Characterization of new Pt(IV)–thiazole complexes: Analytical,spectral, molecular modeling and molecular docking studies and applications in two opposing pathways

New thiazole derivatives were synthesized and fully characterized, then coordinated with PtCl₄ salt. Also, the newly synthesized Pt(IV) complexes were investigated analytically (elemental and thermogravimetric analyses), spectrally (infrared, UV–visible, mass, ¹H NMR, ¹³C NMR, X‐ray diffraction) as well as theoretically (kinetics, modeling and docking). The data extracted led to the establishment of the best chemical and structural forms. Octahedral geometry was the only formula proposed for all complexes, which is favorable for d⁶ systems. The molecular ion peaks from mass spectral analysis coincide with all analytical data, confirming the molecular formula proposed. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) allowed discrimination of features between crystalline particles and other amorphous morphology. By applying Gaussian09 as well as HyperChem 8.2 programs, the best structural forms were obtained, as well as computed significant parameters. Computed parameters such as softness, hardness, surface area and reactivity led us towards application in two opposing pathways: tumor inhibition and oxidation activation. The catalytic oxidation for CO was conducted over PtO₂, which was yielded from calcination of the most reactive complex. The success of catalytic role for synthesized PtO₂ was due to its particulate size and surface morphology, which were estimated from XRD patterns and SEM images, respectively. The antitumor activity was tested versus HCT‐116 and HepG‐2 cell lines. Mild toxicity was recorded for two of the derivatives and their corresponding complexes. This degree of toxicity is more favorable in most cases, due to exclusion of serious side effects, which is coherently attached with known antitumor drugs.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Dynamically Induced Excitonic Instability in Pumped Dirac Materials

Driven and non-equilibrium quantum states of matter have attracted growing interest in both theoretical and experimental studies in condensed matter physics. Recent progress in realizing transient collective states in driven or pumped Dirac materials (DMs) is reviewed herein. In particular, the focus is on optically pumped DMs which are a promising platform for transient excitonic instabilities. Optical pumping combined with the linear (Dirac) dispersion of the electronic spectrum offers a knob for tuning the effective interaction between the photoexcited electrons and holes, and thus provides a way of reducing the critical coupling for excitonic instability. As a result, a transient excitonic condensate could be achieved in a pumped DM while it is not feasible in equilibrium. A unifying theoretical framework is provided for describing transient collective states in 2D and 3D DMs. The experimental signatures are described and numerical estimates of the size of the dynamically induced excitonic gaps and the values of the critical temperatures for several specific systems, are summarized. In addition, general guidelines for identifying promising material candidates are discussed. Finally, comments are provided regarding recent experimental efforts in realizing transient excitonic condensate in pumped DMs, and outstanding issues and possible future directions are outlined.     

Dinuclear gold (I)-di-N-heterocyclic carbene complexes: syntheses,structure, density functional theory calculation and photoluminescence study

The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, ¹H- and ¹³C-NMR data. The ¹³C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]₂·2PF₆ is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λ_em = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm.     

New organoruthenium metallates containing ferrocenecarboxalidine thiosemicarbazones and their nucleic acid/albumin binding and in vitro cytotoxicity

A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh₃]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh₃]Cl was the most active on HT-29 cells.     

Annealing and doping-dependent magnetoresistance in single layer poly(3-hexyl-thiophene) organic semiconductor device

We compare the current density–voltage (J–V) and magnetoconductance (MC) response of a poly(3-hexyl-thiophene) (P3HT) device (Au/P3HT(350 nm)/Al) before and after annealing above the glass transition temperature of 150 °C under vacuum. There is a decrease of more than 3 orders of magnitude in current density due to an increase of the charge injection barriers after de-doping through annealing. An increase, approaching 1 order of magnitude, in the negative MC response after annealing can be explained by a shift in the Fermi level due to de-doping, according to the bipolaron mechanism. We successfully tune the charge injection barrier through re-doping by photo-oxidation. This leads to the charge injection and transport transitioning from unipolar to ambipolar, as the bias increases, and we model the MC response using a combination of bipolaron and triplet-polaron interaction mechanisms.     

Preparation and Characterization of Activated Carbon from Microwave and Conventional Heated Almond Shells Using Phosphoric Acid Activation

Activated carbon production from almond shells using phosphoric acid activation agent was achieved by applying both conventional heating and microwave heating in succession. The morphology and surface properties of activated carbon were studied using thermogravimetric and differential gravimetric analysis, Fourier-transform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller analysis. A surface area of 1128 m²/g was achieved by optimizing the microwave power (500?W), microwave application time (15?minutes), conventional heating time (45?minutes), conventional heating temperature (500?°C), and the phosphoric acid:sample ratio (0.7:1). An adsorption capacity of methylene blue of 148?mg/g and an iodine value of 791?mg/g was obtained for the prepared activated carbon.     

Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Estimation of power density in IMPATT using different materials

ABSTRACT

The RF output power dissipated per unit area is calculated using Runge-Kutta method for the high-moderate-moderate-high (n⁺-n-p-p⁺) doping profile of double drift region (DDR)-based impact avalanche transit time (IMPATT) diode by taking different substrate at Ka band. Those substrates are silicon, gallium arsenide, germanium, wurtzite gallium nitride, indium phosphide and 4H-silicon carbide. A comparative study regarding power dissipation ability by the IMPATT using different material is being presented thereby modelling the DDR IMPATT diode in a one-dimensional structure. The IMPATT based on 4H-SiC element has highest power density in the order of 10¹⁰ Wm^?2 and the Si-based counterpart has lowest power density of order 10⁶ Wm^?2 throughout the Ka band. So, 4H-SiC-based IMPATT should be preferable over others for the power density preference based application. This result will be helpful to estimate the power density of the IMPATT for any doping profile and to select the proper element for the optimum design of the IMPATT as far as power density is concerned in the Ka band. Also, we have focused on variation of power density with different junction temperatures and modelled the heat sink with analysis of thermal resistances.     

Compiler compatible 5.66 Mb/mm2 8T 1R1W register file in 14 nm FinFET technology

1-read/1-write (1R1W) register file (RF) is a popular memory configuration in modern feature rich SoCs requiring significant amount of embedded memory. A memory compiler is constructed using the 8T RF bitcell spanning a range of instances from 32 b to 72 Kb. An 8T low-leakage bitcell of 0.106 μm² is used in a 14 nm FinFET technology with a 70 nm contacted gate pitch for high-density (HD) two-port (TP) RF memory compiler which achieves 5.66 Mb/mm² array density for a 72 Kb array which is the highest reported density in 14 nm FinFET technology. The density improvement is achieved by using techniques such as leaf-cell optimization (eliminating transistors), better architectural planning, top level connectivity through leaf-cell abutment and minimizing the number of unique leaf-cells. These techniques are fully compatible with memory compiler usage over the required span. Leakage power is minimized by using power-switches without degrading the density mentioned above. Self-induced supply voltage collapse technique is applied for write and a four stack static keeper is used for read Vmin improvement. Fabricated test chips using 14 nm process have demonstrated 2.33 GHz performance at 1.1 V/25 °C operation. Overall V_min of 550 mV is achieved with this design at 25 °C. The inbuilt power-switch improves leakage power by 12x in simulation. Approximately 8% die area of a leading 14 nm SoC in commercialization is occupied by these compiled RF instances.