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951.
Jun Liu Kelton A. Schleyer Tyrel L. Bryan Changjian Xie Gustavo Seabra Yongmei Xu Arjun Kafle Chao Cui Ying Wang Kunlun Yin Benjamin Fetrow Paul K. P. Henderson Peter Z. Fatland Jian Liu Chenglong Li Hua Guo Lina Cui 《Chemical science》2021,12(1):239
Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal. 相似文献
952.
Rate coefficients of the reaction O((3)P) + CH(3)OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO(2) with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O(2) and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T) = (2.29 +/- 0.18) x 10(-10) exp[-(4210 +/- 100)T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T) = (2.74 +/- 0.07) x 10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)6-311 + G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311 + G(3df,2p)B3LYP6-311 + G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH + CH(2)OH (1a) and OH + CH(3)O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K. 相似文献
953.
The photocatalytic properties of some cyanogen-and thiocyanogen-based inorganic polymers, such as paracyanogens containing different metals (Hg, Ag, Cu), polythiocyanogens of different iodine contents, polycyanogen and poly (cyanogenthiocyanate), have been tested in two systems. Cu-containing paracyanogen and the iodine-poor polythiocyanogens catalyze the photoreduction of methylviologen under visible light, furthermore the Cu-containing paracyanogen catalyzes the photoreduction of water to hydrogen under UV irradiation.
, , , , (Hg, Ag, Cu), , (), . , , , , , , -.相似文献
954.
Aigars Vītiņš Ģirts Vītiņš Jānis Krastiņš Ints Šteins Ilmārs Zālīte Andrejs Lūsis 《Journal of Solid State Electrochemistry》1998,2(5):299-307
Ceramic specimens have been obtained from the powder of ZrO2-7.5 mol% Y2O3 having a specific surface area of 30 m2/g synthesized in air plasma. The novelty of this research lies in the fact that the plasma process makes it possible to prepare
so-called nanopowders with a particle size less than 100 nm, possessing specific physical, chemical and technological properties.
The sintered density of the specimens was 94–96% of the theoretical value, 6.001 g/cm3. The X-ray diffraction pattern of the specimens corresponded to a face-centered cubic lattice. Impedance in the frequency
range of 100 Hz–15 MHz and d.c. polarization curves in a potential range of −10 to 10 mV were measured in the temperature
range 200–850 °C in heating and cooling cycles. The intragrain, the grain boundary and the total bulk conductivities, the
electrode polarization resistance and their activation energies were determined. The thermal stability of the studied system
was proved in three measurement series up to 600–850 °C in heating and cooling cycles. The results obtained have shown that
the conductivity of ZrO2-7.5 mol% Y2O3 ceramics is not solely a function of temperature, but also depends on the previous thermal state of the ceramics.
Received: 16 October 1997 / Accepted: 19 January 1998 相似文献
955.
956.
V. Z. Vasikov I. A. Serbaev A. M. Gimazetdinov M. S. Miftakhov 《Russian Journal of Organic Chemistry》2007,43(6):915-917
Pantolactone methoxymethyl ether reacted with lithiated 2-trimethylsilyl-1,3-dithiane to give the corresponding ketene dithioacetal and formal monoaddition product of silicon-free 2-lithio-1,3-dithiane at a ratio of 2:1. Possible ways of formation of the latter are discussed. 相似文献
957.
H. Zhang Z. F. Chai H. B. Sun J. L. Zhang H. Ouyang L. Xin Y. D. Chuai 《Journal of Radioanalytical and Nuclear Chemistry》2007,271(1):31-35
The concentrations and distributions of total halogen (TX), extractable organohalogen (EOX) and extractable persistent organohalogen
(EPOX) were determined in 20 kinds of yogurt specimens collected from Chinese supermarkets using neutron activation analysis
(NAA) and gas chromatography equipped with a 63Ni electron capture detector (GC-ECD). The results indicated that the halogens in yogurt mainly existed as non-extractable
organohalogen compounds. About 25–30% of EOX was EPOX. EOCl and EPOCl were the main organohalogen species in yogurt. The average
concentration of the identified organochlorine, such as organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs),
was below 4% of EPOCl. 相似文献
958.
Chiral hydroxyl monophosphane 3 [(2S,3S,4S,5S)-3,4-dihydroxy-2, 5-dimethyl-1-phenylphospholane] and bisphospholanes 5a [1,2-bis[(2S, 3S,4S,5S)-3,4-dihydroxy-2,5-dimethylphospholanyl]benzene] and 5b [1, 2-bis[(2S,3S,4S,5S)-2,5-diethyl-3,4-dihydroxyphospholanyl]benzene] were synthesized from readily available D-mannitol in high yields. Strategies for protection and deprotection of OH-groups in the presence of phosphines have been explored. Rate acceleration in the Baylis-Hillman reaction was observed when a hydroxyl phosphine was used as the catalyst. Rhodium complexes with chiral bisphospholanes are highly enantioselective catalysts for the asymmetric hydrogenation of various kinds of functionalized olefins such as dehydroamino acid derivatives, itaconic acid derivatives, and enamides. An interesting feature of the hydroxyl phospholane system is that hydrogenation of some substrates can be carried out in water with >99% ee and 100% conversion (e.g., itaconic acid). 相似文献
959.
Sarabia Z Hernández D Castell JV van Henegouwen GM 《Journal of photochemistry and photobiology. B, Biology》2000,58(1):32-36
The skin is repeatedly exposed to solar ultraviolet radiation. Photoreaction of drugs in the body may result in phototoxic or photoallergic side effects. Non-steroidal anti-inflammatory drugs, such as tiaprofenic acid (TPA) and the closely related isomer suprofen (SUP) are frequently associated with photosensitive disorders; they may mediate photosensitised damage to lipids, proteins and nucleic acids. Using ex vivo pig skin as a model, we investigated the photodegradation of TPA and SUP, and photobinding of these drugs to protein by means of HPLC analysis and drug-directed antibodies. Both with keratinocytes, which were first isolated from the pig skin and thereafter exposed to UVA and with keratinocytes which were isolated from pig skin after the skin was UVA exposed, time-dependent photodegradation of TPA and SUP was found, beside photoadduct formation to protein. The results of this work show that: (a) TPA and SUP were photodecomposed with similar efficiency; major photoproducts detected were decarboxytiaprofenic acid (DTPA) and decarboxysuprofen (DSUP), respectively. (b) Both drugs form photoadducts, as concluded from recognition by drug-specific antibodies. Pig skin appears to be a good model for studying the skin photosensitising potential of drugs. 相似文献
960.
Sugiyama T Schweinberger E Kazimierczuk Z Ramzaeva N Rosemeyer H Seela F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(2):369-378
2-Aza-2'-deoxyadenosine (2, z2Ad) is synthesized via its 1,N6-etheno derivative 7 and enzymatically deaminated to 2-aza-2'-deoxyinosine (3). Compound 2 is converted into the phosphoramidite building block 10b. This is employed in solid-phase oligonucleotide synthesis. The 2-azapurine base forms a strong base pair with guanine, but a much weaker one with adenine, thymine, and cytosine. Oligonucleotide duplexes with dangling nucleotide residues, such as 2-aza-2'-deoxyadenosine and 7-deaza-2'-deoxyadenosine (4, c7Ad), either on one or both termini, are synthesized, and the thermal stability of the duplexes is correlated with the hydrophobic properties of the dangling nucleotide residues. 相似文献