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We present a combined experimental and theoretical study of the ultrafast transient absorption spectroscopy results of a {Ni2 Dy2 }-compound in DMF, which can be considered as a prototypic molecule for single molecule magnets. We apply state-of-the-art ab initio quantum chemistry to quantitatively describe the optical properties of an inorganic complex system comprising ten atoms to form the chromophoric unit, which is further stabilized by surrounding ligands. Two different basis sets are used for the calculations to specifically identify two dominant peaks in the ground state. Furthermore, we theoretically propagate the compound's correlated many-body wavefunction under the influence of a laser pulse as well as relaxation processes and compare against the time-resolved absorption spectra. The experimental data can be described with a time constant of several hundreds of femtoseconds attributed to vibrational relaxation and trapping into states localized within the band gap. A second time constant is ascribed to the excited state while trap states show lifetimes on a longer timescale. The theoretical propagation is performed with the density-matrix formalism and the Lindblad superoperator, which couples the system to a thermal bath, allowing us to extract relaxation times from first principles.

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We apply X-ray magnetic circular dichroism to study the internal magnetic structure of two very promising star shaped macrocyclic complexes with a CuII3TbIII core. These complexes are rare examples prepared with a macrocyclic ligand that show indications of SMM (Single Molecule Magnet) behavior, and they differ only in ring size: one has a propylene linked macrocycle, [CuII3TbIII(LPr)(NO3)2(MeOH)(H2O)2](NO3)·3H2O (nickname: Cu3Tb(LPr)), and the other has the butylene linked analogue, [CuII3TbIII(LBu)(NO3)2(MeOH)(H2O)](NO3)·3H2O (nickname: Cu3Tb(LBu)). We analyze the orbital and spin contributions to the Cu and Tb ions quantitatively by applying the spin and orbital sum rules concerning the L2 (M4)/L3 (M5) edges. In combination with appropriate ligand field simulations, we demonstrate that the Tb(iii) ions contribute with high orbital magnetic moments to the magnetic anisotropy, whereas the ligand field determines the easy axis of magnetization. Furthermore, we confirm that the Cu(ii) ions in both molecules are in a divalent valence state, the magnetic moments of the three Cu ions appear to be canted due to 3d-3d intramolecular magnetic interactions. For Cu3Tb(LPr), the corresponding element specific magnetization loops reflect that the Cu(ii) contribution to the overall magnetic picture becomes more important as the temperature is lowered. This implies a low value for the 3d-4f coupling.

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A W-band single-crystal EPR study has been performed on a molecular cluster comprising 19 iron(III) ions bridged by oxo- hydroxide ions, Fe(19), in order to investigate magnetic nanosystems with a behavior in between the one of Magnetic NanoParticles (MNP) and that of Single Molecule Magnets (SMM). The Fe(19) has a disk-like shape: a planar Fe(7) core with a brucite (Mg(OH)(2)) structure enclosed in a "shell" of 12 Fe(III) ions. EPR and magnetic measurements revealed an S = 35/2 ground state with an S = 33/2 excited state lying ∼ 8 K above. The presence of other low-lying excited states was also envisaged. Rhombic Zero Field Splitting (ZFS) tensors were determined, the easy axes lying in the Fe(19) plane for both the multiplets. At particular temperatures and orientations, a partially resolved fine structure could be observed which could not be distinguished in powder spectra, due to orientation disorder. The similarities of the EPR behavior of Fe(19) and MNP, together with the accuracy of single crystal analysis, helped to shed light on spectral features observed in MNP spectra, that is a sharp line at g = 2 and a low intensity transition at g = 4. Moreover, a theoretical analysis has been used to estimate the contribution to the total magnetic anisotropy of core and surface; this latter is crucial in determining the easy axis-type anisotropy, alike that of MNP surface.

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We report magnetization and neutron scattering measurements down to 60 mK on a new family of Fe based kagome antiferromagnets, in which a strong local spin anisotropy combined with a low exchange path network connectivity lead to domain walls intersecting the kagome planes through strings of free spins. These produce unfamiliar slow spin dynamics in the ordered phase, evolving from exchange-released spin flips towards a cooperative behavior on decreasing the temperature, probably due to the onset of long-range dipolar interaction. A domain structure of independent magnetic grains is obtained that could be generic to other frustrated magnets.

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The glycosaminoglycan (GAG) family of linear sulphated polysaccharides are involved in most regulatory processes in the extracellular matrix of higher organisms. The relationship between GAG substitution pattern and activity, however, remains unclear and experimental evidence suggests that subtle conformational factors play an important role. The difficulty of modelling these complex charged molecules shifts the burden of investigation towards experimental techniques. Recent advances in complementary physical-chemical, particularly spectroscopy-based approaches are reviewed, together with methods for analysing the resulting complex data. The prospects for combining some of these approaches and fitting them into the wider context of interactions, are also discussed.

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The synthesis and characterisation of a series of novel complexes of type [((tmeda)M-OC(O)-fc-(micro-CO(2)))(2)(micro-H(2)O)] (M = Co, ; M = Ni, ), zwitter-ionic [((pmdta)(H(2)O)Cu(+)-OC(O)-fc-CO(2)(-))(CH(3)OH)] (), and coordination polymer [(tmeda)Cu((OC(O))(2)fc)](n) () (fc = ferrocene-1,1'-diyl, (eta(5)-C(5)H(4))(2)Fe; tmeda = N,N,N',N'-tetramethylethylenediamine; pmdta = 1,1,4,7,7-N,N,N',N'',N''-pentamethyldiethylenetriamine) composed of ferrocene dicarboxylates and [(tmeda)/(pmdta)M](2+) entities is reported. These complexes could be prepared from [M(NO(3))(2)(tmeda)] (M = Co, ; M = Ni, ; M = Cu, ) and [Cu(NO(3))(2)(pmdta)] (), respectively, with stoichiometric amounts of 1,1'-ferrocene dicarboxylic acid () in presence of [n-Bu(4)N]OH-H(2)O. The molecular structures of , , , and in the solid state have been determined by single-crystal X-ray structure analysis. Electrochemical and UV-vis-NIR spectroscopic studies of these complexes are discussed in terms of electronic communication between the redox-active transition metals. In addition, the magnetic properties of and have been studied by susceptibility measurements vs. temperature. In complex , the two cobalt(ii) ions are antiferromagnetically coupled, while in the Ni-Ni coupling is ferromagnetic with J approximately +2.2(1) cm(-1).

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Using numerical optimization algorithm, non-periodic Mo/Si, Mo/Be, and Ni/C broad angular multilayer analyzers have been designed. At the wavelength of 13 nm and the angular range of 45~49 degrees , the Mo/Si and Mo/Be multilayer can provide the plateau s-reflectivity of 65% and 45%, respectively. At 5.7 nm, the s-reflectivity of Ni/C multilayer is 16% in the 44~46 degrees range. The non-periodic Mo/Si broad angular multilayer was also fabricated using DC magnetron sputtering, and characterized using the soft X-ray polarimeter at BESSY. The s-reflectivity is higher than 45.6% over the angular range of 45~49 degrees at 13 nm, where, the degree of polarization is more than 99.98%.

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Spontaneous migrating contractions have been described in the circular muscle of the isolated mouse colon and terminal ileum, however, spontaneous events equivalent to these have not been reported in the longitudinal muscle. The longitudinal muscle shortenings in the colon and ileum, which are of similar form, frequency and pharmacology to the circular muscle colonic and ileal migrating motor complexes (CMMCs and IMMCs), are recorded in the present study. The spontaneous ileal and colonic longitudinal muscle shortenings appear to be neurally organized as they are abolished by tetrodotoxin (1 micro mol L-1), hexamethonium (500 micro mol L-1) and morphine (1 micro mol L-1). Endogenously released nitric oxide slowed the frequency of spontaneous ileal and colonic longitudinal muscle shortenings and 5-hydroxytryptamine increased their frequency. Hyoscine (1 micro mol L-1) abolished longitudinal shortenings in the ileum and reduced the amplitude of longitudinal shortening by approximately 44% in the colon. Shortenings were effectively abolished by nifedipine (1 micro mol L-1). Surgical sectioning of the colon identified that each region of the colon contracted longitudinally in an independent fashion; the distal colon contracted to the greatest amplitude and lowest frequency. The longitudinal preparation is suitable to initially assess the actions of novel pharmacological agents on spontaneous, neurally coordinated, CMMCs and IMMCs in emptied isolated murine intestines.

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This study has used mechanical, together with pressure/volume recordings or electrophysiological recordings, to investigate the spontaneous activity in isolated preparations of mouse colon. In the former preparations, when not distended with fluid, spontaneous colonic migrating motor complexes (CMMCs) were observed using isotonic transducers. When the colons were distended with fluid, CMMCs continued at an increased frequency and in addition were associated temporally, with rises in intraluminal pressure and pulses of distally ejected fluid. 5-Hydroxytryptamine (1 micro mol L-1) or NG-nitro-l-arginine (100 micro mol L-1) increased the frequency of propulsive activity and this activity was abolished by hexamethonium (500 micro mol L-1). In a second preparation, myoelectric complexes recorded from circular muscle cells in colons using intracellular microelectrodes, were found to correlate in frequency and phase with CMMCs. The experiments indicate that CMMCs are intimately related to pressure waves in the fluid-filled viscus and the muscle membrane potential changes that have been recorded during myoelectric complexes are likely to be analogous to those occurring during fluid-filled propulsive activity.

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The mechanisms that underlie the propagation of contractions along the colon are uncertain. We have examined whether spontaneous colonic migrating motor complexes (CMMCs) migrate through a region of muscle paralysis, or through a region where neural transmission was disrupted in the isolated mouse colon. Mouse colon was mounted in a separately perfused three-compartment organ bath and recordings of circular muscle tension were made. Drug application was restricted to the middle compartment. Application of nifedipine (1 micromol L(-1)), an l-type calcium channel antagonist, reduced the contraction amplitude by approximately 94%, without affecting the form of contractions in the proximal and distal compartments. Moreover, CMMCs appeared to remain temporally related in all compartments. In contrast, interruption of neural transmission in the middle compartment by either tetrodotoxin (1.6 micromol L(-1)), hexamethonium (500 micromol L(-1)) or a low-calcium, high-magnesium solution abolished CMMCs in this compartment; contractions recorded in the proximal and distal compartments became slower in frequency and were no longer synchronized. The experiments suggest that there may be more than one 'pacemaker' generating spontaneous CMMCs and that CMMCs can migrate through a region where there is minimal tension generation, but not through a region where neural integrity has been compromised.

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1. Intracellular microelectrodes were used to record spontaneous and evoked inhibitory junction potentials (IJP) from the circular muscle layer of the mid-distal region of the mouse isolated colon in the presence of nifedipine (1 micromol/L) and hyoscine (1 micromol/L). 2. The length of the tissue preparation (> 1 cm) or the presence of the mucosa had no effect on the frequency of spontaneous IJP. 3. Hexamethonium (500 micromol/L) reduced the frequency of spontaneous IJP to approximately 70% of the control frequency, whereas D-tubocurarine (280 micromol/L) reduced the frequency to approximately 17% of control. Apamin (250 nmol/L) abolished all spontaneous IJP activity. 4. The greater inhibition of spontaneous IJP in the presence of D-tubocurarine compared with hexamethonium is discussed as a possible 'apamin-like' effect. 5. Although electrically evoked IJP (single pulse at 15 V, 0.6 msec) were not significantly affected by hexamethonium, D-tubocurarine and apamin reduced the amplitude of evoked IJP to approximately 65 and 50% of control, respectively. 6. These results suggest that the properties of spontaneous IJP cannot be inferred by a study of evoked IJP alone.

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Spontaneous colonic migrating motor complexes (CMMCs) were recorded from circular muscle at three sites along the isolated mouse colon. The interval between CMMCs was decreased from approximately 3 min in control solution, by approximately 55% in a nitric oxide synthase (NOS) inhibitor, N-nitro-L-arginine (L-NNA; 100 micromol L-1). This was associated with a shift in migration direction of CMMCs, such that CMMCs migrated in an oral direction. Application of the endogenous substrate for NOS, L-arginine, at a low concentration used to mimic plasma concentration (134 micromol L-1), or a high concentration (5 mmol L-1) suppressed CMMCs (for at least 15 min) which were replaced by high frequency (10-15 min-1), short duration (half width approximately 1.5 s) contractions of variable amplitudes (largest in the proximal region) until CMMCs resumed. CMMCs remained in the presence of D-arginine (134 micromol L-1 and 5 mmol L-1). Apamin (250 nmol L-1) did not alter the interval between CMMCs, however, additional nonmigrating contractions were observed between the CMMCs in the distal region. In addition to its effects on smooth muscle tone, NO, but not apamin-sensitive channels, plays an important role in suppressing the frequency of migrating contractions in the isolated mouse colon. Consideration should be given to the inclusion of L-arginine, in in vitro experiments where there may be spontaneous activity in NOS containing neurones.

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Hydrothermal reaction of iron(III) chloride, barium chloride and sodium oxalate in a narrow stoichiometry range produces the title compound Ba4(C2O4)Cl2[[Fe(C2O4)(OH)]4] (1). This new iron(II) oxalate crystallises in the tetragonal space group P42/mnm: a = 13.811(3), c = 7.026(2) A. The structure consists of parallel chains of mu2-hydroxy-bridged iron(II) ions. These are connected by bridging oxalates to form an anionic framework with large channels that contain the remaining barium, chloride and oxalate counter ions. Magnetisation studies on an oriented single crystal of 1 revealed a magnetic phase transition at 32 K and a strong easy-plane anisotropy at all temperatures. Above Tc the compound behaves as an S = 2XY antiferromagnetic chain, showing a broad maximum in the susceptibility at about 70 K. We determined the intrachain coupling J and the interchain coupling J' to be -7 cm(-1) and +0.4 cm(-1), respectively. The low-temperature phase is an ordered antiferromagnetic state. Zero- and longitudinal-field muon spin-rotation/relaxation studies support this interpretation; below Tc oscillations in the muon spin-autocorrelation function are observed giving unambiguous evidence for a non-zero sublattice magnetisation and proof of a long-range magnetically ordered state.

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Chemical or electrochemical reduction of the 1,4,7-trithiacyclononane (9S3) complexes [MII(9S3)2][BF4]2 (M = Re (3a) or Tc (3b)) results in instantaneous C-S bond cleavage to yield ethene and the stable MIII thiolate complexes [MIII(9S3)L][BF4] (M = Re (4a) or Tc (4b), L = SCH2CH2SCH2CH2S). Compounds 4 have been characterized by 1H NMR spectroscopy, and the pseudo-octahedral geometry of 4b has been confirmed by X-ray crystallography. Upon electrochemical reduction 4a loses ethene, while 4b can be reversibly reduced to [TcII(9S3)L], which is then further reduced to Tc(I) with loss of ethene. Successive ethene loss is observed in the mass spectra of compounds 3 and 4. The radiosynthesis of 4a with 188Re can be comfortably completed within 10 min starting with 188ReO4- from a 188W/188Re generator, with a radiochemical yield in excess of 90%, and thus represents a practical approach to the preparation of stable 188Re (and 99mTc) thioether complex derivatives/conjugates for clinical use. Crystal data: 4b, C10H20S6Tc, orthorhombic Pbca, a = 12.233(2) A, b = 14.341(2) A, c = 20.726(3) A, Z = 8.

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A 63.9 kDa periplasmic tetrahaem flavocytochrome c(3), designated Ifc(3), was found to be expressed in Shewanella frigidimarina NCIMB400 grown anaerobically with ferric citrate or ferric pyrophosphate as the sole terminal electron acceptor, but not in anaerobic cultures of the bacterium with other respiratory substrates. Ifc(3) was purified to homogeneity and revealed by biochemical, spectroscopic and primary structure analyses to contain four low-spin bis-His-ligated c(3)-haems, with midpoint reduction potentials of -73, -141, -174 and -259 mV. A low-potential flavin was present in the form of non-covalently bound FAD; the protein possessed a unidirectional fumarate reductase activity. Disruption of the chromosomal gene encoding Ifc(3), ifcA, did not lead to a significant change in the rate of Fe(3+) reduction in batch culture. However, during such growth the Ifc(3)-deficient mutant produced both a 35 kDa periplasmic c-type cytochrome and a 45 kDa membrane-associated c-type cytochrome at markedly higher levels than did the parent strain. Nucleotide sequencing data from directly upstream of ifcA indicated the presence of an open reading frame encoding a putative outer-membrane beta-barrel protein of 324 amino acid residues.

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A microorganism which reduces Fe(III) during the fermentation of glucose was isolated from freshwater sediment. The Fe(III) was supplied to enrichment cultures as a soluble complex with the bidentate ligand maltol (3-hydroxy-2-methyl-4-pyrone). Advantages that were afforded by the use of Fe(III)(maltol)3 over previously published methods included negation of the requirement for assays of Fe(II) formation. Because Fe(III)(maltol)3 has a characteristic deep red colour, Fe(III) reduction could be quantified spectrophotometrically by monitoring the disappearance of the complex in liquid cultures. Furthermore, Fe(III) reduction on agar plates containing the complex was apparent by zones of decolourisation around the bacterial colonies. 16S rRNA gene sequencing indicated the isolate to be a strain of Clostridium beijerinckii. Growth experiments were performed on the isolate in batch cultures with varying concentrations of Fe(III) citrate and 50 mM glucose. Increasing the level of Fe(III) citrate present was found to alter the fermentation balance, with less acidic products being formed. The presence of Fe(III) led to increases in the growth rate and growth yield, which were both approximately doubled when the supply of the cation reached 25 mM. A NAD(P)H-dependent Fe(III) reductase activity was localised to the bacterial membrane and found not to be sensitive to respiratory inhibitors. Taken together, these data suggest that dissimilatory Fe(III) reduction by the isolate provides a means of utilising the cation as an electron sink, thus facilitating pyridine nucleotide to be recycled during fermentative metabolism.

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The fumarate reductase of Escherichia coli and other bacteria is a membrane-bound enzyme consisting of four subunits. A soluble periplasmic 64 kDa tetrahaem flavocytochrome c3 from Shewanella frigidimarina NCIMB400 which possesses a catalytic fumarate reductase activity has been crystallized. The crystals belong to space group P212121 with unit-cell parameters a = 72.4, b = 110.1, c = 230.2 A. Assuming a molecular dimer in the asymmetric unit, the crystals contain 65% solvent and, when cryocooled to 100 K, the crystals diffract to at least 3.0 A resolution. The crystals, however, display an inherent lack of isomorphism and the plausibility of a MAD phasing experiment has therefore been investigated by measuring the iron K absorption edge from a single crystal.

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A rare example of a molecular species prepared by solvothermal synthesis is the macrocyclic cobalt phosphonate/carboxylate 1, whose structure is shown schematically. At low temperatures this compound displays spontaneous magnetization due to canted antiferromagnetic ordering, which is very unusual for a discrete molecular material.

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