Use of HNO(3) as the source of NO to prepare a nitric oxide complex of ruthenium

Reaction of cis-Ru(bisox)(2)Cl(2), where bisox is 4,4,4',4'-tetramethyl-2,2'-bisoxazoline, with HNO(3) in 1 : 4 molar proportion in boiling water under N(2) atmosphere and subsequent addition of an excess of NaClO(4).H(2)O yields [Ru(bisox)(HL)(NO)](ClO(4))(NO(3)) (1). HL is a hydrolysed form of bisox where one of the oxazoline rings opens up. X-Ray crystallography shows that 1 contains an octahedral RuN(5)O core. HL binds the metal through an imino N, an amide N and an alcoholic O atom. Reaction of cis-Ru(bisox)(2)Cl(2) with an excess of NaNO(2) in water gives cis-Ru(bisox)(2)(NO(2))(2) (2). On acidification by HClO(4) in methanol, is smoothly converted to cis-[Ru(bisox)(2)(NO(2))(NO)](ClO(4))(2) (3) due to equilibrium (1). [formula: see text] (1) The X-ray crystal structures of 2 and 3 have also been determined. NO binds Ru in 1 and 3 linearly. The Ru-NO bond length in 1 is 1.764(13) A and that in 3 is approximately 1.78 A. All the three complexes have been characterised by FTIR, NMR and ESIMS. The NO stretching frequencies in 1 and 3 are 1897 and 1936 cm(-1) respectively. While 3 reverts back to 2 readily in presence of OH(-) [equilibrium (1)], 1 does not react with OH(-). It is concluded that while in the reaction of cis-Ru(bisox)(2)Cl(2) with HNO(3), bisox is hydrolysed following abstraction of NO from HNO(3), generation of the nitrosyl complex 3 via reaction (1) is not accompanied with such hydrolysis.     

Luminescence,Plasmonic, and Magnetic Properties of Doped Semiconductor Nanocrystals

Introducing a few atoms of impurities or dopants in semiconductor nanocrystals can drastically alter the existing properties or even introduce new properties. For example, mid-gap states created by doping tremendously affect photocatalytic activities and surface controlled redox reactions, generate new emission centers, show thermometric optical switching, make FRET donors by enhancing the excited state lifetime, and also create localized surface plasmon resonance induced low energy absorption. In addition, researchers have more recently started focusing their attention on doped nanocrystals as an important and alternative material for solar energy conversion to meet the current demand for renewable energy. Moreover, the electrical and magnetic properties of the host are also strongly altered on doping. These beneficial dopant-induced changes suggest that doped nanocrystals with proper selections of dopant–host pairs may be helpful for generating designer materials for a wide range of current technological needs. How properties relate to the doping of a variety of semiconductor nanocrystals are summarized in this Review.     

A General Synthetic Approach for Designing Epitope Targeted Macrocyclic Peptide Ligands

We describe a general synthetic strategy for developing high‐affinity peptide binders against specific epitopes of challenging protein biomarkers. The epitope of interest is synthesized as a polypeptide, with a detection biotin tag and a strategically placed azide (or alkyne) presenting amino acid. This synthetic epitope (SynEp) is incubated with a library of complementary alkyne or azide presenting peptides. Library elements that bind the SynEp in the correct orientation undergo the Huisgen cycloaddition, and are covalently linked to the SynEp. Hit peptides are tested against the full‐length protein to identify the best binder. We describe development of epitope‐targeted linear or macrocycle peptide ligands against 12 different diagnostic or therapeutic analytes. The general epitope targeting capability for these low molecular weight synthetic ligands enables a range of therapeutic and diagnostic applications, similar to those of monoclonal antibodies.     

Colloidal CsPbBr3 Perovskite Nanocrystals: Luminescence beyond Traditional Quantum Dots

Traditional CdSe‐based colloidal quantum dots (cQDs) have interesting photoluminescence (PL) properties. Herein we highlight the advantages in both ensemble and single‐nanocrystal PL of colloidal CsPbBr₃ nanocrystals (NCs) over the traditional cQDs. An ensemble of colloidal CsPbBr₃ NCs (11 nm) exhibits ca. 90 % PL quantum yield with narrow (FWHM=86 meV) spectral width. Interestingly, the spectral width of a single‐NC and an ensemble are almost identical, ruling out the problem of size‐distribution in PL broadening. Eliminating this problem leads to a negligible influence of self‐absorption and Förster resonance energy transfer, along with batch‐to‐batch reproducibility of NCs exhibiting PL peaks within ±1 nm. Also, PL peak positions do not alter with measurement temperature in the range of 25 to 100 °C. Importantly, CsPbBr₃ NCs exhibit suppressed PL blinking with ca. 90 % of the individual NCs remain mostly emissive (on‐time >85 %), without much influence of excitation power.     

Effects of cooling rate on the microstructure and solute partitioning in near eutectoid Ti–Cu alloys

The effect of cooling rate on eutectoid decomposition in a near eutectoid (Ti-5.5 at.% Cu) alloy has been investigated in a systematic manner by coupling scanning electron microscopy, transmission electron microscopy and atom probe tomography studies. Thus, the competition between nucleation and growth of proeutectoid α plates from pre-existing β grain boundaries, and eutectoid decomposition (α?+?Ti₂Cu) via a pearlitic mechanism has been studied as a function of cooling rate, using a Jominy-end quenched sample that was cooled from the high-temperature single β phase. When the alloy was subjected to very fast cooling (160?K/s), proeutectoid α plates, supersaturated in Cu, are formed along with a highly refined lamellar eutectoid product between these α plates. In contrast, intermediate (9?K/s) and slow (2?K/s) cooling results in considerably coarser proeutectoid α plates as well as lamellar eutectoid products. With the decrease in the cooling rate, there was a substantial increase in the volume fraction of the lamellar eutectoid product and the composition of all decomposition products approached their equilibrium values. Also, the slowest cooled sample (2?K/s) exhibited substantially rougher and irregular interfaces between the proeutectoid α and the lamellar eutectoid product, which seems to promote the cooperative growth of lamellar α?+?Ti₂Cu. Irrespective of the cooling rate, nucleation of the lamellar eutectoid (α?+?Ti₂Cu) product appears to only occur at the interface between the proeutectoid α plates and the β matrix.     

Effects of screening on the rate of energy loss in degenerate surface layers of compound semiconductors at low lattice temperatures

The energy loss rate of an electron in degenerate surface layers of a compound semiconductor for inelastic interaction with deformation and piezoelectric acoustic phonons is calculated with due account of the screening of the perturbing potential under the condition of low lattice temperature when the approximations of the well known traditional theory is not valid. The numerical results obtained for GaAs and CdS exhibits interesting features, significantly different from what follows if one either makes the traditional approximation of negligible phonon energy or disregards the screening of the scattering potential.     

Role of streaming potential on pulsating mass flow rate control in combined electroosmotic and pressure-driven microfluidic devices

In the present study, we investigate the implications of streaming potential on the mass flow rate control in a microfluidic device actuated by the combined application of a pulsating pressure gradient and a pulsating, externally applied, electric field. We demonstrate that the temporal dynamics due to streaming potential effects may lead to interesting non-trivial aspects of the resultant transport characteristics. Our results highlight the importance of an adequate accounting of the streaming potential effects for temporally tunable mass flow rate control strategies, which may act as a useful design artifice to augment mass flow rates in practical scenarios.     

Effect of metal ions on photoluminescence, charge transport, magnetic and catalytic properties of all-inorganic colloidal nanocrystals and nanocrystal solids

Colloidal semiconductor nanocrystals (NCs) provide convenient "building blocks" for solution-processed solar cells, light-emitting devices, photocatalytic systems, etc. The use of inorganic ligands for colloidal NCs dramatically improved inter-NC charge transport, enabling fast progress in NC-based devices. Typical inorganic ligands (e.g., Sn(2)S(6)(4-), S(2-)) are represented by negatively charged ions that bind covalently to electrophilic metal surface sites. The binding of inorganic charged species to the NC surface provides electrostatic stabilization of NC colloids in polar solvents without introducing insulating barriers between NCs. In this work we show that cationic species needed for electrostatic balance of NC surface charges can also be employed for engineering almost every property of all-inorganic NCs and NC solids, including photoluminescence efficiency, electron mobility, doping, magnetic susceptibility, and electrocatalytic performance. We used a suite of experimental techniques to elucidate the impact of various metal ions on the characteristics of all-inorganic NCs and developed strategies for engineering and optimizing NC-based materials.     

Scaling laws for spreading of a liquid under pressure

We study squeeze flow of two different fluids (castor oil and ethylene glycol) between a pair of glass plates and a pair of perspex plates, under an applied load. The film thickness is found to vary with time as a power-law, where the exponent increases with load. After a certain time interval the area of fluid-solid contact saturates to a nearly steady value. This saturation area, increases with load at different rates for different fluid-solid combinations.     

Anisotropic Strange Star in 5D Einstein-Gauss-Bonnet Gravity

In this paper, we investigated a new anisotropic solution for the strange star model in the context of 5D Einstein-Gauss-Bonnet (EGB) gravity. For this purpose, we used a linear equation of state (EOS), in particular pr=βρ+γ, (where β and γ are constants) together with a well-behaved ansatz for gravitational potential, corresponding to a radial component of spacetime. In this way, we found the other gravitational potential as well as main thermodynamical variables, such as pressures (both radial and tangential) with energy density. The constant parameters of the anisotropic solution were obtained by matching a well-known Boulware-Deser solution at the boundary. The physical viability of the strange star model was also tested in order to describe the realistic models. Moreover, we studied the hydrostatic equilibrium of the stellar system by using a modified TOV equation and the dynamical stability through the critical value of the radial adiabatic index. The mass-radius relationship was also established for determining the compactness and surface redshift of the model, which increases with the Gauss-Bonnet coupling constant α but does not cross the Buchdahal limit.