The first 2-aminophosphasilene, [Ar(Me 3 Si)-N]HSiPAr′ (4, Ar = 2,6-iPr 2 C 6 H 3 , Ar′ = 2,6-Mes 2 C 6 H 3 ), bearing a hydride ligand on the three-coordinate silicon atom has been synthesized and structurally characterized. Both X-ray data of 4 and DFT calculations on the model compound (H 2 N)HSiPH (4′) disclosed that the amino group on the silicon atom results in significant N−Si−P π conjugation.
This study shows lithosphere evolution history in the west North China Craton (NCC) from the early Cretaceous to Quaternary by studying the major element, trace element and Sr-Nd-Hf isotope compositions in Jining basalts of 119.6108.6 Ma, 23.521.9 Ma and 1.30.11 Ma.The early Cretaceous basalts (119.6108.6 Ma) display enriched characteristics with high contents of incompatible elements, high 87 Sr/ 86 Sr i , low ε Nd (t) and low ε Hf (t). These basalts resulted from partial melting of ancient metasomatized lithospheric mantle, and we consider the 119.6108.6 Ma magmatism as indicating lithosphere thinning in the west NCC. Although the Pacific slab seen seismically in the mantle transition zone beneath eastern China is no older than 60 Ma, there exists convincing evidence for the presence of the Paleo-Pacific slab in the transition-zone in the Mesozoic. Thus we propose that the water released from the transition-zone slab hydrated
A C C E P T E D M A N U S C R I P T ACCEPTED MANUSCRIPTthe overlying lithosphere and further converted the base of the lithosphere into asthenosphere. This is the most likely mechanism responsible for the lithosphere thinning in the west NCC and the petrogenesis of the Jining 119.6108.6 Ma basalts. Sr i , high ε Nd (t) and high ε Hf (t). Upwelling and decompression melting of the eastward flowing asthenosphere from beneath western plateaus to beneath eastern hilly plains in the Cenozoic is the most plausible mechanism for the petrogenesis of Jining Cenozoic basalts (both of 23.521.9 Ma and 1.30.11 Ma), but the Jining 1.30.11 Ma basalts must have been produced beneath even thinner lithosphere.Taken together geophysical studies and our petrological and geochemical studies of all these three episodes of the Jining basalts, wepropose that the lithosphere in the west NCC has been thinning since the early Cretaceous and the thinning continues to the present.
Reactions of the aminochlorosilane RSiHCl(2) and disilane R(2)Si(2)HCl(3) (R = (2,6-iPr(2)C(6)H(3))(SiMe(3))N) with an excess of 1,3-bis(tert-butyl)imidazol-2-ylidene resulted in the silylation of the NHC while reaction with the less hindered 1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene yielded an NHC-stabilized aminochlorosilylene.
Nitric oxide (NO)
gas therapy has aroused intense interest in recent
years. l-Arginine (l-Arg) reacts with reactive oxygen
species (ROS) in tumor cells to generate NO. This phenomenon represents
an effective method for tumor therapy. However, endogenous ROS levels
in most types of tumor cells cannot enable an effective reaction.
β-Lapachone is generally used to increase H2O2, which can oxidize guanidine derivatives to form nitric oxide
in tumor cells. In addition, based on the ferrocene (Fc)-catalyzed
Fenton reaction, ·OH is generated from H2O2, and the ONOO– could be generated from an interaction
between ·O2
– (generated through
the Haber–Weiss reaction) and NO. Arg-rich poly(ε-caprolactone)
(PCL)-b-PArg, a macromolecular NO donor, was accurately synthesized
to avoid premature l-Arg leakage during in vivo transport.
In this design, the self-assembled PCL-b-PArg nanoparticles were dressed
with the tumor-shreddable masking (PEG-b-PDMA, a negatively charged
pH-sensitive hydrophilic diblock polymer), to prepare P-lapa-Fc nanoparticles
and hide penetrative capability in the circulation. The experimental
results confirmed that this synergistic therapy based on ROS and NO
had a significant inhibitory effect on cancer cells, thereby providing
new inspiration for NO gas treatment.
Reaction of cyclic diaminochlorosilanes with 1,3-bis(tert-butyl)imidazol-2-ylidene resulted in the facile formation of the corresponding stable and transient diaminosilylenes. This novel dehydrochlorination route could be applied for the generation of four- and five-membered N-heterocyclic silylenes with a range of different substituents under very mild conditions. Activation of an olefinic C−H bond and reduction of a cyclic diaminochlorosilane have been observed for these new transient silylenes.
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