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1.
For a real Enriques surface Y we prove that every homology class in H1(Y (R), Z/2) can be represented by a real algebraic curve if and only if all connected components of Y(R) are orientable. Furthermore, we give a characterization of real Enriques surfaces which are Galois-Maximal and/or Z-Galois-Maximal and we determine the Brauer group of any real Enriques surface Y. 相似文献
2.
A novel supramolecular strategy to prepare bidentate ligands via the assembly of functionalised monomeric ligands on a dimeric zinc(II) porphyrin template is presented; the assembled bidentate ligands show chelating behaviour and their rhodium complexes display enhanced selectivity in the hydroformylation compared to the non-template analogue. 相似文献
3.
Polymeric building blocks containing terminal azide and alkyne functionalities are prepared via atom transfer radical polymerization (ATRP) and used to modularly synthesize block copolymers via 1,3-dipolar cycloaddition reactions, which are quantitative according to SEC measurements. 相似文献
4.
Oosterom GE Reek JN Kamer PC van Leeuwen PW 《Angewandte Chemie (International ed. in English)》2001,40(10):1828-1849
Dendrimers are well-defined hyperbranched macromolecules with characteristic globular structures for the larger systems. These novel polymers have inspired many chemists to develop new materials and several applications have been explored, catalysis being one of them. The recent impressive strides in synthetic procedures increased the accessibility of functionalized dendrimers, resulting in a rapid development of dendrimer chemistry. The position of the catalytic site(s) as well as the spatial separation of the catalysts appears to be of crucial importance. Dendrimers that are functionalized with transition metals in the core potentially can mimic the properties of enzymes, their efficient natural counterparts, whereas the surface-functionalized systems have been proposed to fill the gap between homogeneous and heterogeneous catalysis. This might yield superior catalysts with novel properties, that is, special reactivity or stability. Both the core and periphery strategies lead to catalysts that are sufficiently larger than most substrates and products, thus separation by modern membrane separation techniques can be applied. These novel homogeneous catalysts can be used in continuous membrane reactors, which will have major advantages particularly for reactions that benefit from low substrate concentrations or suffer from side reactions of the product. Here we review the recent progress and breakthroughs made with these promising novel transition metal functionalized dendrimers that are used as catalysts, and we will discuss the architectural concepts that have been applied. 相似文献
5.
Pittelkow M Nielsen CB Broeren MA van Dongen JL van Genderen MH Meijer EW Christensen JB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):5126-5135
Host-guest interactions between the periphery of adamantylurea-functionalized dendrimers (host) and ureido acetic acid derivatives (guest) were shown to be specific, strong and spatially well-defined. The binding becomes stronger when using phosphonic or sulfonic acid derivatives. In the present work we have quantified the binding constants for the host-guest interactions between two different host motifs and six different guest molecules. The host molecules, which resemble the periphery of a poly(propylene imine) dendrimer, have been fitted with an anthracene-based fluorescent probe. The two host motifs differ in terms of the length of the spacer between a tertiary amine and two ureido functionalities. The guest molecules all contain an acidic moiety (either a carboxylic acid, a phosphonic acid, or a sulfonic acid) and three of them also contain an ureido moiety capable of forming multiple hydrogen bonds to the hosts. The binding constants for all 12 host-guest complexes have been determined by using fluorescence titrations by monitoring the increase in fluorescence of the host upon protonation by the addition of the guest. The binding constants could be tuned by changing the design of the acidic part of the guest. The formation of hydrogen bonds gives, in all cases, higher association constants, demonstrating that the host is more than a proton sensor. The host with the longer spacer (propyl) shows higher association constants than the host with the shorter spacer (ethyl). The gain in association constants are higher when the urea function is added to the guests for the host with the longer spacer, indicating a better fit. Collision-induced dissociation mass spectrometry (CID-MS) is used to study the stability of the six motifs using the corresponding third generation dendrimer. A similar trend is found when the six different guests are compared. 相似文献
6.
van Apeldoorn AA van Manen HJ Bezemer JM de Bruijn JD van Blitterswijk CA Otto C 《Journal of the American Chemical Society》2004,126(41):13226-13227
Understanding the degradation behavior of polymeric microspheres is crucial for the successful application of such devices in controlled drug delivery. The degradation mechanism of poly(lactic-co-glycolic acid) (PLGA) microspheres inside phagocytic cells is not known, but different models for degradation in aqueous solution have been proposed. We have used confocal Raman spectroscopy and imaging to study the intracellular degradation of PLGA microspheres inside individual macrophages. Our results show that ingested microspheres degrade in a heterogeneous manner, with a more rapid degradation in the center. Comparison of Raman spectra from degrading beads with those of uningested beads reveals that ester hydrolysis occurs throughout the phagocytosed microspheres, with a selective loss of glycolic acid units. Furthermore, we show that PLGA degradation is a cell-mediated process, possibly caused by the low pH of the phagosome and/or the presence of hydrolytic enzymes. In conclusion, we have demonstrated that the chemical composition of degrading polymers inside cells can be probed by Raman spectral imaging. This technique will expand the capabilities of investigating biomaterial degradation in vivo. 相似文献
7.
Müller C Ackerman LJ Reek JN Kamer PC van Leeuwen PW 《Journal of the American Chemical Society》2004,126(45):14960-14963
Dendrimers, specifically suited to construct site-isolated groups due to their well-defined hyperbranched structure, have been used as a ligand design element for the construction of nickel catalysts for ethylene oligomerization. The dendritic P,O ligand indeed suppresses the formation of inactive bis(P,O)Ni complexes in toluene, as is evident from NMR studies, and, as a consequence, outperforms the parent ligand in catalysis in this solvent. The dendritic effect observed in methanol is more subtle because both the dendritic ligand 1 and the parent 2 form bis(P,O)nickel complexes in solution according to NMR spectroscopy. Unlike the parent complex 8, the dendritic bis(P,O)Ni complex 7 derived from dendrimer ligand 1 is able to dissociate to a mono-ligated species under catalytic conditions, that is, 40 bar ethylene and 80 degrees C, which can enter the catalytic cycle. Indeed, dendritic ligand 1 gives much more active nickel catalysts for the oligomerization in methanol than does 2. 相似文献
8.
Stortelder A Buijs JB Bulthuis J van der Vies SM Gooijer C van der Zwan G 《Journal of photochemistry and photobiology. B, Biology》2005,78(1):53-60
The time-resolved fluorescence properties of the bacteriophage T4 capsid protein gp23 are investigated. The structural characteristics of this protein are largely unknown and can be probed by recording time-resolved and decay-associated fluorescence spectra and intensity decay curves using a 200 ps-gated intensified CCD-camera. Spectral and decay data are recorded simultaneously, which makes data acquisition fast compared to time-correlated single-photon counting. A red-shift of the emission maximum within the first nanosecond of decay is observed, which can be explained by the different decay-associated spectra of fluorescence lifetimes of the protein in combination with dipolar relaxation. In addition, iodide quenching experiments are performed, to study the degree of exposure of the various tryptophan residues. A model for the origin of the observed lifetimes of 0.032 +/- 0.003, 0.39 +/- 0.06, 2.1 +/- 0.1 and 6.8 +/- 0.8 ns is presented: the 32 ps lifetime can be assigned to the emission of a buried tryptophan residue, the 0.4 and 2.1 ns lifetimes to two partly buried residues, and the 6.8 ns lifetime to a single tryptophan outside the bulk of the folded gp23. 相似文献
9.
Determination of lead in phosphate ore and phosphogypsum 总被引:2,自引:0,他引:2
Laser induced breakdown spectroscopy (LIBS) is applied to analyze aqueous solutions of Li(+), Na(+), Ca(2+), Ba(2+), Pb(2+), Cd(2+), Hg(2+) and Er(3+) and suspensions of ErBa(2)Cu(3)O(x) particles (d=0.2 microm). An excimer (308 nm) pumped dye laser with laser pulse at 500 nm and pulse energy at 22+/-2 mJ is used to produce plasma in aqueous solution. Plasma emission lines of the elements are detected by a photodiode array detector. Detection limits of the metal ions are 500 mg/l for Cd(2+), 12.5 mg/l for Pb(2+), 6.8 mg/l for Ba(2+), 0.13 mg/l for Ca(2+), 13 microg/l for Li(+) and 7.5 microg/l for Na(+). No mercury and erbium emission can be detected, even at Hg(2+) and Er(3+) concentrations of up to the g/l range. On the other side, for Er in suspensions of ErBa(2)Cu(3)O(x) particles a more than 10(3) times higher sensitivity is found than for dissolved Er(3+). This result gives a possibility to analyze colloid-borne metal ions with an increased sensitivity. 相似文献
10.
Dirksen A Kleverlaan CJ Reek JN De Cola L 《The journal of physical chemistry. A》2005,109(24):5248-5256
A photoactive supramolecular assembly that is based on the hydrogen-bonded system H1.G2, consisting of a methyl viologen-functionalized barbiturate host (H1) (1-(N-(3,5-bis[[(6-tert-butylacetylamino-2-pyridyl)amino]carbonyl])-phenylacetamide)-1'-methyl-4,4'-bipyridium) and a [Re(Br)(CO)3(barbi-bpy)] (barbi-bpy = 5-[4-(4'-methyl)-2,2'-bipyridyl]methyl-2,4,6-(1H,3H,5H)-pyrimidinetrione) complex as the guest (G2) is described. The host molecule contains a well-known electron accepting group (methyl viologen), whereas the guest system can act as an efficient electron donor in the excited state. Upon self-assembly, the resulting adduct (H1.G2) represents an interesting noncovalently linked donor-acceptor system. The H1.G2 complex has been characterized in acetonitrile-d3 using 1H NMR and diffusion-ordered NMR spectroscopy (DOSY). The photophysical properties of the components and of the assembly have been studied in dichloromethane, in which the assembly has a high binding constant (Kass > or = 2 x 10(5) M(-1)), using time-resolved fluorescence and transient absorption spectroscopy. A detailed investigation of the hydrogen-bonded complex H1.G2 revealed that, upon excitation of the rhenium compound G2, an ultrafast electron-transfer process occurs from the metal-based component to the acceptor unit. The kinetics of the forward and back electron-transfer processes have been determined. 相似文献