Platform Synthetic Lectins for Divalent Carbohydrate Recognition in Water

Biomimetic carbohydrate receptors (“synthetic lectins”) have potential as agents for biological research and medicine. However, although effective strategies are available for “all‐equatorial” carbohydrates (glucose, etc.), the recognition of other types of saccharide under natural (aqueous) conditions is less well developed. Herein we report a new approach based on a pyrene platform with polar arches extending from aryl substituents. The receptors are compatible with axially substituted carbohydrates, and also feature two identical binding sites, thus mimicking the multivalency observed for natural lectins. A variant with negative charges forms 1:2 host/guest complexes with aminosugars, with K₁>3000 m ^?1 for axially substituted mannosamine, whereas a positively charged version binds the important α‐sialyl unit with K₁≈1300 m ^?1.     

Azo‐Coupling Reactions of Para‐X‐Benzenediazonium Cations with 3‐Ethoxythiophene in Acetonitrile

Kinetic studies for the azo‐coupling reactions of 3‐ethoxythiophene 1 with a series of 4‐X‐substituted diazonium cations 2a‐e (X = OCH₃, CH₃, H, Cl, and NO₂) have been investigated in acetonitrile at 20°C. The second‐order rate constants have been employed to determine the nucleophilicity parameters N and s of the thiophene 1 according the Mayr equation. Thus, the nucleophile‐specific parameters N and s of thiophene 1 have been derived and compared with the reactivities of other C‐nucleophiles in acetonitrile (pyrroles, furan, indoles, etc.). The Yukawa–Tsuno plot resulted in an excellent correlation (R² = 0.9980) with an r value of 0.89, suggesting that the nonlinear Hammett plot observed in the present work is due to resonance demand of the π–electron donor substituent of on the –N₂⁺ moiety. Importantly, using the concept of global electrophilicity (ω) proposed by Parr, we successfully predict the electrophilicity parameters E of seven substituted diazonium cations whose experimental data are available.     

The MRSDCI studies of four low-lying electronic states of the BF2 radical

The equilibrium geometries, excitation energies, force constants, and vibrational frequencies for four low-lying electronic states X ²A₁, ²B₁, ²B₂, and ²A₂ of the BF₂ radical have been calculated at the MRSDCI level with a double zeta plus polarization basis set. Our calculated excitation energy for X²A₁ → ²B₁ is in agreement with available experimental data. The electronic transition dipole moments, oscillator strengths for the ²B₁ → X²A₁ and ²B₂ → X²A₁ transitions, radiative lifetimes for the ²B₁ and ²B₂ states, and the spin properties for the X²A₁ state are calculated based on the MRSDCI wave functions, predicting results in reasonable agreement with available experimental data. © 1993 John Wiley & Sons, Inc.     

Carbofunctional sulfur‐containing organosilicon compounds

This review summarizes literature data and the authors’ own research results from the past 14–15 years relating to practical, valuable organosilicon carbofunctional sulfur‐containing compounds of general formula R_4−n Si(S_x R¹)_n , where R is alkyl, arylalkoxyl, aroxyl or even sylatranyl fragment, R¹ is hydrogen, alkyl, aryl, alkenyl, etc., n = 1–3, x = 1–10, having sulfur functional groups such as thiol, sulfide, di‐ and polysulfide, as well as sulfur heteroatomic groups such as thiocarbamide, dioxothiocarbamide, dithiourethane, thiuramdisulfide, etc. The compounds reviewed have been found to be effective, for example, as ingredients for rubber compositions for non‐flammable, water‐ and wear‐proof tires or as ion‐exchanging and complexing sorbents of heavy and noble metals.     

Theoretical studies on the reactions of acetone with chlorine atom and methyl radical

Theoretical investigations are carried out on the reaction multi-channel CH₃COCH₃ + Cl (R1) and CH₃ COCH₃ + CH₃ (R2) by means of direct dynamics methods. The minimum energy path (MEP) is obtained at the MP2/6-31 + G(d,p) level, and energetic information is further refined at the BMC–CCSD (single-point) level. The rate constants are calculated by the improved canonical variational transition state theory (ICVT) with the small-curvature tunneling (SCT) correction in a wide temperature range 200–3,000 K. The theoretical overall rate constants are in good agreement with the available experimental data and are found to be k ₁ = 3.08 × 10⁻¹⁷ T ^2.03exp(−32.96/T) and k ₂ = 1.61 × 10⁻²³ T ^3.53 exp(−3969.51/T) cm³molecule⁻¹s⁻¹. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A shock tube study of the reaction NH2 + CH4 → NH3 + CH3 and comparison with transition state theory

The rate coefficient for NH₂ + CH₄ → NH₃ + CH₃ (R1) has been measured in a shock tube in the temperature range 1591–2084 K using FM spectroscopy to monitor NH₂ radicals. The measurements are combined with a calculation of the potential energy surface and canonical transition state theory with WKB tunneling to obtain an expression for k₁ = 1.47 × 10³ T ^3.01 e^?5001/T(K) cm³ mol^?1 s^?1 that describes available data in the temperature range 300 –2100 K. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 304–309, 2003     

The negative ion mass spectra of mixtures of sulphur and organic compounds. II—the formation of [C5H5 + Sn]− from the mixture of sulphur and ferrocene

The negative ion mass spectra of ferrocene and of a mixture of ferrocene with sulphur were studied. In the spectrum of the mixture, characteristic peaks of [C₅H₅ + S_n]^? (n = 1, 2, 3 etc.) were observed. The structures of these ions are discussed.     

Effects of organometallic cocatalysts on the polymerization of disubstituted acetylenes by TaCl5 and NbCl5

The effects of organometallic cocatalysts on the polymerization of disubstituted acetylenes were investigated. Diphenylacetylene did not polymerize with TaCl₅ alone, while it produced a polymer quantitatively in the presence of appropriate cocatalysts (Me₄Sn, Et₃SiH, etc.). The poly(diphenylacetylene) formed was an insoluble yellow solid. 1-Phenyl-1-alkynes (1-Phenyl-1-butyne and -1-octyne) polymerized with TaCl₅ and NbCl₅ alone to yield polymers whose weight-average molecular weights (M _w's) were ca. 5 × 10⁵. Use of cocatalysts (nBu₄Sn etc.) to the polymerization of these monomers accelerated the reaction, and increased the polymer molecular weights up to ca. 1.5 × 10⁶. The poly(1-phenyl-1-alkynes) were soluble white solids. Internal octynes (2-, 3-, and 4-octynes) gave mixtures of a polymer and cyclotrimers with TaCl₅ alone. In contrast, cyclotrimers formed virtually selectively by addition of cocatalysts. Thus, various effects of organometallic cocatalysts were observed depending on the kind of monomer.     

Solid-state 31P and 109Ag CP/MAS NMR as a powerful tool for studying of silver(I) complexes with N-thiophosphorylated thiourea and thioamide ligands

A family of three- and four-coordinated silver(I) complexes of formulas [Ag(PPh₃)₂L], [Ag(PPh₃)L], and [AgL]_n with N-thiophosphorylated thiourea and thioamide ligands of general formula RC(S)NHP(S)(OPri)₂ [R = Ph, PhNH, iPrNH, tBuNH, NH₂] have been studied by solid-state ¹⁰⁹Ag and ³¹P CPMAS NMR spectroscopy. ¹⁰⁹Ag NMR spectra have provided valuable structural information about Ag coordination, which is in good accordance with the available crystal structure data. The data presented in this work represent a significant addition to the available ¹⁰⁹Ag chemical shifts and chemical shifts anisotropies. The silver chemical shift ranges for different P,S-environments and coordination state were discussed in detail. The ¹J(³¹P–^107/109Ag) and ²J(³¹P–³¹P) values were determined and analyzed.     

A Theoretical Study of LiHe+ n , NaHe+ n , and MgHe+ n Complexes, with n=1, 2, 3, 4

The LiHe⁺ _n , the NaHe⁺ _n , and the MgHe⁺ _n complexes with n=1, 2, 3, 4 were studied using ab initio calculations with the MP2/6-311+G(3df, 3pd) method. The complexes are found to be stable. For the n=1 complexes, previous results were available and the calculations performed are in good agreement with those results. This lends credibility to the results obtained for the complexes with higher n.     

Additional pitfalls of using 1,1‐ADEQUATE for structure elucidation

1,1‐ADEQUATE is a powerful and robust NMR experiment to establish carbon–carbon connectivities using modest sample quantities when cryogenic probe technology is available. Yet potential pitfalls of applying this method are not widely appreciated, such as weak or missing ¹J_CC correlations in strongly coupled ¹³C‐¹³C AB spin systems and unusually large multi‐bond (ⁿJ_CC) correlations associated with particular functional groups. These large ⁿJ_CC correlations observed in 1,1‐ADEQUATE spectra could be mistaken for ¹J_CC correlations. Copyright © 2016 John Wiley & Sons, Ltd.     

Separation of arsenic from germanium oxide targets by dry distillation

Positron-emitting isotopes of arsenic, ⁷⁰As (T _1/2 = 53 min), ⁷¹As (T _1/2 = 64 h), ⁷²As (T _1/2 = 26 h), and ⁷³As (T _1/2 = 17.8 d) are of interest in biomedical investigations using PET. A fast and simple method for their production using low-energy proton and deuteron reactions on enriched Ge-targets is presented. Dry distillation of GeO₂ at 1105 °C during 2 hours provides a separation efficiency of more than 60%. The loss of target material is less than one per cent and the irradiated targets can be used several times. The method allows production of diagnostically useful amounts of positron-emitting arsenic isotopes using accelerators commonly available at PET-centres.     

The valence and Rydberg excited states of CH2: A theoretical exploration

Using the completed active space second‐order perturbation (CASPT2) method, valence and Rydberg excited states of CH₂ molecule are probed with the large atomic natural orbital (ANO‐L) basis set. Five states are optimized and the geometric parameters are in good agreement with the available data in literatures, furthermore, the state of 2¹B₁ is obtained for the first time. Valence and Rydberg excited states of CH₂ are also calculated for the vertical transitions with the ANO‐L+ basis set that is constructed by adding a set of 1s1p1d Rydberg orbitals into the ANO‐L basis set. Two Rydberg states of the p?³A₂ and r?³B₁ at 9.88 and 10.50 eV are obtained for the first time, and the 3a₁ → 3d_yz nature of the state p?³A₂ and the 3a₁ → d_x2?y2 nature of the state r?³B₁ are confirmed. © 2012 Wiley Periodicals, Inc.     

Accurate analytic potential energy function and spectroscopic study for CH(XΠ) radical using coupled-cluster theory in combination with the correlation-consistent quintuple basis set

The coupled-cluster singles-doubles-approximate-triples [CCSD(T)] theory in combination with the correlation-consistent quintuple basis set (aug-cc-pV5Z) is used to investigate the spectroscopic properties of the CH(X²Π) radical. The accurate adiabatic potential energy curve is calculated over the internuclear separation ranging from 0.07 to 2.45 nm and is fitted to the analytic Murrell–Sorbie function, which is employed to determine the spectroscopic parameters, ω_eχ_e, α_e and B_e. The present D_e, R_e, ω_e, ω_eχ_e, α_e and B_e values are of 3.6261 eV, 0.11199 nm, 2856.312 cm⁻¹, 64.9321 cm⁻¹, 0.5452 cm⁻¹ and 14.457 cm⁻¹, respectively. Excellent agreement is obtained when they are compared with the available measurements. With the potential obtained at the CCSD(T)/aug-cc-pV5Z level of theory, a total of 18 vibrational states is predicted when J = 0 by numerically solving the radial Schrödinger equation of nuclear motion. The complete vibrational levels, classical turning points, inertial rotation and centrifugal distortion constants are reproduced for the CH(X²Π) radical when J = 0 for the first time, which are in good agreement with the available RKR data.     

Generalized 1/Z expansion for heteronuclear molecules

We have first studied empirical regularities in various series of heteronuclear diatomic molecules between the energy E, the total number of electrons N, the equilibrium distance R_e and Z? = (Z₁Z₂)^1/2 where Z₁e and Z₂e are the nuclear charges in the diatom. In particular, for various alkali halide series, R_e²|E|/N^5/3 is shown to correlate rather simply with Z?R_e³. Some theoretical basis is afforded by generalizing the 1/Z expansion used early by the writers in work on homonuclear diatomics. Finally, when Z₂/Z₁ → ∞, a model is presented which predicts a finite asymptotic bond length and this prediction is confronted with available experimental data for both heteronuclear diatoms and for the polyatomic series CH₄ to SnH₄.     

FT‐IR Study of Some Carotenoids

Some natural and semisynthetic carotenoids were examined by means of FT‐IR spectroscopy. The IR bands of the characteristic functional groups (CH₃, CH₂, CC, CO, OH, etc.) were assigned when possible. Some special functional groups – without H‐atoms – such as CCC, ‘cross epoxides', etc., which cannot be easily identified by ¹H‐NMR methods, were also detected in the FT‐IR spectra.     

Sterically-crowded pyrroles

The syntheses in good yields of a considerable number of moderately to severely sterically-crowded 1,2,5-trisubstituted pyrroles by means of modifications of the Knorr-Paal condensation are described. Notwithstanding reports to the contrary, the classical procedure; succeeded in moderately sterically-crowded cases, e.g., R² = R⁵ = Me, R¹ = i-Pr, Me₂CHMeCH-, Me₂N-, Ph₂N-, 9-carbazolo, subst. 4-morpholino, 1-piperazino, 1-piperidino, etc. A product-water azeotroping procedure succeeded in more severely sterically-crowded cases e.g., R² = R⁵ = Et, R¹ = i-Pr; R² = R⁵ = Me, R¹ = Me₃CCH₂-, R² = R⁵ = i-Pr, R¹ = PhCH₂-. Highly sterically-crowded pyrroles, e.g., R² = R⁵ = Me, R¹ = t-Bu, adamantyl, PhCH₂CMe₂; R² = R⁵ = Et, R¹ = t-Bu; R¹ = R² = R⁵ = i-Pr; R² = R⁵ = t-Ru, R¹ = Me, Et, PhCH₂-, were obtained using titanium tetrachloride as a Lewis acid catalyst and as a water scavenger. Infrared spectra of the reacting mixtures provided evidence pertinent to the mechanism of the reaction, which is discussed.     

Ab initio study of the low-lying electronic states of the CH2NO2 radical

Ab initio electronic structures calculations are reported for the four low-lying electronic states X ²B₁, ²B₂, ²A₂, and ²A₁ of the CH₂NO₂ radical. The geometric parameters for the ground-state X ²B₁ are predicted by MRSDCI calculations with a double zeta plus polarization basis set. The vertical excitations energies for these electronic states are determined using MRSDCI /DZ +P calculations at the ground-state equilibrium geometry and in agreement with the recent experimental data obtained via PES of the CH₂NO anion. The oscillator strenghts and the radiative lifetimes for these electronic states and the spin properties for the ground state are calculated based on the MRSDCI wave functions, predicting results in good agreement with available experimental data. © 1994 John Wiley & Sons, Inc.     

Thermodynamics of Carbon Dioxide Adsorption on the Protonic Zeolite H‐ZSM‐5

Adsorption of carbon dioxide on H‐ZSM‐5 zeolite (Si:Al=11.5:1) was studied by means of variable‐temperature FT‐IR spectroscopy, in the temperature range of 310–365 K. The adsorbed CO₂ molecules interact with the zeolite Brønsted‐acid OH groups bringing about a characteristic red‐shift of the O? H stretching band from 3610 cm^?1 to 3480 cm^?1. Simultaneously, the ν₃ mode of adsorbed CO₂ is observed at 2345 cm^?1. From the variation of integrated intensity of the IR absorption bands at both 3610 and 2345 cm^?1, upon changing temperature (and CO₂ equilibrium pressure), the standard adsorption enthalpy of CO₂ on H‐ZSM‐5 is ΔH⁰=?31.2(±1) kJ mol^?1 and the corresponding entropy change is ΔS⁰=?140(±10) J mol^?1 K^?1. These results are discussed in the context of available data for carbon dioxide adsorption on other protonic, and also alkali‐metal exchanged, zeolites.     

Rate constant for the reaction of CH3C(O)CH2 radical with HBr and its thermochemical implication

The fast flow method with laser induced fluorescence detection of CH₃C(O)CH₂ was employed to obtain the rate constant of k₁ (298 K) = (1.83 ± 0.12 (1σ)) × 10¹⁰ cm³ mol^?1 s^?1 for the reaction CH₃C(O)CH₂ + HBr ? CH₃C(O)CH₃ + Br (1, ?1). The observed reduced reactivity compared with n‐alkyl or alkoxyl radicals can be attributed to the partial resonance stabilization of the acetonyl radical. An application of k₁ in a third law estimation provides Δ_fH(CH₃C(O)CH₂) values of ?24 kJ mol^?1 and ?28 kJ mol^?1 depending on the rate constants available for reaction ( ‐1 ) from the literature. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 32–37, 2006