Biyclo[2.2.1]heptane as cyclopentane precursor. Part 4 Stereocontrolled syhthesis of a potential intermediate to chromophycane dolastane and clavularane

The regio– and stereoselective synthesis of the keto-esters 20 and 22 are described, the latter being a potential intermediate to several diterpenes. The key steps involve the Diels-Alder cycloaddition between the benzocycloheptenone 5 and cyclopentadiene followed by a regioselective functionalisation of the adduct 6. A remarkable reversal of regioselectivity was observed during oxymercuration of the unsymmetric double bond in 6 and its reduced product 11 leading to 8 and 12 which were subsequently transformed to 20 and 22 respectively.     

2- and 2,7-Substituted para-N-Methylpyridinium Pyrenes: Syntheses,Molecular and Electronic Structures,Photophysical, Electrochemical,and Spectroelectrochemical Properties and Binding to Double-Stranded (ds) DNA

Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm⁻¹. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc⁺ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents.     

Paramagnetic ruthenium(III) cyclometallated complex. Synthesis, spectroscopic studies and electron-transfer properties

The reaction of Ru^II(PPh₃)₃X₂ (X = Cl, Br) with o-(OH)C₆H₄C(H)=N-CH₂C₆H₅ (HL) under aerobic conditions affords Ru^II(L)₂(PPh₃)₂, 1, in which both the ligands (L) are bound to the metal center at the phenolic oxygen (deprotonated) and azomethine nitrogen and Ru^III(L¹)(L²)(PPh₃), 2, in which one L is in bidentate N,O form like in complex 1 and the other ligand is in tridentate C,N,O mode where cyclometallation takes place from the ortho carbon atom (deprotonated) of the benzyl amine fragment. The complex 1 is unstable in solution, and undergoes spontaneous oxidative internal transformation to complex 2. In solid state upon heating, 1 initially converts to 2 quantitatively and further heating causes the rearrangement of complex 2 to the stable RuL₃ complex. The presence of symmetry in the diamagnetic, electrically neutral complex 1 is confirmed by ¹H and ³¹P NMR spectroscopy. It exhibits an Ru^II → L, MLCT transition at 460 nm and a ligand based transition at 340 nm. The complex 1 undergoes quasi-reversible ruthenium(II)—ruthenium(III) oxidation at 1.27V vs. SCE. The one-electron paramagnetic cyclometallated ruthenium(III) complex 2 displays an L → Ru^III, LMCT transition at 658 nm. The ligand based transition is observed to take place at 343 nm. The complex 2 shows reversible ruthenium(III)—ruthenium(IV) oxidation at 0.875V and irreversible ruthenium(III)—ruthenium(II) reduction at −0.68V vs. SCE. It exhibits a rhombic EPR spectrum, that has been analysed to furnish values of axial (6560 cm⁻¹) and rhombic (5630 cm⁻¹) distortion parameters as well as the energies of the two expected ligand field transitions (3877 cm⁻¹ and 9540 cm⁻¹) within the t₂ shell. One of the transitions has been experimentally observed in the predicted region (9090 cm⁻¹). The first order rate constants at different temperatures and the activation parameter ΔH^#/ΔS^# values of the conversion process of 1 → 2 have been determined spectrophotometrically in chloroform solution.     

Finite frames,P-frames and basically disconnected frames

Let \({\mathcal{P}}\) be an ideal of closed quotients of a completely regular frame L and \({\mathcal{R}_{\mathcal{P}}(L)}\) the collection of all functions in the ring \({\mathcal{R}(L)}\) whose support belong to \({\mathcal{P}}\) . We show that \({\mathcal{R}(L)}\) is a Noetherian ring if and only if \({\mathcal{R}(L)}\) is an Artinian ring if and only if L is a finite frame. Using this result, we next show that if \({\mathcal{P}}\) is the ideal of all compact closed quotients of L and L is \({\mathcal{P}}\) -continuous, then \({\mathcal{R}_{\mathcal{P}}(L)}\) is a Noetherian ring if and only if L is finite. Moreover, we show that L is a P-frame if and only if each ideal of \({\mathcal{R}(L)}\) is of the form \({\mathcal{R}_{\mathcal{P}}(L)}\) for some choice of \({\mathcal{P}}\) . We furnish equivalent conditions for \({\mathcal{R}_{\mathcal{P}}(L)}\) to be a prime ideal, a free ideal, and an essential ideal of \({\mathcal{R}(L)}\) separately in terms of the cozero elements of L. Finally, we show that L is basically disconnected if and only if \({\mathcal{R}(L)}\) is a coherent ring.     

Generic cryptographic weakness of k-normal Boolean functions in certain stream ciphers and cryptanalysis of grain-128

This paper considers security implications of k-normal Boolean functions when they are employed in certain stream ciphers. A generic algorithm is proposed for cryptanalysis of the considered class of stream ciphers based on a security weakness of k-normal Boolean functions. The proposed algorithm yields a framework for mounting cryptanalysis against particular stream ciphers within the considered class. Also, the proposed algorithm for cryptanalysis implies certain design guidelines for avoiding certain weak stream cipher constructions. A particular objective of this paper is security evaluation of stream cipher Grain-128 employing the developed generic algorithm. Contrary to the best known attacks against Grain-128 which provide complexity of a secret key recovery lower than exhaustive search only over a subset of secret keys which is just a fraction (up to 5%) of all possible secret keys, the cryptanalysis proposed in this paper provides significantly lower complexity than exhaustive search for any secret key. The proposed approach for cryptanalysis primarily depends on the order of normality of the employed Boolean function in Grain-128. Accordingly, in addition to the security evaluation insights of Grain-128, the results of this paper are also an evidence of the cryptographic significance of the normality criteria of Boolean functions.     

A literature review on dynamic pricing of electricity

Revenue management and dynamic pricing are concepts that have immense possibilities for application in the energy sector. Both can be considered as demand-side management tools that can facilitate the offering of different prices at different demand levels. This paper studies literature on various topics related to the dynamic pricing of electricity and lists future research avenues in pricing policies, consumers’ willingness to pay and market segmentation in this field. Demand and price forecasting play an important role in determining prices and scheduling load in dynamic pricing environments. This allows different forms of dynamic pricing policies to different markets and customers depending on customers’ willingness to pay. Consumers’ willingness to pay for electricity services is also necessary in setting price limits depending on the demand and demand response curve. Market segmentation can enhance the effects of such pricing schemes. Appropriate scheduling of electrical load enhances the consumer response to dynamic tariffs.     

Dialgebra cohomology as a G-algebra

It is well known that the Hochschild cohomology of an associative algebra admits a G-algebra structure. In this paper we show that the dialgebra cohomology of an associative dialgebra has a similar structure, which is induced from a homotopy G-algebra structure on the dialgebra cochain complex .

     

On some results for a class of meromorphic functions having quasiconformal extension

We consider the class \(\Sigma (p)\) of univalent meromorphic functions f on \({\mathbb D}\) having a simple pole at \(z=p\in [0,1)\) with residue 1. Let \(\Sigma _k(p)\) be the class of functions in \(\Sigma (p)\) which have k-quasiconformal extension to the extended complex plane \({\hat{\mathbb C}}\), where \(0\le k < 1\). We first give a representation formula for functions in this class and using this formula, we derive an asymptotic estimate of the Laurent coefficients for the functions in the class \(\Sigma _k(p)\). Thereafter, we give a sufficient condition for functions in \(\Sigma (p)\) to belong to the class \(\Sigma _k(p).\) Finally, we obtain a sharp distortion result for functions in \(\Sigma (p)\) and as a consequence, we obtain a distortion estimate for functions in \(\Sigma _k(p).\)     

Some observations on HC-128

In this paper, we study HC-128 in detail from cryptanalytic point of view. First, we use linear approximation of the addition modulo 2 ⁿ of three n-bit integers to identify linear approximations of g ₁, g ₂, the feedback functions of HC-128. This, in turn, shows that the process of keystream output generation of HC-128 can be well approximated by linear functions. In this direction, we show that the ??least significant bit?? based distinguisher (presented by the designer himself) of HC-128 works for the complete 32-bit word. Using the above linear approximations of g ₁, g ₂, we present a new distinguisher for HC-128 which is slightly weaker than Wu??s distinguisher. Finally, in the line of Dunkelman??s observation, we also study how HC-128 keystream words leak secret state information of the cipher due to the properties of the functions h ₁, h ₂ and present improved results.