The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

Higher order bad loci

Zero-schemes on smooth complex projective varieties, forcing all elements of ample and free linear systems to be reducible, are studied. Relationships among the minimal length of such zero-schemes, the positivity of the line bundle associated with the linear system, and the dimension of the variety are established. Bad linear spaces are also investigated.     

Determination of phosphorus in samples of vegetable origin Mineralization with molten alkali and spectrophotometric determination

For determination of phosphorus in samples of vegetable origin (leaves and wheat flour) decomposition by means of molten alkali is proposed. Two procedures have been studied, one with dry reagents including an auxiliary oxidant, and the other with initially moist alkali with no extra oxidant. The fusion product is easily soluble and produces a solution suitable for elemental analysis. The phosphorus is determined by the molybdenum blue method. The suggested mineralization is rapid, accurate and precise.     

Analysis of primary aliphatic short-chain monoamines by LC in water samples

Several derivatization procedures with o-phthaldialdehyde-N-acetylcysteine (OPA-NAC) were compared for a rapid analysis of primary aliphatic short-chain monoamines in water samples by HPLC using a LiChorospher analytical separation column (100RP₁₈ mm i.d., 5 μm). Both the solution and the solid-support assisted off-line derivatization on C₁₈ SPE cartridges were inadequate options because of beginning degradation processes of the instable isoindol derivatives during their transfer to the analytical column. This problem was precluded with the on-column or solid-support assisted on-line derivatization. In the last mentioned procedure, the derivatization took place in a Hypersil C₁₈ precolumn ( mm i.d., 30 μm) connected with an additional preconcentration step resulting in better detection limits (0.002-0.040 μg ml⁻¹ requiring only 150 μl of water sample) than in the on-column procedure (0.08-0.16 μg ml⁻¹). The improved sample handling, the better control of parameters affecting reaction rates, the fully automation of this method with only 10 min analysis time for each sample are further advantageous. The potential of the solid-support assisted on-line derivatization was outlined and applied to water samples from several sources. Recovery values near 100% were obtained.     

Emission studies of pyrene solutions

Emission spectra of pyrene in hexane have been obtained over a temperature range (from 130 to 260 K) that has not been explored before for concentrations ranging from 10^?4 mole/? to 2 × 10^?2 mole/?. A conventional and new approximation which does not depend on the experimental set-up response functions has been used for evaluating pyrene excimer association energy W_DM and other pyrene parameters. In both methods W_DM agrees quite satisfactorlly, at all concentrations used, with that reported in the literature and obtained by other techniques. However, both approximation fail to yield the right values of the rate parameters at concentrations ? 2 g/?. This set the upper limit of sample solubility to be at C = 2g/? for our range of temperature. Furthermore, the new approximation can probably be used at higher concentration (for higher range of temperature) and even may be used for other organic molecules. There was also no difference in the ratio of the excimer (I_D) to monomer (I_M) quantum yields when an intense laser beam was used as a source of excitation rather than a super-pressure Hg-lamp. This suggested that the concentrations we used might not be large enough. As a result, the laser beam would not create enough density of excited molecules to affect the ratio of I_D/I_M.     

One-pot synthesis of 5-(substituted-amino)pyrazoles

An efficient and mild one-pot synthesis of substituted 5-alkylamino and/or 5-(arylamino)pyrazoles is described. A suitably decorated β-ketoamide, an aryl or alkyl hydrazine and Lawesson's reagent are suspended in THF/Py and gently heated to yield the requisite 5-aminopyrazoles.     

Superoxes,high temperature universal phases in (GC)2

Most of the common classes of organic compounds chromatograph normally on Superoxes. There is no tailing or adverse effect from excessively different activity different activity coefficients. Superoxes are therefore universal phases for gas chromatography. This is also expressed by a wide useful temperature range from ～50° to ～300°. High MW Superox-4 has a MAOT about 20° higher than the lower MW Superox-0.1. Several applications illustrating the versatility of Superox phases in (GC)² are presented.     

Constructing banking networks under decreasing costs of link formation

The structure of networks plays a central role in the behavior of financial systems and their response to policy. Real-world networks, however, are rarely directly observable: banks’ assets and liabilities are typically known, but not who is lending how much and to whom. This paper adds to the existing literature in two ways. First, it shows how to simulate realistic networks that are based on balance-sheet information. To do so, we introduce a model where links cause fixed-costs, independent of contract size; but the costs per link decrease the more connected a bank is (scale economies). Second, to approach the optimization problem, we develop a new algorithm inspired by the transportation planning literature and research in stochastic search heuristics. Computational experiments find that the resulting networks are not only consistent with the balance sheets, but also resemble real-world financial networks in their density (which is sparse but not minimally dense) and in their core-periphery and disassortative structure.