The electron spin resonance spectrum of the trichloromethyl radical in solution

The equation of state PV = - a/V + RT(1 - y)^-4 is shown to be considerably better at high densities than van der Waals' equation PV = - a/V + RT(1 - 4y)^-1 and to be equal in accuracy to two other slightly more complicated equations for PV.     

The anionic coordination polymer {K2[PtII2AgI8(2,2′‐bipyridine)2(O2CCF3)14]}n

The trimetallic compound catena‐poly[dipotassium(I) [bis(2,2′‐bipyridine)di‐μ₃‐trifluoroacetato‐dodeca‐μ₂‐trifluoroacetato‐diplatinum(II)octasilver(I)]], K₂[Pt₂Ag₈(C₂F₃O₂)₁₄(C₁₀H₈N₂)₂], forms an extended structure in the solid state. Electrostatic interactions involving the K⁺ ions play a key role in the formation of the extended structure in three dimensions. The Ag^I ions form one‐dimensional coordination polymers, with alternating Ag₂ and Ag₆ units linked by CF₃CO₂⁻ ligands. Pt...Pt interactions perpendicular to the one‐dimensional polymerization axis provide another element of long‐range order, and electrostatic interactions with K⁺ ions provide connectivity between adjacent polymeric structures.     

Bioanalytical applications of SERS (surface-enhanced Raman spectroscopy)

Surface-enhanced Raman scattering (SERS) is a powerful technique for analyzing biological samples as it can rapidly and nondestructively provide chemical and, in some cases, structural information about molecules in aqueous environments. In the Raman scattering process, both visible and near-infrared (NIR) wavelengths of light can be used to induce polarization of Raman-active molecules, leading to inelastic light scattering that yields specific molecular vibrational information. The development of surface enhancement has enabled Raman scattering to be an effective tool for qualitative as well as quantitative measurements with high sensitivity and specificity. Recent advances have led to many novel applications of SERS for biological analyses, resulting in new insights for biochemistry and molecular biology, the detection of biological warfare agents, and medical diagnostics for cancer, diabetes, and other diseases. This trend article highlights many of these recent investigations and provides a brief outlook in order to assess possible future directions of SERS as a bioanalytical tool.     

Click fleximers: a modular approach to purine base-expanded ribonucleoside analogues

The synthesis of nucleoside analogues incorporating 4-(5-pyrimidinyl)-1,2,3-triazole aglycons as expanded purine nucleobase mimics were accessed using the copper-catalyzed azide-alkyne Huisgen cycloaddition between a ribosyl azide and 5-alkynylpyrimidines. Depending on the nature of the alkyne employed, other nucleoside analogues that possess fluorescence or potential metal-binding properties were prepared. Computational studies were undertaken on the purine analogues and indicate that the heterocycles of the unfused nucleobase prefer a coplanar arrangement and the anti-glycosidic conformer is favoured in most instances.     

3d-Metal derivatives of the [Cu(I)(SO3)4]7- ion: structure and magnetism

The Cu(SO(3))(4)(7-) anion, which consists of a tetrahedrally coordinated Cu(I) centre coordinated to four sulfur atoms, is able to act as a multidentate ligand in discrete and infinite supramolecular species. The slow oxidation of an aqueous solution of Na(7)Cu(SO(3))(4) yields a mixed oxidation state, 2D network of composition Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O. The addition of Cu(II) and 2,2'-bipyridine to an aqueous Na(7)Cu(SO(3))(4) solution leads to the formation of a pentanuclear complex of composition {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(+); a combination of hydrogen bonding and π-π stacking interactions leads to the generation of infinite parallel channels that are occupied by disordered nitrate anions and water molecules. A pair of Cu(SO(3))(4)(7-) anions each act as a tridentate ligand towards a single Mn(II) centre when Mn(II) ions are combined with an excess of Cu(SO(3))(4)(7-). An anionic pentanuclear complex of composition {[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)} is formed when Fe(II) is added to a Cu(+)/SO(3)(2-) solution. Hydrated ferrous [Fe(H(2)O)(6)(2+)] and sodium ions act as counterions for the complexes and are responsible for the formation of an extensive hydrogen bond network within the crystal. Magnetic susceptibility studies over the temperature range 2-300 K show that weak ferromagnetic coupling occurs within the Cu(II) containing chains of Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O, while zero coupling exists in the pentanuclear cluster {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(NO(3))·H(2)O. Weak Mn(II)-O-S-O-Mn(II) antiferromagnetic coupling occurs in Na(H(2)O)(6){[Cu(I)(SO(3))(4)][Mn(II)(H(2)O)(2)](3)}, the latter formed when Mn was in excess during synthesis. The compound, Na(3)(H(2)O)(6)[Fe(II)(H(2)O)(6)](2){[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)}·H(2)O, contained trace magnetic impurities that affected the expected magnetic behaviour.     

Hydrogen adsorption in the metal-organic frameworks Fe2(dobdc) and Fe2(O2)(dobdc)

The hydrogen storage properties of Fe(2)(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and an oxidized analog, Fe(2)(O(2))(dobdc), have been examined using several complementary techniques, including low-pressure gas adsorption, neutron powder diffraction, and inelastic neutron scattering. These two metal-organic frameworks, which possess one-dimensional hexagonal channels decorated with unsaturated iron coordination sites, exhibit high initial isosteric heats of adsorption of -9.7(1) and -10.0(1) kJ mol(-1), respectively. Neutron powder diffraction has allowed the identification of three D(2) binding sites within the two frameworks, with the closest contacts corresponding to Fe-D(2) separations of 2.47(3) and 2.53(5) ?, respectively. Inelastic neutron scattering spectra, obtained from p-H(2) (para-H(2)) and D(2)-p-H(2) mixtures adsorbed in Fe(2)(dobdc), reveal weak interactions between two neighboring adsorption sites, a finding that is in opposition to a previous report of possible 'pairing' between neighboring H(2) molecules.     

Computation of deuterium isotope perturbation of 13C NMR chemical shifts of alkanes: a local mode zero-point level approach

Replacement of H by D perturbs the (13)C NMR chemical shifts of an alkane molecule. This effect is largest for the carbon to which the D is attached, diminishing rapidly with intervening bonds. The effect is sensitive to stereochemistry and is large enough to be measured reliably. A simple model based on the ground (zero point) vibrational level and treating only the C-H(D) degrees of freedom (local mode approach) is presented. The change in CH bond length with H/D substitution as well as the reduction in the range of the zero-point level probability distribution for the stretch and both bend degrees of freedom are computed. The (13)C NMR chemical shifts are computed with variation in these three degrees of freedom, and the results are averaged with respect to the H and D distribution functions. The resulting differences in the zero-point averaged chemical shifts are compared with experimental values of the H/D shifts for a series of cycloalkanes, norbornane, adamantane, and protoadamantane. Agreement is generally very good. The remaining differences are discussed. The proton spectrum of cyclohexane- is revisited and updated with improved agreement with experiment.     

Laser-produced X-ray sources

A formidable array of advanced laser systems are emerging that produce extreme states of light and matter. By irradiating solid and gaseous targets with lasers of increasing energy densities, new physical regimes of radiation effects are being explored for the first time in controlled laboratory settings. One result that is being accomplished or pursued using a variety of techniques, is the realization of novel sources of X-rays with unprecedented characteristics and light–matter interactions, the mechanisms of which are in many cases still being elucidated. Examples include the megajoule class of laser-produced plasmas designed in pursuit of alternative-energy and security applications and the petawatt class of lasers used for fast ignition and X-ray radiographic applications such as medical imaging and real-time imaging of plasma hydrodynamics. As these technologies mature, increased emphasis will need to be placed on advanced instrumentation and diagnostic metrology to characterize the spectra, time structure, and absolute brightness of X-rays emitted by these unconventional sources. Such customized and absolutely calibrated measurement tools will serve as an enabling technology that can help in assessing the overall system performance and progress, as well as identification of the underlying interaction mechanisms of interest to basic and applied strong-field and high-energy-density science.     

In situ synthesis of trisubstituted methanol ligands and their potential as one-pot generators of cubane-like metal complexes

Two different one pot routes to a variety of metal cubane compounds are reported; one route is based on an in situ benzilic acid type rearrangement and the other involves in situ nucleophilic attack at a ketone. Diketosuccinic acid in basic solution in the presence of certain divalent metal ions undergoes a benzilic acid type rearrangement to generate the carbon oxyanion, C(CO(2) (-))(3)O(-), which serves as a cubane-forming bridging ligand in a series of octanuclear complexes of composition [M(8){C(CO(2))(3)O}(4)](H(2)O)(12) (M=Mg, Mn, Fe, Co, Ni, Zn). At the heart of each of these highly symmetrical aggregates is an M(4)O(4) cubane core, each oxygen component of which is provided by the alkoxo centre of a C(CO(2) (-))(3)O(-) ligand. Reaction of 2,2'-pyridil, (2-C(5)H(4)N)COCO(2-C(5)H(4)N), and calcium nitrate in basic alcoholic solution, which proceeds by a similar benzilic acid type rearrangement, gives the cubane compounds, [Ca(4)L(4)(NO(3))(4)] in which L=(2-C(5)H(4)N)(2)C(COOR)O(-) (R=Me or Et). Nucleophilic attack by bisulfite ion at the carbonyl carbon atom of 2,2'-dipyridyl ketone in the presence of certain divalent metals generates the electrically neutral complexes, [{(C(5)H(4)N)(2)SO(3)C(OH)}(2)M] (M=Mn, Fe, Co, Ni, Zn and Cd). Cubane-like complexes [M(4){(C(5)H(4)N)(2)SO(3)C(O)}(4)] (M=Zn, Mn) can be obtained directly from 2,2'-dipyridyl ketone in one-pot reaction systems (sealed tube, 120 degrees C) if a base as weak as acetate ion is present to deprotonate the OH group of the initial [(C(5)H(4)N)(2)SO(3)C(OH)](-) bisulfite addition compound; the [(C(5)H(4)N)(2)SO(3)C(O)](2-) ligand in this case plays the same cubane-forming role as the ligands C(COO(-))(3)O(-) and (2-C(5)H(4)N)(2)C(COOR)O(-) above. When excess sodium sulfite is used in similar one-pot reaction mixtures, the monoanionic complexes, [M(3)Na{(C(5)H(4)N)(2)SO(3)C(O)}(4)](-) (M=Zn, Mn, Co) with an M(3)NaO(4) cubane core, are formed directly from 2,2'-dipyridyl ketone.     

Microfluidic approach for rapid multicomponent interfacial tensiometry

We report a microfluidic instrument to rapidly measure the interfacial tension of multi-component immiscible liquids. The measurement principle rests upon the deformation and retraction dynamics of drops under extensional flow and was implemented for the first time in microfluidics (S. D. Hudson et al., Appl. Phys. Lett., 2005, 87, 081905 (ref. )). Here we describe in detail the instrument design and physics and extend this principle to investigate multicomponent mixtures, specifically two-component drops of adjustable composition. This approach provides fast real-time sigma measurements (on the order of 1 s), the possibility of rapidly adjusting drop composition and utilizes small sample volumes (approximately 10 microL). The tensiometer operation is illustrated with water drops and binary drops (water/ethylene glycol mixtures) in silicone oils. The technique should be particularly valuable for high-throughput characterization of complex fluids.