Optimal descriptors as a tool to predict the thermal decomposition of polymers

Quantitative structure-property relationship for the thermal decomposition of polymers is suggested. The data on architecture of monomers is used to represent polymers. The structures of monomers are represented by simplified molecular input-line entry system. The average statistical quality of the suggested quantitative structure-property relationships for prediction of molar thermal decomposition function $\hbox {Y}_{\mathrm{d},1/2}$ is the following: $\hbox {r}^{2}=0.970 \pm 0.01$ and $\hbox {RMSE}=4.71\pm 1.01\,(\hbox {K}\times \hbox {kg}\times \hbox {mol}^{-1})$ .     

Preparation and Characterization of the Solid Inclusion Compounds of α-, β-Cyclodextrin with Phenylalanine (D-, L- and DL-Phe) and Tryptophan (D-, L- and DL-Trp)

The solid cyclodextrin (α-, β-CD) inclusion compounds of phenylalanine (D-, L- and DL-Phe) and tryptophan (D-, L-?and DL-Trp) were prepared and the stoichiometry of host and guest in the supermolecules was determined to be 1:1 based on elemental analyses. β-CD formed inclusion compounds with α-aromatic amino acid (α-AAA) in higher yield in contradistinction to α-CD. The yields of the α- or β-CD inclusion compounds of a pair of optical isomers of chiral aromatic amino acids and their racemic modification decreased in the order L->DL->D-form. The complexation between CD and α-AAA caused a change in shape, location and diffracted intensity of the X-ray diffraction peaks of both host and guest. The decomposition temperature of the inclusion compounds was not only slightly higher than that of a pure host but also remarkably higher than that of a pure guest. Upon inclusion the signals of CD protons inside the cavity shifted to upfield while those of the protons outside the cavity had only smaller changes, and the proton signals of the aromatic ring of guest shifted to a certain extent. The chemical shift changes of 4-H and 5-H located in small end side of cavity were a bit bigger than those of 2-H and 3-H located in large one, suggesting that aromatic ring of a guest molecule within a host cavity might be kept near small end side of?cavity. An ESI-MS experiment has proved the formation and stability of the 1:1 CD inclusion compounds of α-AAA in aqueous solution.     

DSC study of the decomposition of azodicarbonamide in different media

The decomposition of azodicarbonamide (Genitron AC-2) in the solid state was investigated by DSC. It was found that the decomposition under non-isothermal conditions can be described by the autocatalytic reaction scheme $$X\xrightarrow{{k_1 }}Y,X + Y\xrightarrow{{k'_2 }}2Y$$ where the following dependences hold for the rate constants: $$k_1 = 4.8 \times 10^{19} e - {{243 600} \mathord{\left/ {\vphantom {{243 600} {RT_s - 1}}} \right. \kern-\nulldelimiterspace} {RT_s - 1}}$$ and $$k'_2 = 1.0 \times 10^{13} e - {{133 500} \mathord{\left/ {\vphantom {{133 500} {RT_s - 1}}} \right. \kern-\nulldelimiterspace} {RT_s - 1}}$$ The first pre-exponential factor includes the thermal history of the sample, especially the quick heating to a certain temperature, from which normal slow heating starts. Due to this fast heating, the decomposition reaction of AZDA may be understood as the collapse of its crystal lattice into nucleation centres with critical dimensions.     

Kinetik und Mechanismus des thermischen Zerfalls der Alkansulfohalogenide, 5. Mitt.: Der thermische Zerfall des Äthansulfochlorids bei hohen Temperaturen

A flow system was used for the measurement of the rate of thermal decomposition of ethane sulphonyl chloride at temperatures between 700 and 800° C under adiabatic conditions; a first-order law was found. The temperature dependence of the rate constant can be expressed as $$k = 1.26\cdot 10^{13} \exp ( - 46 000/RT)\sec ^{ - 1} $$ Kinetic and analytic data as well as energetic considerations suggest a radical non-chain character of the decomposition     

Photoelectrochemistry of silicon in HF solution

Photoelectrochemical, photoelectrocatalytic, and electrochemical processes of silicon anodic oxidation and hydrogen evolution in aqueous HF solution are discussed in terms of thermodynamic stability of Si, oxides SiO, SiO₂, and Si surface hydrides. It is shown that photoelectrochemical oxidation of n-type low-resistivity silicon to SiO₂ is catalyzed by Si $^{+}$ photo-hole formation, whereas in the case of p-type Si, the feasibility of this reaction is predetermined by p-type conductivity. It is suggested that anodic oxidation of Si goes through the stage of SiO oxide formation and its subsequent oxidation to SiO₂. Such mechanism accounts for chemical inertness of Si phase in HF solutions as well as for selective, anisotropic, and isotropic etching of Si within E ranges from $-0.5$ to 0.35 V, $0.35-0.8~V,$ and $E > 0.8$ V, respectively. Hydrogen evolution reaction on Si surface proceeds at very large overpotential ( $\geq 0.5$ V) through the stage of surface Si hydride formation: $\mathrm {Si + H_{2}O + e^{-} \rightarrow (SiH)_{surf} + OH^{-}}$ (the rate determining step) and $\mathrm {(SiH)_{surf} + H_{2}O + e^{-} \rightarrow Si + H_{2} + OH^{-}}$ . Illumination-related effects of surface reactions relevant to selective and anisotropic etching and nano/micro-structuring of Si surface are discussed.     

Dynamic pressure thermal analysis of double-base propellants containing RDX

The thermal decomposition of five double-base propellants modified with RDX was studied by dynamic pressure thermal analysis to determine the effect of RDX content (20–60 wt.%) on performance. All have good stability. Both stability and activation energy increase as RDX increases from 20% to 50% then decrease; 50% RDX performs best. The decomposition mechanism is affected by RDX content and temperature. Increasing temperature induces autocatalysis and accelerates decomposition.      

Spectroscopic Studies of the Complexation of Iodine with Antihistamine Drugs in Solvents of Varying Relative Permittivity

The interaction of oxatomide (OXA), azacyclonol (AZA) and chloropheniramine (ClPA) antihistamine drugs with iodine was studied spectrophotometrically in different solvents and at three different temperatures. The electronic, FT-IR, far-IR, and mass spectra of the resulting charge-transfer (CT) complexes were recorded, in addition to thermal analysis. The results obtained show that the stoichiometries of the reactions are all 1:1. The observed time dependence of the CT band and subsequent formation of $ {\text{I}}_{3}^{ - } $ in solution were related to the slow transformation of the initially formed 1:1 (donor: I₂) outer complex to an inner complex (electron donor?Cacceptor), followed by a fast reaction of the inner complex with iodine to form a triiodide ion. The characteristic strong absorptions of $ {\text{I}}_{3}^{ - } $ are observed around 360?nm. The CT-complexes have the formulae [(OXA)I]⁺ $ {\text{I}}_{3}^{ - } $ , [(AZA)I]⁺ $ {\text{I}}_{3}^{ - } $ and [(ClPA)I]⁺ $ {\text{I}}_{3}^{ - } $ . The formation constants (K), molar absorption coefficients (?? _CT), and thermodynamic parameters ??H ^#, ??S ^# and ??G ^# of these interaction have been determined and discussed.     

In vitro magnetic hyperthermia response of iron oxide MNP’s incorporated in DA3, MCF-7 and HeLa cancer cell lines

In the current work, iron oxide magnetic nanoparticles (MNP’s) were synthesized by thermal decomposition of Fe(acac)₃-(iron acetylacetonate) compounds in high-boiling organic solvents containing stabilizing surfactants and examined as possible agents for magnetic hyperthermia treatment, according to their structural, magnetic and heating properties. Three different cancer cell lines (DA3, MCF-7 and HeLa cell lines) were used to assess the suitability of the MNP’s. The experimental results proved that the synthesized MNPs are non-toxic and the uptake efficiency was extremely good. Further, from in vitro hyperthermia results, very fast thermal response was observed (reaching hyperthermia levels in less than 200 s), which minimize the duration of the cell and human body exposure in a high frequency AC external magnetic field.      

A systematic study of the thermal decomposition of tetraalkylammonium haloborates

Thermal decompositions of tetraalkylammonium haloborates, R₄N⁺BX ₄ ^? (whereR=Et orn-Bu, andX=Cl, Br or PhBCl₂), have been studied by both bench pyrolysis and thermoanalytical techniques. The first stage in the thermal decomposition of the haloborates involves the loss of one mole of an alkyl halide with the formation of a 1∶1 complex. Thermal decomposition of the haloborates beyond the stage of formation of haloboranes leads to the evolution of further quantities of alkyl halides together with the corresponding boron trihalide. In many instances the final products were polymeric materials of the general type: .     

Gas-chromatographic determination of the composition of the volatile components of the oleoresins of some species of conifers

Using the method of analytical GLC in a glass capillary column, the compositions have been studied of the volatile fractions of the oleoresins of five species of conifers:Larix decidua,Pinus strobus,Pinus mugo,Picea excelsa, andPinus abies. In the oleoresins 21 monoterpene and 22 sesquiterpene compounds were identified from their relative retention times and with the aid of additives. The main components of the volatile fractions of the oleoresins were α- and β-pinenes and 3-carene among the monoterpenes, and longifolene caryophyllene, δ- and γ-cadinenes and α-murolene among the sesquiterpene compounds. The quantitative analysis of the fractions was carried out by the method of internal normalization from averaged correlation coefficients.     

The mechanism of thermal decomposition of ionic oxalates

A mechanism for the thermal decomposition of ionic oxalates has been proposed on the basis of three quantitative relationships linking the quantitiesr _c/r _i (the ratio of the Pauling covalent radius and the cation radius of the metal atom in hexacoordination) andΣI _i (the sum of the ionization potentials of the metal atom in kJ mol^?1) with the onset oxalate decomposition temperature (T _d) (Eq. 1) the average C-C bond distance (¯d) (Eq. 2), and the activation energy of oxalate decomposition (E _a) (Eq. 3): (1) $$T_d = 516 - 1.4006\frac{{r_c }}{{r_i }}(\sum I_i )^{\frac{1}{2}}$$ (2) $$\bar d = 1.527 + 5.553 \times 10^{ - 6} \left( {122 - \frac{{r_c }}{{r_i }}(\sum I_i )^{\frac{1}{2}} } \right)^2$$ (3) $$E_a = 127 + 1.4853 \times 10^{ - 6} \left( {\left( {\frac{{r_c }}{{r_i }}} \right)^2 \sum I_i - 9800} \right)^2$$ On the basis of these results it is proposed that the thermal decomposition of ionic oxalates follows a mechanism in which the C-O bond ruptures first. From Eq. 3 it is further proposed that strong mutual electronic interactions between the oxalate and the cations restrict the essential electronic reorganization leading to the products, thereby increasingE _a.     

Investigation of thermal decomposition kinetics of taurine

The non-isothermal thermal decomposition of taurine was investigated by means of thermogravimetric analysis (TG) and differential thermal analysis (DTA). The experimental data were treated using Flynn–Wall–Ozawa, Doyle, Kissinger, and ?atava–?esták methods, respectively. The results show that the non-isothermal thermal decomposition mechanism of taurine is classified as phase boundary reaction, and the mechanism function is the Mampel Power law with n = 1. The forms of both integral and differential for the mechanism function are $ G(\alpha ) = \alpha $ and $ f(\alpha ) = 1 $ , respectively. The activation energy and the pre-exponential factor are 167.88 kJ mol^?1 and 1.82 × 10¹³min^?1, respectively.     

Correlation between C-H and C-C spin-spin coupling constants and s character of hybrids calculated by the maximum overlap method

For some thirty hydrocarbons the s character of hybrids obtained by the application of the maximum overlap method have been correlated with C-H and C-C spin-spin coupling constants. The following relationships were obtained: $$J_{{\text{C}}^{{\text{13}}} - {\text{H}}} = 1079a_{{\text{CH}}}^{\text{2}} /(1 + S_{{\text{CH}}}^{\text{2}} ) - 54.9$$ , $$J_{{\text{C}}_{\text{1}}^{{\text{13}}} - {\text{C}}_{\text{2}}^{{\text{13}}} } = 1020.5a_{{\text{C}}_{\text{1}} }^2 a_{{\text{C}}_{\text{2}} }^{\text{2}} /(1 + S_{{\text{CC}}}^{\text{2}} ) - 8.2$$ . Here the coupling constants are expressed in cps units. In the calculation of the maximum overlap hybrids either the experimental bond lengths or a standard bond lengths were used. For the \(J_{{\text{C}}^{{\text{13}}} - {\text{H}}}\) and \(J_{{\text{C}}^{{\text{13}}} - {\text{H}}} \) coupling constants the standard deviations are 0.9 cps and 1.9 cps respectively. It has been suggested that the large additive constant in the \(J_{{\text{C}}^{{\text{13}}} - {\text{H}}}\) correlation may be attributed to the ionic character of C-H bonds. A good agreement with the experimental data strongly supports the idea that the Fermi contact term and the hybridization are dominant factors in determining carbon-hydrogen and carbon-carbon spin-spin coupling constants across one bond, at least in hydrocarbons.     

Reaction of barbituric acid with organic azides and phosphonium ylides

Amination by organic azides has been carried out to provide aminobarbiturates by fusion of a triazole ring to the 5,6-positions of barbituric acid followed by cleavage and thermal elimination of nitrogen, whereas aza-Wittig reaction gave phosphoranylidene barbituric acid salts.      

The principal measure and distributional (p, q)-chaos of a coupled lattice system with coupling constant \varepsilon =1 related with Belusov–Zhabotinskii reaction

We consider the following system coming from a lattice dynamical system stated by Kaneko (Phys Rev Lett, 65:1391–1394, 1990) which is related to the Belusov–Zhabotinskii reaction: $$\begin{aligned} x_{n}^{m+1}=(1-\varepsilon )f\left( x_{n}^{m}\right) +\frac{1}{2}\varepsilon \left[ f(x_{n-1}^{m})+f\left( x_{n+1}^{m}\right) \right] , \end{aligned}$$ where $m$ is discrete time index, $n$ is lattice side index with system size $L$ (i.e., $n=1, 2, \ldots , L$ ), $\varepsilon \ge 0$ is coupling constant, and $f(x)$ is the unimodal map on $I$ (i.e., $f(0)=f(1)=0$ , and $f$ has unique critical point $c$ with $0<c<1$ and $f(c)=1$ ). In this paper, we prove that for coupling constant $\varepsilon =1$ , this CML (Coupled Map Lattice) system is distributionally $(p, q)$ -chaotic for any $p, q\in [0, 1]$ with $p\le q$ , and that its principal measure is not less than $\mu _{p}(f)$ . Consequently, the principal measure of this system is not less than $\frac{2}{3}+\sum _{n=2}^{\infty }\frac{1}{n}\frac{2^{n-1}}{(2^{n}+1) (2^{n-1}+1)}$ for coupling constant $\varepsilon =1$ and the tent map $\Lambda $ defined by $\Lambda (x)=1-|1-2x|, x\in [0, 1]$ . So, our results complement the results of Wu and Zhu (J Math Chem, 50:2439–2445, 2012).     

A thermodynamic study of complexation of 18-crown-6 with Zn2+, Tl+, Hg2+ and {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} cations in acetonitrile-dimethylformamide binary media and study the effect of anion on the stability constant of (18C6-Na+) complex in methanol solutions

The equilibrium constants and thermodynamic parameters for complex formation of 18-crown-6(18C6) with Zn²⁺, Tl⁺, Hg²⁺ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations have been determined by conductivity measurements in acetonitrile(AN)-dimethylformamide(DMF) binary solutions. 18-crown-6 forms 1:1 complexes [M:L] with Zn²⁺, Hg²⁺ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations, but in the case of Tl⁺ cation, a 1:2 [M:L₂] complex is formed in most binary solutions. The thermodynamic parameters ( $ \Delta {\text{H}}^{ \circ }_{{\text{c}}} $ and $ \Delta {\text{S}}^{ \circ }_{{\text{c}}} $ ) which were obtained from temperature dependence of the equilibrium constants show that in most cases, the complexes are enthalpy destabilized but entropy stabilized and a non-monotonic behaviour is observed for variations of standard enthalpy and entropy changes versus the composition of AN/DMF binary mixed solvents. The obtained results show that the order of selectivity of 18C6 ligand for these cations changes with the composition of the mixed solvent. A non-linear relationship was observed between the stability constants (logK_f) of these complexes with the composition of AN/DMF binary solutions. The influence of the $ {\text{ClO}}^{ - }_{{\text{4}}} $ , $ {\text{NO}}^{ - }_{{\text{3}}} $ and $ {\text{Cl}}^{ - } $ anions on the stability constant of (18C6-Na⁺) complex in methanol (MeOH) solutions was also studied by potentiometry method. The results show that the stability of (18C6-Na⁺) complex in the presence of the anions increases in order: $ {\text{ClO}}^{ - }_{{\text{4}}} $  >  $ {\text{NO}}^{ - }_{{\text{3}}} $  >  $ {\text{Cl}}^{ - } $ .     

Thermal analysis of new dimethyl/dibutyl tin(IV) compounds with amino acids

Six diorganotin(IV) compounds with amino acids of general formula [(CH₃)₂SnAACl]₂ and [(CH₃CH₂CH₂CH₂)₂SnAACl]₂ (where AA = l-methioninate, l-cysteinate, and l-tryptophanate) were synthesized by reacting dimethyltin(IV) dichloride (M) and dibutyltin(IV) dichloride (B) with l-methionine (M₁) or l-cysteine (C) or l-tryptophan (T) using acetonitrile as solvent and designated as MM₁, MC, MT, BM₁, BC, and BT. The structural characterization of dimethyltin(IV) and dibutyltin(IV) compounds were done using elemental analysis, FT-IR, ¹H-NMR, ¹³C-NMR, and ¹¹⁹Sn-NMR spectroscopy. The thermal properties of the synthesized compounds were studied by thermogravimetric analysis and differential scanning calorimetry techniques in a dynamic atmosphere of nitrogen. The thermal decomposition mechanisms were similar for compounds MM₁, BM₁, MC, BC, and occurred in one step, while in compounds MT and BT it occurred in two consecutive steps. The TG curves of the MT and BT compounds suggest the loss of the ligand (AA) in the first step, with probable formation of a tin oxide R₂SnO intermediate. At the end of the second step free tin is obtained similar to the MM₁, BM₁, MC, BC in accordance with the stoichiometry of the related compounds.     

Heats of formation of the amino acids re-examined by means of W1-F12 and W2-F12 theories

We have obtained accurate heats of formation for the twenty natural amino acids by means of explicitly correlated high-level thermochemical procedures. Our best theoretical heats of formation, obtained by means of the ab initio W1-F12 and W2-F12 thermochemical protocols, differ significantly (RMSD = 2.3 kcal/mol, maximum deviation 4.6 kcal/mol) from recently reported values using the lower-cost G3(MP2) method. With the more recent G4(MP2) procedure, RMSD drops slightly to 1.8 kcal/mol, while full G4 theory offers a more significant improvement to 0.72 kcal/mol (max. dev. 1.4 kcal/mol for glutamine). The economical G4(MP2)-6X protocol performs equivalently at RMSD = 0.71 kcal/mol (max. dev. 1.6 kcal/mol for arginine and glutamine). Our calculations are in excellent agreement with experiment for glycine, alanine and are in excellent agreement with the recent revised value for methionine, but suggest revisions by several kcal/mol for valine, proline, phenylalanine, and cysteine, in the latter case confirming a recent proposed revision. Our best heats of formation at 298 K ( $\Delta H_{f,298}^{\circ }$ ) are as follows: at the W2-F12 level: glycine ?94.1, alanine $-$ 101.5, serine $-$ 139.2, cysteine $-$ 94.5, and methionine $-$ 102.4  kcal/mol, and at the W1-F12 level: arginine $-$ 98.8, asparagine $-$ 146.5, aspartic acid $-$ 189.6, glutamine $-$ 151.0, glutamic acid $-$ 195.5, histidine $-$ 69.8, isoleucine $-$ 118.3, leucine $-$ 118.8, lysine $-$ 110.0, phenylalanine $-$ 76.9, proline $-$ 92.8, threonine $-$ 149.0, and valine $-$ 113.6 kcal/mol. For the two largest amino acids, an average over G4, G4(MP2)-6X, and CBS-QB3 yields best estimates of $-$ 58.4 kcal/mol for tryptophan, and of $-$ 117.5 kcal/mol for tyrosine. For glycine, we were able to obtain a “quasi-W4” result corresponding to $\hbox {TAE}_e$  = 968.1, $\hbox {TAE}_0$  = 918.6, $\Delta H_{f,298}^{\circ }=-90.0$ , and $\Delta H_{f,298}^{\circ }=-94.0$  kcal/mol.     

Density functional theoretical study of A series of pentazolide compounds \hbox{A}_{\it n}(\hbox{N}_5)_{\rm 6-{\it n}}^{\it q} (A = B, Al, Si, P, and S; n = 1–3; q = +1, 0, −1, −2, and −3)

The structure and the stability of pentazolide compounds $\hbox{A}_{\it n}(\hbox{N}_5)_{\rm 6-{\it n}}^{\it q}$ (A = B, Al, Si, P, and S; n= 1–3; q = +1, 0, ?1, ?2, and ?3), as high energy-density materials (HEDMs), have been investigated at the B3LYP/6-311+G* level of theory. The natural bond orbital analysis shows that the charge transfer plays an important role when the $\hbox{A}_{\it n}(\hbox{N}_5)_{\rm 6-{\it n}}^{\it q}$ species are decomposed to $\hbox{A}_{\it n}(\hbox{N}_5)_{\rm 5-{\it n}}\hbox{N}_3^{\it q}$ and N₂. The more negative charges are transferred from the N₂ molecule after breaking the N₅ ring, the more stable the systems are with respect to the decomposition. Moreover, the conclusion can be drawn that ${\hbox{Al}(\hbox{N}_5)_5^{2-}}$ and ${\hbox{Al}_2(\hbox{N}_5)_4^{2-}}$ are predicted to be suitable as potential HEDMs.