Sharif Digital Repository

The six-coordinated silver(I) complex [Au2Ag(μ-(PPh2)2py)2(OTf)2](OTf), 4 (py = pyridine, OTf = CF3SO3), and the five-coordinated silver(I) complex [Au2Ag(acetone)(μ-(PPh2)2py)2](PF6)3, 6, were prepared by the reaction of the precursor complexes 1(OTf)2 and 1(PF6)2, in which 1 = [Au2(μ-(PPh2)2py)2]2+, with 1 equiv of Ag(OTf) in dichloromethane and excess of Ag(PF6) in a mixture of dichloromethane/acetone, respectively. Also, the five-coordinated silver(I) complex [Au2Ag(μ-(PPh2)2py)2(py)(OTf)](OTf)2, 5, was obtained by the reaction of 4 with pyridine. The clusters 4-6 were characterized using multinuclear NMR spectroscopy and elemental microanalysis. The single-crystal X-ray diffraction... 

A series of bis-metalated phosphorescent [(N^C)2Ir(bipyridine)]+ complexes with systematic variations in the structure and electronic characteristics of the N^C ligands were synthesized and characterized by using elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography. Investigation of the complexes’ spectroscopic properties together with DFT and TD DFT calculations revealed that metal-to-ligand charge transfer (MLCT) and intraligand (LC) transition play key roles in the generation of emissive triplet states. According to the results of theoretical studies, the 3LC excited state is more accurate to consider as an intraligand charge transfer process (ILCT) between N-... 

This paper presents synthesis and photophysical investigation of a very rare type of the ReI diimine complexes, [Re(diimine)(CO)3(OPR3)]+, R = Ph, Cy; diimine – phenanthroline and neocuproine, containing monodentate (unsupported) phosphine oxide ligands. The obtained compounds have been structurally characterized in solid phase by using XRD crystallography, which revealed unusual distortions in the pseudo octahedral rhenium environment, which may be ascribed to intramolecular interligand (phosphine oxide – diimine) interaction rather than to crystal packing effect. Optimization of the ground state structure of these molecules with the DFT method also confirmed intramolecular origin of the... 

In the present work we obtained a series of NIR luminescent platinum(II) complexes with a pincer N^N^C ligand based on the conjugated {benzoimidazo[1,2-a]pyrazine} system with the [Pt(N^N^C)L]n+ structural motif (L = phosphine, alkynyl or pyridine-type ligands). We have also synthesized two complexes with bidentate phosphines that demonstrate different types of coordination: 1) as chelating ligand (in case of 1,2-bis(diphenylphosphino)benzene), that led to de-coordination of pyridine ring of N^N^C ligand and formation of a [Pt(N^C)dppb]+ complex; 2) as a bridging ligand (in case of bis(diphenylphosphino)methane) between two {Pt(N^N^C)} fragments in a dimeric complex of type... 

The combined action of ultraviolet irradiation and microwave heating onto acetonitrile solution of [Re((Formula presented.))(CO)3(NCMe)]OTf ((Formula presented.) =phenantroline and neocuproine) afforded cis,trans-Re((Formula presented.))(CO)2(NCMe)2]+ acetonitrile derivatives. Substitution of relatively labile NCMe with a series of aromatic N-donor ligands (pyridine, pyrazine, 4,4’-bipyridine, N-methyl-4,4’-bipyridine) gave a novel family of the diimine cis,trans-[Re((Formula presented.))(CO)2(L)2]+ complexes. Photophysical studies of the obtained compounds in solution revealed unusually high absorption across the visible region and NIR phosphorescence with emission band maxima ranging from... 

Polyacrylonitrile (PAN) grafted chitosan was prepared by ceric-initiated graft polymerization of acrylonitrile onto chitosan in a homogenous medium. The copolymer chitosan-g-PAN product was then hydrolyzed to yield a novel smart hydrogel (H-chitoPAN) with superabsorbing properties. The influence of add-on values as well as temperature and time of hydrolysis of the initial chitosan-g-PAN on swelling behavior of the hydrogel was evaluated in water and various salt solutions. The swelling kinetics of the superabsorbing hydrogel was studied as well. The hydrogels exhibited ampholytic and pH-sensitivity characteristics. Several sharp swelling changes were observed in lieu of pH variations in a... 

Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) combined to multivariate curve resolution-alternating least-squares (MCR-ALS) is proposed for the resolution and quantification of very complex mixtures of compounds such as polycyclic aromatic hydrocarbons (PAHs) in heavy fuel oil (HFO). Different GC × GC-TOFMS data slices acquired during the analysis of HFO samples and PAH standards were simultaneously analyzed using the MCR-ALS method to resolve the pure component elution profiles in the two chromatographic dimensions as well as their pure mass spectra. Outstandingly, retention time shifts within and between GC × GC runs were not affecting... 

A new inelastic mechanism, detwinning-induced plasticity (DIP), is proposed to model the response of NiTi SMAs to cyclic loading, based on thermodynamic considerations. DIP is incorporated into a constitutive framework for NiTi SMA. The constitutive framework also includes well-established inelastic mechanisms of phase transformation, transformation-induced plasticity, residual martensite, and detwinning. The model is constructed at the single crystal scale using the framework of thermodynamics and a crystal plasticity formulation. An explicit scale-transition rule is adopted for the simulation of polycrystalline materials, allowing direct comparison of the model predictions with published... 

Some mechanical and metallurgical properties of hollow and solid long forged products are compared. The metallurgical properties include such micro- and macro-structural characteristics as the grain size and grain flow patterns. Mechanical evaluation was performed by means of hardness testing. Some theoretical analyses were also carried out. The results indicate that the hollow or mandrel forged products possess better properties. Both the mechanical and metallurgical properties are more uniform and homogeneous through the thickness direction in such products. By contrast, in the solid forged parts, there is a gradient in the micro- and macro-structural properties from the surface to the... 

Today, coordinated expansion planning is one of the key challenges for electricity systems including active distribution networks (ADNs) and transmission networks (TNs) hosting distributed renewable generation as well as large-scale wind energy generation. Accordingly, this study presents a decentralised hybrid robust and stochastic (HR&S) expansion planning optimisation method to determine a robust generation and transmission planning for a TN and stochastic expansion planning for ADNs. The proposed HR&S planning model is formulated with the objective of achieving an effective expansion of both TN&ADN while minimises the investment and operation costs of TN&ADN planning considering wind... 

We theoretically study a hybrid plasmonic-photonic cavity setup that can be used to induce and control long-distance heat transfer between molecular systems through optomechanical interactions. The structure we propose consists of two separated plasmonic nanoantennas coupled to a dielectric cavity. The hybrid modes of this resonator can combine the large optomechanical coupling of the sub-wavelength plasmonic modes with the large quality factor and delocalized character of the cavity mode that extends over a large distance (∼µm). We show that this can lead to effective long-range heat transport between molecular vibrations that can be actively controlled through an external driving laser. ©... 

Gelatin-based functional films were prepared by the addition of grapefruit seed extract (GSE, 5 wt% based on gelatin) and various amounts of TiO2 (0.5, 1.0, 3.0, and 5.0 wt% based on gelatin). TiO2 was evenly dispersed in the gelatin film, but the film surface roughness was increased as the concentration of TiO2 increased. The mechanical strength and water contact angle (WCA) of the composite film were the highest, while the water vapor permeability (WVP) was the lowest when 0.5 wt% TiO2 was used. The addition of GSE slightly reduced the UV light transmittance, but the addition of TiO2 almost completely prevented the UV light transmission. The addition of GSE and TiO2 did not significantly... 

Chitosan was modified with polyacrylonitrile (PAN) through ceric-initiated graft copolymerization. The chitosan-g-PAN product was saponified using sodium hydroxide aqueous solution to prepare a novel superabsorbent hydrogel, H-chitoPAN. Duration of completing the saponification reaction as well as the water absorbency capacity of the hydrogel was decreased with increasing the alkaline concentration. Either chitosan-g-PAN or H-chitoPAN was characterized by FTIR spectroscopy and DSC, TGA, and DTG thermal methods. According to FTIR, all the nitrile groups were converted to carboxylate and carboxamide groups. Both modified chitosans exhibited enhanced thermal stability over chitosan. The... 

We introduce a method by which stochastic processes are mapped onto complex networks. As examples, we construct the networks for such time series as those for free-jet and low-temperature helium turbulence, the German stock market index (the DAX), and white noise. The networks are further studied by contrasting their geometrical properties, such as the mean length, diameter, clustering, and average number of connections per node. By comparing the network properties of the original time series investigated with those for the shuffled and surrogate series, we are able to quantify the effect of the long-range correlations and the fatness of the probability distribution functions of the series... 

Does a dynamical black hole embedded in a cosmological FRW background emit the Hawking radiation where a globally defined event horizon does not exist? What are the differences to the Schwarzschild black hole? What about the first law of black-hole mechanics? We face these questions using the LTB cosmological black-hole model recently published. Using the Hamilton-Jacobi and radial null geodesic methods suitable for dynamical cases, we show that it is the apparent horizon which contributes to the Hawking radiation and not the event horizon. The Hawking temperature is calculated using the two different methods giving the same result. The first law of LTB black-hole dynamics and the thermal... 

Special solutions of the LTB family representing collapsing over-dense regions corresponding to asymptotically closed, open, or flat FRW models are found. These solutions may be considered as representing dynamical mass condensations leading to black holes immersed in a FRW universe. We study the dynamics of the collapsing region, and its density profile. The question of the strength of the central singularity and its nakedness, as well as the existence of an apparent horizon and an event horizon is dealt with in detail, shedding light to the notion of cosmological black holes. Differences to the Schwarzschild black hole are addressed  

Design and implementation of Architecture is a knowledge-driven process. Evaluation and verification the knowledge, in order to ensure its quality, have important role in improving overall design process. Furthermore, Architectural decision making is a complex and multi-criteria decision making problem in which multiple stakeholders make decisions from their perspectives causing overlaps and conflicts in the adopted decisions. Therefore, the requirement for strategies to manage these issues and also to improve coordination and cooperation among the various stakeholders to improve the overall process design is necessary. In this regard, there have been several activities that focus on... 

From gas-solid carbonation studies and product characterization by XRD, carbon elemental analysis, and TG-FTIR profiling of evolved CO2, the presence of water vapour at high relative humidity (>25% RH) was shown to cause a drastic acceleration in the rate of CO2 absorption into MgO and Mg(OH)2 producing magnesite and hydrocarbonated precursors. From thermogravimetric experiments in the vicinity of the dew point, carbonation was shown to proceeded in steps triggered by spontaneous condensation (and re-evaporation) of water. Almost complete conversion to magnesite (MgCO3) and/or hydromagnesite [HM = 4MgCO3·Mg(OH)2·4H2O] was observed in a few hours under rather mild conditions of pressure (PCO2... 

Mixed protein-surfactant adsorption layers can be built up in two different ways. The classical way is when all components adsorb simultaneously from a mixed solution. Alternatively, the components adsorb one after another, i.e. in a sequential way. In the present work, the formation of such surface layers has been studied with the random coil protein β-casein in the presence of added anionic surfactant SDS and compared for two different interfaces: the water-air (W-A) and water-hexane (W-H) interfaces. The used experimental technique is a drop profile analysis tensiometer PAT-1 specially equipped with a coaxial double capillary for drop volume exchange during the experiments. The results... 

Electrospray ionization of 2,6-naphthalenedicarboxylic acid readily affords its doubly deprotonated dicarboxylate dianion (1 2-). This species clusters with background water and added alcohols in an ion trap at ∼10-3 Torr. Sequential solvation is observed to afford mono and dicoordinated ions. Surprisingly, the latter cluster (1 2- • 2TFE) is protonated by 2,2,2-trifluoroethanol (TFE) whereas 1 2-and 1 2- • TFE are not even though δHacid(TFE)=361.7±2.5kcalmol-1 (as given in the NIST website at http://webbook.nist.gov) and the B3LYP/6-31+G(d,p) proton affinities are 384.7 (1 2-), 377.6 (1 2- • TFE), and 362.7 (1 2- • 2TFE) kcal mol-1. That is, only the weakest base in this series, and the...