Solvent-Induced In(III)-MOFs with Controllable Interpenetration Degree Performing High-Efficiency Separation of CO2/N2 and CO2/CH4.

Herein, three In(III)-based metal-organic frameworks (In-MOFs) with different degrees of interpenetration (DOI), namely In-MOF-1, In-MOF-2, and In-MOF-3, constructed by In3+ and Y-shaped ligands 4,4',4″-s-triazine-2,4,6-triyltribenzoate (H3TATB), are successfully synthesized through the ionothermal/solvothermal method. Subsequently, three novel In-MOFs, including noninterpenetration polycatenation, 2-fold interpenetrated, and 4-fold interpenetrated structure, are employed as the platform for systematically investigating the separation efficiency of CO2/N2, CO2/CH4, and CO2/CH4/N2 mixture gas system. Among them, In-MOF-2 shows the highest CO2 uptake capacities at 298 K and simultaneously possesses the low adsorption enthalpy of CO2 (26.4 kJ/mol at low coverage), a feature desirable for low-energy-cost adsorbent regeneration. The CO2/N2 (v: v = 15/85) selectivity of In-MOF-2 reaches 37.6 (at 298 K and 1 bar), also revealing outstanding selective separation ability from flue gases and purifying natural gas, affording a unique robust separation material as it has moderate DOI and pore size. In-MOF-2 shows exceptional stability and feasibility to achieve reproducibility. Aperture adjustment makes In-MOF-2 a versatile platform for selectively capturing CO2 from flue gases or purifying natural gas.

Preparation and Characterization of Transparent Polyimide Nanocomposite Films with Potential Applications as Spacecraft Antenna Substrates with Low Dielectric Features and Good Sustainability in Atomic-Oxygen Environments.

Optically transparent polyimide (PI) films with good dielectric properties and long-term sustainability in atomic-oxygen (AO) environments have been highly desired as antenna substrates in low earth orbit (LEO) aerospace applications. However, PI substrates with low dielectric constant (low-Dk), low dielectric dissipation factor (low-Df) and high AO resistance have rarely been reported due to the difficulties in achieving both high AO survivability and good dielectric parameters simultaneously. In the present work, an intrinsically low-Dk and low-Df optically transparent PI film matrix, poly[4,4'-(hexafluoroisopropylidene)diphthalic anhydride-co-2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane] (6FPI) was combined with a nanocage trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP-POSS) additive in order to afford novel organic-inorganic nanocomposite films with enhanced AO-resistant properties and reduced dielectric parameters. The derived 6FPI/POSS films exhibited the Dk and Df values as low as 2.52 and 0.006 at the frequency of 1 MHz, respectively. Meanwhile, the composite films showed good AO resistance with the erosion yield as low as 4.0 × 10-25 cm3/atom at the exposure flux of 4.02 × 1020 atom/cm2, which decreased by nearly one order of magnitude compared with the value of 3.0 × 10-24 cm3/atom of the standard PI-ref Kapton® film.

Atomic Oxygen-Resistant Polyimide Composite Films Containing Nanocaged Polyhedral Oligomeric Silsesquioxane Components in Matrix and Fillers.

For the development of spacecraft with long-servicing life in low earth orbit (LEO), high-temperature resistant polymer films with long-term atomic oxygen (AO) resistant features are highly desired. The relatively poor AO resistance of standard polyimide (PI) films greatly limited their applications in LEO spacecraft. In this work, we successfully prepared a series of novel AO resistant PI composite films containing nanocaged polyhedral oligomeric silsesquioxane (POSS) components in both the PI matrix and the fillers. The POSS-containing PI matrix film was prepared from a POSS-substituted aromatic diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) and a common aromatic diamine, 4,4'-oxydianline (ODA) and the aromatic dianhydride, pyromellitic dianhydride (PMDA) by a two-step thermal imidization procedure. The POSS-containing filler, trisilanolphenyl POSS (TSP-POSS) was added with the fixed proportion of 20 wt% in the final films. Incorporation of TSP-POSS additive apparently improved the thermal stability, but decreased the high-temperature dimensional stable nature of the PI composite films. The 5% weight loss temperature (T5%) of POSS-PI-20 with 20 wt% of DABA-POSS is 564 °C, and its coefficient of linear thermal expansion (CTE) is 81.0 × 10-6/K. The former is 16 °C lower and the latter was 20.0 × 10-6/K higher than those of the POSS-PI-10 film (T5% = 580 °C, CTE = 61.0 × 10-6/K), respectively. POSS components endowed the PI composite films excellent AO resistance and self-healing characteristics in AO environments. POSS-PI-30 exhibits the lowest AO erosion yield (Es) of 1.64 × 10-26 cm3/atom under AO exposure with a flux of 2.51 × 1021 atoms/cm2, which is more than two orders of magnitude lower than the referenced PI (PMDA-ODA) film. Inert silica or silicate passivation layers were detected on the surface of the PI composite films exposed to AO.

Preparation and Properties of Intrinsically Atomic-Oxygen Resistant Polyimide Films Containing Polyhedral Oligomeric Silsesquioxane (POSS) in the Side Chains.

The relatively poor atomic-oxygen (AO) resistance of the standard polyimide (PI) films greatly limits the wide applications in low earth orbit (LEO) environments. The introduction of polyhedral oligomeric silsesquioxane (POSS) units into the molecular structures of the PI films has been proven to be an effective procedure for enhancing the AO resistance of the PI films. In the current work, a series of POSS-substituted poly (pyromellitic anhydride-4,4'-oxydianiline) (PMDA-ODA) films (POSS-PI) with different POSS contents were synthesized via a POSS-containing diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS). Subsequently, the effects of the molecular structures on the thermal, tensile, optical, and especially the AO-erosion behaviors of the POSS-PI films were investigated. The incorporation of the latent POSS substituents decreased the thermal stability and the high-temperature dimensional stability of the pristine PI-0 (PMDA-ODA) film. For instance, the PI-30 film with the DABA-POSS content of 30 wt% in the film exhibited a 5% weight loss temperature (T5%) of 512 °C and a coefficient of linear thermal expansion (CTE) of 54.6 × 10-6/K in the temperature range of 50-250 °C, respectively, which were all inferior to those of the PI-0 film (T5% = 574 °C; CTE = 28.9 × 10-6/K). In addition, the tensile properties of the POSS-containing PI films were also deteriorated, to some extent, due to the incorporation of the DABA-POSS components. The tensile strength (TS) of the POSS-PI films decreased with the order of PI-0 > PI-10 > PI-15 > PI-20 > PI-25 > PI-30, and so did the tensile modulus (TM) and the elongations at break (Eb). PI-30 showed the TS, TM, and Eb values of 75.0 MPa, 1.55 GPa, and 16.1%, respectively, which were all lower than those of the PI-0 film (TS = 131.0 MPa, TM = 1.88 GPa, Eb = 73.2%). Nevertheless, the incorporation of POSS components obviously increased the AO resistance of the PI films. All of the POSS-PI films survived from the AO exposure with the total fluence of 2.16 × 1021 atoms/cm2, while PI-0 was totally eroded under the same circumstance. The PI-30 film showed an AO erosion yield (Es) of 1.1 × 10-25 cm3/atom, which was approximately 3.67% of the PI-0 film (Es = 3.0 × 10-24 cm3/atom). Inert silica or silicate passivation layers were detected on the surface of the POSS-PI films after AO exposure, which efficiently prevented the further erosion of the under-layer materials.

Study of Electronic and Vibrational Structures of Reduced, Neutral, and Oxidized Ni3(dpa)4X2 Using Density Functional Theory and Raman Spectroscopy.

The electronic and vibrational structures of trinickel metal string complexes [Ni3(dpa)4X2]1-,0,1+ (X = Cl, NCS) were investigated using both theoretical calculations and spectroscopic methods. We used the density functional theory (DFT) method B3LYP*-D3, including less exact exchange energy and the van der Waals interaction of metal ions, to obtain the geometries and vibrational structures, which were found to be in excellent agreement with the experimental data. The ground state of Ni3(dpa)4X2 is an antiferromagnetic (AF) singlet state, and the next state is a quintet state, which was detected using temperature-dependent Raman spectroscopy under a magnetic field. The vibrational structure of the quintet state is nearly identical to that of the AF state, according to the measured Raman spectra, except that the stretching of Ni-Cl is blue-shifted from 282.5 cm-1 in the AF state to 283.8 cm-1 in the quintet state. Two oxidized Ni3 complexes were found to have [Ni3]7+ cores, the doublet [Ni3(dpa)4]3+ without axial ligands and the quartet [Ni3(dpa)4X2]+. Complex [Ni3(dpa)4X2]-, which was produced from a reduction reaction by gold nanoparticles at room temperature, consists of a quartet state as the ground state and a doublet state lying nearby.

Ultra-broadband near-infrared emission CuInS2/ZnS quantum dots with high power efficiency and stability for the theranostic applications of mini light-emitting diodes.

Broadband near-infrared CuInS2/ZnS quantum dots with up to 94.8% quantum yield were synthesized with fast precursor decomposition leading to monomer conversion improvement. In the mini-LED package, the device showed high power efficiency and stability was also demonstrated with a penetration test and vein imaging showing its potential biomedical application in the theranostics field.

Facet-Dependent Reduction Reaction of Diruthenium Metal-String Complexes by Face-to-Face Linked Gold Nanocrystals.

The facet-dependent redox reactions of diruthenium metal-string complexes by gold nanoparticles (AuNPs) are explored by using the surface-enhanced Raman scattering (SERS) technique. Gold nano-rhombic dodecahedrons (AuRDs), gold nanocubes (AuNCs), and gold octahedrons (AuOhs) with exclusive facets {110}, {100}, and {111}, respectively, were synthesized. These AuNPs linked face-to-face by metal-string complexes Ru2M(dpa)4Cl2 (dpa = dipyridyl amino, M = Ni, Cu) with chloride axial ligands serve as both SERS substrates and reducing agents in the reactions. We employ the diruthenium core in these complexes with multiple redox states to study the reduction ability of varied AuNP facets upon plasmonic excitation. In Ru2Ni(dpa)4Cl2, the Ru-Ru stretching mode νRu-Ru str. lies at 327 cm-1 on the SERS substrate AuOh, but this band shifts to 313 cm-1 on the AuRD and AuNC. The diruthenium moiety was reduced to [Ru2]4+ by the AuRD facet {110} and the AuNC {100}. The gold nanorods in the solution prepared with metal-string complexes bridging head-to-head on {111} facets were used for the SERS substrate. The SERS curves of the complexes in these self-assembled head-to-head rods display νRu-Ru str. at 327 cm-1, which is assigned to having an [Ru2]5+ core. Hence, facets {110} and {100} have a reduction reactivity greater than that of {111}. In Ru2Cu(dpa)4Cl2, the νRu-Ru str. is observed to lie at 312 cm-1 on AuRD, but shifts to 320 cm-1 on the AuNC and AuOh. In the latter cases, the diruthenium moiety was reduced to having a charge of 4+ with electronic configuration π*2δ*2, whereas the former case band at 312 cm-1 with a weaker Ru-Ru bonding is also attributed to [Ru2]4+ but with electron configuration π*4. π*4 lies at an energy greater than π*2δ*2. The electrochemical SERS spectra of diruthenium complexes were recorded to verify their oxidation states. Conclusively, these results yield the reduction reactivity of the following facet: {110} > {100} > {111}. According to the results of the redox reactions, the valence states of the diruthenium metal-string complexes are verified. In the [Ru2] n+ core, n = 4 π*4, 4 π*2δ*2, 5 π*2δ*, and 6 π*δ*, and the νRu-Ru str. is 312, 320, 327, and 337 cm-1, respectively.

Ligand-Unsupported Cuprophilicity in the Preparation of Dodecacopper(I) Complexes and Raman Studies.

Synthesis and characterization of two dodecacopper(I) extended metal atom chains (EMAC) assembled by two hexadentate bis(pyridylamido)amidinate-supported hexacopper(I) string complexes (monomers) via the ligand-unsupported cuprophilicity are described. In addition to short unsupported Cu-Cu contacts, two hexacopper fragments in these two dodecacopper EMACs show a bent conformation based on X-ray crystallography. Compared with their THF-bound hexacopper(I) monomers and protonated ligands, these ligand-unsupported cuprophilic interactions are shown to be weak by Raman spectroscopy. DFT calculations suggest the ligand-unsupported cuprophilicity originate from weak attractive orbital interactions, and the strength is estimated to be 2.4 kcal mol-1 .

S- Cis Diene Conformation: A New Bathochromic Shift Strategy for Near-Infrared Fluorescence Switchable Dye and the Imaging Applications.

In this paper, we present a novel charge-free fluorescence-switchable near-infrared (IR) dye based on merocyanine for target specific imaging. In contrast to the typical bathochromic shift approach by extending π-conjugation, the bathochromic shift of our merocyanine dye to the near-IR region is due to an unusual S- cis diene conformer. This is the first example where a fluorescent dye adopts the stable S- cis conformation. In addition to the novel bathochromic shift mechanism, the dye exhibits fluorescence-switchable properties in response to polarity and viscosity. By incorporating a protein-specific ligand to the dye, the probes (for SNAP-tag and hCAII proteins) exhibited dramatic fluorescence increase (up to 300-fold) upon binding with its target protein. The large fluorescence enhancement, near-IR absorption/emission, and charge-free scaffold enabled no-wash and site-specific imaging of target proteins in living cells and in vivo with minimum background fluorescence. We believe that our unconventional approach for a near-IR dye with the S- cis diene conformation can lead to new strategies for the design of near-IR dyes.

Isomerization Reaction of mer- to fac-Tris(2-phenylpyridinato-N,C2')Iridium(III) Monitored by Using Surface-Enhanced Raman Spectroscopy.

We developed a new method by enclosing the complex tris(2-phenylpyridinato-N,C2')Iridium(III), Ir(ppy)3 with surfactant cetyltrimethylammonium bromide (CATB), coated with a thin layer of silica then bonded to the surface of silver nanoparticle. These samples were used to acquire surface-enhanced Raman scattering (SERS) spectra. The thickness of silica layer was controlled to have efficient phosphorescence quenching and Raman enhancement by metal nanoparticle. The SERS spectra of fac- and mer-Ir(ppy)3, recorded at 633 nm excitation, display distinct ring breathing mode features because the total symmetric vibrational bands were enhanced. This provides a convenient means to differentiate these isomers with great sensitivity and to study their isomerization process. A direct conversion reaction of mer- to fac- isomerization is identified with time constant 3.1 min when mer was irradiated with Xe light. Via thermal activation, under moderate conditions (pH 5.5 and 343 K), we observed an intermediate particularly with new bands 320/662 cm-1 after heating for 17.5 h, and then those bands disappeared to form fac-Ir(ppy)3. On the basis of DFT calculations, the intermediate is proposed to contain octahedral N-N Ir(ppy)3-HO-silica structure; band at 320 cm-1 is assigned to iridium oxygen stretching mode νIr-O of this intermediate. Under acidic conditions, pH 1-2 catalyzed by silanol in silica, byproduct with band at 353 cm-1 was observed. According to the SERS bands and the calculation, this byproduct is assigned to be iridium(III) siloxide, and the new band is assigned to νIr-O.

The inhibitory activity of gallic acid against DNA methylation: application of gallic acid on epigenetic therapy of human cancers.

Epigenome aberrations have been observed in tobacco-associated human malignancies. (-)-epigallocatechin-3-gallate (EGCG) has been proven to modulate gene expression by targeting DNA methyltransferases (DNMTs) through a proposed mechanism involving the gallate moiety of EGCG. We show that gallic acid (GA) changes the methylome of lung cancer and pre-malignant oral cell lines and markedly reduces both nuclear and cytoplasmic DNMT1 and DNMT3B within 1 week. GA exhibits stronger cytotoxicity against the lung cancer cell line H1299 than EGCG. We found that GA reactivates the growth arrest and DNA damage-inducible 45 (GADD45) signaling pathway may through the demethylation of CCNE2 and CCNB1 in H1299 cells. To improve the epigenetic anti-cancer activities of oolong tea, we identified a fungus, Aspergillus sojae which can efficiently increase the GA content in oolong tea via a 2-week fermentation process. The fungus dramatically increased GA up to 44.8 fold in the post-fermentation oolong tea extract (PFOTE), resulting in enhanced demethylation effects and a significant reduction in the nuclear abundances of DNMT1, DNMT3A, and DNMT3B in lung cancer cell lines. PFOTE also showed stronger anti-proliferation activities than oolong tea extract (OTE) and increased sensitivity to cisplatin in H1299 cells. In summary, we demonstrate the potent inhibitory effects of GA on the activities of DNMTs and provide a strong scientific foundation for the use of specialized fermented oolong tea high in GA as an effective dietary intervention strategy for tobacco-associated cancers.

Enhanced spectral profile in the study of Doppler-broadened Rydberg ensembles.

Combination of the electromagnetically-induced-transparency (EIT) effect and Rydberg-state atoms has attracted great attention recently due to its potential application in the photon-photon interaction or qubit operation. In this work, we studied the Rydberg-EIT spectra with room-temperature 87Rb atoms. Spectroscopic data under various experimental parameters all showed that the contrast of EIT transparency as a function of the probe field intensity is initially enhanced, reaches a maximum value and then decays gradually. The contrast of spectral profile at the optimum probe field intensity is enhanced by 2-4 times as compared with that at weakest intensity. Moreover, the signal-to-noise ratio of the spectrum can potentially be improved by 1 to 2 orders of magnitude. We provided a theoretical model to explain this behavior and clarified its underlying mechanism. Our work overcomes the obstacle of weak signal in the Rydberg-EIT spectrum caused by an apparent relaxation rate of the Rydberg polariton and weak coupling transition strength, and provides the useful knowledge for the Rydberg-EIT study.

High conversion efficiency in resonant four-wave mixing processes.

We propose a new scheme of the resonant four-wave mixing (FWM) for the frequency up or down conversion, which is more efficient than the commonly-used scheme of the non-resonant FWM. In this new scheme, two control fields are spatially varied such that a probe field at the input can be converted to a signal field at the output. The efficiency of probe-to-signal energy conversion can be 90% at medium's optical depth of about 100. Our proposed scheme works for both the continuous-wave and pulse cases, and is flexible in choosing the control field intensity. This work provides a very useful tool in the nonlinear frequency conversion.

Low-intensity eccentric contractions of the knee extensors and flexors protect against muscle damage.

This study investigated the magnitude and duration of the protective effect of low-intensity eccentric contractions (LowEC) against damage induced by maximal eccentric contractions (MaxEC) of the knee flexors (KF) and extensors (KE). Young men were assigned to 8 experimental groups and 2 control groups (n = 13/group); the experimental groups performed LowEC of KF or KE 2 days (2d), 1 week (1wk), 2 weeks (2wk), or 3 weeks (3wk) before MaxEC, while the control groups performed MaxEC of KF or KE without LowEC. The 2d, 1wk, 2wk, and 3wk groups performed 30 LowEC of KF or 60 LowEC of KE with a load of 10% of maximal voluntary isometric contraction strength on a resistance-training machine, and all groups performed 30 MaxEC of KF or 60 MaxEC of KE on an isokinetic dynamometer. Several muscle damage markers were measured from before to 2 days after exercise (LowEC) or from before to 5 days after exercise (MaxEC). No significant changes in any variables were evident after LowEC. The changes in all variables after MaxEC were smaller (P < 0.05) for the 2d and 1wk groups (e.g., peak creatine kinase activity: 1002 ± 501 IU/L; peak muscle soreness: 13 ± 5 mm) than for the control group (peak creatine kinase activity: 3005 ± 983 IU/L; peak muscle soreness 28 ± 6 mm) for both KE and KF. There were no significant differences between the 2d and 1wk groups or among the 2wk, 3wk, and control groups. These results show that LowEC provided 30%-66% protection against damage induced by MaxEC of KF and KE, and the protective effect lasted 1 week.

Caffeine attenuates acute growth hormone response to a single bout of resistance exercise.

The purpose of this study was to investigate the effects of caffeine consume on substrate metabolism and acute hormonal responses to a single bout of resistance exercise (RE). Ten resistance-trained men participated in this study. All subjects performed one repetition maximum (1RM) test and then performed two protocols: caffeine (CAF, 6 mg·kg(-1)) and control (CON) in counter balanced order. Subjects performed RE (8 exercises, 3 sets of 10 repetitions at 75% of 1RM) after caffeine or placebo ingestion one hour prior to RE. Blood samples collected prior to treatment ingestion (pre-60), immediately prior to RE (pre-exe), and 0, 15, 30 min post to RE (P0, P15, P30) for analysis of insulin, testosterone, cortisol, growth hormone, glucose, free fatty acid and lactic acid. Each experiment was separated by seven days. In this study, statistical analysis of a two-way analysis of variance (treatment by time) with repeated measures was applied. After ingesting caffeine, the concentrations of free fatty acid (pre- exe, P0, P15, P30) in CAF were significantly higher than CON (p < 0.05). Additionally, the responses of GH (P0, P15, P30) in CAF were significantly lower than CON (p < 0.05), whereas the concentrations of insulin, testosterone and cortisol were not different between CAF and CON (p < 0.05) after RE. The results of this study indicated that caffeine ingestion prior to RE might attenuate the response of GH. This effect might be caused by the elevation in blood FFA concentration at the beginning of RE. Key pointsCaffeine ingestion may attenuate the response of GH to a single bout of resistance exercise.The depression of GH response may be caused by the elevation in serum FFA concentration at the beginning of resistance exercise.Caffeine ingestion before resistance exercise may not alert the concentration of cortisol and testosterone.