A novel, sensitive potentiometric hydrocarbon sensor for high-vacuum applications.

A potentiometric device based on interfacing a solid electrolyte oxygen ion conductor with a thin platinum film acts as a robust, reproducible sensor for the detection of hydrocarbons in high- or ultrahigh-vacuum environments. Sensitivities in the order of approximately 5 x 10(-10) mbar are achievable under open circuit conditions, with good selectivity for discrimination between n-butane on one hand and toluene, n-octane, n-hexane, and 1-butene on the other hand. The sensor's sensitivity may be tuned by operating under constant current (closed circuit) conditions; injection of anodic current is also a very effective means of restoring a clean sensing surface at any desired point. XPS data and potentiometric measurements confirm the proposed mode of sensing action: the steady-state coverage of Oa, which sets the potential of the Pt sensing electrode, is determined by the partial pressure and dissociative sticking probability of the impinging hydrocarbon. The principles established here provide the basis for a viable, inherently flexible, and promising means for the sensitive and selective detection of hydrocarbons under demanding conditions.

2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

Selective hydroxylation of small alkanes by the particulate methane monooxygenase

The particulate methane monooxygenase (pMMO) catalyzes the oxidation of methane to methanol under ambient temperatures and pressures. Other small alkanes and alkenes are also substrates of this enzyme. We measured and compared the initial rate constants of oxidation of small alkanes (C1 to C5) catalyzed by pMMO. Both primary and secondary alcohols were formed from oxidation of n-butane and n-pentane. The alcohols produced from alkane oxidation can be further oxidized, probably by pMMO, to aldehydes and ketones. The apparent regioselectivity for n-butane and n-pentane is 100% 2-alcohols because the formation of primary alcohols is slower than further oxidation of these alcohols. The hydroxylation at the secondary carbons is highly stereoselective: (R)-alcohols are preferentially formed. The enantiomeric excess increases slightly with decreasing reaction temperature. The steric course of hydroxylation on primary carbons was also studied by using isotopically substituted ethane: (S)- or (R)-CH_3-CHDT, and (S)- or (R)-CD_3- CHDT and the reactions were found to proceed with 100% retention of configuration. A primary isotopic effect of k_H/k_D=5.0 was observed in these experiments.

Growth of heavily Zn-doped InGaAs at low temperature by LP-MOCVD

Epitaxial growth of Zn-doped InGaAs on InP substrates has been carried out at 550degreesC by LP-MOCVD. Hole concentration as high as 6 x 10(19)cm(-3) has been achieved at the H-2 flow rate of 20 sccm through DEZn bubbler. The lattice constant of Zn-doped InGaAs was found to be dependent on the flow rate of DEZn, and the tensile strain mismatch increases with increasing H-2 flow rate of DEZn. The negative lattice mismatch of heavily Zn-dopped InGaAs may be due to, the small covalent bonding radius of zinc and the combination of butane from ethyl of DEZn,and TEGa. And the latter accelerates the pyrolysis of TEGa, which is the dominant mechanism in determining the negative mismatch of Zn-doped InGaAs. (C) 2003 Elsevier B.V. All rights reserved.

Microwave-assisted hydrothermal synthesis of hydroxy-sodalite zeolite membrane

A high quality pure hydroxy-sodalite zeolite membrane was successfully synthesized on an alpha-Al2O3 support by a novel microwave-assisted hydrothermal synthesis (MARS) method. Influence of synthesis conditions, such as synthesis time, synthesis procedure, etc., on the formation of hydroxy-sodalite zeolite membrane by MAHS method was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and gas permeation measurements. The synthesis of hydroxy-sodalite zeolite membrane by MAHS method only needed 45 min and synthesis was more than 8 times faster than by the conventional hydrothermal synthesis (CHS) method. A pure hydroxy-sodalite zeolite membrane was easily synthesized by MAHS method, while a zeolite membrane, which consisted of NaX zeolite, NaA zeolite and hydroxy-sodalite zeolite, was usually synthesized by CHS method. The effect of preparation procedures had a dramatic impact on the formation of hydroxy-sodalite zeolite membrane and a single-stage synthesis procedure produced a pure hydroxy-sodalite zeolite membrane. The pure hydroxy-sodalite zeolite membrane synthesized by MARS method was found to be well inter-grown and the thickness of the membrane was 6-7 mum. Gas permeation results showed that the hydrogen/n-butane permselectivity of the hydroxy-sodalite zeolite membrane was larger than 1000. (C) 2004 Elsevier Inc. All rights reserved.

Assembly of the highest connectivity Wells-Dawson polyoxometalate coordination polymer: the use of organic ligand flexibility

Through tuning the length of flexible bis(triazole) ligands and different metal ion coordination geometries, four Wells-Dawson polyoxoanion-based hybrid compounds, [Cu-6(btp)(3)(P2W18O62)] center dot 3H(2)O (1) (btp = 1,3-bis(1,2,4-triazol-1-yl)propane), [Cu-6(btb)(3)((P2W18O62) center dot 2H(2)O (2), [Cu-3(btb)(6)(P2W18O62)] center dot 6H(2)O (btb = 1,4-bis(1,2,4-triazol-1-yl)butane) (3), and [Cu-3(btx)(5.5)((P2W18O62) center dot 4H(2)O (btx = 1,6-bis(1,2,4-triazol-1-yl)hexane) (4), were synthesized and structurally characterized. in compound 1, the metal-organic motif exhibits a ladder-like chain, which is further fused by the ennead-dentate [P2W18O62](6-) anions to construct a 3D structure. In compound 2, the metal-organic motif exhibits an interesting Cu-btb grid layer, and the ennead-dentate polyoxoanions are sandwiched by two Cu-btb layers to construct a 3D structure

Rare Earth Pyrophosphates: Effective Catalysts for the Production of Acrolein from Vapor-phase Dehydration of Glycerol

Vapor-phase dehydration of glycerol to produce acrolein was investigated at 320 A degrees C over rare earth (including La, Ce, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, Lu) pyrophosphates, which were prepared by precipitation method. The most promising catalysts were characterized by means of XRD, FT-IR, TG-DTA, BET and NH3-TPD measurements. The excellent catalytic performance of rare earth pyrophosphate depends on the appropriate surface acidity which can be obtained by the control of pH value in the precipitation and the calcination temperature, e.g. Nd-4(P2O7)(3) precipitated at pH = 6 and calcined at 500 A degrees C in the catalyst preparation.

Sulphonated Tetramethyl Poly(ether ether ketone)/Epoxy/Sulphonated Phenol Novolac Semi-IPN Membranes for Direct Methanol Fuel Cells

The sulphonated phenol novolac (PNBS) which was used as a curing agent of epoxy was synthesised from phenol novolac (PN) and 1,4-butane sultone and confirmed by FTIR and H-1 NMR. The degree of sulphonation (DS) in PNBS was calculated by H-1 NMR. The semi-IPN membranes composed of sulphonated tetramethyl poly(ether ether ketone) (STMPEEK) (the value of ion exchange capacity is 2.01 meq g(-1)), epoxy (TMBP) and PNBS were successfully prepared. The semi-IPN membranes showed high thermal properties which were measured by differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) With the introduction of the corss-linked TMBP/PNBS, the mechanical properties, dimensional stability, methanol resistance and oxidative stability of the membranes were improve in comparison to the pristine STMPEEK membrane.

Effect of different VOPO4 phase catalysts on oxidative dehydrogenation of cyclohexane to cyclohexene in acetic acid

alpha(1)-VOPO4, alpha(II)-VOPO4 and beta-VOPO4 have been investigated as catalysts for the gas phase oxidative dehydrogenation (ODH) of cyclohexane to cyclohexene with the addition of acetic acid (HOAc) in the feeds in a fixed bed reactor. Different VOPO4 phases showed different acidity and reducibility. beta-VOPO4 phase is more active than alpha(I)-VOPO4 and alpha(II)-VOPO4 in the ODH without acetic acid addition. In the presence of acetic acid, the acidity of the catalyst may play an important role in the ODH process. Due to higher acidity, alpha(I)-VOPO4 phase catalyst gives better catalytic performances than alpha(I)-VOPO4 and beta-VOPO4 for the ODH of cyclohexane by adding of acetic acid in the reactants.

Asymmetric polymerization of menthyl methacrylate by anionic catalysts

In this paper, (-)menthyl methacrylate((-)MnMA) was polymerized at -78degreesC in toluene with three types of anionic catalysts, which were complexes of fluorenyllithium with (-)sparteine -((-)-Sp), (S, S)-(+)-2, 3-dimethoxy-1, 4-bis(dimethylamino)butane((+)DDB) and N,N,N,N'-tetramethylethylenediamine(TMEDA), and the chiral optical property of the obtained polymer was studied. The circular dichroism (CD) spectrum of the polymer showed negative Cotton effect.

Studies on the alkylation of isobutane with butene over WO3/ZrO2 strong solid acid (I) - Effect of preparation, load of WO3 and calcination temperature

A series of WO3/ZrO2 strong solid acid prepared under different conditions were studied. Their crystal structures, surface properties and acidities were determined by means of XRD, DTA-TG, H-2- TPR, Laser Raman and acidity measurements. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in tetragonal phase, the addition of WO3 plays an important role to stabilize tetragonal phase of ZrO2 and thus the catalyst had a considerable surface area. WO3 in WO3/ZrO2 was dispersed and crystalized in WO3 crystalite on ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, which acts as the strong solid acid site. The catalytic properties of WO3/ZrO2 strong solid acid for alkylation of iso-butane with butene under the different conditions were investigated. They had a better reaction performance than other strong solid acids, a parallel relationship could be drawn between the catalytic activity and the amount of acid sites as well as the acidic strength of the catalysts.

Gas separation with organo-soluble high performance aromatic polyimide films

An organo-soluble polyimide based on 4,4'-(1,4-phenylenedioxy)diphthalic anhydride and 2,2'-dimethyl-4,4'-methylenedianiline was synthesized by two-step polycondensation accompanied by chemical imidization. Polyimide films were prepared by spray casting onto glass substrates. The study focused on the separation of carbon dioxide (CO2) from natural gas and the enrichment of methane (CH4) from butane (C4H18). The permeability and permselectivity coefficients of these gases were determined.

Asymmetric polymerization of the mixture of TrMA and MMA initiated by chiral complexes

A mixture of triphenylmethyl methacrylate (TrMA) and methyl methacrylate (MMA) was polymerized with chiral anionic initiator, such as fluorenyl lithium-(-)-sparteine [FlLi-(-)-Sp] and fluorenyl lithium-(+)-2S,3S-dimethoxy-1,4-bis(dimethylamino) butane [FlLi-(+)-DDB] in toluene at -78 degrees C. The results show that after the stable helix formed, when FlLi-(+)-DDB was used as the initiator, TrMA and MMA could be copolymerized, whereas when FlLi-(-)-Sp was used, the two monomers tended to be selectively polymerized into two polymers. This phenomenon has been explained by the existence of helix-selective polymerization. (C) 1997 John Wiley & Sons, Inc.

SYNTHESIS AND PROPELLER-PROPELLER TRANSITION OF OPTICALLY-ACTIVE POLY(DIPHENYL-O-TOLYLMETHYL METHACRYLATE)

Diphenyl-o-tolylmethyl methacrylate (DPTMA) was synthesized and polymerized using initiators of organolithium complexes with (+) - (2S,3S) -dimethoxy-1,4-bis(dimethylamino) butane (DDB) and (-) -sparteine (Sp) as the chiral ligands. DDB was suitable for its complex effective to prepare optically active poly(diphenyl-o-tolylmethyl methacrylate) (PDPTMA) with one-handed helical conformation, whereas only low-molecular weight polymer was formed when Sp was used as ligand due to the repulsive hindrance between the triarylmethyl group and the ligand. A new mutarotation, propeller-propeller transition, was observed for PDPTMA from the optical rotation curves and CD spectra in THF solution. The equivalent period of PDPTMA was estimated to be 14 angstrom based on the x-ray diffraction. (C) 1993 John Wiley & Sons, Inc.

SYNTHESIS AND PROPELLER PROPELLER TRANSITION OF OPTICALLY-ACTIVE POLY(DIPHENYL-O-METHOXYPHENYLMETHYL METHACRYLATE)

Diphenyl-o-methoxyphenylmethyl methacrylate was polymerized with several organolithium complexes of chiral ligand such as (-)-sparteine (Sp) and (S,S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane (DDB). (+)-DDB was effective in preparing a polymer of high optical rotation, whereas (-)-Sp only gave oligomers with low optical rotation for the repulsive hindrance between the bulky ester group and the rigid ligand. The optical rotation of the polymer decreased rapidly to a constant value due to the propeller-propeller transition, which has been demonstrated by H-1 n.m.r. and circular dichroic spectra.