An ab initio analysis of the electronic structure and harmonic frequencies of nickel porphyrin

Ab initio calculations are performed to understand the geometry, electronic structure, and vibrational frequencies of nickel porphyrin (NiP). Hartree-Fock (HF) and second-order perturbation (MP2) theories are applied with polarized basis sets. The calculated geometrical parameters are in very good agreement with the crystal structure determination. The electronic structure and bonding are analyzed in terms of complexation and correlation effects. Not unexpectedly, the HF depiction of the metal-porphyrin interaction is rather ionic while ligand σ donation is dominant at the MP2 level. Scaled HF frequencies of NiP and its isotopomers are in very good agreement with observed infrared and resonance Raman data. Received: 7 January 1997 / Accepted: 6 May 1997     

Textile/Metal–Organic‐Framework Composites as Self‐Detoxifying Filters for Chemical‐Warfare Agents

The current technology of air‐filtration materials for protection against highly toxic chemicals, that is, chemical‐warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self‐cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal–organic framework (MOF) materials to develop advanced self‐detoxifying adsorbents of chemical‐warfare agents containing hydrolysable P? F, P? O, and C? Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air‐permeation properties of the textiles with the self‐detoxifying properties of the MOF material.     

Alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-hexopyranoses: a new entry to chiral polyhydroxylated 2-azido-1-halo-1-alkenes

A new general two-step methodology for the synthesis of chiral fluoro, chloro, bromo and iodo vinyl azides from carbohydrate-derived halohydrins has been developed. The anomeric alkoxyl radical fragmentation of 3-azido-2,3-dideoxy-2-halo-pyranoses under oxidative conditions with (diacetoxyiodo)benzene and iodine gave 2-azido-1,2-dideoxy-1-halo-1-iodo-alditols, which by chemoselective dehydroiodination afforded (Z,E)-2-azido-1,2-dideoxy-1-halo-4-O-formyl-pent-1-enitols in good overall yields. Preliminary thermolysis and photochemical studies of these compounds for the synthesis of hitherto unknown disubstituted 2-halo-3-alkyl-2H-azirines have also been accomplished.     

Low-load rotor-synchronised Hahn-echo pulse train (RS-HEPT) 1H decoupling in solid-state NMR: factors affecting MAS spin-echo dephasing times

Transverse dephasing times T(2)' in spin-echo MAS NMR using rotor-synchronised Hahn-echo pulse-train (RS-HEPT) low-load (1)H decoupling are evaluated. Experiments were performed at 300 and 600 MHz for (13)CH-labelled L-alanine and (15)NH(delta)-labelled L-histidine.HCl.H(2)O, together with SPINEVOLUTION simulations for a ten-spin system representing the crystal structure environment of the (13)CH carbon in L-alanine. For 30 kHz MAS and nu(1)((1)H) = 100 kHz at 300 MHz, a RS-HEPT T(2)' value of 17 +/- 1 ms was obtained for (13)CH-labelled L-alanine which is approximately 50% of the XiX T(2)' value of 33 +/- 2 ms. Optimum RS-HEPT decoupling performance is observed for a relative phase of alternate RS-HEPT pi-pulses, Deltaphi = phi'- phi, between 40 and 60 degrees . For experiments at 600 MHz and 30 kHz MAS with (13)CH-labelled L-alanine, the best RS-HEPT (nu(1)((1)H) = 100 kHz) T(2)' value was 3 times longer than that observed for low-power continuously applied sequences with nu(1)((1)H) < or =40 kHz, i.e. corresponding to the same average power dissipated in the probe. A marked improvement in RS-HEPT (1)H decoupling is observed for increasing MAS frequency: at 55.6 kHz MAS, a best RS-HEPT T(2)' value of 34 +/- 5 ms was recorded for (13)CH-labelled L-alanine. Much improved RS-HEPT broadband performance was also observed at 55.6 kHz MAS as compared to 30 kHz MAS.     

Synthesis of ynones by palladium-catalyzed acylation of terminal alkynes with acid chlorides

Phosphane-free oxime-derived palladacycle 2 is an efficient precatalyst for the copper-free acylation of terminal alkynes with different carboxylic acid chlorides in toluene in the presence of 3 equiv of TEA as base, giving the corresponding ynones in good yields. The coupling reaction can normally be performed under air or under inert atmosphere when very low catalyst loadings (10(-3) mol % Pd) (turnover numbers (TONs) up to 23,000, turnover frequencies (TOFs) up to 958 h(-1)) or sensitive carboxylic acid chlorides are used. In addition, Pd(OAc)(2) has been shown as an efficient catalyst for the ligandless process, although usually working under higher loading conditions. This new protocol allows one to perform the synthesis of ynones at 110 degrees C, at room temperature, or under microwave irradiation conditions.     

Generation of new landomycins by combinatorial biosynthetic manipulation of the LndGT4 gene of the landomycin E cluster in S. globisporus

A 3 kb DNA fragment from the Streptomyces globisporus 1912 landomycin E (LaE) biosynthetic gene cluster (lnd) was completely sequenced. Three open reading frames were identified, lndGT4, lndZ4, and lndZ5, whose probable translation products resemble a glycosyltransferase, a reductase, and a hydroxylase, respectively. Studies of generated mutants from disruption and complementation experiments involving the lndGT4 gene allowed us to determine that LndGT4 controls the terminal L-rhodinose sugar attachment during LaE biosynthesis and that LndZ4/LndZ5 are responsible for the unique C11-hydroxylation of the landomycins. Generation of the novel landomycins F, G, and H in the course of these studies provided evidence for the flexibility of lnd glycosyltransferases toward their acceptor substrates and a basis for initial structure-activity relationships within the landomycin family of antibiotics.     

Vibrational molecular quantum computing: basis set independence and theoretical realization of the Deutsch-Jozsa algorithm

The phase of quantum gates is one key issue for the implementation of quantum algorithms. In this paper we first investigate the phase evolution of global molecular quantum gates, which are realized by optimally shaped femtosecond laser pulses. The specific laser fields are calculated using the multitarget optimal control algorithm, our modification of the optimal control theory relevant for application in quantum computing. As qubit system we use vibrational modes of polyatomic molecules, here the two IR-active modes of acetylene. Exemplarily, we present our results for a Pi gate, which shows a strong dependence on the phase, leading to a significant decrease in quantum yield. To correct for this unwanted behavior we include pressure on the quantum phase in our multitarget approach. In addition the accuracy of these phase corrected global quantum gates is enhanced. Furthermore we could show that in our molecular approach phase corrected quantum gates and basis set independence are directly linked. Basis set independence is also another property highly required for the performance of quantum algorithms. By realizing the Deutsch-Jozsa algorithm in our two qubit molecular model system, we demonstrate the good performance of our phase corrected and basis set independent quantum gates.     

A crystalline sponge based on dispersive forces suitable for X-ray structure determination of included molecular guests

A crystalline porous material showing one-dimensional (1-D) rectangular micropores (12 × 9 Ų) has been assembled from a semirigid macrocyclic tetraimine and EtOAc as the templating agent. The 1-D nature of the material is intrinsic to the conformationally rigid structure of a macrocyclic sub-unit bearing four cyclohexylidene residues. The multiple dispersive forces established among the aliphatic residues glutted the 1-D channels and provided thermal stability to the material at temperatures below 160 °C. Upon removal of the template, the structure of the empty solid exhibited permanent microporosity (S _BET = 342 m² g^–1). Being a true molecular sponge, the channel framework of this material allowed the inclusion of a variety of molecular sample guests without compromising its crystalline nature. Remarkably, this crystalline material enabled the structure determination by X-ray diffraction of the included molecules. Theoretical studies demonstrated the vital role played by the dispersive forces in the overall stabilization of the crystal packing.     

Advanced oxidation processes for decolorization of aqueous solution containing acid red G azo dye

Some investigations concerning the decolorization of Acid Red G azo dye by photooxidation with hydrogen peroxide were performed. The influences of pH, oxidant concentration, and the presence of Fe²⁺ or other metal ions (Co²⁺, Cu²⁺, Ni²⁺, Mn²⁺) as potential catalysts, were investigated. The best results were obtained in the presence of ferrous ions in acid and neutral media. The other ions are not as effective as Fe²⁺ for dye decolorization. Co²⁺ and Cu²⁺ ions have a catalytic action, at low concentration, within a wide range of pH. Ni²⁺ and Mn²⁺ ions have no catalytic effect in photooxidation with hydrogen peroxide at acid Ni²⁺ and Mn²⁺ ions have no catalytic effect in photooxidation with hydrogen peroxide at acid pH values, but show a weak action in alkaline media.     

Oligomerization and regioselective hydrosilylation of styrenes catalyzed by cationic allyl nickel complexes bearing allylphosphine ligands

The complexes [Ni(eta(3)-CH(2)CHCH(2))Br(kappa(1)P-PR(2)CH(2)CH=CH(2))] (R = Ph 1, (i)Pr2 ) and [Ni(eta(3)-CH(2)C(R')CH(2))(kappa(1)P-PR(2)CH(2)CH=CH(2))(2)][BAr'(4)] (R' = H, R = Ph 4a, R = (i)Pr 4b; R' = CH(3), R = Ph 5a, R = (i)Pr 5b; Ar' = 3,5-C(6)H(3)(CF(3))(2)) have been prepared and characterized. The X-ray crystal structures of 1, 2 and 5b have been determined. 4a-b and 5a-b are catalyst precursors for the oligomerization of RC(6)H(4)CH=CH(2) to oligostyrene (R = H) or oligo(4-methylstyrene) (R = CH(3)) respectively, without the need of a co-catalyst such as methylalumoxane. The catalytic activities range from moderate to high. The oligomerization reactions are carried out in the temperature interval 25-40 degrees C in 1,2-dichloroethane, using an olefin/catalyst ratio equal to 200, yielding oligostyrenes with a high isotactic fraction content P(m), with M(n) in the range 700-1900 Dalton, and polydispersities between 1.22 and 1.64. The cationic complexes 4a-b and 5a-b are also effective catalyst precursors for the hydrosilylation reactions of styrene or 4-methylstyrene with PhSiH(3) in 1,2-dichloroethane at 40 degrees C using an olefin/catalyst ratio equal to 100, leading selectively to RC(6)H(4)CH(SiH(2)Ph)CH(3) (R = H, CH(3)) in 50-79% yield.