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.     

Influence of structural and chemical properties on electron transport in mesoporous ZnO-based dye-sensitized solar cell

Ionics - Two chemical bath deposition (CBD) solutions were prepared at two different temperatures of 60 and 80 °C for dye-sensitized solar cell (DSSC) application. The deposition time...     

Notions and relations for RKA-secure permutation and function families

The theory of designing block ciphers is mature, having seen significant progress since the early 1990s for over two decades, especially during the AES development effort. Nevertheless, interesting directions exist, in particular in the study of the provable security of block ciphers along similar veins as public-key primitives, i.e. the notion of pseudorandomness (PRP) and indistinguishability (IND). Furthermore, recent cryptanalytic progress has shown that block ciphers well designed against known cryptanalysis techniques including related-key attacks (RKA) may turn out to be less secure against RKA than expected. The notion of provable security of block ciphers against RKA was initiated by Bellare and Kohno, and subsequently treated by Lucks. Concrete block cipher constructions were proposed therein with provable security guarantees. In this paper, we are interested in the security notions for RKA-secure block ciphers. In the first part of the paper, we show that secure tweakable permutation families in the sense of strong pseudorandom permutation (SPRP) can be transformed into secure permutation families in the sense of SPRP against some classes of RKA (SPRP–RKA). This fact allows us to construct a secure SPRP–RKA cipher which is faster than the Bellare–Kohno PRP–RKA cipher. We also show that function families of a certain form secure in the sense of a pseudorandom function (PRF) can be transformed into secure permutation families in the sense of PRP against some classes of RKA (PRP–RKA). We can exploit it to get various constructions secure against some classes of RKA from known MAC algorithms. Furthermore, we discuss how the key recovery (KR) security of the Bellare–Kohno PRP–RKA, the Lucks PRP–RKA and our SPRP–RKA ciphers relates to existing types of attacks on block ciphers like meet-in-the-middle and slide attacks. In the second part of the paper, we define other security notions for RKA-secure block ciphers, namely in the sense of indistinguishability (IND) and non-malleability, and show the relations between these security notions. In particular, we show that secure tweakable permutation families in the sense of IND (resp. non-malleability) can be transformed into RKA-secure permutation families in the sense of IND (resp. non-malleability).     

Physical, structural, and luminescence studies of Nd3+ doped MgO-ZnO borate glass

A series of borate glass of the system xNd₂O₃-5MgO-20ZnO-(75 ? x)B₂O₃, where x = 0.5, 1.0,1.5, 2.0, and 2.5 was successfully fabricated using melt quench method. The properties of the glass were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), absorption and luminescence spectra. The upconversion properties of Nd³⁺ doped borate glass were observed by using 574 nm excitation wavelength corresponding to ⁴ I _15/2 → ² H _114/2 transition. The emission bands centered at 460, 500 and 620 nm which corresponding to the Nd³⁺ transitions, ⁴ F _7/2 → ⁴ I _15/2, ² H _11/2 → ⁴ I _15/2, and ⁴ F _9/2 → ⁴ I _15/2 respectively were observed at room temperature. The presence of Nd³⁺ in borate based glass could intensify the upconversion luminescence spectra as it can potentially be used as host materials for upconversion lasers.     

Synthesis of a palladium(II) complex of a <Emphasis Type="Italic">N</Emphasis>-heterocylic carbene via transmetalation: crystal structure and antibacterial studies

An Ag(I)-N-heterocylic carbene (NHC) complex, [Ag(L)₂]PF₆ (L = 1-(2′-methylbenzyl)-3-(2″-propyl)benzimidazolium), was used as a transfer agent for the synthesis of a Pd(II)–NHC complex, formulated as [PdCl(L)₂(MeCN)]PF₆ (Pd1). The complex Pd1 was characterized by ¹H and ¹³C NMR, FTIR spectroscopy and elemental analysis. Single crystal X-ray diffraction analysis reveals that the Pd(II) atom has a square planar geometry. This complex was screened for its antibacterial potential against the Gram-negative bacteria Escherichia coli (ATCC 25922) and the Gram-positive bacteria Staphylococcus aureus (ATCC 12600). These results are compared with those obtained for a standard antibiotic, ampicillin, and also the corresponding Ag(I)–NHC complex.     

Anion Directed Self‐Assembly of One‐Dimensional and Two‐Dimensional Coordination Polymers Containing Bridging Diphosphine Ligands

The reactions of 1,2‐bis(diphenylphosphanyl)ethane (dppe) with different silver(I) salts facilitated the formation of 1D and 2D coordination polymers, [Ag(dppe)(OAc)]_n · nH₂O ( 1 ) and [Ag₂(dppe)_1.5(NO₃)₂]_n ( 2 ), respectively. The complexes were characterized by elemental analysis, ATR‐IR spectroscopy, ¹H NMR, ¹³C NMR, and ³¹P NMR spectroscopy, and single‐crystal X‐ray diffraction. Structural analysis revealed that complex 1 exhibits a 1D infinite wavy structure, in which each silver(I) ion is bridged by dppe ligands. Structure 2 has a 2D topologically promising architecture that displays a 6.6.6 graphitic net, which corresponds to hnd topology. The nitrate ions and dppe ligands are in a μ₂ bridging mode and support the formation of this net. Moreover, significant π–π interactions between the phenyl rings in the apertures of (6,3) grid stabilized complex 2 .     

Bacterial Reduction of Cr(VI) at Technical Scale—The Malaysian Experience

The bacterial reduction of Cr(VI) from industrial wastewater was evaluated using a 2.0-m³ bioreactor. Liquid pineapple waste was used as a nutrient for the biofilm community formed inside the bioreactor. The use of rubber wood sawdust as packing material was able to immobilize more than 10⁶?CFU?mL^?1 of Acinetobacter haemolyticus cells after 3?days of contact time. Complete reduction of 15?C240?mg?L^?1 of Cr(VI) was achieved even after 3?months of bioreactor operation. Cr(VI) was not detected in the final effluent fraction indicating complete removal of Cr from solution from the flocculation/coagulation step and the unlikely re-oxidation of Cr(III) into Cr(VI). Impatiens balsamina L. and Gomphrena globosa L. showed better growth in the presence of soil?Csludge mixture compared to Coleus scutellarioides (L.) Benth. Significant amounts of Cr accumulated at different sections of the plants indicate its potential application in Cr phytoremediation effort. The bacterial-based system was also determined not to be detrimental to human health based on the low levels of Cr detected in the hair and nail samples of the plant operators. Thus, it can be said that bacterial-based Cr(VI) treatment system is a feasible alternative to the conventional system especially for lower Cr(VI) concentrations, where sludge generated can be used as growth supplement for ornamental plant as well as not detrimental to the health of the workers.     

Coinage metal complexes of N‐heterocyclic carbene bearing nitrile functionalization: Synthesis and photophysical properties

A new series of N‐heterocyclic carbene (NHC) ligand precursors ( 1 and 2 ) with their [Ag(I)(NHC)₂]PF₆ complexes ( 3 and 4 ) and [ClAu(I)(NHC)] complexes ( 5 and 6 ) are reported. Complexes 5 and 6 were synthesized via transmetalation reaction using either 3 or 4 and AuCl(SMe₂) as reactants, respectively. All the synthesized compounds were fully characterized using elemental analyses and Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies. In the crystal structures of 3 , 5 and 6 , the Ag(I) and Au(I) ions are in a linear geometry. The entire structure of 3 is stabilized by significant π–π interactions, while the structures of 5 and 6 are stabilized with the presence of aurophilic interactions between the adjacent Au(I) ions as well as CH–π or π–π interactions. From photoluminescence studies, complexes 5 and 6 show dual‐emission characteristics. The higher‐energy fluorescence originates from ¹XLCT mixed with ¹MLCT, while the lower‐energy phosphorescence is ascribed to ³XLCT and ³MLCT with small contribution of ³ILCT, as evidenced by density functional theory (DFT) and time‐dependent DFT calculations of the modelled molecules.     

The optical properties of trivalent rare earth ions (Er3+) doped borotellurite glass

Erbium doped borotellurite glass has been fabricated by using conventional melting method. The density and molar volume have been calculated and analyzed while their optical properties were studied by measuring the optical absorption and luminescence spectra at room temperature. From the XRD results, since the patterns do not exhibit any diffraction line thus it confirms their amorphous nature. It is found that the density of the glass samples increased and the molar volume decreased with respect to Er ions content. Meanwhile, the upconversion emissions centered at 487, 523, 558, 642, 695 and 782 nm have been observed under the 650 nm excitation in the ⁴ F _9/2 level. Some other results will be analysed and discussed in details.     

NHC–Silver(I) Complexes as Chemical Nucleases; Synthesis,Crystal Structures,and Antibacterial Studies

A series of N‐heterocyclic carbene (NHC) precursors, 1‐methoxylethyl‐3‐allylimidazolium hexafluorophosphate ( 1 ), 1‐ethyl‐3‐allylimidazolium hexafluorophosphate ( 2 ), and 1‐pentyl‐3‐allylimidazolium hexafluorophosphate ( 3 ) were synthesized. These salts were treated with Ag₂O to afford their corresponding mononuclear Ag(I)‐NHC complexes, namely 1‐methoxylethyl‐3‐allylimidazolium silver(I) hexafluorophosphate ( 4 ), 1‐ethyl‐3‐allylimidazolium silver(I) hexafluorophosphate ( 5 ), and 1‐pentyl‐3‐allylimidazolium silver(I) hexafluorophosphate ( 6 ), respectively. These compounds were characterized by physicochemical and spectroscopy techniques. Compounds 4 and 5 were structurally characterized by single crystal X‐ray diffraction, and their stability in solution was investigated and found to be acceptable for the antibacterial studies. These new NHC precursors and their respective Ag–NHC complexes were screened for their antibacterial activities against Staphylococcus aureus (ATCC 12600) and Escherichia coli (ATCC 25922). Compounds 1–3 showed no inhibition, whereas 4–6 inhibited the growth of these bacteria. The nuclease activities of the reported compounds against plasmid DNA and RNA were assessed by gel electrophoresis, and the results indicate that complexes 5 and 6 can degrade both DNA and RNA in the absence of an oxidant.