Anionic clusters with a homoatomic [Ge₉] core are species with Ge atoms in low oxidation states. In this study their reaction with early-transition-metal complexes was investigated. We report the syntheses of Ti(III) complexes of silylated [Ge₉] Zintl clusters, which are rare examples of molecular complexes with Ge-Ti interactions. The neutral species [Cp₂(MeCN)Ti(η¹-Ge₉{Si(TMS)₃}₃)] (<b>1</b>) was obtained by the reaction of K[Ge₉{Si(TMS)₃}₃] with [Cp₂TiCl]₂ in toluene as dark orange crystals, whereas the reaction of K₂[Ge₉{Si(TMS)₃}₂] with [Cp₂TiCl]₂ in thf and subsequent recrystallization from toluene resulted in dark green crystals of K₃[Cp₂Ti(η¹-Ge₉{Si(TMS)₃}₂)₂] (<b>2</b>). Compound <b>2</b> contains the trianion [Cp₂Ti(η¹-Ge₉{Si(TMS)₃}₂)₂]^3- (<b>2a</b>), which can be described either as a [Cp₂Ti]⁺-bridged [Ge₉{Si(TMS)₃}₂]^2- dimer or as a heavily distorted tetrahedral Ti(III) complex bearing two germanide cluster ligands. Both compounds display donor-acceptor interactions between single Ge vertex atoms of the [Ge₉] clusters and Ti(III). Compounds <b>1</b> and <b>2</b> were characterized by single-crystal X-ray diffraction, EPR spectroscopy, and elemental analysis.

The title compounds, mu-oxido-bis[(tert-butylselenolato)bis(eta(5)-cyclopentadienyl)niobium(IV)] toluene solvate, [Nb(2)(C(5)H(5))(4)(C(4)H(9)Se)(2)O] x C(7)H(8), and mu-selenido-bis[(tert-butylselenolato)bis(eta(5)-cyclopentadienyl)niobium(IV)], [Nb(2)(C(5)H(5))(4)(C(4)H(9)Se)(2)Se], consist of niobium(IV) centres each bonded to two eta(5)-coordinated cyclopentadienyl groups and one tert-butylselenolate ligand and are the first organometallic niobium selenolates to be structurally characterized. A bridging oxide or selenide completes the niobium coordination spheres of the discrete dinuclear molecules. In the oxide, the O atom lies on an inversion centre, resulting in a linear Nb-O-Nb linkage, whereas the selenide has a bent bridging group [Nb-Se-Nb = 139.76 (2) degrees]. The difference is attributable to strong pi bonding in the oxide case, although the effects on the Nb-C and Nb-Se(t)Bu bond lengths are small.

BACKGROUND

The effect of different proportions of recast dental alloys on the color of overlying opaque porcelain (OP) is unknown.

OBJECTIVE

The purpose of this study was to compare the color of OP applied on 2 different proportions (50% and 100%) of recast alloys with the color of commercially available shade tabs of OP.

METHODS

Six different metal alloy systems (2 base: Metalloy CC, Cr-Co [B-MCC]; Heraenium NA, Ni-Cr [B-HNA]; 3 noble: Cerapall 2, Pd-Au [N-CP2]; Triumph, Pd-Ag [N-T]; V-Deltaloy, Au-Pd [N-VD]; and 1 high-noble: V-Gnathos Plus, Au-Pt [HN-GP]) were selected for the fabrication of disk-shaped specimens (10 mm in diameter, 1 mm in thickness). Each alloy was divided into 2 subgroups: 50% new alloy with 50% recast alloy (n=3) and 100% recast alloy (n=3). OP (B1) was applied (0.1 mm) to all specimens. The color coordinates (L*, a*, b*) of each specimen and the corresponding commercially available OP shade tab (control) were measured with a spectroradiometer, and color differences between specimens and control group were calculated. Data were statistically analyzed (2-way ANOVA, Ryan-Einot-Gabriel-Welsch multiple range test, α=.05).

RESULTS

For each alloy, ΔL*(L(control)(-)L(recastalloy)) values for the 2 subgroups were not statistically different from each other. The Δa* and Δb* of different proportions of N-CP2, B-HNA, N-VD, and HN-GP were not statistically different within the alloys. However, the a* values of 100% recast N-T and B-MCC were significantly closer to the a* values of the control group, and the b* values of 50% recast B-MCC were significantly closer to the b* values of the control group (P<.05). Delta E(control-recast) alloy values for different proportions of alloys were not statistically different. However, color differences did not meet the criterion of clinical acceptability (ΔE=3.46).

CONCLUSIONS

According to the results of this study, the different proportions (50% and 100%) of recast alloys used have similar effects on the color of OP. Differences between the final color of OP on the recast alloys used and the color of OP shade guide tabs did not meet the criterion of clinical acceptability considered in this study.

Not the expected insertion into a S-S bond but rather substitution of one NR unit takes place in the reaction of [Cp2 Ti(CO)2 ] with cyclic tetrasulfurdiimides 1,4-S4 (NR)2 . The product obtained contains the novel ligand S4 NR and serves as precursor in the synthesis of small SN heterocycles not accessible before (see below).

Reaction of the 30-electron benzylidyne complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-CO)] with excess Ph2 SiH2 under visible-UV irradiation yields the silylene-bridged complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-SiPh2 )]. This compound undergoes selective oxidation with O2 to give the unsaturated complex [Mo2 Cp2 (μ-CPh)(μ-PCy2 )(μ-κ(1) :κ(1) -OSiPh2 )], which contains an unprecedented bridging diphenylsilanone ligand, as confirmed by X-ray diffraction analysis and DFT calculations. The bonding within the central Mo2 SiO ring of this complex approaches the extreme description of a dimetallacyclosiloxane according to the relevant solid-state bond lengths and theoretical calculations.

BACKGROUND

Age-related muscle loss is characterised by a progressing decrease in muscle mass, strength and function. Besides resistance training and physical activity, appropriate nutrition that is rich in protein, especially branched-chain amino acids, is very important to support training effects and positively influence the protein synthesis to degradation ratio.

OBJECTIVE

The purpose of this study was to evaluate the effect of a 12-week leucine-rich amino acid supplementation in combination with moderate training.

METHODS

Forty-eight healthy subjects exercised for 30 min three times per week and received either a leucine-rich amino acid supplementation or a placebo. Before and after supplementation, volunteers performed an exhaustive eccentric exercise protocol. Maximal concentric strength, muscle soreness, creatine kinase (CK), type II collagen collagenase cleavage neoepitope (C2C), C propeptide of type II procollagen (CP2) and safety assessments were performed before exercise and after 3, 24, 48 and 72 hours.

RESULTS

The supplementation with leucine resulted in reduced loss of strength at 0 and 3 hours after downhill walking compared with the placebo (p=0.0439). The reduction of C2C/CP2 ratio deflection was significantly increased (p=0.038) due to leucine compared with the placebo. The same tendency could be observed for the recovery phase. No significant supplement effects for muscle soreness and CK could be observed.

CONCLUSIONS

The principle findings show that leucine-rich amino acid supplementation can counteract the negative effects of eccentric exercise. The treatment resulted in a reduction of exercise-induced strength loss.

The recombinant phytochrome of the moss Ceratodon purpureus (CP2) expressed in Saccharomyces cerevisiae and reconstituted with phycocyanobilin (PCB) was investigated using fluorescence spectroscopy. The pigment had an emission maximum at 670 nm at low temperature (85 K) and at 667 nm at room temperature (RT) and an excitation maximum at 650-652 nm at 85 K (excitation spectra could not be measured at RT). Both spectra had a half-band width of approx. 30-35 nm at 85 K. The fluorescence intensity revealed a steep temperature dependence with an activation energy of fluorescence decay (Ea) of 5.9-6.4 and 12.6-14.7 kJ mol(-1) in the interval from 85 to 210 K and from 210 to 275 K, respectively. The photochemical properties of CP2/PCB were characterised by the extent of the red-induced (lambda(a) = 639 nm) Pr conversion into the first photoproduct lumi-R at 85 K (gamma1) of approximately 0.07 and into Pfr at RT (gamma2) of approximately 0.7. From these characteristics, CP2/PCB can be attributed to the Pr" photochemical type with gamma1 < or = 0.05, which comprises the minor phyA fraction (phyA"), phyB, Adiantum phy1 and Synechocystis Cph1 in contrast to the major phyA' fraction (Pr' type with gamma1 = 0.5). Within the Pr" type, it is closer to phyA" than to phyB and Cph1.

OBJECTIVE

To investigate the anti-inflammatory activity of different fractions and glutinol (isolated compound), using nitric oxide synthase and cyclooxygenase (COX) inhibition as an indication of anti-inflammatory activity.

METHODS

Anti-inflammatory activity was evaluated using an in vitro assay determining the inhibition of the activity of pro-inflammatory enzyme model. Cyclooxygenases and inducible nitric oxide synthase are crucial enzymes involved in the pathogenesis of many chronic inflammatory conditions.

RESULTS

Sub-fraction F3.3 that was derived from n-hexane fraction of PA leaves significantly inhibited (P = 0.01) the catalytic activity of COX-2 (IC50 = 0.67 μg/mL) better than isolated compound, glutinol (IC50 = 1.22 μg/mL), compound 2 (CP2) (IC50 = 1.71 μg/mL) and sub-fraction F3.3.0 (IC50 = 1.30 μg/mL). A similar trend was observed in investigation of the inhibition of nitric oxide synthesis in RAW 264.7 cells by F3.3, glutinol, CP2 and F3.3.0. Inducible COX-2 and inducible nitric oxide synthase are among potent signalling enzymes that exacerbate inflammation.

CONCLUSIONS

Bioactive sub-fractions (F3.3 and F3.3.0) derived from the n-hexane fraction of PA had good anti-inflammatory activity, and the isolated compound, and glutinol may be useful as a template for the development of new anti-inflammatory drugs.

The tissue environment is exceptionally complex, with well-controlled biochemical communication occurring between similar and dissimilar cells, as well as, between these cells and local extracellular matrices (ECM). In order to build an artificial ECM that can directly affect regional cell populations, a designer system should allow for controlled degradation, molecular release, and reorganization as related to local cellular function. (RADA)4 self-assembling peptide (SAP) hydrogels are excellent candidates for precisely tuned ECMs, or nanoscaffolds, with several beneficial qualities. They are a class of materials with uncomplicated fabrication and potentially allow for a diverse set of release strategies for many types of bioactive ligands. Enzyme-induced degradation and release of peptide sequences, synthesized within the SAP for on-demand cell signalling, could prove impactful to a plethora of human health applications. However, the degradation products and their release kinetics from these nanoscaffolds may greatly affect the overall system. To address this, enzyme kinetics in self-assembled hydrogels were studied by tethering matrix metalloproteinase 2 (MMP-2) cleavable peptide substrates of differing activities to the C-terminus of (RADA)4. High and low activity sequences, GPQG+IASQ (CP1) and GPQG+PAGQ (CP2), were respectively chosen for tunable release. When incubated with 5 nM MMP-2, over 3 days, both CP1 and CP2 sequences showed product formation values of ~32 and ~9% of the original substrate, respectively. On-demand product formation was found to be dependent upon both SAP composition and enzyme concentrations, and could be tuned over the course of several days and weeks. Despite the fact that the self-assembling peptides are not directly cleavable by MMP-2, the CP1 and CP2 nanoscaffold morphology was visibly degraded by the protease. This degradation yielded a lower fractal dimensions for the matrix and suggested clearance of these materials may be possible over time.

During July 2008, sandy loam soil samples were collected near the rhizosphere of Kentucky bluegrass (Poa pratensis L.) and tall fescue (Festuca arundinacea Schreb.) at a depth of 15 to 20 cm from Caledonia Park, Toronto, Canada. Samples were suspended in water and nematodes were collected on sieves with 250- and 74-μm openings. Among the nematodes recovered were one species of Longidorus Micoletzky, 1922 (4) and one species of Trichodorus Cobb, 1913. The Trichodorus species (2), was identified as T. primitivus (de Man, 1880) Micoletzky, 1922, in which females have rod-like sclerotized pieces parallel to the vagina lumen, each with dimensions of 3.1 × 1.2 μm and at a distance of 2 to 3 μm from each other; and males have spicules with a wide nonoffset capitulum and very narrow blade, three ventromedian cervical papillae (CP), and three precloacal supplements with the anterior one at the level of the capitulum of retracted spicules. Males showed unusual variation in the position of CP2 (i.e., posterior to the onchiostyle region, except for one specimen with CP2 located within the posterior onchiostyle region, which is typical for the species). The morphometric data for nine males are: L, 665 to 805 μm; a, 23.0 to 27.5; b, 3.7 to 5.2; c, 46 to 56; onchiostyle, 47 to 52 μm; and spicules, 32.5 to 40.5 μm. Measurements for 13 females are: L, 630 to 775 μm; a, 20.5 to 24.8; b, 3.5 to 5.5; c, 75.5 to 158.5; and V, 54 to 61%. To our knowledge, this is the first report of T. primitivus in Canada. According to Chen et al. (1), the Longidorus species was identified as L. elongatus (de Man, 1876) Micoletzky, 1922 (3). The morphometric data for females (n = 13) are: L, 5.1 to 6.0 mm; a, 78.5 to 106.5; b, 11.5 to 13.5; c, 86.0 to 120.5; V, 45.5 to 53.0%; odontostyle, 79 to 91 μm; odontophore, 57.5 to 66.5 μm; and tail length, 44.5 to 59.0 μm. Males were not found. Four juvenile stages were identified. J1 (n = 2) with a body length of 1.1, 1.2 mm and replacement/functional odontostyle 59, 59/53.5, 54.5 μm, J2 (n = 2) with L: 1.7, 2.0 mm and replacement/functional odontostyle 62.5, 68.0/58.7 μm, 59.0, J3 (n = 2): L: 2.8, 3.0 mm and replacement/functional odontostyle 76.5, 77/66.5, 67.0 μm and J4 (n = 2) with L: 3.6, 3.8 mm and replacement/functional odontostyle 87.0, 90.5/75.0, 77.5 μm. Due to large morphometric overlap in Longidorus species identification, 2,472 bp of the near full-length 18S and the internal transcribed spacer 1 region of rDNA (Accession No. GU199044) were sequenced. The Blastn search of the partial 18S revealed 100% identity with a population of L. elongatus from Scotland (GenBank No. AY687992, 1,707 bp compared), 99% identity (3 bp difference, 1,707 bp compared) with a population of L. elongatus from Iran (EU503141) and 99% identity (4 bp difference, 1,707 bp compared) with a population of L. elongatus (AF036594, sample location unknown). A Blastn search of the 18S and ITS region revealed only 1 to 3 bp differences with two populations of L. elongatus from Switzerland (AJ549986 and AJ549987) and a population of L. elongatus (AF511417) from Scotland. These molecular data further confirmed the identity of the population from Canada to be L. elongatus. References: (1) Q. Chen et al. Fundam. Appl. Nematol. 20:15, 1997. (2) W. Decraemer. Kluwer Academic Publishers, Dordrecht, the Netherlands, 1995. (3) J. G. de Man. Tijdschr. Ned. Dierk. Ver. 2:78, 1876. (4) H. Micoletzky. Archiv. Naturgesch. 87:1, 1922.

Viral-based nanoplatforms rely on balancing the delicate array of virus properties to optimally achieve encapsidation of foreign materials with various potential objectives. We investigated the use of Maize rayado fino virus (MRFV)-virus-like particles (VLPs) as a multifunctional nanoplatform and their potential application as protein cages. MRFV-VLPs are composed of two serologically related, carboxy co-terminal coat proteins (CP1 and CP2) which are capable of self-assembling in Nicotiana benthamiana plants into 30nm particles with T=3 symmetry. The N-terminus of CP1 was targeted for genetic modification to exploit the driving forces for VLP assembly, packaging and retention of RNA in vivo and in vitro. The N-terminus of MRFV-CP1 contains a peptide sequence of 37 amino acids which has been predicted to have an alpha-helical structure, is rich in hydrophobic amino acids, facilitates CP-RNA interactions, and is not required for self-assembly. Amino acid substitutions were introduced in the 37 amino acid N-terminus by site-directed mutagenesis and the mutant VLPs produced in plants by a Potato virus X (PVX)-based vector were tested for particle stability and RNA encapsidation. All mutant CPs resulted in production of VLPs which encapsidated non-viral RNAs, including PVX genomic and subgenomic (sg) RNAs, 18S rRNA and cellular and viral mRNAs. In addition, MRFV-VLPs encapsidated GFP mRNA when was expressed in plant cells from the pGD vector. These results suggest that RNA packaging in MRFV-VLPs is predominantly driven by electrostatic interactions between the N-terminal 37 amino acid extension of CP1 and RNA, and that the overall species concentration of RNA in the cellular pool may determine the abundance and species of the RNAs packaged into the VLPs. Furthermore, RNA encapsidation is not required for VLPs stability, VLPs formed from MRFV-CP1 were stable at temperatures up to 70°C, and can be disassembled into CP monomers, which can then reassemble in vitro into complete VLPs either in the absence or presence of RNAs.

Ceruloplasmin (CP) is the major plasma antioxidant and copper transport protein. Monoclonal antibodies (mAbs) against human CP were produced and characterized. A total of five hybridoma cell lines were established (<em>CP2</em>, CP10, <em>CP2</em>0, <em>CP2</em>5, CP30). From the epitope mapping analysis, two subgroups of mAbs recognize different peptide fragments were identified. When the purified CP was incubated with the mAbs, the ferroxidase activity of CP was inhibited up to a maximum 57 %. Immunoblotting with various tissue homogenates indicated that all the mAbs specifically recognize a single protein band of 130 kDa. They also appear to be extensively cross-reactive among different mammalian including human and avian sources. These results demonstrated that only one type of immunologically similar CP is present in all of the mammalian tissues including human. The CP mAbs could be of great benefit to design the diagnostic kit for CP-related diseases such as Wilson's disease.

In the present work, we focus on the development of CePO₄-CeO₂ composite nanorods with peroxidase mimetic activity for the sensitive detection of hydrogen peroxide and glucose. The Ce³⁺/PO₄^3- molar ratio (CP10:1, CP5:1, CP2:1) in the hydrothermal reaction controlled the formation of pure CePO₄, CePO₄-CeO₂ composite nanozymes with different percentages of CeO₂, and its crystal structure. A higher Ce³⁺/PO₄^3- molar ratio (CP10:1 or CP5:1) was required to obtain CePO₄-CeO₂ composite nanostructure, while a lower Ce³⁺/PO₄^3- molar (CP2:1) ratio was sufficient to fabricate pure CePO₄ nanorods. In the presence of hydrogen peroxide, the prepared nanozymes catalyze the oxidation of chromogenic substrate 3,3',5,5'-tetramethylbenzidine (TMB). Steady state kinetic analysis based on the Michaelis-Menten model revealed that CP10:1 showed excellent affinity toward the TMB ( K_m = 0.236 mM and V_max = 8.78 × 10^-8 M s^-1) in comparison to the catalytic activity of CP5:1 and CP2:1 and horseradish peroxidase ( K_m = 0.434 mM and V_max = 10.0 × 10^-8 M s^-1). The superior peroxidase activity of CePO₄-CeO₂ composite nanozymes can be ascribed to the enhanced redox switching between Ce³⁺ ↔ Ce⁴⁺ sites from the CePO₄ and CeO₂ lattice, respectively. The colorimetric detection of hydrogen peroxide and glucose showed a linear response around 150 μM concentration with the limits of detection (LOD) of 2.9 and 4.1 μM, respectively.

Collagen is the main structural and most abundant protein in the human body, and it is routinely extracted and analysed in scientific archaeology. Its degree of preservation is, therefore, crucial and several approaches are used to determine it. Spectroscopic techniques provide a cost-effective, non-destructive method to investigate the molecular structure, especially when combined with multivariate statistics (chemometric approach). In this study, we used FTIR-ATR spectroscopy to characterise collagen extracted from skeletons recovered from necropoleis in NW Spain spanning from the Bronze Age to eighteenth century AD. Principal components analysis was performed on a selection of bands and structural equation models (SEM) were developed to relate the collagen quality indicators to collagen structural change. Four principal components represented: (i) Cp1, transformations of the backbone protein with a residual increase in proteoglycans; (ii) Cp2, protein transformations not accompanied by changes in proteoglycans abundance; (iii) Cp3, variations in aliphatic side chains and (iv) Cp4, absorption of the OH of carbohydrates and amide. Highly explanatory SEM models were obtained for the traditional collagen quality indicators (collagen yield, C, N, C:N), but no relationship was found between quality and δ¹³C and δ¹⁵N ratios. The observed decrease in C and N content and increase in C:N ratios is controlled by the degradation of protein backbone components and the relative preservation of carbon-rich compounds, proteoglycans and, to a lesser extent, aliphatic moieties. Our results suggest that FTIR-ATR is an ideal technique for collagen characterization/pre-screening for palaeodiet, mobility and radiocarbon research.

Inhibitors of protein-protein interactions can be developed through a number of technologies to provide leads that include cell-impermeable molecules. Redesign of these impermeable leads to provide cell-permeable derivatives can be challenging and costly. We hypothesised that intracellular toxicity of leads could be assessed by microinjection prior to investing in the redesign process. We demonstrate this approach for our development of inhibitors of the protein-protein interaction between inducible nitric-oxide synthase (iNOS) and SPRY domain-containing SOCS box proteins (SPSBs). We microinjected a lead molecule into AD-293 cells and were able to perform an intracellular toxicity assessment. We also investigated the intracellular distribution and localisation of injected inhibitor using a fluorescently-labelled analogue. Our findings show that a lead peptide inhibitor, CP2, had no toxicity even at intracellular concentrations four orders of magnitude higher than its K_d for binding to SPSB2. This early toxicity assessment justifies further development of this cell-impermeable lead to confer cell permeability. Our investigation highlights the utility of microinjection as a tool for assessing toxicity during development of drugs targeting protein-protein interactions.

Keywords: Cell imaging; Drug development; Intra-cellular delivery; Microinjection; Peptide; Protein-protein interactions; Toxicity.

Background: Accumulation of hyperphosphorylated tau (pTau) protein is associated with synaptic dysfunction in Alzheimer's disease (AD). We previously demonstrated that neuroprotection in familial mouse models of AD could be achieved by targeting mitochondria complex I (MCI) and activating the adaptive stress response. Efficacy of this strategy on pTau-related pathology remained unknown.

Objective: To investigate the effect of specific MCI inhibitor tricyclic pyrone compound CP2 on levels of human pTau, memory function, long term potentiation (LTP), and energy homeostasis in 18-month-old 3xTg-AD mice and explore the potential mechanisms.

Methods: CP2 was administered to male and female 3xTg-AD mice from 3.5-18 months of age. Cognitive function was assessed using the Morris water maze. Glucose metabolism was measured in periphery using a glucose tolerance test and in the brain using fluorodeoxyglucose F18 positron-emission tomography (FDG-PET). LTP was evaluated using electrophysiology in the hippocampus. The expression of key proteins associated with neuroprotective mechanisms were assessed by western blotting.

Results: Chronic CP2 treatment restored synaptic activity in female 3xTg-AD mice; cognitive function, levels of synaptic proteins, glucose metabolism, and energy homeostasis were improved in male and female 3xTg-AD mice. Significant reduction of human pTau in the brain was associated with increased activity of protein phosphatase of type 2A (PP2A), and reduced activity of cyclin-dependent kinase 5 (CDK5) and glycogen synthase kinase 3β (GSK3β).

Conclusion: CP2 treatment protected against synaptic dysfunction and memory impairment in symptomatic 3xTg-AD mice, and reduced levels of human pTau, indicating that targeting mitochondria with small molecule specific MCI inhibitors represents a promising strategy for treating AD.

Keywords: 3xTg-AD transgenic mice; Alzheimer’s disease; electrophysiology; fluorodeoxyglucose F18 positron-emission tomography; human tau protein; mitochondrial complex I; small molecule therapeutics.

A scaling theory of replica symmetry breaking (RSB) in the Sherrington-Kirkpatrick (SK) model is presented in the framework of critical phenomena for the scaling regime of large RSB orders kappa , small temperatures T , and small (homogeneous) magnetic fields H . We employ the pseudodynamical picture [R. Oppermann, M. J. Schmidt, and D. Sherrington, Phys. Rev. Lett. 98, 127201 (2007)], where two critical points CP1 and CP2 are associated with the order function's pseudodynamical limits lim_{a->>infinity}q(a)=1 and lim_{a-->0}q(a)=0 at (T=0 , H=0 , 1kappa=0) . CP1 - and CP2 -dominated contributions to the free energy functional F[q(a)] require an unconventional scaling hypothesis. We determine the scaling contributions in accordance with detailed numerical self-consistent solutions for up to 200 orders of RSB. Power laws, scaling functions, and crossover lines are obtained. CP1 -dominated behavior is found for the nonequilibrium susceptibility, which decays like chi_{1}=kappa;{-53}f_{1}(Tkappa;{-53}) , for the entropy, which obeys S(T=0) approximately chi_{1};{2} , and for the subclass of diverging parameters a_{i}=kappa;{53}f_{a_{i}}(Tkappa;{-53}) [describing Parisi box sizes m_{i}(T) identical witha_{i}(T)T ], with f_{1}(zeta) approximately zeta and f_{a_{i}}(zeta) approximately 1zeta for zeta->>infinity , while f(0) is finite. CP2 -dominated behavior, controlled by the magnetic field H while temperature is irrelevant, is retrieved in the plateau height (or width) of the order function q(a) according to q_{pl}(H)=kappa;{-1}f_{pl}(H;{23}kappa;{-1}) with f_{pl}mid R:(zeta)mid R:_{zeta->>infinity} approximately zeta and f_{pl}(0) finite. Divergent characteristic RSB orders kappa_{CP1}(T) approximately T;{-35} and kappa_{CP2}(H) approximately H;{-23} , respectively, describe the crossover from mean field SK- to RSB-critical behavior with rational-valued exponents extracted with high precision from our RSB data. The order function q(a) is obtained as a fixed-point function q(a) of RSB flow, in agreement with integrated fixed-point energy and susceptibility distributions.

The present study investigates the event-related oscillations underlying the motion-onset response (MOR) evoked by sounds moving at different velocities. EEG was recorded for stationary sounds and for three patterns of sound motion produced by changes in interaural time differences. We explored the effect of motion velocity on the MOR potential, and also on the event-related spectral perturbation (ERSP) and inter-trial phase coherence (ITC) calculated from the time-frequency decomposition of EEG signals. The phase coherence of slow oscillations increased with an increase in motion velocity similarly to the magnitude of cN1 and cP2 components of the MOR response. The delta-to-alpha inter-trial spectral power remained at the same level up to, but not including, the highest velocity, suggesting that gradual spatial changes within the sound did not induce non-coherent activity. Conversely, the abrupt sound displacement induced theta-alpha oscillations which had low phase consistency. The findings suggest that the MOR potential could be mainly generated by the phase resetting of slow oscillations, and the degree of phase coherence may be considered as a neurophysiological indicator of sound motion processing.

Keywords: auditory motion; event-related oscillations; motion onset response; sound localization.

CCND2-C12orf5-FGF23-FGF6 locus at human chromosome 12p13.32 and CCND1-ORAOV1-FGF19-FGF4 locus at human chromosome 11q13.3 are paralogous regions (paralogons) within the human genome. FGF23 is the causative factor for tumor-induced osteomalacia (TIO), a paraneoplastic disorder characterized by hypophosphatemia and skeletal undermineralization, and also for autosomal dominant hypophosphatemic rickets (ADHR). Here, rat Fgf6 and Fgf23 complete coding sequences were determined by using bioinformatics. Rat Fgf6 and Fgf23 genes, consisting of three exons, were located within AC103292.6 rat genome sequence. Rat Fgf6 and Fgf23 genes were clustered in tail-to-head manner with an interval of about 52 kb. Human FGF6 and FGF23 genes were clustered in tail-to-head manner with an interval of about 54 kb. Intergenic conserved region (IGCR) within the FGF6-FGF23 gene cluster was identified based on the evolutionary conservation. Human FGF6-FGF23 IGCR (nucleotide position 111648-112242 of AC008012.8 genome sequence) and rat Fgf6-Fgf23 IGCR (nucleotide position 156318-156894 of AC103292.6 genome sequence) showed 77.6% total nucleotide identity. CP2, E47, CREB and PAX4 binding sites were conserved among human FGF6, rat Fgf6, and mouse Fgf6 promoters. GATA and E47 binding sites were conserved among human FGF23, rat Fgf23, and mouse Fgf23 promoters. Because mouse Fgf23 mRNA was expressed in dendritic cells and activated spleen, tumor infiltrating dendritic cells are candidate sources of FGF23 secretion in TIO patients. This is the first report on comparative genomics analyses on human FGF6-FGF23 gene cluster and rodents Fgf6-Fgf23 gene cluster.

The novel sandwich complex Cp2*Al2I2, which was recently synthesized by Minasian and Arnold, has been characterized using ab initio and density functional methods. A large family of related compounds was also investigated. Although a few Al(II)–Al(II) bonds are known, this is the first such bond to be supported by Cp-type ligands. In addition, in the remarkable Cp4*Al4 synthesis by Roesky, Cp2*Al2I2 is the Al(II) intermediate; Cp4*Al4 is important as a precursor to novel organoaluminum species. Halogen and ligand effects on the Al–Al bond in Cp2*Al2I2 were systematically explored by studying a series of 20 Cp2*Al2I2 derivatives using density functional theory with relativistic basis sets for the halogens. Comparison was made with the focal point treatment, which uses extrapolation to estimate the full configuration interaction and complete basis set limit energy. Torsional potential energy curves, natural population analyses, and enthalpies of hydrogenation were computed. Using the focal point approach, torsional barriers were computed with 0.05 kcal mol(–1) uncertainty. The interplay of steric and electronic effects on the torsional potential energy curves, enthalpies of dehydrogenation reactions, and geometries is discussed. In species with small ligands (R = H, Me), hyperconjugative effects determine the torsional landscape, whereas steric repulsions dominate in species with Cp* alkyl ligands. Species with Cp ligands represent an intermediate case, thus providing insight into how ligands modulate the structures and properties of small metal clusters.

The tritopic organometallic ligand trans-MeSC₆H₄C≡CPt(PMe₃)₂(C≡N) (L1) was prepared from cis-PtCl₂(PMe₃)₂ and p-ethynyl(methyl thioether)benzene. Its versatility was shown with the formation of [CuX(L1)]_n coordination polymers (CPs) with CuX salts in MeCN (X = I (CP1), CN (CP2), SCN (CP3)). These CPs were characterized by X-ray crystallography, thermal gravimetric analysis (TGA), and IR and Raman spectroscopy. CP1 consists of a 1D head-to-tail chain formed by tricoordinated -C≡N-CuI(η²-C≡C)- linkages, whereas CP2 is built upon a central (CuCN)_n zigzag chain bearing dangling L1s held by -C≡N-Cu bonds. Finally, CP3 exhibits 2D sheets secured by Cu-N≡C-/-(Me)S-Cu bondings and transversal Cu-S-C≡N-Cu bridges. Concurrently, the CPs formed with AgX (X = NO₃^- (CP4 and CP5), CF₃CO₂^- (CP6) PF₆^- (CP7)) exhibits 2D sheets with guest molecules (anion, solvents) inside the tight pores or between layers. These new materials are emissive: L1 (λ_0-0 ∼465 nm), CP1-CP7 (500 < λ_max < 620 nm). Their photophysical properties (absorption and emission spectra, emission lifetimes (∼0.2 < τ_e < 120 μs), and quantum yields in the solid state at 77 and 298 K) were analyzed. The various natures of the emissive excited states were addressed by density functional theory (DFT) and time-dependent DFT (TDDFT) computations. For CP1, this state is a triplet halide or pseudohalide to ligand charge transfer ³XLCT (CT = charge transfer; X = I; L = L1) and for CP2, it is ³XLCT (X = CN; L = L1). However, for CP3, it is ³XLCT (X = SCN; L = L1). For CP4, the T₁ state is described as a [MeSC₆H₄(η²-C≡C)-Ag(NO₃)]₂ → [Pt]/C≡CC₆H₄SMe CT.

The reversible hydrostatic pressure dependent DC magnetic behavior of the ferromagnetically ordered electron transfer salt [Fe(III)Cp2*](•+)[TCNE](•-) (Cp* = pentamethylcyclopentadienide; TCNE = tetracyanoethylene) was studied up to 12.2 kbar. A significant departure from the ambient pressure ferromagnetic behavior was observed under pressure. The temperature dependent magnetization data were typical of a ferromagnet at ambient pressure but exhibited an extreme reduction with increasing applied pressure, while metamagnetic-like behavior was evident in the field dependent magnetization data at 4.2 kbar and above. Hence, the decrease of the intermolecular separations due to increasing pressure enhances the nearest neighbor couplings, leading to an increase in magnetic ordering temperature, T(c). Furthermore, the presence of a metamagnetic-like behavior suggests an increase of the antiferromagnetic contribution to the interchain interactions. The low field magnetization data indicate that spin canting is induced by pressure, leading to a canted antiferromagnetic phase with a much lower magnetization than the low-pressure ferromagnetic state. This unprecedented magnetic behavior is consistent with the field, temperature, and pressure dependences of the magnetization below 20 K.

The effect of alkaline earth metal alkoxides on the protonation of zirconocene dichloride was investigated. This approach enabled the design of compounds with preset molecular structures for generating high-purity binary metal oxide perovskites MZrO3 (M=Ba(2+), Sr(2+), Ca(2+)). Single-source molecular precursors [Ba4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2(η(2) -HOR)2 (HOR)2 Cl4], [Sr4 Zr2 (μ6 -O)(μ3 ,η(2)-OR)8 (OR)2 (HOR)4 Cl4], [Ca4 Zr2 (μ6-O)(μ3 ,η(2)-OR)8 (OR)2 Cl4], and [Ca6 Zr2 (μ2 ,η(2)-OR)12 (μ-Cl)2 (η(2) -HOR)4 Cl6 ]⋅8 CH2 Cl2 were prepared via elimination of the cyclopentadienyl ring from Cp2 ZrCl2 as CpH in the presence of M(OR)2 and alcohol ROH (ROH=CH3OCH2 CH2OH) as a source of protons. The resulting complexes were characterized by elemental analysis, IR and NMR spectroscopy, and single-crystal X-ray diffraction. The compounds were then thermally decomposed to MCl2 /MZrO3 mixtures. Leaching of MCl2 from the raw powder with deionized water produced highly pure perovskite-like oxide particles of 40-80 nm in size. Luminescence studies on Eu(3+)-doped MZrO3 revealed that the perovskites are attractive host lattices for potential applications in display technology.

A Vancomycin intermediate resistant strain of Staphylococcus aureus (S. aureus) labeled as CP2 (MIC 16 microg/ml) was isolated from an in-patient of local Cardiac Hospital of Karachi. CP2 showed typical characters of Vancomycin intermediate resistant S. aureus (VISA) i.e. high level of oxacillin resistance, thickened cell wall with rough surface and reduced autolytic activities associated with murein hydrolase (MH) enzyme. This strain may have acquired vancomycin resistance due to long term exposure to antibiotic during the treatment of the patient. Therefore, it implicates the importance of monitoring the usage and also to control of the abuse of antibiotics for prevention of any further proliferation of this type of notorious bugs.