of the nanotube. In general, different (n,m) SWCNTs have different infinite tube energetics, as well as very different energetic trends that vary significantly with length, diameter, and capping.     

Citrinin revisited: from monomers to dimers and beyond

Detailed chemical analysis of the solid phase fermentation of an Australian Penicillium citrinum isolate has returned the known compounds citrinin (1), phenol A acid (6), dihydrocitrinone (7) and dihydrocitrinin (8), together with a novel cytotoxic dimer, dicitrinin A (5). Dicitrinin A (5) was determined to be a dimerised artefact of the major co-metabolite citrinin, and its structure solved by spectroscopic analysis and chemical modification. Analysis of the products encountered during the controlled decomposition of citrinin led to the discovery of additional citrinin dimers and delineated a plausible mechanistic pathway linking all monomeric and dimeric citrinin degradation products.     

Absolute rate coefficient of the OH + CH(3)C(O)OH reaction at T = 287-802 K. The two faces of pre-reactive H-bonding

The rate constants for the reaction OH + CH3C(O)OH --> products (1) were determined over the temperature range 287-802 K at 50 and 100 Torr of Ar or N2 bath gas using pulsed laser photolysis generation of OH by CH3C(O)OH photolysis at 193 nm coupled with OH detection by pulsed laser-induced fluorescence. The rate coefficient displays a complex temperature dependence with a sharp minimum at 530 K, indicating the competition between a reaction proceeding through a pre-reactive H-bonded complex to form CH3C(O)O + H2O, expected to prevail at low temperatures, and a direct methyl-H abstraction channel leading to CH2C(O)OH + H2O, which should dominate at high temperatures. The temperature dependence of the rate constant can be described adequately by k1(287-802 K) = 2.9 x 10(-9) exp{-6030 K/T} + 1.50 x 10(-13) exp{515 K/T} cm3 molecule(-1)(s-1), with a value of (8.5 +/- 0.9) x 10-13 cm3 molecule(-1)(s-1) at 298 K. The steep increase in rate constant in the range 550-800 K, which is reported for the first time, implies that direct abstraction of a methyl-H becomes the dominant pathway at temperatures greater than 550 K. However, the data indicates that up to about 800 K direct methyl-H abstraction remains adversely affected by the long-range H-bonding attraction between the approaching OH radical and the carboxyl -C(O)OH functionality.     

Sixteen Eisenstein series

S. Ramanujan gave fourteen families of series in his Second Notebook in Chap. 17, Entries 13–17. In each case he gave only the first few examples, giving us the motivation to find and prove a general formula for each family of series. The aim of this paper is to develop a powerful tool (four versatile functions f ₀,f ₁,f ₂, and f ₃) to collect all of Ramanujan’s examples together.      

On the number of primitive representations of integers as sums of squares

Formulas for the number of primitive representations of any integer n as a sum of k squares are given, for 2 ≤ k ≤ 8, and for certain values of n, for 9 ≤ k ≤ 12. The formulas have a similar structure and are striking for their simplicity. Dedicated to Richard Askey on the occasion of his 70th birthday. 2000 Mathematics Subject Classification Primary—11E25; Secondary—05A15, 33E05.     

Predicting the Performance of Granulation Binders Through Micro‐Mechanistic Observations

The selection of an appropriate polymeric binder to be used to agglomerate drug with excipients is a critical issue for the development of high shear wet granulation processes for pharmaceutical tablet systems. The aim of the study reported here is to determine the potential for successful granulation through measurement of the interactions of two polymer binder solutions, hydroxypropyl methylcellulose (HPMC) and polyvinyl‐pyrrolidone (PVP), with individual paracetamol drug crystals. A novel micro‐force balance (MFB) has been used to measure different parameters of the crystal‐to‐binder interaction, including the forces exerted by axially strained liquid bridges formed between either two paracetamol crystals or between a reservoir of binder solution and a single paracetamol crystal, the paracetamol‐to‐binder wettability, the post rupture volume distribution and the residue deposited on each crystal. Video images of the separation sequences were obtained simultaneously for analysis of bridge geometry, contact angles, volume distribution and binder residues. It was found that the formation of liquid bridges and their ability to bond particles together depends on the amount of binder left on a crystal after contacting a reservoir of binder (for example, large binder drop). Crystals in contact with HPMC were able to retain more liquid from a binder reservoir than those contacted with PVP solutions. This behaviour is seen to be more important to the final granule strength than the liquid binding force holding particles together in the wet agglomerate.     

The prediction of atomic kinetic energies from coordinates of surrounding atoms using kriging machine learning

A novel design of a next-generation force field considers not only the electronic inter-atomic energy but also intra-atomic energy. This strategy promises a faithful mapping between the force field and the quantum mechanics that underpins it. Quantum chemical topology provides an energy partitioning in which atoms have well-defined electronic kinetic energies, and we are interested in capturing how they respond to changes in the positions of surrounding atoms. A machine learning method called kriging successfully creates models from a training set of molecular configurations that can then be used to predict the atomic kinetic energies occurring in previously unseen molecular configurations. We present a proof-of-concept based on four molecules of increasing complexity (methanol, N-methylacetamide, glycine and triglycine). We test how well the atomic kinetic energies can be modelled with respect to training set size, molecule size and elemental composition. For all atoms tested, the mean atomic kinetic energy errors fall below 1.5 kJ mol^?1, and far below this in most cases. This represents errors all under 0.5 % and thus the kinetic energies are well modelled using the kriging method, even when using modest-to-small training set sizes.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Airborne gamma-ray emitters from Fukushima detected in New York State

An air-sampling network that operates continuously as part of New York State’s environmental surveillance program collected radionuclides emitted as a result of the Fukushima nuclear accident. Samples were collected, typically for 7 days each, by drawing ~600 m³ of air through a particulate-collecting filter followed in series by a canister containing activated charcoal. Additional air sampling was implemented at ~3-day intervals at two locations. Gamma-ray spectroscopy was used to confirm the detection of ¹³¹I, ¹³⁷Cs, ¹³⁴Cs, and ⁷Be in the particulate phase at all sites, with maximum concentrations near 1,260, 160, 160, and 5,200 μBq/m³, respectively. Gas-phase ¹³¹I, collected on activated charcoal, exhibited a maximum concentration of 3,400 μBq/m³ at the sites. Assessment of radionuclide levels in the air samples suggests that there were minimal health impacts from the airborne radionuclides as the activities contributed an insignificant amount to the annual human dose.     

Density functional theory studies of interactions of ruthenium-arene complexes with base pair steps

Density functional theory (DFT) calculations have been performed to determine the strength and geometry of intermolecular interactions of "piano-stool" ruthenium arene complexes, which show potential as anticancer treatments. Model complexes with methane and benzene indicate that the coordinated arene has C-H···π acceptor ability similar to that of free benzene, whereas this arene acts as a much stronger C-H donor or partner in π-stacking than free benzene. The source of these enhanced interactions is identified as a combination of electrostatic and dispersion effects. Complexes of Ru-arene complexes with base-pair step fragments of DNA, in which the arene has the potential to act as an intercalator, have also been investigated. Binding energies are found to be sensitive to the size and nature of the arene, with larger and more flexible arenes having stronger binding. π-stacking and C-H···π interactions between arene and DNA bases and hydrogen bonds from coordinated N-H to DNA oxygen atoms, as well as covalent Ru-N bonding, contribute to the overall binding. The effect of complexation on DNA structure is also examined, with larger rise and more negative slide values than canonical B-DNA observed in all cases.