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1.
It is often necessary to measure a spectrum of tumor markers in oncology. We have developed a simultaneous multiplexing immunoassay method to determine six tumor markers: -fetoprotein (AFP), carcinoma embryonic antigen (CEA), beta-human chorionic gonadotropin (β-HCG), carbohydrate antigen 125 (CA 125), carbohydrate antigen 19-9 (CA 19-9) and carbohydrate antigen 15-3 (CA 15-3). F(ab′) 2 fragments of six capture antibodies were prepared and printed as microarrays on silylated slides to perform sandwich immunoassays with the use of an avidin–biotin system for amplified fluorescence signals. Each antigen with different concentrations was detected to assemble its calibration curve, and combinations of different markers were determined to examine the specificity of simultaneous detection based on the F(ab′) 2 microarrays. Some clinical samples were analyzed to compare with results obtained with the use of immunoradiometric assay (IRMA) method. Wide range calibration curve and its R-value were obtained for each analyte. Calibration curves concentrations were 0–640 μg/l for CEA, AFP and β-HCG, and 0–1280 kU/l for CA 125, CA 19-9 and CA 15-3. The antibody fragments microarray system bears comparison with conventional immunoassays and may find feasible application in measurement of series markers in oncology and other areas of medicine. 相似文献
2.
Photolysis of compounds of the type [Re(CCMe 2R)(OR′) 2] (R = Me or Ph; OR′ = O′Bu, OCMe 2(CF 3), or OCMe(CF 3) 2) in benzene with a medium pressure mercury lamp yields compounds of the type [Re(OR′) 2] 2(μ-CCMe 2R) 2 in an intramolecular and irreversible manner. [Re(CCMe 2R)(OR′) 2] 2 and [Re(OR′) 2] 2(μ-CCMe 2R) 2 (OR′ = O′Bu or OCMe 2(CF 3) 2) both react with excess carbon monoxide in several solvents to afford the dimers [Re(OR′) 2(CO)] 2(μ-CCMe 2R) 2 quantitatively. An X-ray study of [Re(O tBu) 2(CO)] 2 (μ-C tBu) 2 shows it to consist of two distorted trigonal bipyramids connected by two symmetrically bridging neopentylidyne ligands. The unbridged dimers of general formula [Re(CCMe 2R)(OR′) 2] 2 do not react readily with simple substrates such as phosphines, olefins, or acetylenes, although [Re(CCMe 2R)(O tBu) 2] 2 can be oxidized by iodine to yield Re(CCMe 2R)(O tBu) 2I 2 in good yield. In contrast, {Re[OCMe(CF 3) 2] 2} 2(μ-C tBu) 2 reacts with one equivalent of phenylacetylene to give a species in which one of the two bridging alkylidyne ligands is retained. 相似文献
3.
Toluene solutions of M 2(NMe 2) 6 (M = Mo, W) react with mesitylene selenol (Ar′SeH) to give M 2(SeAr′) 6 complexes. MO 2(OR) 6 (R = tBu, CH 2tBu) react with excess> 6 fold) Ar′SeH to give Mo 2 (SeAr′) 6, whilst W 2(OR) 6(py) 2 (R = iPr, CH 2tBu) react with excess (> 6 fold) Ar′SeH to give W 2(OR) 2(SeAr′) 4. Reaction of MO 2(OPr i) 6 with Ar′SeH produces Mo 2(OPr i) 2 (SeAr′) 4 which crystallizes in two different space groups. These areneselenato complexes are air-stable and insoluble in common organic solvents. X-ray crystallographic studies revealed that the Mo 2(SeAr′) 6 and W 2(SeAr′) 6 compounds are isostructural in the solid state and adopt ethane-like staggered configurations with the following important structural parameters, M---M (W---W/Mo---Mo) 2.3000(11)/2.2175(13) Å, M---Se 2.430 (av.)/2.440 (av.) Å, M---M---SE 97.0° (av.)°. In the solid state W 2(O iPr) 2(SeAr′) 4 adopts the anti-configuration with crystallographically imposed Ci symmetry and W---W 2.3077(7) Å, W---Se 2.435 (av.) Å, W---O 1.858(6) Å; W---W---SE 100.27(3)°, 93.8(3)° and W---W---O 108.41(17)°. Mo 2(OPr i) 2(SeAr′) 4 crystallizes in both P
and A2/ a space groups in which the molecules are isostructural with each other and the tungsten analogue. Important bond lengths and angles are Mo---Mo 2.180(24) Å, Mo---Se 2.432(av.) Å, Mo---O 1.872(9) Å, Mo---Mo---Se 99.39(9)°, 94.71(8)°, Mo---Mo---O 107.55(28)°. 相似文献
4.
In order to gain information about the coordinating properties of the chelating ligands Me 2XGeMe 2(CH 2) 2X′Me 2 (abbr. XGeCCX′) the chemical and spectroscopic results obtained during the synthesis of the M(CO) 4(XGeCCX′) complexes (M = Cr, Mo, W; X, X′ = N, P, As) are critically discussed and compared with the results for the analogous five-membered ring chelates M(CO) 4(KGeCX′). 相似文献
5.
A structural study of odd-numbered n-alkane (C n) binary mixtures (C 21 : C 23) was carried out on powder samples using a Guinier-de Wolff camera with increasing concentration of n-C 23 at 293 K. Despite the reports in the literature, these molecular alloys do not form an orthorhombic continuous homogeneous solid solution to C21 from C23 at “low temperature”. Instead, as already observed in two even-numbered Cn systems, X-ray diffraction results show the existence of seven solid solutions as the molar concentration of C23 increases: four terminal solid solutions, denoted β0(C21)β0(C23), isostructural with the “low temperature” phase of pure C21 and C23 (Pbcm), β′0(C21) and β′0(C23), identical to the phase β′0 which appears in pure C23 above the δ transition, and three orthorhombic intermediate solid solutions, designated β″1, β′1 and β″2. On the basis of powder X-ray photographs, the phases β″1 and β″2 (C21 : C23) are indistinguishable, and they are isostructural with the intermediate solid solution β″ of the even-numbered Cn binary systems (C22 : C24) and (C24 : C26). The phase β′1(C21 : C23) is also isostructural with the two indistinguishable intermediate solid solutions β′1 and β′2 of the molecular alloys (C22 : C24) and (24 : C26). From this study and our other laboratory results, the sequences of appearance of the solid solutions and the structural identities between these phases are established at “low temperature” for all the binary molecular alloys of consecutive Cn (odd-odd, even-even or odd-even: 19 < n < 27) when increasing the solute concentration. 相似文献
6.
The fabrication of antibody thin film using both protein G and oligonucleotide was carried out by self-assembly (SA) technique for immunosensor. A mixture of 11-mercaptoundecanoic acid (MUA) and oligonucleotide with thiol (SH) end group was self-assembled of gold (Au) surface for two-dimensional (2D) configuration. Protein G was chemically adsorbed on the 11-MUA surface, and then the antibody was immobilized on the protein G region. On the immobilized single-stranded DNA, the complementary DNA–antibody conjugate was hybridized for the oriented immobilization of antibody. The formation of self-assembled 11-MUA/oligonucleotide layer, protein G immobilization, antibody layer, and antigen binding was investigated using surface plasmon resonance (SPR). The topographies of the fabricated surfaces were observed by atomic force microscopy (AFM). When compared with the amount of antigen binding on the antibody thin film fabricated by protein G only, the proposed biosurface fabricated with both protein G and oligonucleotide showed better binding capacity, which implicates the improvement of the detection limit. 相似文献
7.
The diol R 2C(SiMe 2OH) 2 (R = Me 3Si) has been shown to react with: SO 2Cl 2 to give R 2
Me 2; SOCl 2 to give R 2C(SiMe 2Cl) 2; Me 3SiI or Me 3SiCl to give R 2C(SiMe 2OSiMe 3) 2; R′COCl; (R′ = Me or CF 3) to give R 2C(SiMe 2O 2CR′)-(SiMe 2Cl); (R′CO) 2O (R′ = Me or CF 3 to give R 2C(SiMe 2O 2CR′) 2; with MeOH containing acid to give R 2C(SiMe 2OMe) 2; with neutral MeOH to give R 2C-(SiMe 2OMe) 2 and probably R 2
Me 2; MeLi to give R 2C(SiMe 2OLi) 2 (and the latter to react with PhMeSiF 2 to give R 2
Me 2). The diacetate R 2C(SiMe 2O 2CMe) 2 reacts with CsF in MeCN to give R 2C(SiMe 2F) 2; it does not react with NaN 3 or KSCN in MeCN, but the bis(trifluoroacetate) reacts with these salts with KOCN to give R 2C(SiMe 2X) 2 (X = N 3, NCS, NCO). 相似文献
8.
The preparation and characterisation of three new gold(I) phosphine derivatives of the ferraborane, HFe 4(CO) 12BH 2 are reported. In HFe 4(CO) 12(AuPPh 3)BH (2), the AuPPh 3 fragment formally replaces an Fe---H---B bridging hydrogen atom in the parent compound HFe 4(CO) 12BH 2. A comparison between 2 and the structurally characterised di-gold derivative, Fe 4(CO) 12(AuPPh 3) 2BH (1) is made to gain insight into the relative site preference for the heavy metal fragments in 1. Preparation of the bis(triethylphosphine)gold(I) derivative of HFe 4(CO) 12BH 2 from the PPN + salt of its conjugate base illustrates a novel exchange reaction between the PPh 3 groups in the PPN + cation and the initially, gold-associated PEt 3 groups. This leads to a distribution of products Fe 4(CO) 12(AuPR 3(AuPR′ 3BH where R = R′ = Ph (1) or R = R′ = Et (3) or R = Ph and R′ = et (4). 相似文献
9.
Liquid crystalline 4-XC 6H 4N=NC 6H 4X-4′ [X = C 4H 9 (1a), C 1OH 21 (1b), OC 4H 9 (1c), OC 8H 17(1d)] can be easily prepared in high yields from the corresponding anilines. In order to study the influence of metals on the thermal properties of these materials, we have obtained adducts [AuCl 3(4-C 4H 9OC 6H 4N=NC 6H 4OC 4H 9-4′)] (2) and [Ag(OC1O 3)L 2] [L = 4-XC 6H 4N=NC 6H 4X-4′; X = OC 4H, (3a), OC 8H 17 (3b)]. The silver adducts show themotropic behaviour. Mercuriation of dialkylazobenzenes 1a-b takes place with [Hg(OAc) 2] and LiCl to give [Hg(R)Cl] [R = C 6H 3(N=NC 6H 4X-4′)-2, X-5; X = C 4H 9 (bpap) (4a), C 10H 21 (dpap) (4b)] while dialkoxyazobenzenes 1c–d require [Hg (OOCCF 3) 2] to obtain [Hg(R)Cl] [R = C 6H 3(N---NC 6H 4X-4′)-2, X-5; X = OC 4H 9 (bxpap) (4c), OC 8H 17 (4d)]. 4a-c react with NaI to give [HgR 2] [R= bpap (5a), dpap (5b), bxpap (5c), oxpap (5d)l. Both chloroaryl-, 4a and 4c, and diaryl-mercurials, 5a and 5c, act readily as transmetailating agents towards [Me 4N] [AuCl 4] in the presence of [Me 4N]Cl to give [Au(η 2-R)Cl 2] [R = bpap (6a), bxpap (6b)]. After reaction of [AuCl 3(tht)] (tht = tetrahydrothiophene) with [Me 4N]Cl and 4b (1:2:1), [Me 4N][Au(dpap)Cl 3] (7) can be isolated. C---H activati bxpap (8b)]. None of the complexes 4–8 shows mesomorphic behaviour. 相似文献
10.
The reactions of M(CO) 4(R′-DAB) (M = Mo) or W; R′-DAB = R′-N=CHCH=NR′ (R′ = i-propyl, t-butyl, or cyclohexyl) with SnCl 4 in dichloromethane solution result in the formation, in high yield, of the orange, diamagnetic, seven-coordinate oxidative-addition products M(CO) 3(R′-DAB)(SnCl 3)Cl. The reactions of Mo(CO) 3(R′-DAB)(SnCl 3)Cl (R′ = i-Pr or Cy) with an excess of alkyl isocyanide RNC (R = CHMe 2, CMe 3, or C 6H 11) in the presence of KPF 6 lead to the formation of [Mo(CNR) 4(R′-DAB)Cl]PF 6 or [Mo(CNR) 5(R′-DAB)](PF 6) 2 depending upon the reaction stoichiometry and reaction conditions. The monocationic chloro species are converted to [Mo(CNR) 5(R′-DAB)](PF 6) 2 upon reflux with the stoichiometric amount of RNC. Under similar reactions conditions M(CO) 3(t-Bu-DAB)(SnCl 3)Cl (M = Mo or W) derivatives react with alkyl isocyanides with the reductive-elimination of the elements of SnCl 4 and the formation of octahedral M(CO) 3(CNR)(t-Bu-DAB). The dark red compounds [Mo(CNCMe 3) 5(R′-DAB)](PF 6) 2 (R′ = i-Pr or Cy) react readily with cyanide ions at ambient temperatures in methanol to yield [Mo(CNCMe 3) 4(R′-DAB)(CN)]PF 6. Attempts to thermally dealkylate the parent complexes [Mo(CNCMe 3) 5(R′-DAB)](PF 6) 2 (R′ = i-Pr or Cy) to these same cyano species were unsuccessful. 相似文献
11.
The reaction of (η 5-cyclopentadienyl)(η 4-tetraphenylcyclobutadiene)cobalt (1) with excess Cr(CO) 6 yielded several heterometallic compounds: 2, 3 (3′ and 3″), 4 and 5 with, respectively, one, two, three and four phenyl rings complexed with Cr(CO) 3 fragment(s). These compounds were characterized by mass, infrared, 1H and 13C NMR spectra. The crystal structure of 5 was determined. In 5 the four Cr(CO) 3 fragments are on the same side of the CpCo fragment; whereas, the two Cr(CO) 3 fragments of 3′, the precursor of 5, are pointed in a different direction from the CpCo fragment. The cyclopentadienyl ring shows a static disorder around the axis that passes through the cobalt and the centre of the ring. 相似文献
12.
The reactions of MnRe(CO) 10 with As 2(CF 3) 4 and MnCo(CO) 9 with P 2(CF 3) 4, As 2(CF 3) 4, S 2(CF 3) 2, Se 2(CF 3) 2, (CF 3) 2EI (E = P, As), (CF 3) 2AsH, (CF 3) 2AsE′CF 3 (E′ = S, Se), (CF 3) 2PSeCF 3, Me 2AsI and (CF 3) 2PPMe 2, respectively, have been studied under various conditions. Besides already known mono- and binuclear compounds the heteronuclear complexes MnRe(CO) 8[As(CF 3) 2] 2 and MnCo(CO) 7[E(CF 3) 2] 2 (E = P, As) are formed. The reactions proceed via cleavage of the M---M′ bond and formation of the mononuclear species Mn(CO) 5X and M′(CO) nY (M′ = Re, n = 5; M′ = Co, n = 4). 相似文献
13.
Reaction of phosphorus ylides Ph 3PCHC(O)C 6H 4NO 2 (Y′) and ( p-tolyl) 3PCHC(O)C 6H 4Cl (Y″) with HgX 2 (X = Cl, Br and I) in equimolar ratios using methanol as solvent leads to binuclear products. The bridge-splitting reaction of binuclear complex [(Y″) · HgI 2] 2 by DMSO yields the mononuclear complex [(Y″) · HgI 2 · DMSO]. This bridge-splitting reaction can be also a method for the synthesis of mononuclear products. C-coordination of ylides and O-coordination of DMSO are demonstrated by single crystal X-ray analyses of binuclear complexes of [(Y′) · HgI 2] 2 and [(Y″) · HgI 2] 2 and mononuclear complex of [(Y″) · HgI 2 · DMSO]. Characterization of the obtained compounds was also performed by elemental analysis, IR, 1H, 31P, and 13C NMR. Theoretical studies on Hg(II) complexes of Y′ show that the cis-like isomers are about 4–12 kcal/mol less stable than the trans-like structures and the relative energy of cis- and trans-like isomers significantly depends on the size of the bridging halide. These studies on mercury complexes of Y″ show that, formation of mononuclear complexes in DMSO solution in which DMSO acts as a ligand, energetically is more favorable than that of binuclear complexes. 相似文献
14.
Protonation of the lithium triphospha-cyclopentenyl salt Li (P 3C 2Bu t2RR′) (R=(Me 3Si) 2CH-, R′=Bu n) with HCl affords the new 2,3-dihydro-1 H-[1,2,4] triphosphole P 3C 2Bu t2(H) (Bu n)CH(SiMe 3) 2 which has been structurally characterised as its [W(CO) 5] complex. 相似文献
15.
Whilst mono(silyl)triazenes R′N=N---NR′(SiR 3) and organyl triazenes R′N=N---NR′ 2 are of comparable thermal stability and decay by a radical reaction, bis(silyl)triazenes R′N=N---N(SiR 3) 2 (R′=aryl, R=Me, Et, OMe) decompose at room temperature in a non-radical reaction to yield amines R′N(SiR 3) 2 and nitrogen. Kinetic investigations of the mechanism of the non-radical thermolysis of triazenes show that the rate of the thermolysis of R′N=N---N(SiR 3) 2 is determined both from an isomerisation equilibrium forming (R 3Si)R′N---N=N(SiR 3) and from the rate of decomposition of this compound to the thermolysis products. Tris(silyl)triazenes, (R 3Si) 2N---N=N(SiR 3), hitherto not synthesized, are expected to be even more unstable than the bis(silyl)triazenes which have been examined by us. 相似文献
16.
In this paper, we summarise our recent research interest in the hydrothermal synthesis and structural characterisation of multi-dimensional coordination polymers. The use of N-(phosphonomethyl)iminodiacetic acid (also referred to as H 4pmida) in the literature as a versatile chelating organic ligand is briefly reviewed. This molecule plays an important role in the formation of centrosymmetric dimeric [V 2O 2(pmida) 2] 4− anionic units, which were first used by us as building blocks to construct novel coordination polymers. Starting with [V 2O 2(pmida) 2] 4− in solution, we have isolated [M 2V 2O 2(pmida) 2(H 2O) 10] species (where M 2+ = Mn 2+, Co 2+ or Cd 2+) via the hydrothermal synthetic approach, which were then employed for the construction of [CdVO(pmida)(4,4′-bpy)(H 2O) 2]·(4,4′-bpy) 0.5·(H 2O), [CoVO(pmida)(4,4′-bpy)(H 2O) 2]·(4,4′-bpy) 0.5, [Co(H 2O) 6][CoV 2O 2(pmida) 2(pyr)(H 2O) 2]·2(H 2O) and [Cd 2V 2O 2(pmida) 2(pyr) 2(H 2O) 4]·4(H 2O) by the inclusion of bridging organic ligands in the reactive mixtures, such as pyrazine (pyr) and 4,4′-bipyridine (4,4′-bpy). These materials can contain channel systems, and exhibit magnetic behaviour, not only due to the V 4+ centres but also to the transition metal centres which establish the links between neighbouring dimeric [V 2O 2(pmida) 2] 4− anionic units. A closely related anionic moiety, [Ge 2(pmida) 2(OH) 2] 2−, was engineered to allow the study of such crystalline hybrid materials using one- and two-dimensional high-resolution solid-state NMR. 相似文献
17.
Addition of 1,4-dithiols to dichloromethane solutions of [PtCl 2(P-P)] (P-P = (PPh 3) 2, Ph 2P(CH 2) 3PPh 2, Phd 2P(CH 2) 4PPh 2; 1,4-dithiols = HS(CH 2) 4SH, (−)DIOSH 2 (2,3- O-isopropylidene-1,4-dithiol-l-threitol), BINASH 2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt 3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph 2P(CH 2) 3PPh 2, Ph 2P(CH 2) 4PPh 2; dithiolato = −S(CH 2) 4S −, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh 3) 2] and [Pd(S(CH 2) 4S)(Ph 2P(CH 2) 3PPh 2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC1 2 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl 2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%. 相似文献
18.
The coordination of 1,5-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,5-pentanedione (BPMPPD) and 2,2′-bipyridine (bipy) with lanthanide ions in water-alcohol solution has been studied. Binuclear complexes of the types : Ln 2(BPMPPD) 3(bipy) 2· nH 2O ( n = 2 for Y, n = 4 for Eu, Gd, Dy, Ho, Er, Tm and Yb); Ln 2(BPMPPD) 3bipy· nH 2O ( n = 10 for La, n = 3 for Pr, Nd, Sm and Tb) were formed. The compounds were characterized by elemental analysis, molar conductance, IR, UV, 1H NMR spectroscopy, thermogravimetric analysis and fluorescence spectra. 相似文献
19.
The reactions of R 2PPR 2 (R = Me, Et, Ph) and (MeP) 5 with Me 3−nAs(NMe 2) n ( n = 1, 2, 3) and of Me 2PPMe 2 with Me 2AsNR′ 2 (R′ = Et, Pr n, and Pr i) were investigated as a function of time at room temperature using 1H and 31P NMR spectroscopy. For the diphosphine/Me 2AsNR′ 2 reactions, the NMR spectral data suggest a reaction pathway involving the initial formation of R 2PAsMe 2 and the respective acyclic dialkylaminophosphine, R 2PNR′ 2. The P---As intermediate then symmetrizes to R 2PPR 2 and Me 2AsAsMe 2, the parent aminoarsine is completely consumed, and additional R 2PNR′ is formed. The relative rate of aminophosphine production is dependent upon the nature of the substituent on the phosphorus and nitrogen atoms. For systems involving MeAs(NMe 2) 2 and As(NMe 2) 3 as reactants, the intermediates could not be characterized, but the products were the expected aminophosphine and (MeAs) 5 or elemental arsenic, respectively. (MeP) 5 reacts to give MeP(NMe 2) 2 and the expected As---As bonded species. A comparison of the reactivity of these systems with analogous diarsine/aminoarsine systems is discussed. The results of the NMR study were utilized in designing a convenient, high yield, synthetic route to acyclic aminophosphines. 相似文献
20.
The study of the reactivity of [Pt 2M 4(CCR) 8] (M=Ag or cu; R=Ph or tBu) towards different neutral and anionic ligands is reported. This study reveals that reactions of the phenylacetylide derivatives [Pt 2M 4(CCPh) 8] with anionic, X − (X=Cl or Br) or neutral donors (CN tBu or py) in a molar ratio 1:4 (m/donor ratio 1:1) yield the trinuclear anionic (NBu 4) 2[{Pt(CCPh) 4 (MX) 2] (M=Ag or Cu, X =Cl or Br) or neutral [{Pt(CCPh0 4=sAGL) 2] (L=CN tBu or py) complexes, respectively. The crystal structure of (NBu 4) 2[{Pt(CCPh) 4}(CuBr) 2](4) shows that the anion is formed by a dianionic Pt(CCPh) 4 fragment and two neutral CuBr units joined through bridging alkynyl ligands. All the alkynyl groups are σ bonded to Pt and η 2-coordinated to a Cu atom which have an approximately trigonal-planar geometry. By contrast, similar reactions with [Pt 2M 4(CC tBu) 8] (molar ratio M/donor 1:1) afford hexanuclear dianionic (NBu 4) 2[Pt 2M 4(CC tBu) 8X 2] or neutral [Pt 2Ag 4(CC tBu0 8Py 2]. Only by treatment with a large exces of Br − (molar ratio M/Br − 1:2) are the trinuclear complexes (NBu 4) 2[{Pt(CC tBu 4 (MBr) 2] (M=Ag, Cu) obtained. Attempted preparations of analogous complexes with phosphines (L′=PPh 3 or PEt 3) by reactions of [Pt 2M 4(CCR 8] with L′ leads to displacement of alkynyl ligands from platinum and formation of neutral mononuclear complexes [ trans-Pt(CCR) 2L′ 2]. 相似文献
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