Nickel-catalyzed carboxylation of aryl and vinyl chlorides employing carbon dioxide.

Nickel-catalyzed carboxylation of aryl and vinyl chlorides employing carbon dioxide has been developed. The reactions proceeded under a CO(2) pressure of 1 atm at room temperature in the presence of nickel catalysts and Mn powder as a reducing agent. Various aryl chlorides could be converted to the corresponding carboxylic acid in good to high yields. Furthermore, vinyl chlorides were successfully carboxylated with CO(2). Mechanistic study suggests that Ni(I) species is involved in the catalytic cycle.

Inhibitory effects of everolimus in combination with paclitaxel on adriamycin-resistant breast cancer cell line MDA-MB-231.

OBJECTIVE: We aimed to evaluate the therapeutic effects of paclitaxel in combination with mTOR inhibitor everolimus on adriamycin-resistant breast cancer cell line MDA-MB-231 (MDA-MB-231/ADR). MATERIALS AND METHODS: MDA-MB-231/ADR cells were treated with different concentrations of paclitaxel and everolimus. The IC50 values after 48 h of treatment were measured by the MTT assay. The apoptosis rate and cell cycle were detected by flow cytometry. The protein expressions of Akt, PI3K, mTOR, p-pI3K, p-AKT and p-mTOR were detected by Western blot. RESULTS: When paclitaxel at ≥1.56 µg/ml was used, the growth of MDA-MB-231/ADR cells was inhibited more significantly than that of control group (P < 0.05). After treatment with ≥6.25 µg/ml everolimus, the cell growth was also suppressed more significantly (P < 0.05). The IC50 values of everolimus and paclitaxel were 32.50 µg/ml and 7.80 µg/ml, respectively. The inhibition rate of paclitaxel plus everolimus was significantly enhanced with increasing paclitaxel concentration (P < 0.001). After treatment with 7.80 µg/ml paclitaxel, the two drugs had best synergistic inhibitory effects on proliferation. Compared with drugs alone, the combination significantly promoted apoptosis (P < 0.001). The paclitaxel + everolimus group had significantly more cells in the G0-G1 phase than those of control and individual drug groups (P < 0.001). Everolimus significantly decreased mTOR and p-mTOR expressions compared with those of control group (P < 0.001). Compared with everolimus alone, the combination reduced the expressions more significantly (P < 0.05). Paclitaxel decreased the expression levels of PI3K, p-PI3K and p-AKT. Compared with paclitaxel alone, the combination significantly promoted the reduction of PI3K, p-PI3K and p-AKT expressions (P < 0.05). CONCLUSION: Everolimus can enhance the effect of paclitaxel on MDA-MB-231/ADR cells, inhibit cell proliferation, induce apoptosis and arrest cell cycle in the G1 phase mainly by down-regulating the expressions of key proteins in the mTOR signaling pathway.

Emission enhancement and chromism in a salen-based gel system.

A new salicylideneaniline-based organogelator has been synthesized, and it can gelatinize organic solvents, including cyclohexane, toluene, benzene, and some mixed solvents. SEM images show that it has self-assembled into 1-D nanofibers, which further cross-link to form 3-D network. On the basis of the results of small-angle XRD and the optimized molecular length by semiempirical quantum calculations, the gelators are supposed to pack into a unimolecular lamellar structure with a period of 3.01 nm. Significantly, reversible chromism is realized with respect of the tautomerism between the NH and OH forms during the sol-gel freezing repetition. Furthermore, the gel can emit intense green light, and the fluorescent quantum yield of the gel is approximately 600 times higher than that of the solution. The aggregation-induced emission enhancement is ascribed to the formation of J aggregation and the inhibition of intramolecular rotation in the gel state.

One-Step Integrated Surface Modification To Build a Stable Interface on High-Voltage Cathode for Lithium-Ion Batteries.

As one of the most promising cathode materials for next-generation energy storage applications, spinel LiNi0.5Mn1.5O4 (LNMO) has been highlighted due to many advantages. However, it is still hindered by poor electrochemical stability derived from the bulk/interface structure degradation and side reactions under high working voltage. In this work, fast ion conductor Li3V2(PO4)3 (LVPO) is adopted to modify the surface of spinel LNMO by a one-step facile method to harvest the maximum benefit of interface properties. It is found that 1 wt % LVPO-LNMO exhibits the most excellent cycling performances, retaining great capacity retention of 87.8% after 500 cycles at room temperature and 82.4% for 150 cycles at 55 °C. Moreover, the rate performance is also significantly improved (90.4 mAh g-1 under 20C). It is revealed that the LVPO-involved layer could effectively suppress the surface side reactions under high working voltage, which mainly contributes to an improved interface with desirable structural stability and excellent kinetics behavior without sacrificing the surface electrochemical activity in an electrochemical environment. Thus, the dissolution of transition-metal ions is effectively mitigated, avoiding further structure degradation of the bulk material. Especially, it is also established that the vanadium (V) ions in LVPO could be to a certain extent migrated into the surface lattice of LNMO to generate a V-involved transition layer (Li-Ni-Mn-V-O surface solid solution), which greatly co-contributes to the enhanced electrochemical performances owing to the prominently depressed charge-transfer resistance.

Stabilizing a high-voltage LiNi0.5Mn1.5O4 cathode towards all solid state batteries: a Li-Al-Ti-P-O solid electrolyte nano-shell with a host material.

LiNi0.5Mn1.5O4 (LNMO) spinel has drawn increasing attention due to its high voltage, stabilized electrochemical performance and safety features as a cathode for lithium-ion batteries. However, the main challenge lies in its unstable surface structure, especially at elevated temperatures. In this paper, we decorate the LNMO precursor with a solid electrolyte of Li1.4Al0.4Ti1.6(PO4)3 (LATP) via a facile sol-gel method, followed by a co-crystallization process at 820 °C, to successfully generate a LATP modification shell at the surface of LNMO. The LATP modification shell could not only optimize the morphology of LNMO including the limitation of particle growth and control of crystalline orientation, but also realize ion doping during the co-crystallization process. By tuning the LATP contents, the 2 wt% LATP modification is found to be the most effective at balancing the interfacial stability and Li+ diffusion kinetics of LNMO, as well as enhancing its rate capability and capacity retention at high temperatures. As a result, the 2 wt% LATP-modified LNMO cathode exhibits a high reversible capacity of 84.8 mA h g-1 after 500 cycles with a capacity retention of 68.9%, and a superior rate capability (102.0 mA h g-1 at 20 C) at room temperature. Moreover, this electrode also delivers a good capacity retention of 85.7% after 100 cycles at 55 °C, which is ascribed to the stabilized interface with a LATP protective layer.

Novel carbazole-based organogels modulated by tert-butyl moieties.

tert-Butyl groups can modulate the self-assembling properties of carbazole derivatives; organogel fibers with a bright blue emission are generated, directed by the cooperation of hydrogen bonding as well as pi-pi interactions.

Integrated Surface Functionalization of Li-Rich Cathode Materials for Li-Ion Batteries.

As candidates for high-energy density cathodes, lithium-rich (Li-rich) layered materials have attracted wide interest for next-generation Li-ion batteries. In this work, surface functionalization of a typical Li-rich material Li1.2Mn0.56Ni0.17Co0.07O2 is optimized by fluorine (F)-doped Li2SnO3 coating layer and electrochemical performances are also enhanced accordingly. The results demonstrate that F-doped Li2SnO3-modified material exhibits the highest capacity retention (73% after 200 cycles), with approximately 1.2, 1.4, and 1.5 times of discharge capacity for Li2SnO3 surface-modified, F-doped, and pristine electrodes, respectively. To reveal the fundamental enhancement mechanism, intensive surface Li+ diffusion kinetics, postmortem structural characteristics, and aging tests are performed for four sample systems. The results show that the integrated coating layer plays an important role in addressing interface compatibility, not only limited in stabilizing the bulk structure and suppressing side reactions, synergistically contributing to the performance enhancement for the active electrodes. These findings not only pave the way to commercial application of the Li-rich material but also shed new light on surface modification in batteries and other energy storage fields.

Phosphorus(V) porphyrins with axial carbazole-based dendritic substituents.

[structure: see text] Three phosphorus(V) porphyrins with axial carbazole-based dendritic substituents (D-A-D) have been designed and synthesized, which are nonfluorescent due to their effective electron transfer from the carbazole dendron to the excited porphyrin within the dendritic matrix. The incident photon to current conversion efficiencies (IPCE) spectra demonstrate that the molecular structure of the dendrimers can significantly affect the photovoltaic response to the visible light.

Triphenyl benzene-bridged fluorescent silsesquioxane: shape-controlled hybrid silicas by hydrolytic conditions.

A new silsesquioxane molecule was synthesized, in which triphenyl benzene was connected with three Si(OC2H5)3 groups using three urea groups as the bridge. The molecule could self-assemble through the intermolecular H-bonding among urea groups and pi-pi interaction of triphenyl benzene core in the solution and it could also be transferred into hybrid silicas by hydrolysis. When the non-preorganized silsesquioxane was hydrolyzed, isolated spherical hybrid silica was gained. However, when the silsesquioxane was preorganized before the hydrolyzation uniform interconnected spherical hybrid silica and intertwined nanofibrous one could be generated under acidic and basic conditions, respectively. The photoluminescence (PL) spectra of the obtained hybrid silicas showed that they still kept the emission properties of their precursor silsesquioxane, and the shift of the emission bands was due to the pi-pi interaction of triphenyl benzene in the course of polycondensation.

Mutation of the light-induced yellow leaf 1 gene, which encodes a geranylgeranyl reductase, affects chlorophyll biosynthesis and light sensitivity in rice.

Chlorophylls (Chls) are crucial for capturing light energy for photosynthesis. Although several genes responsible for Chl biosynthesis were characterized in rice (Oryza sativa), the genetic properties of the hydrogenating enzyme involved in the final step of Chl synthesis remain unknown. In this study, we characterized a rice light-induced yellow leaf 1-1 (lyl1-1) mutant that is hypersensitive to high-light and defective in the Chl synthesis. Light-shading experiment suggested that the yellowing of lyl1-1 is light-induced. Map-based cloning of LYL1 revealed that it encodes a geranylgeranyl reductase. The mutation of LYL1 led to the majority of Chl molecules are conjugated with an unsaturated geranylgeraniol side chain. LYL1 is the firstly defined gene involved in the reduction step from Chl-geranylgeranylated (Chl(GG)) and geranylgeranyl pyrophosphate (GGPP) to Chl-phytol (Chl(Phy)) and phytyl pyrophosphate (PPP) in rice. LYL1 can be induced by light and suppressed by darkness which is consistent with its potential biological functions. Additionally, the lyl1-1 mutant suffered from severe photooxidative damage and displayed a drastic reduction in the levels of α-tocopherol and photosynthetic proteins. We concluded that LYL1 also plays an important role in response to high-light in rice.

Porphyrins with four monodisperse oligocarbazole arms: facile synthesis and photophysical properties.

A series of novel monodisperse, well-defined, star-shaped molecules T(OCAn)Ps (n = 2-6) with a central porphyrin core and four oligocarbazole arms are synthesized from the corresponding formyl-substituted oligocarbazoles via Adler reaction. The obtained star-shaped porphyrins are intrinsically two-dimensional nanosized molecules, and the diameter of compound T(OCA6)P is 7.4 nm, representing one of the largest known star-shaped conjugated systems. Their photophysical properties have been investigated by absorption and steady-state fluorescence spectroscopy, together with the corresponding monodisperse oligocarbazole aldehyde precursors. It is found that the light-harvesting capability of T(OCAn)Ps increases with the increasing length of the arms and reaches the maximum when n = 6. A selective excitation of the oligocarbazole arms leads to the typical emission from the porphyrin cores, indicating occurrence of photoinduced intramolecular energy transfer, and the energy transfer efficiency decreases from T(OCA2)P to T(OCA6)P owing to the Förster energy-transfer process. Accordingly, the longest effective distance for Förster energy transfer is estimated to be ca. 3 nm in our system. Such star-shaped porphyrins may find applications in photonic devices, with respect to their intense emission of red light. Notably, the monodisperse oligocarbazole aldehyde precursors give twisted intramolecular charge-transfer (TICT) excited states and luminescence in polar solvents with large Stokes shifts.

Carbazole-based organogel as a scaffold to construct energy transfer arrays with controllable fluorescence emission.

A diaryldiketopyrrolopyrrole derivative functionalized with phenothiazine moieties (DPPP) was synthesized and introduced into the ordered 4-(3,6-di-tert-butyl-9H-carbazol-9-yl)benzamide (TBCB) organogel system. It was found that TBCB-based gel became a scaffold to make DPPP molecules line up along the gel fibers, resulting in new self-assembled arrays, whose XRD patterns were quite different from those of the neat TBCB gel and DPPP crystal. In the composite gel, the occurrence of a partial energy transfer from the excited light-harvesting antenna of TBCB to the DPPP acceptor was confirmed on the basis of time-dependent and time-resolved fluorescence investigations. Remarkably, the composite gel could emit intense red light or purplish white light by tuning the excitation wavelength. Such ordered soft materials with color-tunable emission may possess potential applications in sensor and photonic devices.

Helical stacking tuned by alkoxy side chains in pi-conjugated triphenylbenzene discotic derivatives.

We report on the synthesis and self-assembly of a new series of discotic molecules containing triphenylbenzene as the core and alkoxy side chain with varying length. It was found that compounds 3 a-c, 4 b and 5 b could form stable gels in several apolar solvents. Transmission electron microscopy (TEM) images revealed that their morphologies were very different for the different alkoxy-substituted organogels. In toluene or hexane, 3 b and 3 c resulted in both left- and right-handed helical fibers, whereas 3 a resulted in straight rigid fibers; 4 b and 5 b resulted in most straight fibers with a few twisted fibers. The results from FT-IR and UV/Vis absorption spectroscopy indicated that the hydrogen bonding and pi-pi interactions were the main driving forces for the formation of the self-assembled gels. Further detailed analysis of their aggregation modes were conducted by UV-visible absorption spectra and X-ray diffraction (XRD) measurements. Based on these findings, the influence of these peripheral alkoxy substituents on the gel formation and the aggregation mode were discussed. The special enhanced fluorescent emissions, which resulted from aggregation, were also found in the gel phase.

Synthesis and self-assembly of dichalcone substituted carbazole-based low-molecular mass organogel.

We report the synthesis and self-assembly of a new pi-conjugated dichalcone substituted carbazole-based low molecular mass organogelator. It could form stable gels in most halogen-aromatic solvents. The transmission electron microscopy (TEM) images revealed that the gel formed fibrous structures with diameter of 50-100 nm, which consisted of several thinner fibers. The FT-IR, UV-vis and XRD results suggested that the H-bonds and pi-pi interactions were the main driving forces for the formation of the self-assembled gel, in which the U-shaped molecules were stacked into lamellar structures. The fluorescent spectra showed that the emission of the xerogel red-shifted markedly compared with the sol state, which resulted from the aggregation of the molecules.