Prospects of thermal analysis in polymer research

A survey and an analysis of the publications concerned in thermal analysis (TA) published in four renowned journals during the years 1965–1974 were performed. The published data were evaluated from three points of view: TA methods used for polymers, properties and phenomena studied by TA methods, types of polymers investigated by TA methods. From the statistical data were derived the future trends for the application of particular TA methods in polymer science.     

Enantiomers of polarized alkenes: chromatographic enrichment and thermal interconversion

(+)- and (?)-$\text{1}$ as well as (+)- and (?)-$\text{2}$ were partially separated by liquid chromatography on triacetylcellulose; racemizations resulted in the barriers (Table 2) to rotation via planarized transition states.     

The crystal structure of Hf3As

Hf₃As has a monoclinic unit cell of dimensions a = 15.3898(14) Å, b = 5.3795(5) Å, c = 15.330(14) Å, β = 90.291(6)°. A structure proposal based on space group $\text{C2}\text{c}$ (No. 15) has been refined by the least-squares method using a Rietveld-type fullprofile analysis of Guinier-Hägg X-ray powder film intensity data. The Hf₃As structure is an intermediate between the Fe₃P and the Ti₃P types. The atomic coordination follows rules formulated earlier for representatives of the Fe₃PTi₃PV₃S family of structures.     

The influence of “two-phase” synthesis conditions on blown film extrusion of LDPE

LDPE synthesized under two-phase conditions is known to have a good balance of blown film properties. Good optical properties and high impact strength are characteristic for two-phase LDPE grades. In order to obtain systematic information, LDPE was synthesized at several different pressures with two different melt index levels. Blown film was extruded at different output rates and melt temperatures. The influence on haze and dart drop impact was studied. Two-phase conditions were found to improve haze and dart drop impact and the improvement was impressive, especially for the low melt index grades. By increasing the output rate, the dart drop values were further improved. The influence of melt temperature on dart drop impact goes through an optimum and overall haze decreases with increasing melt temperature. For films made from two-phase grades, dart drop impact decreases as internal haze increases. For corresponding internal haze values, the films made from single-phase grades have lower dart drop values and they are somewhat scattered.     

Synthesis of new OBAN's and further studies on positioning of the catalytic group

Two new zinc ion dependent oligonucleotide based artificial nucleases (OBAN's) have been synthesized. These consist of 2'-O-methyl modified RNA oligomers conjugated to 5-amino-2,9-dimethylphenanthroline (neocuproine)via a urea linker. OBAN 4 carries the catalytic group on a linker extending from the C-4 of an internal cytosine moiety. OBAN 5 has two neocuproine units attached, each to linkers extending from the C-5 position of uridine moieties, one placed internally and the other at the at the 5'-end of the oligonucleotide. The key step in the synthesis of the OBAN systems is conjugation of the catalytic group to the respective amino linkers of the modified oligonucleotides. This is achieved by first converting the 5-amino-2,9-dimethylphenanthroline to the phenylcarbamate. The reaction of this neocuproine phenylcarbamate with the oligonucleotide carrying one or two primary aliphatic amines in aqueous buffer (at pH 8.5) leads to nearly quantitative formation of the urea-linked conjugates. Both OBAN systems were found to cleave RNA in the bulged out regions formed from the non-complementary part of the target sequences, in the presence of Zn(II) ions. Differences in efficiency between these and previously reported systems are discussed.     

Four levels of pattern recognition

Problems of pattern recognition in chemistry and other subjects can be divided conveniently into four different types depending on the level of scope of the problem.(1) Classification into one of a number of defined classes. As an example blood samples taken from persons known to be either controls or welders are considered. The problem is whether trace element concentrations in these samples contain information on whether or not a person is a welder.(2) Level 1 plus the possibility that an object is an outlier, i.e. does not belong to any of the defined classes. As an example, the üse of ¹³C-n.m.r. data to decide whether 2-substituted norbornanes have the exo or endo structure is discussed. (2A) Level 2, asymmetric. This situation occurs when one class does not have a systematic structure, but another class is homogeneous and can be described by a level 2 model. This occurs in the classification of materials or compounds as good or bad, active or inactive, and in binary classifications. As an example the use of trace element data to classify steel samples as having good or poor properties of strength is discussed.(3) Level 2 plus the ability to relate the variables measured to external properties of continuous character. As an example, the classification of a series of chemical compounds as β -receptor blockers, β -receptor stimulants, or neither, on the basis of their structural variables is discussed. In addition, relations between these structural variables and the measured biological activity are sought within each of the two classes.(4) Level 3 with the difference that several external property variables in the objects are measured. It may be desirable to use variables of the objects both for classification and for relations to several property variables: such examples are numerous in analytical chemistry.     

Studies on stereoselective approaches to β-carboline derivatives

Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected. Dedicated to Professor Károly Lempert on his 80th birthday.     

Site-selective labeling strategies for screening by NMR

NMR based screening has become an important tool in the pharmaceutical industry. Methods that provide information on the location of small molecule binding sites on the surface of a drug target (e. g. SAR-by-NMR and related techniques) are of particular interest. In order to extend the applicability of such techniques to drug targets of higher molecular weight, selective labeling strategies may be employed. Dual-amino acid selective labeling and site directed non-native amino acid replacement (SNAAR) allow for the selective detection of NMR resonances of a specific amino acid residue. This results in significantly reduced spectral complexity, which not only enables application to higher molecular weight systems, but also eliminates the need for sequential resonance assignment in order to identify the binding site. Regio-selective (or segmental) labeling of an entire protein domain of a multi domain protein may also be achieved. Labeling only a selected part of a multi domain protein (e. g. a catalytic or ligand binding domain) is an attractive way to simplify the spectral interpretation without disturbing the system under study.     

Dioxomolybdenum(VI) complexes of 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone

Mixed ligand complexes of dioxomolybdenum(VI) with 2-hydroxybenzaldehyde 4-phenyl-S-methylthiosemicarbazone (H₂L) were prepared with the formula [MoO₂(L)D] (D = H₂O, methyl, n-butyl, and n-undecyl alcohol, DMF, DMSO, pyridine, 4-picoline, and 3,5-lutidine). The compounds were characterized by elemental analysis, IR and ¹H NMR spectroscopy. The thermal decomposition of the compounds were investigated by using TGA, DTG, and DTA methods in air, and the thermal behavior depending on the second ligand molecule was discussed. A single crystal of the DMF coordinated complex was studied by X-ray diffractometry. The text was submitted by the authors in English.     

Dilute and concentrated solutions of polystyrene in trans-decalin close to and far from the θ-temperature—II. Osmotic pressure measurements

Osmotic pressure measurements on polystyrene ($\text{M}{}_{\mathrm{n}}\text{= 396. 000}$) in trans-decalin for concentrations up to 140 kg m^?3 and from 20 to 40 are reported. The θ-temperature is 20.8 . The ratio

where c⁺ is the concentration at which a homogeneous segment distribution is assumed to prevail, increases with temperature up to the plateau value of 0.7. From the temperature dependence of the osmotic pressure, the partial molar enthalpy. Δh₁, and entropy, Δs₁. of mixing are found to be positive. The solvent-solute interaction parameter increases linearly with concentration at all temperatures.