A highly selective colorimetric and ratiometric fluorescent chemodosimeter for imaging fluoride ions in living cells

A simple but highly selective colorimetric and ratiometric fluorescent chemodosimeter was designed and synthesized to detect fluoride ions (F(-)) in aqueous solution and living cells by virtue of the strong affinity of F(-) toward silicon.     

Location of Si vacancies and [Ti(OSi)4] and [Ti(OSi)3OH] sites in the MFI framework: a large cluster and full ab initio study

Titanium silicalite-1 (TS-1) is an important catalyst for selective oxidation reactions. However, the nature and structure of the active sites and the mechanistic details of the catalytic reactions over TS-1 have not been well-understood, leaving a continuous debate on the genesis of active sites on the TS-1 surface in the literature. In this work, the location of Si vacancies and [Ti(OSi)(4)] and [Ti(OSi)(3)OH] sites in the MFI (Framework Type Code of ZSM-5 (Zeolite Socony Mobile-Five)) framework has been studied using a full ab initio method with 40T clusters with a Si:Ti molar ratio of 39:1. It was shown that the former four energetically favorable sites for Si vacancies are T6, T12, T4, and T8 and for Ti centers of [Ti(OSi)(4)] are T10, T4, T8 and T11, being partially the same sites. Whether by replacing Si vacancies or substituting the fully coordinated Si sites, the most preferential site for Ti is T10, which indicates that the insertion mechanism does not affect the favorable sites of Ti in the MFI lattice. For the defective [Ti(OSi)(3)OH] sites, it was found that the Si vacancy at T6 with a Ti at its neighboring T9 site (T6-def-T9-Ti pair) is the most energetically favorable one, followed by a T6-def-T5-Ti pair with a small energy gap. These findings are significant to elucidate the nature of the active sites and the mechanism of reactions catalyzed by TS-1 and to design the TS-1 catalyst.     

Substance P conjugated to CdTe quantum dots triggers cytosolic calcium concentration oscillations and induces quantum dots internalization in the pancreatic carcinoma cell line AR4-2J

Highly fluorescent CdTe quantum dots (QDs) stabilized by 3-mercaptopropionic acid were prepared by an aqueous solution approach and used as a fluorescent label to link substance P (SP) in studying the interaction of SP with NK-1 receptor, which was expressed on the AR4-2J cell line. Nonspecific adsorptions of CdTe QDs on the AR4-2J cell membrane were observed, whereas the QD-SP conjugates successfully crossed the cell membrane and entered the cytosol. SP is a neurotransmitter, and neurotransmitter-induced calcium concentration oscillation is a common phenomenon in diverse cells especially of secretory type. Cytosolic calcium concentration responses were studied in the AR4-2J cell line during stimulation with SP and QD-SP conjugates. The oscillations triggered by SP and QD-SP conjugates were dose-dependent and very similar. Such QD-SP conjugates readily internalized into the cytosol as would be expected of an active NK-1 ligand. Therefore QD-SP conjugates could be used successfully to study ligand and NK-1 receptor interactions in live cells. Our research may provide a meaningful reference for congener research.     

Photodissociation Dynamics of Benzaldehyde (C6H5CHO) at 266, 248, and 193 nm

The photodissociation of gaseous benzaldehyde (C₆H₅CHO) at 193, 248, and 266 nm using multimass ion imaging and step‐scan time‐resolved Fourier‐transform infrared emission techniques is investigated. We also characterize the potential energies with the CCSD(T)/6‐311+G(3df,2p) method and predict the branching ratios for various channels of dissociation. Upon photolysis at 248 and 266 nm, two major channels for formation of HCO and CO, with relative branching of 0.37:0.63 and 0.20:0.80, respectively, are observed. The C₆H₅+HCO channel has two components with large and small recoil velocities; the rapid component with average translational energy of approximately 25 kJ mol^?1 dominates. The C₆H₆+CO channel has a similar distribution of translational energy for these two components. IR emission from internally excited C₆H₅CHO, ν₃ (v=1) of HCO, and levels v≤2, J≤43 of CO are observed; the latter has an average rotational energy of approximately 13 kJ mol^?1 and vibrational energy of approximately 6 kJ mol^?1. Upon photolysis at 193 nm, similar distributions of energy are observed, except that the C₆H₅+HCO channel becomes the only major channel with a branching ratio of 0.82±0.10 and an increased proportion of the slow component; IR emission from levels ν₁ (v=1) and ν₃ (v=1 and 2) of HCO and v≤2, J≤43 of CO are observed; the latter has an average energy similar to that observed in photolysis at 248 nm. The observed product yields at different dissociation energies are compared to statistical‐theory predicted results based on the computed singlet and triplet potential‐energy surfaces.     

Mechanistic Insights into the Ni‐Catalyzed Reductive Carboxylation of C−O Bonds in Aromatic Esters with CO2: Understanding Remarkable Ligand and Traceless‐Directing‐Group Effects

The mechanism of the Ni⁰‐catalyzed reductive carboxylation reaction of C(sp²)?O and C(sp³)?O bonds in aromatic esters with CO₂ to access valuable carboxylic acids was comprehensively studied by using DFT calculations. Computational results revealed that this transformation was composed of several key steps: C?O bond cleavage, reductive elimination, and/or CO₂ insertion. Of these steps, C?O bond cleavage was found to be rate‐determining, and it occurred through either oxidative addition to form a Ni^II intermediate, or a radical pathway that involved a bimetallic species to generate two Ni^I species through homolytic dissociation of the C?O bond. DFT calculations revealed that the oxidative addition step was preferred in the reductive carboxylation reactions of C(sp²)?O and C(sp³)?O bonds in substrates with extended π systems. In contrast, oxidative addition was highly disfavored when traceless directing groups were involved in the reductive coupling of substrates without extended π systems. In such cases, the presence of traceless directing groups allowed for docking of a second Ni⁰ catalyst, and the reactions proceed through a bimetallic radical pathway, rather than through concerted oxidative addition, to afford two Ni^I species both kinetically and thermodynamically. These theoretical mechanistic insights into the reductive carboxylation reactions of C?O bonds were also employed to investigate several experimentally observed phenomena, including ligand‐dependent reactivity and site‐selectivity.     

3D metal-organic frameworks based on lanthanide-seamed dimeric pyrogallol[4]arene nanocapsules

Two novel 3D metal-organic frameworks(MOFs)with cds network,{[Me NH_3]_7[Ln_8(Pg C_2)_2(H_2O)_y(HCOO)_7]}_n·x(Solvent)(FJI-Y4,FJI=Fujian Institute,Ln=Gd,y=12;FJI-Y5,Ln=Dy,y=11;Pg C_2=C-ethylpyrogallol[4]arene),based on unprecedented dimeric pyrogallol[4]arene-based Ln_8metal-organic nanocapsule(MONC)supramolecular building blocks and formate linkers,have been prepared under solvothermal conditions.To our best of knowledge,they present not only the first two examples of 3D hierarchical structures constructed from MONCs in metal-pyrogallol[4]arene system,but also the first two examples of MOFs based on lanthanide MONCs.Remarkably,the inner cavity volume of the Ln_8capsule in FJI-Y4 and FJI-Y5 is approximately151?~3,which is larger than those found in previous transition metal-seamed dimeric Pg C_n-based MONCs.Magnetic investigation on FJI-Y4 suggests a significant magnetocaloric effect(23.97 J kg~(-1)K~(-1),ΔH=7 T,2.5 K),while FJI-Y5 exhibits slow relaxation of the magnetization.     

An In situ Study on the Orderly Crystal Growth of Pluronic F127 Block Copolymer Blended with and without Ionic Liquid during Isothermal Crystallization

Isothermal crystallization behavior of Pluronic F127 blended with and without an ionic liquid (IL) was investigated by in situ polarized optical microscopy (POM) and Fourier transform infrared spectroscopy (FTIR). For the pure F127, the POM and FTIR results showed that the spherulite size and crystallinity of F127 increased with the melting temperature increasing to 60, 80, and 135°C. This could be explained by the flexibility of the polymer chain at high melting temperatures. For the F127 blended with IL, the POM results showed that the morphology of F127 evolved from spherulite to dendritic segregation and fibrous crystal with the increasing IL content. FTIR results indicated that hydrogen bonds were formed between F127 and IL, and the intensity of the hydrogen bonds became strengthened gradually with increasing IL content. The effect of hydrogen bonds on the morphology evolution of F127/IL is discussed.     

Organocatalytic enantioselective sulfa-Michael addition of thiocarboxylic acids to β-trifluoromethyl-α,β-unsaturated ketones for the construction of stereogenic carbon center bearing a sulfur atom and a trifluoromethyl group

An organocatalyzed asymmetric sulfa-Michael addition of thiocarboxylic acids to β-trifluoromethyl-α,β-unsaturated ketones with a chiral bifunctional amine-squaramide as the catalyst is presented. A wide range of chiral ketone compounds bearing a sulfur atom and a trifluoromethyl group at the stereogenic carbon center could be obtained with excellent results (up to 99% yield, 97% ee) under mild conditions. The developed catalytic system is well-tolerated to both (E)-and (Z)-β-trifluoromethylated-α,β-unsaturated ketones.     

11.2% Efficiency all-polymer solar cells with high open-circuit voltage

Herein,we fabricated all-polymer solar cells(all-PSCs)based on a fluorinated wide-bandgap p-type conjugated polymer PM6 as the donor,and a narrow bandgap n-type conjugated polymer PZ1 as the acceptor.In addition to the complementary absorption and matching energy levels,the optimized blend films possess high cystallinity,predominantly face-on stacking,and a suitable phase separated morphology.With this active layer,the devices exhibited a high V_(oc)of 0.96 V,a superior J_(sc)of 17.1 mA cm~(-2),a fine fill factor(FF)of 68.2%,and thus an excellent power conversion efficiency(PCE)of 11.2%,which is the highest value reported to date for single-junction all-PSCs.Furthermore,the devices showed good storage stability.After 80 d of storage in the N_2-filled glovebox,the PCE still remained over 90%of the original value.Large-area devices(1.1 cm~2)also demonstrated an outstanding performance with a PCE of 9.2%,among the highest values for the reported large-area all-PSCs.These results indicate that the PM6:PZ1 blend is a promising candidate for scale-up production of large area high-performance all-PSCs.     

On the Understandings of Dielectric Constant and Its Impacts on the Photovoltaic Efficiency in Organic Solar Cells

Dielectric constant(ε)is an important parameter affecting the power conversion efficiency of organic solar cells(OSC).Increasingεof bulk heterojunctions in general can benefit the performance of OSCs,as an increasedεwill reduce the influence of Coulomb interaction between weakly bound electron-hole pairs on charge-transfer states or bimolecular recombination involving mobile carriers to reduce geminate and nongeminate losses.In this review,we overview the current understandings on dielectric constant and its impacts on exciton dissociation and voltage losses in OSCs and summarize recent efforts attempting to modify the dielectric properties of OSC materials through synthetic approaches.We further discuss the commonly adopted techniques for determining the parameter ofεwith stressing the testing conditions that may affect the accuracy of results.At last,we suggest that novel experimental methods to improve the dielectric constant and resultant physical processes in OSCs will be appreciated,which helps enrich the existing strategy reservoir toward enhancement of photovoltaic efficiencies.