Chemistry of the diazeniumdiolates. 3. Photoreactivity

We have found O(2)-substituted diazeniumdiolates, compounds of structure R(2)N-N(O)=NOR' that are under development for various possible pharmaceutical uses, to be rather photosensitive. With R = ethyl and R' = methyl, benzyl, or 2-nitrobenzyl, the observed product distributions suggest that two primary pathways are operative. A minor pathway involves the extrusion of nitrous oxide (N(2)O) with simultaneous generation of R(2)N(*) and R'O(*), which may then form amines, aldehydes, and alcohols. The major reaction pathway is an interesting photochemical cleavage of the N=N bond to form a nitrosamine (R(2)NN=O) and an oxygen-substituted nitrene (R'ON). The intermediacy of the O-nitrene was inferred from the production of abundant oxime, via rearrangement of the O-nitrene to a C-nitroso compound (R'ON --> O=NR'), and subsequent tautomerization to the more stable oxime. Involvement of the O-nitrene was confirmed by trapping with 2,3-dimethyl-2-butene to form the aziridine and with oxygen to generate the nitrate ester. 2-Nitro substitution on the benzyl derivative had surprisingly little effect on the reaction course. For each compound examined, minor amounts of nitric oxide (NO), presumably produced by secondary photolysis of the nitrosamine, were observed. Time-resolved infrared experiments provided additional support for the above reaction pathways and confirmed that the nitrosamine is a primary photoproduct. We have also found that the relative contributions of the reaction pathways can be altered in certain derivatives. For example, when R' = 2,4-dinitrophenyl, the contribution of the nitrosamine/O-nitrene-forming pathway was diminished. Pharmacological implications of these results are discussed.     

Polysaccharides ofUngernia. XIII. Carbohydrates of the leaves of the genusUngernia

The present communication gives the results of an investigation of the carbohydrates isolated from the leaves of eight species ofUngernia. From a single sample were successively extracted the water-soluble polysaccharides, the glucofructans, the pectin substances, and the hemicelluloses. The qualitative and quantitative monosaccharide compositions of the carbohydrates isolated were determined, and the characteristics of the pectin substances are given.Deceased.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 647–650, September–October, 1984.     

Research on the aromas. On the aroma of coffee. I

The analysis of a coffee concentrate is described: 202 constituents have been identified, 154 of which for the first time. Some of these compounds are new chemicals; their synthesis is described. Most identifications are based upon mass spectrometry combined in many cases with IR. spectrometry and comparison with reference compounds. MS. and IR. data are given in detail. The analysis shows that a large number of minor constituents is present, many of which could not be identified.     

Catalysis in aprotic solvents. Effect of the polarity of the catalyst.

The catalytic constants for the $\text{n}$-butylaminolysis of sultones in aprotic-apolar solvents are linearly correlated with a combination of the hydrogen-bonding parameter and the polarity parameter of the catalyst.     

On the Influence of Elastic Modes on the N.M.R. Lineshapes of Polymer Liquid Crystals

Abstract

We have studied the influence of thermally excited orientational fluctuations on the N.M.R. lineshape of a nematic monodomain. The influence is characterized by a static order parameter S _stat whose theoretical expression in terms of viscoelastic parameters is derived. This model is applied to the proton N.M.R. spectrum of a thermotropic main chain polymer. The values of S _stat are deduced from the study of the changes of the N.M.R. lineshape as a function of the angle between the static magnetic field and the nematic director. Good agreement is obtained with theoretical values calculated using estimated values of the Leslie viscosity coefficients and the Frank elastic constants. The importance of an accurate knowledge of S _stat for a number of problems is stressed.     

Analysis of the equations for the temperature dependence of the retention index. I. Relation between equations.

The relation between the parameters of several equations for the retention index temperature dependence was established, taking the hyperbola deduced from the retention theory as starting point. The transformation factors depend only on methylene contributions to the thermodynamic functions of solution and temperature. Their evolution with the mean temperature of the range was illustrated for SE-30 and Carbowax-20M glass capillary columns. On this basis the post-run standardisation of dI/dT values at a reference mean temperature is possible. Examples and statistical correlation between series of parameters from different equations for perfumery solutes were shown.     

On the Influence of Elastic Modes on the N.M.R. Lineshapes of Polymer Liquid Crystals

We have studied the influence of thermally excited orientational fluctuations on the N.M.R. lineshape of a nematic monodomain. The influence is characterized by a static order parameter S_stat whose theoretical expression in terms of viscoelastic parameters is derived. This model is applied to the proton N.M.R. spectrum of a thermotropic main chain polymer. The values of S_stat are deduced from the study of the changes of the N.M.R. lineshape as a function of the angle between the static magnetic field and the nematic director. Good agreement is obtained with theoretical values calculated using estimated values of the Leslie viscosity coefficients and the Frank elastic constants. The importance of an accurate knowledge of S_stat for a number of problems is stressed.     

Research on the aromas. On the aroma of coffee. II. Pyrazines and pyridines

Pyrazines and pyridines occurring in a coffee concentrate are analyzed by two procedures. 24 compounds have been identified and the presence of some 10 more is revealed. The syntheses, mass and infrared spectral data of reference compounds are given.     

Theoretical analysis of the influence of the adsorption process on the voltammetric curves in the case of a second order adsorption step followed by a first order charge transfer reaction: Part III. Variation of the transfer coefficient and application to semiconductor electrodes in l.p.s.v. and s.s.c.v.

The kinetic behaviour of a two-step sequential reaction including a 2nd order adsorption process is treated theoretically in the case of semiconductor electrodes. It is shown that the electronic structure of the semiconductor can be taken into account in some simplified cases by introducing a formal transfer coefficient comprised between 0 and 1 and potential independent. In both linear potential sweep voltammetry and steady state cyclic voltammetry, the usual characteristic features (E_M, _M, i_M) of the voltammetric curves are calculated as a function of the sweep rate for different values of the transfer coefficient.     

The application of C-N.M.R. spectroscopy to the determination of the stereochemistry of Diels-Alder adducts

Long-range (³J) ¹³C-H coupling is a reliable probe to evaluate the stereochemistry of cycloaddition products. The method is best applied to carbonyl containing adducts but not restricted to them. Several structures have been revised and new ones evaluated.     

Ovine luteinizing hormone. VI. Analysis of the misclassification errors in the separation of intrapituitary isohormones by chromatofocusing.

Luteinizing hormone (LH) in extracts of the ovine (o) anterior pituitary gland elutes as eight or more distinct peaks when analyzed by chromatofocusing on pH 10.5-7 gradients [Keel et al., Biol. Reprod., 36 (1987) 1102]. In order to examine the efficacy of this approach to identify the distinct charge isomers of oLH, a pool of pituitary extracts was de-salted by flow dialysis and chromatofocused on a pH 10.5-7 gradient. The immunoreactive oLH eluted in nine distinct peaks which were coded with letters beginning with the most basic form. The fractions corresponding to each peak were pooled, dialyzed and lyophilized. Each peak was then re-chromatofocused on a pH 10.5-7 gradient except for the immunoreactive oLH eluting in peak A' because of the small amount present in this peak. Each peak, except for F and H, also consisted of a small percentage of immunoreactive oLH associated with adjacent peaks. This was plausible because chromatofocusing does not generally yield baseline resolution of peaks. Peak H eluted in a broad manner and was contaminated with significant amounts of isohormones F, G and Z. In contrast, peaks B, E, F, G and Z almost completely eluted in the anticipated regions. Thus, it appears that analysis of oLH charge isomers by chromatofocusing yields minimal misclassification errors and that the misclassification errors observed are associated with molecular forms which comprise a relatively small percentage of the oLH in pituitary extracts.     

Pseudomonas cytochrome c peroxidase. XIII. pH-denaturation of the enzyme.

The effect of pH on the oxidized Pseudomonas cytochrome c peroxidase molecule was studied by measuring the peroxidatic activity, the sedimentation velocity, the circular dichroic spectra in the far UV and Soret regions, and the optical absorption spectra of the enzyme in the pH range 2.5-13.0 at a constant ionic strength (micron = 0.1). The enzyme was stable in a narrow pH region, pH 6.0 - 7.4. In the low pH range the gross tertiary structure was observed to change quite simultaneously with the enzymatic activity and secondary structure. The optical absorption spectra indicated that there were no coordinated internal protein liqands in the 6th coordination positions of the heme prosthetic groups at the lowest pH studied. In the high pH range the secondary structure and the protein environment of hemes were observed to remain stable after the tertiary structure had changed and the activity had decreased. According to the optical absorption spectra the 6th internal protein ligands of hemes were retained at the highest pH studied.     

On the synthesis of ecdysone. IV. On insect hormones. The synthesis of the natural skin shedding hormone

Ecdysone ( 9 ), a hormone responsible for the skin shedding process of arthropoda, has been synthesized. (20S)-2β,3β-Diacetoxy-20-formyl-5β-pregn-7-en-6-one was prepared from the corresponding carboxylic acid and converted into ecdysone by a GRIGNARD reaction with 2-methyl-3-butyn-2-ol tetrahydropyran-2-yl ether, followed by hydrogenation of the triple bond, removal of the protecting groups, and hydroxylation in the 14α-position. C-22-isoecdysone was obtained as a by-product.     

Polysaccharides ofUngernia. VII. Partial hydrolysis of the mannan of the bulbs ofU. vvedenskyi

4-O--D-Manopyranosyl-D-mannose, O--D-mannopyranosyl-(l4)-O--D-mannopyranosyl-(14)-D-mannose, and 0--D-mannopyranosyl-(14)-O--D-mannopyranosyl-(l4)-O--D-mannopyranosyl-(l4)-D-mannose have been isolated fron the products of the partial hydrolysis of ungeromannan-V, obtained fron the bulbs ofUngernia vvedneskyi, and have been identified. This set of oligosaccharides confirms the regular structure of the carbohydrate chain of ungeromannan-V, which consists of a linear sequence of -14-bound D-mannose residues.DeceasedTranslated from Khimiya Prirodnykh Soedineii, No. 4, pp. 434–436, July–August, 1981.     

On the Use of the Knox Equation. II. the Efficiency Measurement Problem

Abstract

The Knox equation, which relates the reduced plate height, h, to the reduced linear velocity, v, has a great importance in column and stationary phase testing. Significant A, B, and C terms of the Knox equation cannot be obtain with erroneous plate heights, h. Four methods for efficiency determination, the inflection (0.6H) method, the height/area method, an asymmetry based (0.1H) method and the moment method, were critically compared using 200 real chromatograms. Efficiency obtained using Gaussian assuming methods were highly overestimated, while the asymmetry based method gave quite acceptable results. Using the exponentially modified Gaussian model, it is demonstrated that the b/a ratio (the sum b + a is the peak-width at 10% of the peak height) is not an empirical figure of merit but can be related to a “peak skew” expression.     

An N.M.R. study of the solution chemistry of vanadium pentafluoride

¹⁹F n.m.r. spectroscopy has been to investigate the solution chemistry of vanadium pentafluoride in a wide range of solvents. It is shown that VF₅ is a remarkably weak F^- acceptor even in the VF₅/AgF/HF system, and that it acts as a weak base in SbF₅ to give a fluxional mixed polymer.     

Characterization of the FKBP.rapamycin.FRB ternary complex

Rapamycin is an important immunosuppressant, a possible anticancer therapeutic, and a widely used research tool. Essential to its various functions is its ability to bind simultaneously to two different proteins, FKBP and mTOR. Despite its widespread use, a thorough analysis of the interactions between FKBP, rapamycin, and the rapamycin-binding domain of mTOR, FRB, is lacking. To probe the affinities involved in the formation of the FKBP.rapamycin.FRB complex, we used fluorescence polarization, surface plasmon resonance, and NMR spectroscopy. Analysis of the data shows that rapamycin binds to FRB with moderate affinity (K(d) = 26 +/- 0.8 microM). The FKBP12.rapamycin complex, however, binds to FRB 2000-fold more tightly (K(d) = 12 +/- 0.8 nM) than rapamycin alone. No interaction between FKBP and FRB was detected in the absence of rapamycin. These studies suggest that rapamycin's ability to bind to FRB, and by extension to mTOR, in the absence of FKBP is of little consequence under physiological conditions. Furthermore, protein-protein interactions at the FKBP12-FRB interface play a role in the stability of the ternary complex.     

N.M.R. and X-ray diffraction of the 7,7'-disodiumcromoglycate-water lyomesophases

Aqueous solutions of 7,7'-disodiumcromoglycate (7,7'-DSCG) form a variety of mesophases, whose natures depend on concentration and temperature. We have used optical microscopy, N.M.R. (of ²H, ¹⁷O and ²³Na) and X-ray techniques to construct a phase diagram for this system and to characterize the various mesophases. In the concentration range 3 to 25 wt % 7,7'-DSCG four different mesophases are found. On cooling the isotropic solution an opaque gel phase is first obtained, followed on further cooling by a birefringent glassy liquid. At concentrations below 14wt% it is nematic, while at higher concentrations it appears to be a different, more ordered, phase. At lower temperatures a hexagonal phase is formed which finally solidifies on cooling to - 15°C. The N.M.R. and X-ray characteristics of these mesophases are discussed.     

Cyclopolymerization. II. Mechanism of the free-radical polymerization of N-n-propyldimethacrylamide

The mechanism of cyclopolymerization was investigated by using N-n-propyldimethacrylamide (PDMA). Completely cyclized polymers were formed on polymerization of PDMA by a radical initiator. Moreover, those copolymers of PDMA and various monomers, such as styrene, methyl methacrylate, and vinyl acetate, obtained did not contain any detectable pendent double bonds. The kinetic investigation showed that the termination reaction proceeded between the cyclized radicals. The attempted polymerization of N-n-propyl-N-isobutyrylmethacrylamide, the monofunctional counterpart of PDMA, was failed. These results appear to confirm that cyclopolymerization of PDMA proceeds through a concerted mechanism which has been proposed for the mechanism of the cyclopolymerization of various difunctional monomers. Measurement of the ESR spectra of propagating radical has, however, revealed that the rate-determining step of the cyclopolymerization of PDMA is not intermolecular propagation but intramolecular cyclization, which indicates that the cyclization reaction proceeds in a stepwise way. This apparent contradiction was explained based upon thermodynamic considerations.     

Quinquagenary of the Scientific Work of Prof. W. Zielenkiewicz

Prof. Wojciech Zielenkiewicz was born in Warsaw on 6 June 1933. He studied chemistry at the Warsaw University and graduated in 1955. His master thesis in the field of nuclear chemistry dealt with the enrichment of bromobenzene by the Szilard-Chalmers method. Since 1955 his professional career has mostly been related to the Institute of Physical Chemistry of the Polish Academy of Sciences (PAS) founded in the same year. Initially, Wojciech Zielenkiewicz worked under the supervision of Prof. Wojciech Świętosławski. This cooperation had a powerful influence on Zielenkiewicz both as a researcher and as a person. His strong interest in thermochemistry at that time resulted partly from his research interest and partly from his attraction to one of the students doing her diploma who later became his wife. Zielenkiewicz’s PhD thesis carried out under Świętosławski’s supervision concerned the thermochemistry of cement hydration. For the purposes of this work, Zielenkiewicz constructed his first calorimeter – a labyrinth flow calorimeter which was a modified version of the first such calorimeter constructed by Świętosławski and Malawski in 1935. The calorimeter was applied for the determination of the heat of cement hardening. After his PhD, Zielenkiewicz worked on several other calorimeters for the study of heat of cement hydration with the quasi-adiabatic method as well as on ‘conduction’ calorimeters for the examination of the first phase of cement hydration. This activity resulted in a monograph Calorimetry and Thermochemistry of Cement written in collaboration with T. Krupa and published in 1975. In the following years, his scientific interests were focused mostly on various aspects of the transfer of heat energy in time, i.e. thermokinetics. He constructed a number of calorimeters for this type of measurements and, together with his co-workers, elaborated new numerical methods of determination of thermokinetics. Those methods were assessed at international symposia on thermokinetics organised by Zielenkiewicz in cooperation with the French Association of Calorimetry and Thermal Analysis (AFCAT). In this period, he established regular cooperation with scientists from France, Spain, and the USA. Research on thermokinetics includes not only theoretical studies but also experimental works. Most of the experiments conducted at the Department of Calorimetry headed by Prof. Zielenkiewicz were connected with inclusion compounds, particularly Werner complexes as well as porfyrine derivatives. In the last twenty years, Zielenkiewicz conducted research in the scope of biomolecules. The study resulted in the determination of thermodynamic properties of over 60 derivatives of nucleic acid bases and the establishment of new correlations between enthalpic, volume, and structural properties of the compounds examined. His most recent interests concerned the study of enthalpic processes of protein salting. Zielenkiewicz’s long and intensive work in the field of calorimetry and thermokinetics has appeared in numerous books and publications presenting his research results. He is the author of 7 monographs, a number of chapters in a monograph and about 200 scientific publications. They include, among others, Analysis of Course of Heat Effect in n-n Calorimeters, Signal Processing of Calorimetric System, Dynamic Theory (later translated into Russian and published in Russia), Advances in Calorimetry and Thermochemistry, Theory of Calorimetry written together with E. Margas and published in 2002 by Kluwer and the most recent book, Calorimetry, published in 2005. Prof. Zielenkiewicz has also been active as a supervisor. He assisted and supported the realisation of 14 completed PhD theses of the employees at the Institute of Physical Chemistry and is supervising 3 more students of the Institute. Moreover, he has been involved in the realization of several more PhD theses both in Poland and abroad. For many years Prof. Zielenkiewicz combined his activity on research with research coordination. He managed the organizational units of the Polish Academy of Sciences as the Director General of the PAS and as a Deputy Scientific Secretary. For 6 years he was a Scientific Secretary of the Division of Mathematical, Physical and Chemical Sciences of PAS. In the years 1968–2003 he headed the Laboratory and Department of Calorimetry and he was a director of the Institute of Physical Chemistry for 19 years. His directorship in the Institute happened in a very difficult period for Poland, i.e. when the Marshall Law was introduced in 1981. As numerous employees of the Institute were involved in the illegal Solidarity movement at that time, the position of a director of such an institution was extremely uncomfortable and required great abilities in dealing with the communist authorities in such a way as to protect those employees. It must be said that Prof. Zielenkiewicz faced this challenge with success. Prof. Zielenkiewicz was also an initiator of the Polish conferences on calorimetry and thermal analysis. The first one was held over 30 years ago. These conferences created an opportunity for Polish researchers to exchange their opinions and learn about the world research trends. Numerous outstanding scientists were guests at these conferences. Many of them are members of the Polish Society of Calorimetry and Thermal Analysis. Prof. Zielenkiewicz has been awarded many state and foreign medals and distinctions, among others, Wojciech Świętosł;awski’s Medal and the Calvet Award given by the French Association of Calorimetry and Thermal Analysis (AFCAT) as well as the most prominent Polish state orders including the Order of Polonia Restituta (the Knight’s Cross) and the Order of Labour Banner. He is a corresponding member of the Polish Academy of Sciences and the Royal Academy of Sciences in Barcelona. Dr. Paweł Gierycz