Unusual heme-histidine bond in the active site of a chaperone

The heme chaperone CcmE is essential for the delivery of heme to c-type cytochromes. It forms an unusual transient, yet covalent, bond between an essential histidine, H130, and heme. We report on the discovery of the chemical structure of this bond solved by NMR, where the heme vinyl is cross-linked at the beta carbon to the Ndelta1 of H130. As this type of heme linkage has not been described previously in any cytochrome or hemoprotein, it represents a novel type of heme-histidine complex.     

Effect of steps on the decomposition of CH3O at PdZn alloy surfaces

The decomposition of methoxide (CH(3)O) on a PdZn alloy is considered to be the rate-limiting step of steam re-forming of methanol over a Pd/ZnO catalyst. Our previous density functional (DF) studies (Langmuir 2004, 20, 8068; Phys. Chem. Chem. Phys. 2004, 6, 4499) revealed only a very low propensity of defect-free flat (111) and (100) PdZn surfaces to promote C-H or C-O bond breaking of CH(3)O. Thus, we applied the same DF periodic slab-model approach to investigate these two routes of CH(3)O decomposition on PdZn(221) surfaces that expose Pd, (221)(Pd), and Zn, (221)(Zn), steps. C-H bond cleavage of CH(3)O is greatly facilitated on (221)(Pd): the calculated activation energy is dramatically reduced, to approximately 50 kJ mol(-1) from approximately 90 kJ mol(-1) on flat PdZn surfaces, increasing the rate constant by a factor of 10(8). The lower barrier is mainly due to a weaker interaction of the reactant CH(3)O and an enhanced interaction of the product CH(2)O with the substrate. The activation energy for C-O bond scission did not decrease on the (221)(Pd) step. On the (221)(Zn) step, the calculated reaction barriers of both decomposition routes are even higher than on flat surfaces, because of the stronger adsorption of CH(3)O. Steps (and other defects) appear to be crucial for methanol steam re-forming on Pd/ZnO catalyst; the stepped surface PdZn(221)(Pd) is a realistic model for studying the reactivity of this catalyst.     

Water Reduction and Dihydrogen Addition in Aqueous Conditions With ansa-Phosphinoborane

Ortho-phenylene-bridged phosphinoborane (2,6-Cl₂Ph)₂B-C₆H₄-PCy₂ 1 was synthesized in three steps from commercially available starting materials. 1 reacts with H₂ or H₂O under mild conditions to form corresponding zwitterionic phosphonium borates 1-H₂ or 1-H₂O . NMR studies revealed both reactions to be remarkably reversible. Thus, when exposed to H₂, 1-H₂O partially converts to 1-H₂ even in the presence of multiple equivalents of water in the solution. The addition of parahydrogen to 1 leads to nuclear spin hyperpolarization both in dry and hydrous solvents, confirming the dissociation of 1-H₂O to free 1 . These observations were supported by computational studies indicating that the formation of 1-H₂ and 1-H₂O from 1 are thermodynamically favored. Unexpectedly, 1-H₂O can release molecular hydrogen to form phosphine oxide 1-O . Kinetic, mechanistic, and computational (DFT) studies were used to elucidate the unique “umpolung” water reduction mechanism.     

Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.     

Key Role of a-Top CO on Terrace Sites of Metallic Pd Clusters for CO Oxidation

Pd-based catalysts are the most widely used for CO oxidation because of their outstanding catalytic activity and thermal stability. However, fundamental understanding of the detailed catalytic processes occurring on Pd-based catalysts under realistic conditions is still lacking. In this study, we investigated CO oxidation on metallic Pd clusters supported on Al₂O₃ and SiO₂. High-angle annular dark-field scanning transmission electron microscopy revealed the formation of similar-sized Pd clusters on Al₂O₃ and SiO₂. In contrast, CO chemisorption analysis indicated a gradual change in the dispersion of Pd (from 0.79 to 0.2) on Pd/Al₂O₃ and a marginal change in the dispersion (from 0.4 to 0.24) on Pd/SiO₂ as the Pd loading increased from 0.27 to 5.5 wt %; these changes were attributed to differences in the metal-support interactions. Diffuse reflectance infrared Fourier-transform spectroscopy revealed that fewer a-top CO species were present in Pd supported on Al₂O₃ than those in Pd supported on SiO₂, which is related to the morphological differences in the metallic Pd clusters on these two supports. Despite the different dispersion profiles and surface characteristics of Pd, O₂ titration demonstrated that linearly bound CO (with an infrared signal at 2090 cm⁻¹) reacted first with oxygen in the case of CO-saturated Pd on Al₂O₃ and SiO₂, which suggests that a-top CO on the terrace site plays an important role in CO oxidation. The experimental observations were corroborated by periodic density functional calculations, which confirmed that CO oxidation on the (111) terrace sites is most plausible, both kinetically and thermodynamically, compared to that on the edge or corner sites. This study will deepen the fundamental understanding of the effect of Pd clusters on CO oxidation under reaction conditions.     

Coinage Metal Complexes of Bis(quinoline-2-ylmethyl)phenylphosphine-Simple Reactions Can Lead to Unprecedented Results

The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline-2-ylmethyl)phenylphosphine ( bqmpp ) towards selected Cu^I, Ag^I and Au^I species is described. The resulting X-ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN)₄]BF₄, compound 1 [Cu₂(bqmpp)₂](BF₄)₂ is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π-stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). Cu^I complex 2 [Cu₄Cl₃(bqmpp)₂]BF₄ contains a rarely observed Cu₄Cl₃ cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF₆] with the ligand leads to a dinuclear compound ( 3 ) in solution as confirmed by ³¹P{¹H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3 , a tris(quinoline-2-ylmethyl)bisphenyl-phosphine ( tqmbp ) compound [Ag₂(tqmbp)₂](SbF₆)₂ 4 is formed by elimination of quinaldine. The Au(I) compound [Au₂(bqmpp)₂]PF₆ ( 5 ) is prepared as expected and shows a linear arrangement of two phosphine ligands around Au^I.     

Purification of Hydrogen from CO with Cu/ZSM-5 Adsorbents

The transition to a hydrogen economy requires the development of cost-effective methods for purifying hydrogen from CO. In this study, we explore the possibilities of Cu/ZSM-5 as an adsorbent for this purpose. Samples obtained by cation exchange from aqueous solution (AE) and solid-state exchange with CuCl (SE) were characterized by in situ EPR and FTIR, H₂-TPR, CO-TPD, etc. The AE samples possess mainly isolated Cu²⁺ cations not adsorbing CO. Reduction generates Cu⁺ sites demonstrating different affinity to CO, with the strongest centres desorbing CO at about 350 °C. The SE samples have about twice higher Cu/Al ratios, as one H⁺ is exchanged with one Cu⁺ cation. Although some of the introduced Cu⁺ sites are oxidized to Cu²⁺ upon contact with air, they easily recover their original oxidation state after thermal treatment in vacuum or under inert gas stream. In addition, these Cu⁺ centres regenerate at relatively low temperatures. It is important that water does not block the CO adsorption sites because of the formation of Cu⁺(CO)(H₂O)_x complexes. Dynamic adsorption studies show that Cu/ZSM-5 selectively adsorbs CO in the presence of hydrogen. The results indicate that the SE samples are very perspective materials for purification of H₂ from CO.     

Mechanism of the cyclization of dimethyl diethynyl silane with selenium tetrabromide: Computational and structural studies, and monitoring

The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr₄ to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr₄ conversion into bimolecular complex Br₂?SeBr₂, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using ¹H NMR method.     

Solid state NMR characterization of individual compounds and solid solutions formed in Sc(2)O(3)--V(2)O(5)--Nb(2)O(5)--Ta(2)O(5) system

In this study, (51)V, (45)Sc and (93)Nb MAS NMR combined with satellite transition spectroscopy analysis were used to characterize the complex solid mixtures: VNb(9(1-x))Ta(9x)O(25), ScNb((1-x))Ta(x)O(4) and ScNb(2(1-x))Ta(2x)VO(9) (x = 0, 0.3, 0.5, 0.7, 1.0). This led us to describe the structures of Sc and V sites. The conclusions were based on accurate values for (51)V quadrupole coupling and chemical shift tensors obtained with (51)V MAS NMR/SATRAS for VNb(9)O(25), VTa(9)O(25) and ScVO(4). The (45)Sc NMR parameters have been obtained for Sc(2)O(3), ScVO(4), ScNbO(4) and ScTaO(4). On the basis of (45)Sc NMR and data available from literature, the ranges of the (45)Sc chemical shift have been established for ScO(6) and ScO(8). The gradual change of the (45)Sc and (51)V NMR parameters with x confirms the formation of solid solutions in the process of synthesis of VNb(9(1-x))Ta(9x)O(25) and ScNb((1-x))Ta(x)O(4), in contrast to ScNb(2(1-x))Ta(2x)VO(9). The cation sublattice of ScNb((1-x))Ta(x)O(4) is found to be in octahedral coordination. The V sites in VNb(9(1-x))Ta(9x)O(25) are present in the form of slightly distorted tetrahedra. The (93)Nb NMR parameters have been obtained for VNb(9)O(25).     

Characterization of the diradical *NSNSC-CNSSN* and [NSNSC-CNSSN][MF6]n (n=1, 2). The first observation of an excited triplet state in dimers of 7pi -CNSSN* radicals

Preparation and full characterization of the main-group diradical *NSNSC-CNSSN*, 8, the MF6- salt (As, Sb) of radical cation +NSNSC-CNSSN*, 8*+, and the AsF6- salt of the dication +NSNSC-CNSSN+, 82+, are presented. 8, a=6.717 (4), b=11.701(2), c=8.269(3) A, alpha=gamma=90, beta=106.69(3) degrees, monoclinic, space group P21/n, Z=4, T=203 K; 8SbF6, a=6.523(2), b=7.780(2), c=12.012(4) A, alpha=91.994(4), beta=96.716(4), gamma=09.177(4) degrees, triclinic, space group P, Z=2, T=198 K; 8[AsF6]2, a=12.7919(14), b=9.5760(11), c=18.532(2) A, alpha=gamma=90, beta=104.034(2) degrees, monoclinic, space group Pn, Z=6, T=198 K. Preparation of 8MF6 was carried out via a reduction of [CNSNS]2[MF6]2 (M=As, Sb) with either ferrocene or a SbPh3-NBu4Cl mixture. In the solid state, diamagnetic 8SbF6 contains centrosymmetric dimers [8*+]2 linked via two-electron four-centered pi*-pi* interactions with a thermally excited triplet state as detected by electron paramagnetic resonance (EPR). This is the first observation of a triplet excited state for a 7pi 1,2,3,5-dithiadiazolyl radical dimer. The singlet-triplet gap of the [-CNSSN*]2 radical pair was -1800+/-100 cm(-1) (-22+/-1 kJ/mol) with the ZFS components |D|=0.0267(6) cm(-1) and |E|=0.0012(1) cm(-1), corresponding to an in situ dimerization energy of ca. -11 kJ/mol. Cyclic voltammetry measurements of 8[AsF6]2 showed two reversible waves associated with a stepwise reduction of the two isomeric rings [E1/2 (+2/+1)=1.03 V; E1/2 (+1/0)=0.47 V, respectively]. 8MF6 (M=As, Sb) was further reduced to afford the mixed main-group diradical 8, containing two isomeric radical rings. In solution, 8 is thermodynamically unstable with respect to *NSSNC-CNSSN*, but is isolable in the solid state because of its low solubility in SO2. Likewise, 8SbF6, 8 is dimeric, with pi*-pi* interactions between different isomeric rings, and consequently diamagnetic; however, a slight increase in paramagnetism was observed upon grinding [from C=6.5(3)x10(-4) emu.K/mol and temperature-independent paramagnetism (TIP)=1.3(1)x10(-4) emu/mol to C=3.2(1)x10(-3) emu.K/mol and TIP=9.0(1)x10(-4) emu/mol], accompanied by an increase in the lattice-defect S=1/2 sites [from 0.087(1) to 0.43(1)%]. Computational analysis using the multiconfigurational approach [CASSCF(6,6)/6-31G*] indicated that the two-electron multicentered pi*-pi* bonds in [8*+]2 and [8]2 have substantial diradical characters, implying that their ground states are diradicaloid in nature. Our results suggest that the electronic structure of organic-radical ion pairs, for example, [TTF*+]2, [TCNE*-]2, [TCNQ*-]2, [DDQ*-]2, and related pi dimers, can be described in a similar way.