Coordination Site Selective Occupation Strategy for Tuning the Photosalient Effects of Photoactive Cd Complexes.

The application of photo responsive crystals to useful actuation demands a rational design to elicit controllable movement. The [2+2] photocycloaddition reaction triggers mechanical motion  using associated photosalient (PS) effects. We herein report a coordination site selective occupation strategy to modulate the arrangement of C=C bonds and thereby tune the PS effect. Replacing or repositioning the donor atom at one end of the linear ligand allowed for a greater level of molecular structural flexibility, facilitating [2+2] photocycloaddition. The distance between photoreactive centres and coordination sites was adjusted by ligand design to regulate PS behavior. This work suggests new avenues for modulating PS movement to achieve useful motion.

Stereoselective Solid-State Synthesis of Biologically Active Cyclobutane and Dicyclobutane Isomers via Conformation Blocking and Transference.

Conformations in the solid state are typically fixed during crystallization. Transference of "frozen" C=C conformations in 3,5-bis((E)-2-(pyridin-4-yl)vinyl)methylbenzene (CH3-3,5-bpeb) by photodimerization selectively yielded cyclobutane and dicyclobutane isomers, one of which (Isomer 2) exhibited excellent in vitro anti-cancer activity towards T-24, 7402, MGC803, HepG-2, and HeLa cells.

Electron and surface engineering of Ni2P/MnP4 heterojunction as high performance bifunctional electrocatalyst for amperage-level overall water splitting.

Producing hydrogen through electrocatalytic overall water splitting with ampere-level current density is still limited by the high cost and poor stability of electrocatalysts. In this work, a new type Ni2P/MnP4 heterojunction composite material was designed and prepared as bifunctional electrocatalyst. Based on XPS spectra and theoretical calculation, the formation of Ni2P/MnP4 heterojunction successfully modulates the local electronic structure of Ni2P and enhances the ionization of H and Ni by increasing the electron transfer rate. Moreover, the special nanovilli structure and superhydropholic/superaerophobic surface of Ni2P/MnP4 heterojunction accelerates the transfer of electrolyte and gaseous products. Benefiting from these advantages, the as-prepared Ni2P/MnP4/CF not only exhibits superior electrocatalytic performance, which can release 10 mA/cm2 current density with a low overpotential of 69 mV and 247 mV for HER and OER respectively, but also shows admirable stability of continuous overall water splitting to drive 1000 mA/cm2 for 180 h without notable activity degradation. We believe this material possesses outstanding potential for industrial applications, and our strategy may provide a new pathway to design relative materials.

260 fs, 403 W coherently combined fiber laser with precise high-order dispersion management.

An ultrafast fiber laser system comprising two coherently combined amplifier channels is reported. Within this system, each channel incorporates a rod-type fiber power amplifier, with individual operations reaching approximately 233 W. The active-locking of these coherently combined channels, followed by compression using gratings, yields an output with a pulse energy of 504 µJ and an average power of 403 W. Exceptional stability is maintained, with a 0.3% root mean square (RMS) deviation and a beam quality factor M2 < 1.2. Notably, precise dispersion management of the front-end seed light effectively compensates for the accumulated high-order dispersion in subsequent amplification stages. This strategic approach results in a significant reduction in the final output pulse duration for the coherently combined laser beam, reducing it from 488 to 260 fs after the gratings compressor, while concurrently enhancing the energy of the primary peak from 65% to 92%.

Clean hundred-µJ-level sub-6-fs blue pulses generated with helium-assisted solid thin plates.

In this work, 85 µJ, 5.5 fs pulses spanning 350-500 nm with 96% energy concentrated on the main pulse are generated by pulse compression using a helium-assisted, two-stage solid thin plate apparatus. To the best of our knowledge, these are the highest energy sub-6 fs blue pulses obtained to date. Furthermore, during the spectral broadening process, we observe that solid thin plates are much more easily damaged by blue pulses in a vacuum than in a gas-filled environment at the same field intensity. Helium, with the highest ionization energy and extremely low material dispersion, is adopted to create a gas-filled environment. Thus, the damage to solid thin plates is eliminated, and high-energy, clean pulses can be obtained with only two commercially available chirped mirrors in a chamber. Furthermore, the excellent output power stability of 0.39% root mean square (rms) fluctuations over 1 h is maintained. We believe that few-cycle blue pulses at the hundred-µJ level can open the door to numerous new ultrafast and strong-field applications in this spectral region.

Constructing Built-in Electric Field in Heterogeneous Nanowire Arrays for Efficient Overall Water Electrolysis.

Efficient bifunctional electrocatalysts for hydrogen and oxygen evolution reactions are key to water electrolysis. Herein, we report a built-in electric field (BEF) strategy to fabricate heterogeneous nickel phosphide-cobalt nanowire arrays grown on carbon fiber paper (Ni2 P-CoCH/CFP) with large work function difference (ΔΦ) as bifunctional electrocatalysts for overall water splitting. Impressively, Ni2 P-CoCH/CFP exhibits a remarkable catalytic activity for hydrogen and oxygen evolution reactions to obtain 10 mA cm-2 , respectively. Moreover, the assembled lab-scale electrolyzer driven by an AAA battery delivers excellent stability after 50 h electrocatalysis with a 100 % faradic efficiency. Computational calculations combining with experiments reveal the interface-induced electric field effect facilitates asymmetrical charge distributions, thereby regulating the adsorption/desorption of the intermediates during reactions. This work offers an avenue to rationally design high-performance heterogeneous electrocatalysts.

Coordination Polymer-Mediated Molecular Surgery for Precise Interconversion of Dicyclobutane Compounds.

A Cd(II)-based coordination polymer {[Cd2(5-F-1,3-bpeb)2(FBA)4]·H2O}n (CP1) was obtained from Cd(II) salt, 5-fluoro-1,3-bis[2-(4-pyridyl)ethenyl]benzene (5-F-1,3-bpeb), and p-fluorobenzoic acid (HFBA). Within the one-dimensional chain structure of CP1, a pair of 5-F-1,3-bpeb was arranged in a face-to-face style. Upon UV irradiation and heat treatment, multiple cyclobutane isomers, including specific monocyclobutanes (1 with an endo-cyclobutane ring in CP1-1 and 1' with an exo-cyclobutane ring in CP1-1') and dicyclobutanes (endo,endo-dicyclobutane 2α in CP1-2α, exo,endo-dicyclobutane 2ß in CP1-2ß, and exo,exo-dicyclobutane 2γ in CP1-2γ) were stereoselectively produced. These isomers could be interconverted inside the CP via cutting/coupling specific bonds, which may be regarded as a type of molecular surgery. The precision of cutting/coupling relied on the thermal stability of the cyclobutanes and the alignment of the reactive alkene centers. The conversion processes were tracked through nuclear magnetic resonance, in situ powder X-ray diffraction, and IR spectroscopy. This approach can be considered as skeletal editing to construct complex organic compounds directly from one precursor.

Facile Strategy for Preparing a Rosin-Based Low-k Material: Molecular Design of Free Volume.

Low-k dielectrics are urgently needed in modern integrated circuits. The introduction of free volume instead of porous structures has become a powerful strategy to reduce the k value. According to this strategy, the biomass resource rosin-containing hydrogenated phenanthrene ring was introduced into benzocyclobutene (BCB) resin to reduce the k value; then a rosin-based BCB monomer was successfully synthesized. Meanwhile, the BCB monomer without a rosin skeleton was prepared. After converting the monomers into thermo-crosslinked materials, notably that the rosin skeleton has a great influence on the free volume and k value of the material. The fractional free volume and k value of the former are 26% and 2.44, respectively, and those of the latter are 14% and 2.84, respectively. In addition, the distances between molecular chains and the density of the former are 0.60 nm and 1.06 g cm-3, respectively; those of the latter are 0.56 nm and 1.28 g cm-3, respectively. These data show that introducing hydrogenated phenanthrene rings occupies part of the space and hinders the packing of molecular chains, which increases the distance between molecular chains and reduces the density of the polymer, resulting in an increasing free volume and a reducing k value. Notably that introducing hydrogenated phenanthrene rings cannot affect other properties of the material. Therefore, this research indicates that introducing rosin skeletons can prepare high-performance materials, which provide some promising low-k materials for the development of electronics and microelectronics.

Controllable multiple-step configuration transformations in a thermal/photoinduced reaction.

Solid-state photochemical reactions of olefinic compounds have been demonstrated to represent powerful access to organic cyclic molecules with specific configurations. However, the precise control of the stereochemistry in these reactions remains challenging owing to complex and fleeting configuration transformations. Herein, we report a unique approach to control the regiospecific configurations of C = C groups and the intermediates by varying temperatures in multiple-step thermal/photoinduced reactions, thus successfully realizing reversible ring closing/opening changes using a single-crystal coordination polymer platform. All stereochemical transitions are observed by in situ single-crystal X-ray diffraction, powder X-ray diffraction and infrared spectroscopy. Density functional theory calculations allow us to rationalize the mechanism of the synergistic thermal/photoinduced transformations. This approach can be generalized to the analysis of the possible configuration transformations of functional groups and intermediates and unravel the detailed mechanism for any inorganic, organic and macromolecular reactions susceptible to incorporation into single-crystal coordination polymer platforms.

Study on Influencing Factors of Frailty in Elderly Patients with Type II Diabetes.

The purpose of this study was to analyze the influencing factors of frailty in elderly patients with type II diabetes. 332 elderly patients with type II diabetes admitted to our hospital from May 2018 to December 2019 were selected as the study subjects. The degree of frailty was evaluated by the Fried fragility phenotype scale, and the general information and the clinical data of patients were collected by inquiry and questionnaire survey. After that, all the data were analyzed by SPSS 20.0. Univariate analysis showed that there were significant differences in age, medication types, dietary habits, exercise tolerance, exercise capacity, body balance, coordination ability, urinary incontinence, anxiety, etc., in elderly patients with type II diabetes who suffered from different degrees of frailty (P < 0.01). In addition, there were significant differences in the presence of coronary heart disease, heart failure, atrial fibrillation, pulmonary diseases, osteoarticular diseases, anemia, and other blood diseases of elderly patients with type II diabetes who suffered from different degrees of frailty (P < 0.01). Multiple Logistic regression analyses indicated that weakened exercise tolerance, reduced exercise capacity, atrial fibrillation, anemia, and other blood diseases were the influencing factors of the frailty in elderly patients with type II diabetes. The degree of frailty in elderly patients with diabetes is affected by many factors, such as exercise tolerance, exercise capacity, atrial fibrillation, anemia, and other blood diseases; thus, reasonable intervention should be implemented for elderly patients with type II diabetes according to the influencing factors so as to effectively relieve frailty.

Tunable photosalient behaviours within coordination polymers via functional molecular prearrangements.

Four Cd(II)/diene coordination polymers (CPs) with similar 1D chain motifs exhibit different photosalient (PS) behaviours in response to UV light. The [2+2] photoreaction between the CC groups within these CPs results in diverse PS behaviours of their crystals with different CC pair arrangements. The interesting PS behaviours of these CPs can be applied in design and fabrication of advanced photoactuating materials.

Generation of 5.2 fs, energy scalable blue pulses.

In this Letter, ultrashort blue pulses spanning 350-500 nm are generated by combining the broadband frequency doubling technology with the two-stage multiplate continuum (MPC) generation scheme. We prepare relatively broadband input pulses and use a two-stage configuration for MPC generation, allowing us to employ thinner and less solid plates for further spectral broadening. Therefore, the deteriorations of the spectral phase, energy conversion efficiency, and beam quality, which occur more easily for 400 nm pulses, are effectively suppressed. After fine dispersion management, we obtain clean 5.2 fs blue pulses with a root-mean-square energy stability of 0.69% over one hour and excellent beam quality. Furthermore, lower than 8% energy loss during the spectral broadening process at each stage is achieved. The overall optimized performances and energy scalability of this blue pulse, as well as the possibility of further compressing the pulse duration, are likely to motivate more strong-field research with sub-cycle time resolution in this extended wavelength range.

New structurally diverse photoactive cadmium coordination polymers.

Four structurally diverse coordination polymers 1-4 (CP1-CP4) were designed and constructed from Cd(II) ions and various carboxyl ligands (H2oba, 4,4'-oxydibenzoic acid; H2bpa, (E)-4,4'-(ethene-1,2-diyl)dibenzoic acid; H2pbda, 4,4'-((1,3-phenylenebis(methylene))bis(oxy))dibenzoic acid) and the alkene containing ligand (CH3-bpeb, 4,4'-((1E,1'E)-(2,5-dimethyl-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine). CP1-CP4 possess Cd2 binuclear secondary building units (SBUs). The geometry of the dicarboxylate ligands and the reaction conditions determined the final structure with a variety of motifs. CP1 possesses an interdigitated 2D structure, while CP2 consists of a 1D channel-like motif with isolated CH3-bpeb molecules embedded in the channels. The solid-state structure of CP3 consists of two unique layers interpenetrated to form a 2D + 2D → 2D polycatenated backbone, while a 1D channel-like motif filled by isolated CH3-bpeb molecules was observed for CP4. In all four coordination polymers pairs of CH3-bpeb molecules were bound or encapsulated by the Cd2 secondary building units at an appropriate distance and orientation for solid-state [2 + 2] photodimerization of one pair of CC bonds. Desolvation of CP3 with heat resulted in a decrease in solid-state fluorescence and a slowing of the rate of solid-state photodimerization.

Tuning the configuration of the flexible metal-alkene-framework affords pure cycloisomers in solid state photodimerization.

The photochemical [2+2] cycloaddition of 3,5-bis-(2-(pyridin-4-yl)vinyl)pyridine (bpvp) in the flexible Cd-based metal-alkene frameworks produced different isomeric photoproducts depending on the auxiliary and guest molecules. The bulkiness of the guest molecules influenced the conformation of the ligand, and thus the outcome of the cycloaddition reaction.

Synergistic effects of layer-by-layer films for highly selective and sensitive electrochemical detection of trans-resveratrol.

Trans-resveratrol (TRA) possesses a variety of pharmacological activities, making important to explore simple, inexpensive, and reliable analytical methods for identification and quantification of it. We report on the synergistic effects originated from layer-by-layer films of graphene (Gr)-gold nanoparticles (Au) and molecularly imprinted polymers (MIPs) modified glassy carbon electrode (GCE) for electrochemical detection of TRA. To construct the TRA electrochemical sensor (GCE|Gr-Au/MIPs), the films of Gr-Au, MIPs were step by step formed onto GCE via in-situ and controllable electrodeposition and polymerization processes. The compositions, morphologies, and electrochemical properties of obtained films were investigated by various methods. Under the optimized experimental conditions, the electrochemical sensor showed superior performance toward selective and sensitive determination of TRA with K3[Fe(CN)6] as electrochemical signal probe. The electrochemical sensor was applied to determine TRA in real samples with good accuracy and recovery, verifying the broad and practical application prospects for foods and medicines analysis.

CircRNA-ACAP2 contributes to the invasion, migration, and anti-apoptosis of neuroblastoma cells through targeting the miRNA-143-3p-hexokinase 2 axis.

BACKGROUND: Circulating RNAs (Circ-RNAs) are tightly related to the processes of neuroblastoma. The circ-ACAP2 has been reported as dysregulated in various cancers; however, its biological roles and mechanisms in neuroblastoma remain largely unclear. METHODS: We collected 40 neuroblastoma tissues and adjacent noncancerous tissues. Quantitative reverse transcription polymerase chain reaction (qRT-RCR) or western blot were used to examine ACAP2, miR-143-3p, and HK2 abundances. Cell migration, invasion, glycolysis, and apoptosis were assessed via wound healing, transwell, glucose uptake and lactate, 3-(4,5-diamethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay, and flow cytometry. The association between circRNA, microRNA (miRNA), and messenger RNA (mRNA) was examined by dual-luciferase reporter analysis and RNA immunoprecipitation. RESULTS: The abundances of ACAP2 and HK2 were remarkedly increased in neuroblastoma tissues and cell lines. Silencing ACAP2 significantly constrained neuroblastoma cell migration, invasion, and glycolysis, and promoted apoptosis. Bioinformatics prediction, luciferase assay, and RNA pull-down assay consistently demonstrated that ACAP2 sponged miR-143-3p to downregulate its expression in neuroblastoma cells. Furthermore, we identified that hexokinase 2, a glycolysis key enzyme, was a direct target of miR-143-3p in neuroblastoma cells. Rescue of miR-143-3p in ACAP2-overexpressing cells effectively mitigated the influence of ACAP2 on neuroblastoma cell processes. CONCLUSIONS: Our study revealed biological roles and molecular mechanisms for circ-ACAP2 in the oncogenic characteristics of neuroblastoma, facilitating the development of circRNA-based treatment approaches for anti-brain tumor therapy.

Novel plant flavonoid electrochemical sensor based on in-situ and controllable double-layered membranes modified electrode.

Identification and quantification of plant flavonoids are critical to pharmacokinetic study and pharmaceutical quality control due to their distinct pharmacological functions. Here we report on a novel plant flavonoid electrochemical sensor for sensitive and selective detection of dihydromyricetin (DMY) based on double- layered membranes consisting of gold nanoparticles (Au) anchored on reduced graphene oxide (rGO) and molecularly imprinted polymers (MIPs) modified glassy carbon electrode (GCE). Both rGO-Au and MIPs membranes were directly formed on GCE via in-situ electrochemical reduction and polymerization processes step by step. The compositions, morphologies, and electrochemical properties of membranes were investigated with X-ray powder diffractometry (XRD), Fourier transform infrared spectrum (FTIR), Field emission scanning electron microscopy (FESEM) combined with various electrochemical methods. The fabricated electrochemical sensor labeled as GCE│rGO-Au/MIPs exhibited excellent performance in determining of DMY under optimal experimental conditions. A wide linear detection range (LDR) ranges from 2.0×10-8 to 1.0×10-4 M together with a low limit of detection (LOD) of 1.2×10-8 M (S/N = 3) were achieved. Moreover, the electrochemical sensor was employed to determine DMY in real samples with satisfactory results.

Modulating the regioselectivity of solid-state photodimerization in coordination polymer crystals.

Coordination polymers [Cd(1,4-bpeb)(L1)] (1), [Zn2(1,4-bpeb)2(L2)2(SO42-)2] (2) and [Cd(1,4-bpeb)(L3)] (H2O) (3) (H2L1, 3-[2-(3-hydroxy-phenoxymethyl)-benzyloxy]-benzoic acid; HL2, 1H-Indazole-3-carboxylic acid; H3L3, benzene-1,2,3-tricarboxylic acid; 1,4-bpeb, 1,4-bis[2-(4-pyridyl)vinyl]benzene have been synthesized under solvothermal conditions. Complexes 1-3 underwent photodimerization in the solid-state to give quantitative yields of single isomeric products. The choice of carboxyl ligands L and metal center determined the arrangement of 1,4-bpeb ligands, which in turn directed the regiochemistry of the final photoproducts. The solid-state network structures of cadmium based 1 and 3 had 1,4-bpeb pairs aligned face-to-face with both C[double bond, length as m-dash]C centres in each ligand at an appropriate distance and alignment for photodimerization to give the corresponding para-[2.2]cyclophane (pCP) exclusively. By contrast, compound 2 possessed dinuclear (ZnSO4)2 metallocycles that positioned the 1,4-bpeb "arms" face-to-face, but with C[double bond, length as m-dash]C centres offset at an appropriate distance for only one pair to undergo [2 + 2] cycloaddition to yield a single stereoisomer of the monocyclobutane photo-product bpbpvpcb. This work highlights crystal engineering design principles that can be used to facilitate regio- and stereospecificity in solid-state transformations.

Amino group decorated coordination polymers for enhanced detection of folic acid.

A series of fluorescent coordination polymers (CPs) {[Cd2(CH3-bpeb)2(BDC)2] CP1, (BDC)0.5/(NH2-BDC)0.5-CP1, (BDC)0.34/(NH2-BDC)0.66-CP1, (BDC)0.25/(NH2-BDC)0.75-CP1, (BDC)0.2/(NH2-BDC)0.8-CP1, (NH2-BDC)-CP1} were prepared from conjugated ligand 4,4'-((2-methyl-1,4-phenylene)bis(ethene-2,1-diyl))bipyridine (CH3-bpeb), terephthalic acid (BDC), aminoterephthalic acid (NH2-BDC) and CdSO4 under solvothermal conditions. The fluorescence of aqueous suspensions of these CPs was quenched by folic acid (FA) in a concentration dependent manner. The efficiency of quenching increasing with an increased proportion of NH2-BDC ligand in the CP with (NH2-BDC)-CP1 exhibiting a low detection limit of 1.7 × 10-7 M.

2D CoOOH Sheet-Encapsulated Ni2P into Tubular Arrays Realizing 1000 mA cm-2-Level-Current-Density Hydrogen Evolution Over 100 h in Neutral Water.

Water electrolysis at high current density (1000 mA cm-2 level) with excellent durability especially in neutral electrolyte is the pivotal issue for green hydrogen from experiment to industrialization. In addition to the high intrinsic activity determined by the electronic structure, electrocatalysts are also required to be capable of fast mass transfer (electrolyte recharge and bubble overflow) and high mechanical stability. Herein, the 2D CoOOH sheet-encapsulated Ni2P into tubular arrays electrocatalytic system was proposed and realized 1000 mA cm-2-level-current-density hydrogen evolution over 100 h in neutral water. In designed catalysts, 2D stack structure as an adaptive material can buffer the shock of electrolyte convection, hydrogen bubble rupture, and evolution through the release of stress, which insure the long cycle stability. Meanwhile, the rich porosity between stacked units contributed the good infiltration of electrolyte and slippage of hydrogen bubbles, guaranteeing electrolyte fast recharge and bubble evolution at the high-current catalysis. Beyond that, the electron structure modulation induced by interfacial charge transfer is also beneficial to enhance the intrinsic activity. Profoundly, the multiscale coordinated regulation will provide a guide to design high-efficiency industrial electrocatalysts.