4‐Chloro­aceto­phenone [1‐(4‐methoxyphenyl)­ethyl­idene]­hydra­zone

The crystal structure of the title mixed azine, C₁₇H₁₇ClN₂O, contains four independent mol­ecules, A–D, and mol­ecule B is disordered. All four mol­ecules have an N—N gauche conformation, with C—N—N—C torsion angles of 136.5 (4), 137.0 (4), ?134.7 (4) and ?134.7 (4)°, respectively. The phenyl rings are also somewhat twisted with respect to the plane defined by C_ipso and the imine bond. On average, the combined effect of these twists results in an angle of 64.7° between the best planes of the two phenyl rings. Arene–arene double T‐contacts are the dominant intermolecular inter­action. The methoxy‐substituted phenyl ring of one azine mol­ecule interacts to form a T‐contact with the methoxy‐substituted phenyl ring of an adjacent mol­ecule and, similarly, two chloro‐substituted phenyl rings of neighboring mol­ecules interact to form another T‐contact. The only exception is for mol­ecule B, for which the disorder leads to the formation of T‐­contacts between methoxy‐ and chloro‐substituted phenyl rings. The prevailing structural motif of T‐contact formation between like‐substituted arene rings results in a highly dipole‐parallel‐aligned crystal structure.     

Molecular-beacon-based tricomponent probe for SNP analysis in folded nucleic acids

Hybridization probes are often inefficient in the analysis of single‐stranded DNA or RNA that are folded in stable secondary structures. A molecular beacon (MB) probe is a short DNA hairpin with a fluorophore and a quencher attached to opposite sides of the oligonucleotide. The probe is widely used in real‐time analysis of specific DNA and RNA sequences. This study demonstrates how a conventional MB probe can be used for the analysis of nucleic acids that form very stable (T_m>80 °C) hairpin structures. Here we demonstrate that the MB probe is not efficient in direct analysis of secondary structure‐folded analytes, whereas a MB‐based tricomponent probe is suitable for these purposes. The tricomponent probe takes advantage of two oligonucleotide adaptor strands f and m. Each adaptor strand contains a fragment complementary to the analyte and a fragment complementary to a MB probe. In the presence of a specific analyte, the two adaptor strands hybridize to the analyte and the MB probe, thus forming a quadripartite complex. DNA strand f binds to the analyte with high affinity and unwinds its secondary structure. Strand m forms a stable complex only with the fully complementary analyte. The MB probe fluorescently reports the formation of the quadripartite associate. It was demonstrated that the DNA analytes folded in hairpin structures with stems containing 5, 6, 7, 8, 9, 11, or 13 base pairs can be detected in real time with the limit of detection (LOD) lying in the nanomolar range. The stability of the stem region in the DNA analyte did not affect the LOD. Analytes containing single base substitutions in the stem or in the loop positions were discriminated from the fully complementary DNA at room temperature. The tricomponent probe promises to simplify nucleic acid analysis at ambient temperatures in such applications as in vivo RNA monitoring, detection of pathogens, and single nucleotide polymorphism (SNP) genotyping by DNA microarrays.     

Design of an Intercalating Linker Leading to the First Efficiently 5′,5′‐Linked Alternate‐Strand Hoogsteen Triplex with High Stability and Specificity

This is the first report describing the design, synthesis, and incorporation of an intercalating linker leading to an efficiently 5′,5′‐linked alternate strand Hoogsteen triplex. Using molecular modeling, the 5′,5′ problem was solved in a rather simple way. The two relatively distant 5′‐ends have been connected with a molecule that provides rigidity to the structure, while being flexible enough to allow stacking upon all four strands. The synthesis of the core of the designed molecule was conducted by Sonogashira coupling of an appropriately substituted iodobenzene with 1,3‐diethynylbenzene to give a conjugated system with three benzene rings interconnected with triple bonds. For the alternate‐strand triplex obtained with the intercalating linker, the stability obtained is higher than that of the corresponding homotriplex of equivalent total length and with the same nucleotides. This is deduced from a 5° higher melting temperature of the alternating triplex. The sensitivity towards mismatches in the alternate‐strand triplex is in the same range (ΔT_m=?13° to ?19°) as those observed for homotriplexes.     

Crystal structure of a liquid crystal non‐symmetric dimer: cholesteryl 4‐[4‐(4‐n‐butylphenylethynyl)phenoxy]butanoate

The crystal structure of cholesteryl 4‐[4‐(4‐n‐butylphenylethynyl)phenoxy]butanoate [phase sequence: Cr 155°C (46.1?J?g^?1) SmA 186.8°C (1.5?J?g^?1) TGB‐N* 204.7 (6?J?g^?1) I] has been solved from single crystal X‐ray diffraction data. The compound crystallizes in the monoclinic space group P2₁ with unit cell parameters: a?=?13.129(2), b?=?9.3904(10), c?=?17.4121(8)?Å, β?=?92.790(7)°, Z?=?2. The structure has been solved by direct methods and refined to R?=?0.0606 for 3?250 observed reflections. The bond distances and angles are in good agreement with the corresponding values for compounds containing phenyl and cholesterol moieties. The phenyl rings A and B are planar. The dihedral angle between the least‐squares planes of the two phenyl rings is 28°. The cholesterol moiety has the usual structure: the C and E rings have chair conformations, and the D and F rings adopt half‐chair conformations. The molecules in the unit cell are arranged in an antiparallel manner. The crystal structure is stabilized by an intermolecular C–H…O contact of 2.989(10)?Å.     

Bis{2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ido‐κ2N,N′}nickel(II): a supramolecular structure formed by C—H...π hydrogen bonds

In the title compound, [Ni(C₁₂H₁₁N₂)₂], the Ni^II cation lies on an inversion centre and has a square‐planar coordination geometry. This transition metal complex is composed of two deprotonated N,N′‐bidentate 2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ide ligands around a central Ni^II cation, with the pyrrolide rings and imine groups lying trans to each other. The Ni—N bond lengths range from 1.894 (3) to 1.939 (2) Å and the bite angle is 83.13 (11)°. The Ni—N(pyrrolide) bond is substantially shorter than the Ni—N(imino) bond. The planes of the phenyl rings make a dihedral angle of 78.79 (9)° with respect to the central NiN₄ plane. The molecules are linked into simple chains by an intermolecular C—H...π interaction involving a phenyl β‐C atom as donor. Intramolecular C—H...π interactions are also present.     

Synthesis of polyphenylquinoxaline copolymers via aromatic nucleophilic substitution reactions of an A‐B quinoxaline monomer

A self‐polymerizable quinoxaline monomer (A‐B) has been synthesized and polymerized via aromatic nucleophilic substitution reactions. An isomeric mixture of self‐polymerizable quinoxaline monomers—2‐(4‐hydroxyphenyl)‐3‐phenyl‐6‐fluoroquinoxaline and 3‐(4‐hydroxyphenyl)‐2‐phenyl‐6‐fluoroquinoxaline—was polymerized in N‐methyl‐2‐pyrrolidinone (NMP) to afford high molecular weight polyphenylquinoxaline (PPQ) with intrinsic viscosities up to 1.91 dL/g and a glass‐transition temperature (T_g) of 251 °C. A series of comonomers was polymerized with A‐B to form PPQ/polysulfone (PS), PPQ/polyetherether ketone (PEEK), and PPQ/polyethersulfone (PES) copolymers. The copolymers readily obtained high intrinsic viscosities when fluorine was displaced in NMP under reflux. However, single‐electron transfer (SET) side reactions, which limit molecular weight, played a more dominant role when chlorine was displaced instead of fluorine. SET side reactions were minimized in the synthesis of PPQ/PS copolymers through mild polymerization conditions in NMP for longer polymerization times. Thus, the T_g's of PES (T_g = 220 °C), PEEK (T_g = 145 °C), and PS (T_g = 195 °C) were raised through the incorporation of quinoxaline units into the polymer. Copolymers with high intrinsic viscosities resulted in all cases, except in the case of PPQ/PEEK copolymers when 4,4′‐dichlorobenzophenone was the comonomer. © 2001 John Wiley & Sons, Inc. J Polym Sci A Part A: Polym Chem 39: 2037–2042, 2001     

Duplex‐Selective Ruthenium‐Based DNA Intercalators

We report the design and synthesis of small molecules that exhibit enhanced luminescence in the presence of duplex rather than single‐stranded DNA. The local environment presented by a well‐known [Ru(dipyrido[3,2‐a:2′,3′‐c]phenazine)L₂]²⁺‐based DNA intercalator was modified by functionalizing the bipyridine ligands with esters and carboxylic acids. By systematically varying the number and charge of the pendant groups, it was determined that decreasing the electrostatic interaction between the intercalator and the anionic DNA backbone reduced single‐strand interactions and translated to better duplex specificity. In studying this class of complexes, a single Ru^II complex emerged that selectively luminesces in the presence of duplex DNA with little to no background from interacting with single‐stranded DNA. This complex shows promise as a new dye capable of selectively staining double‐ versus single‐stranded DNA in gel electrophoresis, which cannot be done with conventional SYBR dyes.     

A cis‐stilbene derivative

The title compound, 4′‐methoxy‐α,2,3′,4‐tetra­nitro­stilbene, C₁₅H₁₀N₄O₉, crystallizes in the centrosymmetric space group P2₁/c with one mol­ecule in the asymmetric unit. The phenyl rings are inclined to one another and form a dihedral angle of 57.4 (1)°. The size of this angle is a result of intermolecular C—H⃛O interactions involving the phenyl H atoms. The torsion angle between the phenyl rings, −7.5 (3)°, indicates a cis geometry between them. The methoxy group is almost coplanar with the phenyl ring, and the nitro groups are twisted with respect to the phenyl rings because of the short H⃛O contacts. The crystal packing is stabilized by C—H⃛O hydrogen bonds, and the intermolecular hydrogen bonds form a C(12) graph‐set chain running along the [010] direction.     

Electrochemical Detection of Asymmetric PCR Products by Labeling with Osmium Tetroxide

Single stranded DNA‐targets from asymmetric polymerase chain reaction (PCR) of a sequence of the gram positive, spore forming bacterium Clostridium acetobutylicum were detected by square‐wave voltammetry after labeling with osmium tetroxide bipyridine and hybridization with DNA capture probes immobilized on gold electrodes. The asymmetric PCR, performed with a 10‐fold excess of the forward‐primer, was used without any further purification for hybridization with protective strands and covalent labeling with osmium tetroxide bipyridine. Square‐wave voltammetric signals of 20 nmol/L targets were significantly higher at 50 °C compared with 23 °C hybridization temperature. A fully noncomplementary protective strand yielded thoroughly modified targets unable for further hybridization. Coupling this with thermal discrimination opens new opportunities for sequence specific DNA detection.     

Syntheses and properties of new aromatic polybenzoxazoles bearing ether and phenylethylidene or 1‐phenyl‐2,2,2‐trifluoroethylidene linkages

Two new bis(ether acyl chloride)s, 1,1‐bis[4‐(4‐chloroformylphenoxy)phenyl]‐1‐phenylethane and 1,1‐bis[4‐(4‐chloroformylphenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane, were prepared from readily available reagents. Aromatic polybenzoxazoles with both ether and phenylethylidene or 1‐phenyl‐2,2,2‐trifluoroethylidene linkages between phenylene units were obtained by a conventional two‐step procedure including the low‐temperature solution polycondensation of the bis(ether acyl chloride)s with three bis(o‐aminophenol)s, yielding poly(o‐hydroxyamide) precursors, and subsequent thermal cyclodehydration. The intermediate poly(o‐hydroxyamide)s exhibited inherent viscosities of 0.39–0.98 dL/g. All of the poly(o‐hydroxyamide)s were amorphous and soluble in polar organic solvents such as N,N‐dimethylacetamide, and most of them could afford flexible and tough films via solvent casting. The poly(o‐hydroxyamide)s exhibited glass‐transition temperatures (T_g's) of 129–194 °C and could be thermally converted into corresponding polybenzoxazoles in the solid state at temperatures higher than 300 °C. All the polybenzoxazoles were amorphous and showed an enhanced T_g but a dramatically decreased solubility with to respect to their poly(o‐hydroxyamide) precursors. They exhibited T_g's of 216–236 °C through differential scanning calorimetry and were stable up to 500 °C in nitrogen or air, with 10% weight‐loss temperatures being recorded between 538 and 562 °C in nitrogen or air. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 914–921, 2003     

Stereoregular P(MMA)‐clay nanocomposites by metallocene catalysts: In situ synthesis and stereocomplex formation

This contribution reports the synthesis and characterization of stereochemically controlled, as well as crystalline stereocomplex, P(MMA)‐clay nanocomposites using metallocene complexes and alane‐intercalated clay activators. The ligand elimination and exchange reactions involving Lewis acids E(C₆F₅)₃ (E = Al, B) and an organically modified montmorillonite clay were employed to synthesize the alane‐intercalated clay activators. When combined with dimethyl metallocenes of various symmetries, these clay activators brought about efficient MMA polymerizations leading to in situ polymerized, stereochemically controlled P(MMA)‐intercalated clay nanocomposites. The most noticeable thermal property enhancement observed for the clay nanocomposite P(MMA), when compared with the pristine P(MMA) having similar molecular weight and stereomicrostructure, has a considerable increase in T_g (≥10 °C). Mixing of dilute THF solutions of two diastereomeric nanocomposites in a 1:2 isotactic to syndiotactic ratio, followed by reprecipitation or crystallization procedures, yielded unique double‐stranded helical stereocomplex P(MMA)‐clay nanocomposites with a predominantly exfoliated clay morphology. Remarkably, the resulting crystalline stereocomplex P(MMA) matrix is resistant to the boiling‐THF extraction and its clay nanocomposites exhibit high T_m of 201 to 210 °C. Furthermore, the stereocomplex P(MMA)‐clay nanocomposite shows a one‐step, narrow decomposition temperature window and a single, high maximum rate decomposition temperature of 377 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2581–2592, 2007     

A ruthenium(II)–porphyrin–carbene complex with a weakly bonded methanol ligand

The title di­phenyl­carbene porphyrin complex (di­phenyl­carbenyl‐κC)(methanol‐κO)(5,10,15,20‐tetra‐p‐tolyl­por­phy­rin­ato‐κ⁴N)ruthenium(II) methanol solvate, [Ru­(C₁₃H₁₀)(C₄₈H₃₆N₄)(CH₄O)]·CH₄O, has a six‐coordinate Ru atom with a methanol mol­ecule as the second axial ligand. The carbene fragment is slightly distorted from an ideal sp² configuration, with a C(phenyl)—C(carbene)—C(phenyl) angle of 112.2 (3)°. The Ru—C bond length of 1.845 (3) Å is comparable with other carbene complexes. The two phenyl rings of the carbene ligand are perpendicular to the carbene plane. Methanol solvate mol­ecules link the methanol ligands of adjacent porphyrin complexes via hydrogen bonds.     

A novel one‐dimensional double‐chain‐like ZnII coordination polymer: poly[bis(1‐benzyl‐1H‐imidazole‐κN3)tris(μ‐cyanido‐κ2C:N)(cyanido‐κC)disilver(I)zinc(II)]

One of most interesting systems of coordination polymers constructed from the first‐row transition metals is the porous Zn^II coordination polymer system, but the numbers of such polymers containing N‐donor linkers are still limited. The title double‐chain‐like Zn^II coordination polymer, [Ag₂Zn(CN)₄(C₁₀H₁₀N₂)₂]_n, presents a one‐dimensional linear coordination polymer structure in which Zn^II ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each Zn^II ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1‐benzyl‐1H‐imidazole (BZI) ligands, giving a five‐coordinated Zn^II ion. Interestingly, there are strong intermolecular Ag^I…Ag^I interactions between terminal and bridging dicyanidoargentate(I) units and C—H…π interactions between the phenyl rings of BZI ligands of adjacent one‐dimensional linear chains, providing a one‐dimensional linear double‐chain‐like structure. The supramolecular three‐dimensional framework is stabilized by C—H…π interactions between the phenyl rings of BZI ligands and by Ag^I…Ag^I interactions between adjacent double chains. The photoluminescence properties have been studied.     

Syntheses and properties of novel fluorinated polyamides based on a bis(ether‐carboxylic acid) or a bis(ether amine) extended from bis(4‐hydroxyphenyl)phenyl‐2,2,2‐trifluoroethane

Two series of novel fluorinated aromatic polyamides were prepared from 1,1‐bis[4‐(4‐carboxyphenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic diamines or from 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic dicarboxylic acids with the phosphorylation polyamidation technique. These polyamides had inherent viscosities ranging from 0.51 to 1.54 dL/g that corresponded to weight‐average and number‐average molecular weights (by gel permeation chromatography) of 36,200–80,000 and 17,200–64,300, respectively. All polymers were highly soluble in aprotic polar solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylacetamide, and some could even be dissolved in less‐polar solvents like tetrahydrofuran. The flexible and tough films cast from the polymer solutions possessed tensile strengths of 76–94 MPa and initial moduli of 1.70–2.22 GPa. Glass‐transition temperatures (T_g's) and softening temperatures of these polyamides were observed in the range of 185–268 °C by differential scanning calorimetry or thermomechanical analysis. Decomposition temperatures (T_d's) for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. Almost all the fluorinated polyamides displayed relatively higher T_g and T_d values than the corresponding nonfluorinated analogues. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 420–431, 2003     

1,2‐Ph2‐9‐I‐1,2‐closo‐C2B10H9

The title compound, 9‐iodo‐1,2‐di­phenyl‐1,2‐dicarba‐closo‐dodecaborane(9), C₁₄H₁₉B₁₀I, has the expected pseudo‐icosahedral cluster geometry, with a cage C—C distance of 1.724 (4) Å, comparable to that in the non‐iodinated parent. However, the twist angles, θ, of the phenyl rings are 2.1 (6) and 27.6 (5)°, the latter being unusually large.     

The effect of molecular planarity on crystal non‐centrosymmetry in benzyl­idene–aniline derivatives

In the title compound, N‐(2‐methoxy­phenyl)‐4‐nitro­benzyli­deneamine, C₁₄H₁₂N₂O₃, the two phenyl rings make a dihedral angle of 48.0 (2)° and the nitro group is at an angle of 6.5 (1)° with respect to its attached phenyl ring. In the crystal structure, mol­ecules are related as centrosymmetric pairs through π–π interactions and are further connected through strong C—H?O hydrogen bonds [C?O 3.4259 (17) Å and C—H?O 167°], forming molecular stacks along [100]. These stacks associate further through longer C—H?O interactions, forming two‐dimensional networks. In the c direction, there are only weak van der Waals interactions. The relationship between the molecular planarity and its centrosymmetry is also briefly described.     

Studies on the Extension of Sequence‐independence and the Enhancement of DNA Triplex Formation

A more elaborate sequence‐independent triple‐helix formation viability study was carried out and extended from a recombination‐like triple‐helical DNA motif of a previous study (J. Mol. Recognition 14, 122–139 (2001)). The intended triple‐helix was formed by mixing one part of a DNA hairpin duplex and one part of a single (or third) strand identical to one of the duplex strands and complementary to the other strand. In contrast to the common purine and pyrimidine motifs in triple‐stranded DNA, the strands of the recombination‐like motif are not monotonously built from pyrimidine only, or purine only, in the sequence. The stability of the recombination‐like motif triplexes with varying sequences was monitored by UV thermal melting curves. The results showed that the order of the stability of the R‐form DNA base triads (J. Mol. Biol., 239, 181–200 (1994)) is G*(G ○ C) > C*(C ○ G) > A*(A ○ T) >T*(T ○ A) (the Watson‐Crick base pair is denoted in the parentheses) in 200 mM NaCl, at pH 7. In an attempt to increase the stability of the triplex in the recombination‐like motif, we replaced cytidine by 5‐methylcytidine (^mC) of the third strand. There is a general trend that ^mC modification stabilizes the complex (<2 °C per ^mC). The complex is furthermore stabilized by Mg²⁺ ion. The Tm increases from 7 to 2 °C from less stable to highly stable triplex by 20 mM Mg²⁺ ion in solution.     

(E)‐N‐Benzyl­idene‐3‐chloro‐4‐fluoro­aniline

The title mol­ecule, C₁₃H₉ClFN, is substantially planar. The phenyl and 3‐chloro‐4‐fluoro­phenyl rings are on opposite sides of the C=N bond. There is an intermolecular C—H?F short contact with a C?F distance of 3.348 (2) Å and a C—H?F angle of 137.4 (1)°. The mol­ecules are held in layers parallel to the bc plane.     

Methyl 3‐(4‐methoxyphenyl)prop‐2‐enoate

The title mol­ecule, C₁₁H₁₂O₃, is almost planar, with an average deviation of the C and O atoms from the least‐squares plane of 0.146 (4) Å. The geometry about the C=C bond is trans. The phenyl ring and –COOCH₃ group are twisted with respect to the double bond by 9.3 (3) and 5.6 (5)°, respectively. The endocyclic angle at the junction of the propenoate group and the phenyl ring is decreased from 120° by 2.6 (2)°, whereas two neighbouring angles around the ring are increased by 2.3 (2) and 0.9 (2)°. This is probably associated with the charge‐transfer interaction of the phenyl ring and –COOCH₃ group through the C=C double bond. The mol­ecules are joined together through C—H?O hydrogen bonds between the methoxy and ester groups to form characteristic zigzag chains extended along the c axis.     

Synthesis and polymerization of new self‐polymerizable quinoxaline monomers

Extended self‐polymerizable poly(phenylquinoxaline) monomer mixtures {i.e.,2‐[4‐(4‐hydroxyphenoxy)phenyl]‐3‐phenyl‐6‐chloroquinoxaline and 3‐[4‐(4‐hydroxy phenoxy)phenyl]‐2‐phenyl‐6‐chloroquinoxaline, 2‐[4‐(4‐hydroxyphenoxy)phenyl]‐3‐phenyl‐6‐fluoroquinoxaline and 3‐[4‐(4‐hydroxyphenoxy)phenyl]‐2‐phenyl‐6‐fluoroquinoxaline, and 2‐(4‐fluorophenyl)‐3‐phenyl‐6‐(4‐hydroxyphenoxy)quinoxaline and 3‐(4‐fluorophenyl)‐2‐phenyl‐6‐(4‐hydroxyphenoxy)quinoxaline} more flexible and nucleophilic than a previously reported monomer mixture [i.e., 3‐(4‐hydroxyphenyl)‐2‐phenyl‐6‐fluoroquinoxaline and 2‐(4‐hydroxyphenyl)‐3‐phenyl‐6‐fluoroquinoxaline] were synthesized. The monomer mixtures were then polymerized into high‐molecular‐weight polymers. A sample was obtained, through a chlorine displacement reaction, that was a semicrystalline polymer with an intrinsic viscosity of 1.11 dL/g in m‐cresol at 30 ± 0.1 °C and two melting temperatures at 339 and 377 °C in the first differential scanning calorimetry scan. There was a melting temperature at 328 °C without a detectable glass‐transition temperature (T_g) when the sample was subjected to a second differential scanning calorimetry scan. The samples from fluorine displacement reactions were completely amorphous polymers. They had intrinsic viscosities of 0.53–0.90 dL/g in m‐cresol at 30 ± 0.1 °C and T_g's of 220–224 °C. The polymer samples from fluorine displacement reactions were evaluated with gel permeation chromatography and matrix‐assisted laser desorption/ionization time‐of‐flight analyses, which monitored the existence of certain amounts of cyclic oligomers. The thin films of the polymers had room‐temperature tensile strengths of 97–113 MPa, room‐temperature Young's moduli of 2.30–2.35 GPa, and room‐temperature elongations at break of 40–150%. The melt viscosity decreased from 10⁷ to less than 10⁴ Pa s at 310 °C as the frequency was increased from 10^?2 to 10² rad/s. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 78–91, 2005