The molecular hydrogen complex of osmium,[trans-en2Os(η-H2)]2+(en,entlylendediamine) is a new 1H NMR recognition probe for biomolecules.By using this probe,the coordination between deoxyguanylic acid (dGMP) and four ...The molecular hydrogen complex of osmium,[trans-en2Os(η-H2)]2+(en,entlylendediamine) is a new 1H NMR recognition probe for biomolecules.By using this probe,the coordination between deoxyguanylic acid (dGMP) and four metal anticancer complexes,titanocene dichloride,(C2H5)2SnCl2(phen),(C2H5)2SnCl2 and cis-piatm are studied in D2O under the condition near the physiological one.The results show that the former three complexes mainly and strongly coordinate with the phosphate oxygen of dGMP,while cisplatin mainly coordinates with N(7) of dGMP展开更多
High-temperature nuclear magnetic resonance(NMR)has proven to be very useful for detecting the temperatureinduced structural evolution and dynamics in melts.However,the sensitivity and precision of high-temperature NM...High-temperature nuclear magnetic resonance(NMR)has proven to be very useful for detecting the temperatureinduced structural evolution and dynamics in melts.However,the sensitivity and precision of high-temperature NMR probes are limited.Here we report a sensitive and stable high-temperature NMR probe based on laser-heating,suitable for in situ studies of metallic melts,which can work stably at the temperature of up to 2000 K.In our design,a well-designed optical path and the use of a water-cooled copper radio-frequency(RF)coil significantly optimize the signal-to-noise ratio(S/NR)at high temperatures.Additionally,a precise temperature controlling system with an error of less than±1 K has been designed.After temperature calibration,the temperature measurement error is controlled within±2 K.As a performance testing,^(27)Al NMR spectra are measured in Zr-based metallic glass-forming liquid in situ.Results show that the S/NR reaches 45 within 90 s even when the sample's temperature is up to 1500 K and that the isothermal signal drift is better than0.001 ppm per hour.This high-temperature NMR probe can be used to clarify some highly debated issues about metallic liquids,such as glass transition and liquid-liquid transition.展开更多
To construct pulsed high magnet, with rapid adjustments to large changes in the field strength, it is a mandatory acces-sory to development a special NMR probes to provide a precise real-time map of the magnetic field...To construct pulsed high magnet, with rapid adjustments to large changes in the field strength, it is a mandatory acces-sory to development a special NMR probes to provide a precise real-time map of the magnetic field. In order to do so, it is necessary to understand the variations of the spin transition and susceptibility of NMR samples in a time dependent longitudinal field. This work analyzes the effect on the spin transition by a time dependent longitudinal field. For a 1/2 spin system, we have derived a simple formula for the prediction of the probabilities of occupation of the 1/2 and ?1/2 states in a non-static field. We also calculate the magnetic susceptibility of the water and give an analysis of the effect on the magnetic susceptibility in a time dependent longitudinal field and RF frequency.展开更多
In this paper the results of dynamic NMR studies on ethylmethylamino-tertiary-butyl-phenylborane (EMABPB) with or without light are reported. The NMR data were recorded on a Bruker 400 MHz NMR equipped with our custom...In this paper the results of dynamic NMR studies on ethylmethylamino-tertiary-butyl-phenylborane (EMABPB) with or without light are reported. The NMR data were recorded on a Bruker 400 MHz NMR equipped with our custom-made optical probe and with our custom-made 450 watts (W) monochromatic light sources. The molecular photochemistry including twisted intramolecular charge-transfer-excited-state (TICT) of the EMABPB in several solvents has been investigated. These results indicate that the aminoborane demonstrates multiple configurations in CD3Cl and CD2Cl2 resulting in the shifts of the signals of the alkyl groups on the nitrogen and boron. This indicates that there are some time-dependent changes at constant temperature over the irradiation interval. At ﹣60°C and the presence of light (λ = 265 nm), we observed a large change in the populations of the two sites, and this by itself indicates a modification in the rotation around the boron nitrogen bond in the excited state. By considering the existence of the TICT state, many important energy technologies may be developed with higher efficiency by controlling the back-electron transfer processes.展开更多
基金Project supported by the National Natural Science Foundation of Chinathe Natural Science Foundation of Shanxi Provincethe Youth Science Foundation of Shanxi Province
文摘The molecular hydrogen complex of osmium,[trans-en2Os(η-H2)]2+(en,entlylendediamine) is a new 1H NMR recognition probe for biomolecules.By using this probe,the coordination between deoxyguanylic acid (dGMP) and four metal anticancer complexes,titanocene dichloride,(C2H5)2SnCl2(phen),(C2H5)2SnCl2 and cis-piatm are studied in D2O under the condition near the physiological one.The results show that the former three complexes mainly and strongly coordinate with the phosphate oxygen of dGMP,while cisplatin mainly coordinates with N(7) of dGMP
基金Project supported by the Instrument Developing Project of the Chinese Academy of Sciences(Grant No.YZ201639)the National Key R&D Program of China(Grant No.2018YFA0703604)+1 种基金the National Natural Science Foundation of China(Grant Nos.51922102,92163108,and 52071327)the Zhejiang Provincial Natural Science Foundation of China(Grant No.LR18E010002)。
文摘High-temperature nuclear magnetic resonance(NMR)has proven to be very useful for detecting the temperatureinduced structural evolution and dynamics in melts.However,the sensitivity and precision of high-temperature NMR probes are limited.Here we report a sensitive and stable high-temperature NMR probe based on laser-heating,suitable for in situ studies of metallic melts,which can work stably at the temperature of up to 2000 K.In our design,a well-designed optical path and the use of a water-cooled copper radio-frequency(RF)coil significantly optimize the signal-to-noise ratio(S/NR)at high temperatures.Additionally,a precise temperature controlling system with an error of less than±1 K has been designed.After temperature calibration,the temperature measurement error is controlled within±2 K.As a performance testing,^(27)Al NMR spectra are measured in Zr-based metallic glass-forming liquid in situ.Results show that the S/NR reaches 45 within 90 s even when the sample's temperature is up to 1500 K and that the isothermal signal drift is better than0.001 ppm per hour.This high-temperature NMR probe can be used to clarify some highly debated issues about metallic liquids,such as glass transition and liquid-liquid transition.
文摘To construct pulsed high magnet, with rapid adjustments to large changes in the field strength, it is a mandatory acces-sory to development a special NMR probes to provide a precise real-time map of the magnetic field. In order to do so, it is necessary to understand the variations of the spin transition and susceptibility of NMR samples in a time dependent longitudinal field. This work analyzes the effect on the spin transition by a time dependent longitudinal field. For a 1/2 spin system, we have derived a simple formula for the prediction of the probabilities of occupation of the 1/2 and ?1/2 states in a non-static field. We also calculate the magnetic susceptibility of the water and give an analysis of the effect on the magnetic susceptibility in a time dependent longitudinal field and RF frequency.
文摘In this paper the results of dynamic NMR studies on ethylmethylamino-tertiary-butyl-phenylborane (EMABPB) with or without light are reported. The NMR data were recorded on a Bruker 400 MHz NMR equipped with our custom-made optical probe and with our custom-made 450 watts (W) monochromatic light sources. The molecular photochemistry including twisted intramolecular charge-transfer-excited-state (TICT) of the EMABPB in several solvents has been investigated. These results indicate that the aminoborane demonstrates multiple configurations in CD3Cl and CD2Cl2 resulting in the shifts of the signals of the alkyl groups on the nitrogen and boron. This indicates that there are some time-dependent changes at constant temperature over the irradiation interval. At ﹣60°C and the presence of light (λ = 265 nm), we observed a large change in the populations of the two sites, and this by itself indicates a modification in the rotation around the boron nitrogen bond in the excited state. By considering the existence of the TICT state, many important energy technologies may be developed with higher efficiency by controlling the back-electron transfer processes.
