Functionalized Silver-Ion-Mediated α-dC/β-dC Hybrid Base Pairs with Exceptional Stability: α-d-5-Iodo-2′-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Silver-mediated α-dC–Ag⁺–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T_m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag⁺–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.     

Solid Lipid Nanoparticles (SLNs): Preparation and Properties of Calix[4]resorcinarene Derived Systems.

Solid Lipid Nanoparticles (SLNs) have been prepared fromc-2,c-8,c-14,c-20-tetraundecyl-4,6,10,12,16,18,22,24-octahydroxyresorc[4]areneas colloidal suspensions. Photon Correlation Spectroscopy studies revealed aparticle hydrodynamic diameter of 150 nm. Non-contact mode Atomic ForceMicroscopy allows observation of the particles as slightly flattened sphericalobjects of 236 (±40) nm diameter and 145 (±40) nm height. Thestudy of the preparation parameters showed that shear force does not affectthe hydrodynamic size of the SLNs. In contrast, the viscosity and the pH ofthe aqueous phase, the amphiphile concentration in the organic phase and thevolume of organic phase used, all lead to variation in the size of the particles.In term of post preparation parameters only the ionic strength has been shownto affect significantly the particle size; while the pH of the storing solution,microwave, ultrasonic and thermal treatments do not. Short and long-termstability studies have been performed to measure the effect of the ionic strengthon the stability of the particles. The use of carbohydrate cryoprotectants does notallow re-dispersion of the colloidal suspension after freeze-drying.     

Enumeration of three-dimensional convex polygons

A self-avoiding polygon (SAP) on a graph is an elementary cycle. Counting SAPs on the hypercubic lattice ℤ ^d withd≥2, is a well-known unsolved problem, which is studied both for its combinatorial and probabilistic interest and its connections with statistical mechanics. Of course, polygons on ℤ ^d are defined up to a translation, and the relevant statistic is their perimeter. A SAP on ℤ ^d is said to beconvex if its perimeter is “minimal”, that is, is exactly twice the sum of the side lengths of the smallest hyper-rectangle containing it. In 1984, Delest and Viennot enumerated convex SAPs on the square lattice [6], but no result was available in a higher dimension. We present an elementar approach to enumerate convex SAPs in any dimension. We first obtain a new proof of Delest and Viennot's result, which explains combinatorially the form of the generating function. We then compute the generating function for convex SAPs on the cubic lattice. In a dimension larger than 3, the details of the calculations become very cumbersome. However, our method suggests that the generating function for convex SAPs on ℤ ^d is always a quotient ofdifferentiably finite power series.     

Latin Squares without Orthogonal Mates

In 1779 Euler proved that for every even n there exists a latin square of order n that has no orthogonal mate, and in 1944 Mann proved that for every n of the form 4k + 1, k ≥ 1, there exists a latin square of order n that has no orthogonal mate. Except for the two smallest cases, n = 3 and n = 7, it is not known whether a latin square of order n = 4k + 3 with no orthogonal mate exists or not. We complete the determination of all n for which there exists a mate-less latin square of order n by proving that, with the exception of n = 3, for all n = 4k + 3 there exists a latin square of order n with no orthogonal mate. We will also show how the methods used in this paper can be applied more generally by deriving several earlier non-orthogonality results.     

A Tin(IV) Porphyrin with Two Axial Organometallic NCN‐Pincer Platinum Units

A tin(IV) porphyrin was combined with two axial NCN‐pincer platinum(II) fragments by utilizing the oxophilicity of the apical positions on the tin atom and the acidic nature of the NCN‐pincer platinum derived benzoic acid. The solid‐state structure determined by X‐ray crystallography revealed some close contacts between the pincer complexes and the meso‐p‐tolyl subsitutents of the porphyrin. It was shown by ¹H NMR spectroscopy that these close contacts were not present in solution and that this compound can potentially act as a novel building block for supramolecular architectures.     

Mode beating in spot-size converter lasers

An anomalous modulation in the wavelength spectrum has been observed in lasers with spot-size converters. This intensity modulation is shown to be caused by beating between the fundamental lasing mode and radiation modes in the taper. This results in a periodic modulation in the net gain spectrum, which causes wavelength jumps between adjacent net gain maxima, and a drive current dependent spectral width that is expected to affect system performance. The amplitude of this spectral modulation is reduced significantly by either using an angled rear-facet which reflects the beating radiation modes away from the laser axis, or by using a nonlinear, adiabatic taper.     

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