Aminocyclodextrins to facilitate the deprotonation of 4-tert-butyl-alpha-nitrotoluene

6A-Amino-6A-deoxy-beta-cyclodextrin enhances the rate of the deprotonation of 4-tert-butyl-alpha-nitrotoluene. The rate constants for reaction of the cyclodextrin-bound species, kinc = 4 x 10(-3), 9 x 10(-3) and 19 x 10(-3) s(-1), at pH 6.0, 6.5 and 7.0, respectively, in 0.1 mol dm(-3) aqueous phosphate buffer containing 1% methanol at 298 K. These rate constants correspond to a rate acceleration (kinc/kun) of ca. 10 times at each pH. Under the same conditions, 6A-dimethylamino-6A-deoxy-beta-cyclodextrin and 6A-(2-aminoethylamino)-6A-deoxy-beta-cyclodextrin are more effective; at pH 6.0, 6.5 and 7.0, for the former, kinc = 3 x 10(-2), 7 x 10(-2) and 12 x 10(-2) s(-1), whilst for the latter, kinc = 4 x 10(-2), 5 x 10(-2) and 9 x 10(-2) s(-1), respectively. Each cyclodextrin also decreases the pKa of the nitrotoluene, from 6.8 in free solution, to 6.2 when bound. The accelerated deprotonation by 6A-amino-6A-deoxy-beta-cyclodextrin is reflected in the enhanced rates of hydrogen-deuterium exchange of the nitrotoluene in deuterium oxide, and in the conjugate addition of the nitrotoluene to methyl vinyl ketone in aqueous solution.     

Investigation of transannular cyclisations of verticillanes to the taxane ring system

Treatment of either the verticillenes (3), (6), (13) or (14) with Lewis acids fails to produce the corresponding taxane carbon framework $\text{viz}$ (2), and instead only products, e.g. (8), (9), (16), of rearrangement of the epoxide rings in the substrates are obtained.     

Letter to the Editor

Abstract

Dear Sir

With respect to the article “Collection and Analysis of Rainwater etc.” (Slanina et al., vol. 7, pp. 161-176), my remarks on this article (vol. 9, pp. 221-223) and the answer of Mr. Slanina (vol. 9, pp. 223-225), I should like to make my final remarks as follows.     

About the stereoelectronics of the intramolecular addition of allylsilanes to aldehydes

(Z)-omega-Trimethylsilyl-(omega-2)-alken-1-ols are readily accessible by consecutive superbase metalation and silylation of (omega-1)-alken-1-ols. These versatile intermediates may be oxidized to give the corresponding (Z)-omega-trimethylsilyl-(omega-2)-alkenals which, in the presence of trifluoroacetic acid, can be converted into 2-vinylcycloalkanols such as 2-vinylcyclohexanol (2), isopulegol (4), and bis(2-vinylcyclobutyl) ether (8). The stereochemical outcome of these cyclization reactions suggests the interference of a novel electrodynamic effect.     

Adaptation of the ORAC assay to the common laboratory equipment and subsequent application to antioxidant plastic films

The oxygen radical absorbance capacity (ORAC) method has been adapted to the instrumental laboratory and optimized for the determination of the antioxidant capacity of a novel active packaging. As the ORAC assay requires the monitorization of a reaction at controlled temperature by means of the fluorescence signal decrease over time, specific instrumental is usually necessary. In this work, a common liquid chromatographic device has been adapted to perform the ORAC assay, leaving it accessible to any laboratory. Using this adaptation, five different essential oils have been determined resulting in the following antioxidant order: clove (2.66 g Trolox per gram of essential oil), oregano (2.25), cinnamon (1.93), rosemary (1.66), and ginger (1.47). After incorporating the essential oils to the film, its antioxidant capacity has also been checked and related to the concentration of essential oil as well as the thickness of the active film. The results point out that for the same amount of essential oil incorporated measured as grams per square meter, thicker films have more antioxidant capacity than the thinner and more concentrated ones. Furthermore, the antioxidant capacity found in the films was always higher than expected taking into account the amount of essential oil incorporated. Some likely explanations have been proposed, leading to the improvement of the antioxidant film under development.     

Application of arsenite reduction to the potentiometric determination of gold and to the analysis of mixtures and alloys

The present work is an application of iodide to the reduction of gold(III), in an attempt to develop new method for gold(III) based on potentiometric back-titration of the excess of iodide with mercury(II). Although it was proved by calculation that the reduction of tetrachloroaurate to the metal should proceed quantitatively to completion, yet our experiments showed that the reduction under ordinary conditions, gave Au(I) in the form of a white precipitate of AuI. We succeeded to push the reduction with iodide to the metal by an excess of ethanol-ether catalyzed iodide at somewhat elevated temperature.With the experimental conditions established a reliable procedure have been developed involving a potentiometric finish which enabled accurate determination of gold(III), either alone or in some of its alloys.     

A step-wise approach to the determination of the lower limit of analysis of the calibration line

A method is presented of stipulating the extension of the calibration line in analytical chemistry. The method is based on a combination of chemometric data interpretation and the calculation of the minimum standard deviation (STDEV) of experiments. From the depiction of the STDEV of a straight line versus the residuals, the more favorable concentration range of calibration could be obtained by iteration using only a few steps. This condition links the lower limit of analysis (LLA) to an upper limit of analysis (ULA), and, thus, completes the statistically appropriate extension of the calibration line. In addition, a minimum STDEV of measurement was expressed in terms of the STDEV on the slope (s _a ) and on the intercept (s _b ), and the calculation was performed by using a modified version of the law of propagation of errors (LPE). The method was validated on experiments of gas chromatography (GC), liquid chromatography (LC), electrochemistry, flow-injection analysis (FIA), atomic emission spectrometry (AES), flame atomic absorption spectrometry (FAAS), and inductively coupled-plasma mass spectrometry (ICP-MS). A novel definition of the ULA was proposed as the concentration where the response started to deviate significantly from linearity, also taking into account the level of uncertainty. The proposed method facilitates the determination of the concentration range of calibration and LLA in one working operation. In order to promote reliability, it was proposed that the number of repetitions of analysis should be high, preferably above 100, in order to fulfill the conditions of the central-limit theorem. The text was submitted by the author in English.     

Application of the Weisz Ring oven technique to the separation and identification of micro-quantities of some less familiar cations

Summary Use of the ring oven in separation and identification of mixtures of less familiar metal ions has been described. Separation of metal ions from the following mixtures has successfully been carried out: 1. UO₂(II) and Th(IV), 2. Th(IV) and Ce(IV), 3. Pd(II) and Au(III), 4. Pt(IV) and Au(III), 5. Ce(III) and Ce(IV), 6. UO₂(II), Th(IV) and Ti(IV), 7. Th(IV), Ti(IV) and Ce(IV), 8. Th(IV), Ce(IV) and Zr(IV), 9. Ti(IV), V(V) and Zr(IV), 10. Mo(VI), V(V) and W(VI) and 11. Be(II), Al(III) and Mg(II). In the case of binary mixtures, the separation was in the form of a central spot and a concentric ring; in ternary mixtures the metals were precipitated in a central spot and two concentric rings.

---

Zusammenfassung Zur Trennung und Identifizierung folgender Gemische seltenerer Metallionen wurde der Ringofen mit Erfolg verwendet: 1. UO₂(II) und Th(IV), 2. Th(IV) und Ce(IV), 3. Pd(II) und Au(III), 4. Pt(IV) und Au(III), 5. Ce(III) und Ce(IV), 6. UO₂(II), Th(IV) und Ti(IV), 7. Th(IV), Ti(IV) und Ce(IV). 8. Th(IV), Ce(IV) und Zr(IV), 9. Ti(IV), V(V) und Zr(IV), 10. Mo(VI), V(V) und W(VI) und 11. Be(II), Al(III) und Mg(II). Bei binären Gemischen erfolgt die Trennung in einen zentralen Fleck und einen Ring, bei ternären Mischungen in einen Fleck und zwei konzentrische Ringe.

---

Résumé On a décrit l'utilisation du four annulaire pour la séparation et l'identification de mélanges d'ions métalliques moins courants. On a effectué la séparation des ions métalliques à partir des mélanges suivants: 1. UO₂(II) et Th(IV), 2. Th(IV) et Ce(IV), 3. Pd(II) et Au(III), 4. Pt(IV) et Au(III), 5. Ce(III) et Ce(IV), 6. UO₂(II), Th(IV) et Ti(IV), 7. Th(IV), Ti(IV) et Ce(IV), 8. Th(IV), Ce(IV) et Zr(IV), 9. Ti(IV), V(V) et Zr(IV), 10. Mo(VI), V(V) et W(VI) et 11. Be(II), Al(III) et Mg(II). Dans le cas des mélanges binaires, la séparation se présentait sous forme d'une tache centrale et d'un anneau concentrique; chez les mélanges ternaires, les métaux étaient précipités en une tache centrale et deux anneaux concentriques.

     

Affinity of the elements in group VI of the periodic table to tumors and organs]

In order to investigate the tumor affinity radioisotopes, chromium (51Cr), molybdenum (99Mo), tungsten (181W), selenium (75Se) and tellurium (127mTe)--the elements of group VI in the periodic table--were examined, using the rats which were subcutaneously transplanted with Yoshida sarcoma. Seven preprarations, sodium chromate (Na251CrO4), chromium chloride (51CrCl3), normal ammonium molybdate ((NH4)299MoO7), sodium tungstate (Na2181WO4), sodium selenate (Na275SeO4), sodium selenite (Na275SeO3) and tellurous acid (H2127mTeO3) were injected intravenously to each group of tumor bearing rats. These rats were sacrificed at various periods after injection of each preparation: 3 hours, 24 hours and 48 hours in all preparations. The radioactivities of the tumor, blood, muscle, liver, kidney and spleen were measured by a well-type scintillation counter, and retention values (in every tissue including the tumor) were calculated in percent of administered dose per g-tissue weight. All of seven preparations did not have any affinity for malignant tumor. Na251CrO4 and H2127mTeO3 had some affinity for the kidneys, and Na275SeO3 had some affinity for the liver. Na2181WO4 and (NH4)299MoO4 disappeared very rapidly from the blood and soft tissue, and about seventy-five percent of radioactivity was excreted in urine within first 3 hours.     

A Stereodivergent Approach to the Synthesis of gem-Diborylcyclopropanes

We report a designed stereodivergent strategy for the synthesis of gem-diborylcyclopropanes. The reaction provides a highly modular approach to prepare cyclopropane ring variants bearing gem-(Bpin,Bpin), gem-(Bpin,Bdan), and gem-(Bpin,BF₃K), with outstanding levels of stereocontrol. This was achieved by diastereoselective Pd-catalyzed cyclopropanation reactions of gem-diborylalkenes with α-diazoarylacetates and α-diazoaryl-trifluoromethyl. The key to the success of this general protocol was the diastereoselective trifluorination reaction of gem-diborylcyclopropanes, followed by the stereospecific interconversion of the trifluoroborate salts into the Bdan group.     

Contribution to the crystal chemistry of tetrametaphosphates (I)

Crystal structures of K₄P₄O₁₂ · 2H₂O and of two polymorphs of Na₂K₂P₄O₁₂ · 2H₂O are reported. K₄P₄O₁₂ · 2H₂O is triclinic P1 with a = 8.153(4), b = 8.222(4), c = 11.154(8) Å, α = 97.33(5), β = 95.46(5), γ = 88.92(5)°, and Z = 2. R = 0.021 for 2898 reflections. Na₂K₂P₄O₁₂ · 2H₂O has two crystalline forms: a triclinic one ($\text{P}\text{1}$) with a = 11.366(8), b = 7.908(5), c = 7.929(5) Å, α = 90.07(5), β = 106.85(5), γ = 95.66(5)°, and Z = 2, and a tetragonal one (P4₁) with a = 7.928(5), c = 21.66(2), and Z = 4. The crystal structures of the first and second crystalline forms have been solved with final R values of 0.022 for 2505 reflections and 0.036 for 1347 reflections, respectively. Crystal data and chemical preparations are given for Na₂(NH₄)₂P₄O₁₂ · 2H₂O and Na₂Rb₂P₄O₁₂ · 2H₂O, both isotypic with the triclinic form of Na₂K₂P₄O₁₂ · 2H₂O. Unit-cell dimensions are, respectively, a = 11.547(8), b = 8.012(5), c = 8.044(5) Å, α = 89.76(5), β = 106.22(5), and γ = 94.78(5)°, for the ammonium salt, and a = 11.577(8), b = 8.006(5), c = 8.032(5) Å, α = 89.79(5), β = 106.58(5), and γ = 95.19(5)° for the rubidium salt. In addition the crystal structures of the two crystalline forms of Na₄P₄O₁₂ · 4H₂O were reexamined in order to localize the hydrogen atoms and refine their positions.     

Contribution to the study of the sorption of radionuclides on hydrated oxides

The mechanism of¹⁰⁶Ru(III),¹⁰⁶RuNO(II),¹⁴⁴Ce(III),¹⁴⁷Pm(III),⁸⁵Sr(II),¹³¹I⁻,³⁵SO ₄ ²⁻ , and H₂ ³²PO ₄ ²⁻ radionuclide sorption on hydrated ferrous, ferric, aluminium and chromic hydrated oxides was studied. The dependence of sorption on the pH has shown that in a certain range of pH values it is the ion exchange of the radionuclide for a proton or a hydroxyl group of the oxide that probably plays a decisive role in the sorption process. The sorption depends considerably on the pH in the whole range of studied, but its decrease with cations in alkaline media and its increase with I⁻ ion in acidic media does not agree with the above sorption mechanism. Similarly, the course of the dependence of sorption on the sorbent concentration does not indicate ion exchange to be the only mechanis, but it indicates a more complicated sorption process. Probably the sorption of colloidal forms of the radionuclides proceeds, too.     

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra-tert-butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.     

Semiempirical MO approach to the mechanism of the NIS-mediated nucleophilic addition to glycals: multicomponent intermediates as models to tackle reactivity in organic chemistry

A proposition for the nucleosidation mechanism of five-membered glycals promoted by N-iodo-succinimide (NIS), leading to 2′-deoxy-2′-iodo-β-nucleosides, is presented herein supported by semiempirical MO calculations. The proposed mechanism goes through the formation of multicomponent molecular intermediates that drastically diminish the total energy values when compared to charged intermediates (via iodonium species). The nucleosidation step was performed establishing either bicomponent (dihydrofuran–NIS) or tricomponent (dihydrofuran–NIS–silylated nucleobase) intermediates. The latter possibility has been shown to be the most likely (according also to DFT calculations), and suggests that the mechanism should take place in a concerted fashion. According to the tricomponent pathway, we have studied the stereoselectivity of the process, finding that the activation energy for the β-nucleosidation step is between ∼6 kcal/mol (AM1) and ∼10 kcal/mol (PM3) more favorable than that of the corresponding α-anomer, in agreement with the experimental results. The final step consists in an intramolecular silyl-transfer process accompanied by the NIS cleavage (in a different way depending on the calculation method employed), giving rise to the ultimate formation of N-silyl-succinimide.     

Sorption of perfluorochemicals to granular activated carbon in the presence of ultrasound

Perfluorochemicals (PFCs) are emerging pollutants of increasing public health and environmental concern due to their worldwide distribution, environmental persistence, and bioaccumulation potential. Activated carbon adsorption is an effective method to remove PFCs from water. Herein, we report on the sorption of four PFCs: perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorobutane sulfonate (PFBS), and perfluorobutanoate (PFBA), from deionized water (MQ) and landfill groundwater (GW) by granular activated carbon (GAC) in the absence and presence of 20 kHz ultrasound. In all cases, the adsorption kinetics were found to be well-represented by a pseudosecond-order model, with maximum monolayer sorption capacity and initial sorption rate values following the orders q(e)(PFOS) > q(e)(PFOA) > q(e)(PFBS) > q(e)(PFBA) and v(0)(PFOS) > v(0)(PFBS) > v(0)(PFOA) > v(0)(PFBA), respectively. The equilibrium adsorption was quantified by the BET multilayer absorption isotherm, and the monolayer sorption capacity increased with increasing PFC chain length: q(m)(PFOS) > q(m)(PFOA) > q(m)(PFBS) > q(m)(PFBA). The equilibrium PFC sorption constants, q(e) and q(m), and the sorption kinetic constants, v(0) and k(2), were greater in Milli-Q water than in landfill groundwater with or without pretreatment, indicating competition for sorption sites by natural and cocontaminant groundwater organics. Ultrasonic irradiation significantly increased the PFC-GAC sorption kinetics, 250-900%, and slightly increased the extent of PFC equilibrium adsorption, 5-50%. The ultrasonic PFC-GAC sorption kinetics enhancement increased with increasing PFC chain length, suggesting ultrasound acts to increase the PFC diffusion rate into GAC nanopores.     

A convergent approach to the synthesis of multimetallic dithiolene complexes

Controlled base hydrolysis of one or both of the protected 1,2-dithiolene chelates of 1,3,5,7-tetrathia- s-indacene-2,6-dione (OCS 2C 6H 2S 2CO) enables the stepwise synthesis of di- and trimetallic complexes with 1,2,4,5-benzenetetrathiolate as the connector. Treatment of OCS 2C 6H 2S 2CO with MeO (-), followed by [NiBr 2(dcpe)] [dcpe = 1,2-bis(dicyclohexylphosphino)ethane], yields [(dcpe)Ni(S 2C 6H 2S 2CO)] ( 4). The reaction of 4 with EtO (-), followed by [MX 2(dcpe)] (X = halide), yields [(dcpe)Ni(S 2C 6H 2S 2)M(dcpe)] [M = Ni ( 5a), Pd ( 5b)]. Deprotection of the 1,3-dithiol-2-one group of 4, followed by introduction of (1)/ 2 equiv of MX 2 and then I 2, yields the neutral trimetallic compounds [(dcpe)Ni(S 2C 6H 2S 2)] 2M [M = Ni ( 6a), Pt ( 6b)]. Tetrahedralization at nickel is observed in 5a, which density functional theory calculations attribute to second-order Jahn-Teller effects, while 6a and 6b display an end-to-end folding of approximately 46 degrees . A color darkening is observed in moving from 4 to compounds 6 due to the increasing size of the conjugated metal-organic pi system. Intense, broad absorptions in the near-IR are observed for 6a and 6b.     

Cascade catalysis for the homogeneous hydrogenation of CO2 to methanol

This communication demonstrates the homogeneous hydrogenation of CO(2) to CH(3)OH via cascade catalysis. Three different homogeneous catalysts, (PMe(3))(4)Ru(Cl)(OAc), Sc(OTf)(3), and (PNN)Ru(CO)(H), operate in sequence to promote this transformation.     

Interaction Between Tangeretin and Ovalbumin to Reduce the Allergic Effects of Ovalbumin

Food allergy has become a worldwide problem. To find an effective way to reduce the allergic effect of allergen is an interesting topic. In this work, the interaction between ovalbumin(OVA) and tangeretin was studied by means of spectroscopy, molecular docking calculation and animal experiment. As the results show, static quenching of fluorescence intensity happened due to the interaction between OVA and tangeretin. Binding constants, binding sites, and thermometric parameters were obtained. The conformation changing of OVA occurred due to the interaction between it and tangeretin. The molecular docking calculation results show that the epitopes Arginine 84(ARG84), Leucine 87(LEU87), Asparagine 88(ASN88), Serine 103(SER103), Arginine 104(ARG104), Leucine 124(LEU124), Arginine 126(ARG126), Glycine 127(GLY127), Glycine 128(GLY128) and Tryptohan 148(TRP148) of OVA were occupied by tangeretin after the docking, which means tangeretin may have some inhibition effects. As the results of animal experiments, the amount of IgE and lung tissue sections of female BALB/c mice in different groups show that tangeretin with different concentrations has better effects than dexamethasone. In conclusion, the tangeretin may have the effects to reduce the allergic effects of OVA via occupying the IgE-binding epitopes of OVA.     

CO rebinding to protoheme: investigations of the proximal and distal contributions to the geminate rebinding barrier

The rebinding kinetics of CO to protoheme (FePPIX) in the presence and absence of a proximal imidazole ligand reveals the magnitude of the rebinding barrier associated with proximal histidine ligation. The ligation states of the heme under different solvent conditions are also investigated using both equilibrium and transient spectroscopy. In the absence of imidazole, a weak ligand (probably water) is bound on the proximal side of the FePPIX-CO adduct. When the heme is encapsulated in micelles of cetyltrimethylammonium bromide (CTAB), photolysis of FePPIX-CO induces a complicated set of proximal ligation changes. In contrast, the use of glycerol-water solutions leads to a simple two-state geminate kinetic response with rapid (10-100 ps) CO recombination and a geminate amplitude that can be controlled by adjusting the solvent viscosity. By comparing the rate of CO rebinding to protoheme in glycerol solution with and without a bound proximal imidazole ligand, we find the enthalpic contribution to the proximal rebinding barrier, H(p), to be 11 +/- 2 kJ/mol. Further comparison of the CO rebinding rate of the imidazole bound protoheme with the analogous rate in myoglobin (Mb) leads to a determination of the difference in their distal free energy barriers: DeltaG(D) approximately 12 +/- 1 kJ/mol. Estimates of the entropic contributions, due to the ligand accessible volumes in the distal pocket and the xenon-4 cavity of myoglobin ( approximately 3 kJ/mol), then lead to a distal pocket enthalpic barrier of H(D) approximately 9 +/- 2 kJ/mol. These results agree well with the predictions of a simple model and with previous independent room-temperature measurements of the enthalpic MbCO rebinding barrier (18 +/- 2 kJ/mol).     

Interaction of the halobacterial transducer to a halorhodopsin mutant engineered so as to bind the transducer: Cl- circulation within the extracellular channel

An alkali-halophilic archaeum, Natronomonas pharaonis, contains two rhodopsins that are halorhodopsin (phR), a light-driven inward Cl- pump and phoborhodopsin (ppR), the receptor of negative phototaxis functioning by forming a signaling complex with a transducer, pHtrII (Sudo Y. et al., J. Mol. Biol. 357 [2006] 1274). Previously, we reported that the phR double mutant, P240T/F250Y(phR), can bind with pHtrII. This mutant itself can transport Cl-, while the net transport was stopped upon formation of the complex. The flash-photolysis data were analyzed by a scheme in which phR --> 4 P1 --> P2 --> 4 P3 --> P4 --> phR. The P3 of the wild-type and the double mutant contained two components, X- and O-intermediates. After the complex formation, however, the P3 of the double mutant lacked the X-intermediate. These observations imply that the X-intermediate (probably the N-intermediate) is the state having Cl- in the cytoplasmic binding site and that the complex undergoes an extracellular Cl- circulation because of the inhibition of formation of the X-intermediate.