Unconventional Spin Relaxation Involving Localized Vibrational Modes in Ho Single-Atom Magnets.

We investigate the spin relaxation of Ho single atom magnets on MgO/Ag(100) as a function of temperature and magnetic field. We find that the spin relaxation is thermally activated at low field, while it remains larger than 1000 s up to 30 K and 8 T. This behavior contrasts with that of single molecule magnets and bulk paramagnetic impurities, which relax faster at high field. Combining our results with density functional theory, we rationalize this unconventional behavior by showing that local vibrations activate a two-phonon Raman process with a relaxation rate that peaks near zero field and is suppressed at high field. Our work shows the importance of these excitations in the relaxation of axially coordinated magnetic atoms.

Spin Excitations in a 4f-3d Heterodimer on MgO.

We report on the magnetic properties of HoCo dimers as a model system for the smallest intermetallic compound of a lanthanide and a transition metal atom. The dimers are adsorbed on ultrathin MgO(100) films grown on Ag(100). New for 4f elements, we detect inelastic excitations with scanning tunneling spectroscopy and prove their magnetic origin by applying an external magnetic field. In combination with density functional theory and spin Hamiltonian analysis, we determine the magnetic level distribution, as well as sign and magnitude of the exchange interaction between the two atoms. In contrast to typical 4f-3d bulk compounds, we find ferromagnetic coupling in the dimer.

Hybrid opto-chemical doping in Ag nanoparticle-decorated monolayer graphene grown by chemical vapor deposition probed by Raman spectroscopy.

The novel opto-chemical doping effect in Ag nanoparticle-decorated monolayer graphene grown by chemical vapor deposition has been investigated using Raman spectroscopy for the first time. We used both noble metal nanoparticles and optical excitation, in a hybrid opto-chemical route, to tune the doping level in graphene. Metal nanoparticle-induced chemical effects and laser power-induced substrate effects alter the doping nature of graphene from p- to n-type. Compared with earlier studies, the proposed method significantly lowers the laser intensity required for optical power-dependent doping, resulting in prevention of damage to the sample due to local heating. Some other interesting observations are the enhanced peak intensity in the Raman spectrum of graphene, enhancement of the D-band intensity and the introduction of G-band splitting. This novel, cheap and easily implemented hybrid optical-chemical doping strategy could be very useful for tuning graphene plasmons on the widely used Si/SiO2 substrates for various photonic device applications.

Molecular Characterization and Computational Modelling of New Delhi Metallo-ß-Lactamase-5 from an Escherichia coli Isolate (KOEC3) of Bovine Origin.

Emergence of antimicrobial resistance mediated through New Delhi metallo-ß-lactamases (NDMs) is a serious therapeutic challenge. Till date, 16 different NDMs have been described. In this study, we report the molecular and structural characteristics of NDM-5 isolated from an Escherichia coli isolate (KOEC3) of bovine origin. Using PCR amplification, cloning and sequencing of full blaNDM gene, we identified the NDM type as NDM-5. Cloning of full gene in E. coli DH5α and subsequent assessment of antibiotic susceptibility of the transformed cells indicated possible role of native promoter in expression blaNDM-5. Translated amino acid sequence had two substitutions (Val88Leu and Met154Leu) compared to NDM-1. Theoretically deduced isoelectric pH of NDM-5 was 5.88 and instability index was 36.99, indicating a stable protein. From the amino acids sequence, a 3D model of the protein was computed. Analysis of the protein structure elucidated zinc coordination and also revealed a large binding cleft and flexible nature of the protein, which might be the reason for broad substrate range. Docking experiments revealed plausible binding poses for five carbapenem drugs in the vicinity of metal ions. In conclusion, results provided possible explanation for wide range of antibiotics catalyzed by NDM-5 and likely interaction modes with five carbapenem drugs.

Magnetism of Ho and Er atoms on close-packed metal surfaces.

We investigated the magnetic properties of individual Ho atoms adsorbed on the (111) surface of Pt, which have been recently claimed to display single ion magnetic behavior. By combining x-ray absorption spectroscopy and magnetic dichroism measurements with ligand field multiplet calculations, we reveal a ground state which is incompatible with long spin relaxation times, in disagreement with former findings. A comparative study of the ground state and magnetic anisotropy of Ho and Er on Pt(111) and Cu(111) emphasizes the different interaction of the 4f orbitals with localized and delocalized substrate states. In particular, we find a striking rotation of the magnetization easy axis for Er, which changes from out of plane on Pt(111) to in plane on Cu(111).

Interplay of lattice-spin-orbital coupling and Jahn-Teller effect in noncollinear spinel TixMn1-x(FeyCo1-y)2O4: a neutron diffraction study.

Local magnetostructural changes and dynamical spin fluctuations in doubly diluted spinel TixMn1‒x(FeyCo1‒y)2O4has been reported by means of neutron diffraction and magnetization studies. Two distinct sets of compositions (i)x(Ti) = 0.20 andy(Fe) = 0.18; (ii)x(Ti) = 0.40 andy(Fe) = 0.435 have been considered for this study. The first compound of equivalent stoichiometry Ti0.20Mn0.80Fe0.36Co1.64O4exhibits enhanced tetragonal distortion across the ferrimagnetic transition temperatureTC= 258 K in comparison to the end compound MnCo2O4(TC∼ 180 K) with a characteristic ratioct/√2atof 0.99795(8) demonstrating robust lattice-spin-orbital coupling. However, in the second case Ti0.40Mn0.60Fe0.87Co1.13O4with higherB-site compositions, the presence of Jahn-Teller ions with distinct behavior appears to counterbalance the strong tetragonal distortion thereby ceasing the lattice-spin-orbital coupling. Both the investigated systems show the coexistence of noncollinear antiferromagnetic and ferrimagnetic components in cubic and tetragonal settings. On the other hand, the dynamical ac-susceptibility,χac(T) reveals a cluster spin-glass state with Gabay-Toulouse (GT) like mixed phases behaviour belowTC. Such dispersive behaviour appears to be sensitive to the level of octahedral substitution. Further, the field dependence ofχac(T) follows the weak anisotropic GT-line behaviour with crossover exponent Φ lies in the range 1.38-1.52 on theH-Tplane which is in contrast to theB-site Ti substituted MnCo2O4spinel that appears to follow irreversible non-mean-field AT-line behaviour (Φ âˆ¼ 3 +δ). Finally, the Arrott plots analysis indicates the presence of a pseudo first-order like transition (T< 20 K) which is in consonance with and zero crossover of the magnetic entropy change within the frozen spin-glass regime.

Probing the incoherent admixture of low and high-spin states of Co in (LaPr)CoO3perovskite: focus on structural phase transitions.

We report the mixed valence and intermediate spin-state (IS) transitions in Pr substituted LaCoO3perovskites in the form of bulk and nanostructures. Various compositions (x) of La1-xPrxCoO3(0 ⩽x⩽ 0.9) were synthesized using the sol-gel process under moderate heat treatment conditions (600 °C). The structural analysis of these compounds reveals a phase crossover from the monoclinic phase (space group, s.g.:I2/a) to an orthorhombic one (s.g.:Pbnm), and a rhombohedral phase (s.g.:R-3c) to an orthorhombic one (s.g.:Pnma) in the bulk and nanostructures, respectively, for the composition range 0 ⩽x⩽ 0.6. Such a structural transformation remarkably reduces the Jahn-Teller distortion factor ΔJT: 0.374 → 0.0016 signifying the dominant role of the IS state (SAvg= 1) of trivalent Co ions in the investigated system. Magnetization measurements reveal the ferromagnetic (FM) nature of bulk LaCoO3along with a weak antiferromagnetic (AFM) component coexisting with an FM component. This coexistence results in a weak loop-asymmetry (zero-field exchange-bias effect ∼134 Oe) at low temperatures. Here the FM ordering occurs due to the double-exchange interaction (JEX/kB∼ 11.25 K) between the tetravalent and trivalent Co ions. Significant decrease in the ordering temperatures was noticed in the nanostructures (TC∼ 50 K) as compared to the bulk counterpart (∼90 K) due to the finite size/surface effects in the pristine compound. However, the incorporation of Pr leads to the development of a strong AFM component (JEX/kB∼ 18.2 K) and enhances the ordering temperatures (∼145 K forx= 0.9) with negligible FM correlations in both bulk and nanostructures of LaPrCoO3due to the dominant super-exchange interaction: Co3+/4+‒O‒Co3+/4+. Further evidence of the incoherent mixture of low-spin (LS) and high-spin (HS) states comes from theM-Hmeasurements which yields a saturation magnetization ofMS∼ 275 emu mol-1(under the limit of 1/H→ 0) consistent with the theoretical value of 279 emu mol-1corresponding to the spin admixture: 65% LS + 10% IS of trivalent Co along with 25% of LS Co4+in the bulk pristine compound. A similar analysis yields: Co3+[30% LS + 20% IS] + Co4+[50% of LS] for the nanostructures of LaCoO3,yet the Pr substitution decreases the spin admixture configuration. The Kubelka-Munk analysis of the optical absorbance results in a significant decrease in the optical energy band gap (Eg:1.86 → 1.80 eV) with the incorporation of Pr in LaCoO3which corroborates the above results.

Reentrant canonical spin-glass dynamics and tunable field-induced transitions in (GeMn)Co2O4Kagomé lattice.

We report on the reentrant canonical semi spin-glass characteristics and controllable field-induced transitions in distorted Kagomé symmetry of (GeMn)Co2O4. ThisB-site spinel exhibits complicated, yet interesting magnetic behaviour in which the longitudinal ferrimagnetic (FiM) order sets in below the Néel temperatureTFN∼ 77 K due to uneven moments of divalent Co (↑ 5.33µB) and tetravalent Mn (↓ 3.87µB) which coexists with transverse spin-glass state below 72.85 K. Such complicated magnetic behaviour is suggested to result from the competing anisotropic superexchange interactions (JAB/kB∼ 4.3 K,JAA/kB∼ -6.2 K andJBB/kB∼ -3.3 K) between the cations, which is extracted following the Néel's expression for the two-sublattice model of FiM. Dynamical susceptibility (χac(f, T)) and relaxation of thermoremanent magnetization,MTRM(t) data have been analysed by means of the empirical scaling-laws such as Vogel-Fulcher law and Power law of critical slowing down. Both of which reveal the reentrant spin-glass like character which evolves through a number of intermediate metastable states. The magnitude of Mydosh parameter (Ω âˆ¼ 0.002), critical exponentzυ= (6.7 ± 0.07), spin relaxation timeτ0= (2.33 ± 0.1) × 10-18s, activation energyEa/kB= (69.8 ± 0.95) K and interparticle interaction strength (T0= 71.6 K) provide the experimental evidences for canonical spin-glass state below the spin freezing temperatureTF= 72.85 K. The field dependence ofTFobtained fromχac(T) follows the irreversibility in terms of de Almeida-Thouless mean-field instability in which the magnitude of crossover scaling exponent Φ turns out to be ∼2.9 for the (Ge0.8Mn0.2)Co2O4. Isothermal magnetization plots reveal two field-induced transitions across 9.52 kOe (HSF1) and 45.6 kOe (HSF2) associated with the FiM domains and spin-flip transition, respectively. Analysis of the inverse paramagnetic susceptibilityχp-1χp=χ-χ0after subtracting the temperature independent diamagnetic termχ0(=-3 × 10-3emu mol-1Oe-1) results in the effective magnetic momentµeff= 7.654µB/f.u. This agrees well with the theoretically obtainedµeff= 7.58µB/f.u. resulting the cation distributionMn0.24+↓A[Co22+↑]BO4in support of the Hund's ground state spin configurationS=3/2andS= 1/2of Mn4+and Co2+, respectively. TheH-Tphase diagram has been established by analysing all the parameters (TF(H),TFN(H),HSF1(T) andHSF2(T)) extracted from various magnetization measurements. This diagram enables clear differentiation among the different phases of the (GeMn)Co2O4and also illustrates the demarcation between short-range and long-range ordered regions.

Engineering atomic-scale magnetic fields by dysprosium single atom magnets.

Atomic scale engineering of magnetic fields is a key ingredient for miniaturizing quantum devices and precision control of quantum systems. This requires a unique combination of magnetic stability and spin-manipulation capabilities. Surface-supported single atom magnets offer such possibilities, where long temporal and thermal stability of the magnetic states can be achieved by maximizing the magnet/ic anisotropy energy (MAE) and by minimizing quantum tunnelling of the magnetization. Here, we show that dysprosium (Dy) atoms on magnesium oxide (MgO) have a giant MAE of 250 meV, currently the highest among all surface spins. Using a variety of scanning tunnelling microscopy (STM) techniques including single atom electron spin resonance (ESR), we confirm no spontaneous spin-switching in Dy over days at ≈ 1 K under low and even vanishing magnetic field. We utilize these robust Dy single atom magnets to engineer magnetic nanostructures, demonstrating unique control of magnetic fields with atomic scale tunability.

Fine needle aspiration (FNA) of soft tissue tumours (STT).

OBJECTIVES: The cytological findings of 50 ST Ts were evaluated aiming to determine the role of FNA in diagnosis of STTs METHODS: Fifty patients with soft tissue tumours underwent FNA in the preoperative investigation during a one year period. The smears were stained with Papanicolaou and May-Graunvald Giemsa stains. RESULTS: Forty-four cases were reported as benign, whereas 2 were malignant. Four cases revealed insufficient material. The malignant STTs were small round cell tumour and malignant spindle cell tumour. Cytological and histological correlation could be achieved in 40 cases. The overall sensitivity and specificity were 25% and 100% respectively with overall accuracy of 80%. CONCLUSION: A reliable diagnosis of STTs can be made with FNA when supported by other clinical and other diagnostic data.

Magnetic remanence in single atoms.

A permanent magnet retains a substantial fraction of its saturation magnetization in the absence of an external magnetic field. Realizing magnetic remanence in a single atom allows for storing and processing information in the smallest unit of matter. We show that individual holmium (Ho) atoms adsorbed on ultrathin MgO(100) layers on Ag(100) exhibit magnetic remanence up to a temperature of 30 kelvin and a relaxation time of 1500 seconds at 10 kelvin. This extraordinary stability is achieved by the realization of a symmetry-protected magnetic ground state and by decoupling the Ho spin from the underlying metal by a tunnel barrier.

Cognitive deficits following traumatic brain injury produced by controlled cortical impact.

Traumatic brain injury produces significant cognitive deficits in humans. This experiment used a controlled cortical impact model of experimental brain injury to examine the effects of brain injury on spatial learning and memory using the Morris water maze task. Rats (n = 8) were injured at a moderate level of cortical impact injury (6 m/sec, 1.5-2.0 mm deformation). Eight additional rats served as a sham-injured control group. Morris water maze performance was assessed on days 11-15 and 30-34 following injury. Results revealed that brain-injured rats exhibited significant deficits (p less than 0.05) in maze performance at both testing intervals. Since the Morris water maze task is particularly sensitive to hippocampal dysfunction, the results of the present experiment support the hypothesis that the hippocampus is preferentially vulnerable to damage following traumatic brain injury. These results demonstrate that controlled cortical impact brain injury produces enduring cognitive deficits analogous to those observed after human brain injury.

Opioid modulation of attention-related responses: peripheral-to-central progression and development of mu influence as learning occurs.

Endogenous opioids modulate attention-related bradycardiac responses evoked by novel stimuli and Pavlovian conditioned signals, and these effects are distinct from those of endogenous opioids on memory. We investigated the role of peripheral opioid receptors in modulating attention and Pavlovian learning, in rabbits tested for bradycardiac orienting responses to novel tones, and for Pavlovian conditioning and extinction of cardiac discrimination. Pretraining, IV treatment with the opiate antagonist naloxone-HCl (0.1-0.5 mg/kg) facilitated initial development of Pavlovian conditioned discrimination and delayed its later extinction, compared to saline vehicle, as previously observed. Pretraining treatment with its peripherally acting analog, quaternary naloxone-methiodide (1.29-6.47 mg/kg), also promoted initial development, but not extinction, of discrimination, and it reduced the magnitude of bradycardiac orienting responses and of tachycardiac unconditioned responses. Treatment with the selective mu-antagonist peptide CTOP (10-30 microg/kg) facilitated conditioned responses and reduced unconditioned responses, somewhat later during training, but it did not reliably affect extinction or orienting responses. These results confirm an important role of peripheral opioids in regulating attentional and associative functions involved in orienting and the earliest stage of Pavlovian learning, prior to development of central opioid regulation of later associative, hedonic and mnemonic functions. These findings also suggest that cardiovascular opioid receptors might mediate peripheral opioid influences on attention and early association formation, via modulation of cardiac responses to stimuli and autonomic sensory feedback to the brain.

Effects of cocaine prior to and during bupropion maintenance in cocaine-abusing volunteers.

The effects of cocaine were examined prior to and during bupropion maintenance in nonopioid-dependent cocaine abusers. Prior to bupropion maintenance, subjects underwent an experimental session during which repeated cocaine doses (0, 50, 100 mg/70 kg) were administered intranasally. Then subjects were maintained on bupropion (150 and 300 mg per day) and underwent experimental sessions as before. Cocaine, regardless of bupropion, produced dose-related increases in several stimulant-like self-reports, performance and cardiovascular measures. Bupropion decreased POMS ratings of friendliness and vigor, regardless of cocaine dose. Bupropion enhanced and attenuated cocaine-induced increases in ratings on the LSD and BG subscales of the ARCI, respectively. These results suggest that bupropion does not alter the acute subjective or cardiovascular effects of cocaine in a robust manner.

Delta-opioid stimulation by BW373U86 promotes autonomic reactivity to stressors and alters attention-related cardiac responses in rabbits.

The nonpeptide delta-opioid agonist BW373U86 (3 to 300 micrograms/kg) was tested in rabbits for effects on heart rate, cardiac orienting and Pavlovian conditioned responses to tones, and unconditioned cardiac and somatomotor responses to signaled and unsignaled shocks. BW373U86 did not alter shock-evoked somatomotor reflexes and had few effects on the development or retention of Pavlovian conditioned heart rate discrimination. However, BW373U86 appeared to modulate cardiac conditioning indirectly, by facilitating sympathetic reflexes evoked by the signaled stressor, and the dose effect was U-shaped within the dose range tested. The pronounced tachycardiac effect of BW373U86 was completely blocked, or rapidly reversed, by the selective delta-opiate antagonist naltrindole. BW373U86 was more potent in increasing signaled than unsignaled shock-evoked tachycardia, suggesting release of an endogenous substance (e.g., a delta-opioid) because of the Pavlovian conditioning contingency.

Individual differences in humans responding under a cocaine discrimination procedure: discriminators versus nondiscriminators.

Twenty-six cocaine-abusing volunteers were trained to discriminate cocaine (80 mg/70 kg, p.o.) from placebo. On the basis of a discrimination acquisition criterion (i.e., >80% drug-appropriate responding for 4 consecutive sessions within 8-10 sessions), 18 participants were classified as discriminators (Ds) and 8 as nondiscriminators (NDs). Relative to Ds, NDs reported a greater amount of cocaine use per time. During the training phase, NDs showed significantly lower ratings than Ds on a stimulant ratings scale, regardless of the training drug condition. During the test-of-acquisition phase, cocaine-induced increases in scores on ratings of drug strength, anxious-nervous and cocaine high, as well as on a euphoria ratings scale, were significantly greater in Ds than NDs, relative to placebo. These results suggest that drug use history, general arousal level, and drug sensitivity may be important variables influencing the acquisition of cocaine versus placebo discrimination in cocaine abusers.

Chemical modification of cellulosic biopolymer and its use in removal of heavy metal ions from wastewater.

Use of biological macromolecules for wastewater remediation process has become the topic of intense research mostly driven by growing concerns about the depletion of petroleum oil reserves and environmental problems. So in view of technological significance of cellulosic biopolymers in various fields, the present study is an attempt to synthesize cellulosic biopolymers based graft copolymers using free radical polymerization. The resulting cellulosic polymers were characterized by Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermogravimetric (TGA) analysis. Furthermore, modified cellulosic biopolymer was used in removal of Cu(2+), Zn(2+), Cd(2+) and Pb(2+) toxic metal ions from wastewater. The effects of pH, contact time, temperature and metal ions concentration were studied in batch mode experiments. Langmuir and Dubinin-Radushkevich (D-R) models were used to show the adsorption isotherm. The maximum monolayer capacity qm calculated using Langmuir isotherm for Cu(2+), Zn(2+), Cd(2+), Pb(2+) metal ions were 1.209, 0.9623, 1.2609 and 1.295mmol/g, respectively. The thermodynamic parameters ΔH° and ΔG° values for metal ions adsorption on modified cellulosic biopolymer showed that adsorption process was spontaneous as well as exothermic in nature.