Achieving Long-Lived Charge Separated State through Ultrafast Interfacial Hole Transfer in Redox Sites-Isolated CdS Nanorods for Enhanced Photocatalysis.

As opposed to natural photosynthesis, a significant challenge in a semiconductor-based photocatalyst is the limited hole extraction efficiency, which adversely affects solar-to-fuel efficiency. Recent studies have demonstrated that photocatalysts featuring spatially isolated dual catalytic oxidation/reduction sites can yield enhanced hole extraction efficiencies. However, the decay dynamics of excited states in such photocatalysts have not been explored. Here a ternary barbell-shaped CdS/MoS2 /Cu2 S heterostructure is prepared, comprising CdS nanorods (NRs) interfaced with MoS2 nanosheets at both ends and Cu2 S nanoparticles on the sidewall. By using transient absorption (TA) spectra, highly efficient charge separation within the CdS/MoS2 /Cu2 S heterostructure are identified. This is achieved through directed electron transfer to the MoS2 tips at a rate constant of >8.3 × 109 s-1 and rapid hole transfer to the Cu2 S nanoparticles on the sidewall at a rate of >6.1 × 1010 s-1 , leading to an exceptional overall charge transfer constant of 2.3 × 1011 s-1 in CdS/MoS2 /Cu2 S. The enhanced hole transfer efficiency results in a remarkably prolonged charge-separated state, facilitating efficient electron accumulation within the MoS2 tips. Consequently, the ternary CdS/MoS2 /Cu2 S heterostructure demonstrates a 22-fold enhancement in visible-light-driven H2 generation compare to pure CdS nanorods. This work highlights the significance of efficient hole extraction in enhancing the solar-to-H2 performance of semiconductor-based heterostructure.

Single-atom nanozymes: classification, regulation strategy, and safety concerns.

Nanozymes, nanomaterials possessing enzymatic activity, have been studied extensively by researchers. However, their complex composition, low density of active sites, and inadequate substrate selectivity have hindered the maturation and widespread acceptance of nanozymes. Single-atom nanozymes (SAzymes) with atomically dispersed active sites are leading the field of catalysis due to their exceptional performance. The maximum utilization rate of atoms, low cost, well-defined coordination structure, and active sites are the most prominent advantages of SAzymes that researchers favor. This review systematically categorizes SAzymes based on their support type and describes their specific applications. Additionally, we discuss regulation strategies for SAzyme activity and provide a comprehensive summary of biosafety challenges associated with these enzymes.

An elaborate biomolecular keypad lock based on electrochromism of viologen derivatives and bioelectrocatalytic reduction of CO2 at supramolecular hydrogel film electrodes.

Herein, the short peptide N-fluorenemethoxycarbonyl diphenylalanine (Fmoc-FF) was used to immobilize both diallyl viologen (DAV) and the enzyme formate dehydrogenase (FDH) to form Fmoc-FF/DAV/FDH supramolecular hydrogel films on an electrode surface by a simple solvent-controlled self-assembly method. The DAV component in the films exhibited multiple properties, such as electrochromism and electrofluorochromism, and acted as an electrochemical mediator. A high efficiency of bioelectrocatalytic reduction of CO2 to formate (HCOO-) was obtained by the natural FDH enzyme and the artificial coenzyme factor DAV both immobilized in the same films. The supramolecular hydrogel films with CO2, voltage and light as stimulating factors and current, fluorescence and UV-vis extinction as responsive signals, were further applied for the construction of complex biomolecular logic systems and information encryption. A 3-input/7-output biomolecular logic gate and several logic devices, including an encoder/decoder, a parity checker, and a keypad lock, were constructed. Especially, the biomolecular keypad lock with 3 types of signals as outputs significantly enhanced the security level of information encryption. In this work, a supramolecular self-assembly interface was simply fabricated with complex biomolecular computational functions using immobilized molecules as the computational core, greatly broadening the application range of supramolecular hydrogel films and providing an idea for new designs of bioinformation encryption through the use of a simple film system.

Numerical and Experimental Investigation on a "Tai Chi"-Shaped Planar Passive Micromixer.

(1) Background: Microfluidic chips have found extensive applications in multiple fields due to their excellent analytical performance. As an important platform for micro-mixing, the performance of micromixers has a significant impact on analysis accuracy and rate. However, existing micromixers with high mixing efficiency are accompanied by high pressure drop, which is not conducive to the integration of micro-reaction systems; (2) Methods: This paper proposed a novel "Tai Chi"-shaped planar passive micromixer with high efficiency and low pressure drop. The effect of different structural parameters was investigated, and an optimal structure was obtained. Simulations on the proposed micromixer and two other micromixers were carried out while mixing experiments on the proposed micromixer were performed. The experimental and simulation results were compared; (3) Results: The optimized values of the parameters were that the straight channel width w, ratio K of the outer and inner walls of the circular cavity, width ratio w1/w2 of the arc channel, and number N of mixing units were 200 µm, 2.9, 1/2, and 6, respectively. Moreover, the excellent performance of the proposed micromixer was verified when compared with the other two micromixers; (4) Conclusions: The mixing efficiency M at all Re studied was more than 50%, and at most Re, the M was nearly 100%. Moreover, the pressure drop was less than 18,000 Pa.

Lithium-ion diffusion in the grain boundary of polycrystalline solid electrolyte Li6.75La3Zr1.5Ta0.5O12 (LLZTO): a computer simulation and theoretical study.

Lithium-ion diffusion ability in solid electrolytes is crucial for the performance and safety of lithium-ion batteries. However, the lithium-ion diffusion coefficient of Li6.75La3Zr1.5Ta0.5O12 (LLZTO) measured experimentally is much lower than that simulated theoretically because LLZTO exists widely in the polycrystalline form rather than in the single-crystal form. Herein, we focus on the construction of grain boundaries in polycrystalline materials to address this key issue. An amorphous structure is created by randomly throwing atoms into a virtual box, where the chemical bonds are broken and rearranged through continuous heating and annealing operations, resulting in a stable framework structure. The lithium-ion diffusion coefficients of polycrystalline LLZTO and single-crystal LLZTO calculated via Ab initio molecular dynamics (AIMD) are consistent with the experimental data in trend. Furthermore, the analysis of the grain boundary composed of the secondary phase in polycrystalline LLZTO reveals that the continuous -O-M-O- metal oxide grid with low formation energy per atom restricts the lithium-ion migration. The lithium-ion migration barriers calculated utilizing density functional theory (DFT) also demonstrate the obstacle of the grain boundary from another perspective.

TICT-Based Near-Infrared Ratiometric Organic Fluorescent Thermometer for Intracellular Temperature Sensing.

Fluorescent thermometers with near-infrared (NIR) emission play an important role in visualizing the intracellular temperature with high resolution and investigating the cellular functions and biochemical activities. Herein, we designed and synthesized a donor-Π-acceptor luminogen, 2-([1,1'-biphenyl]-4-yl)-3-(4-((E)-4-(diphenylamino)styryl) phenyl) fumaronitrile (TBB) by Suzuki coupling reaction. TBB exhibited twisted intramolecular charge transfer-based NIR emission, aggregation-induced emission, and temperature-sensitive emission features. A ratiometric fluorescent thermometer was constructed by encapsulating thermosensitive NIR fluorophore TBB and Rhodamine 110 dye into an amphiphilic polymer matrix F127 to form TBB&R110@F127 nanoparticles (TRF NPs). TRF NPs showed a good temperature sensitivity of 2.37%·°C-1, wide temperature response ranges from 25 to 65 °C, and excellent temperature-sensitive emission reversibility. Intracellular thermometry experiments indicated that TRF NPs could monitor the cellular temperature change from 25 to 53 °C for Hep-G2 cells under the photothermal therapy agent heating process, indicating the considerable potential applications of TRF NPs in the biological thermometry field.

High-efficiency fluorescent and magnetic multimodal probe for long-term monitoring and deep penetration imaging of tumors.

High-quality multimodal imaging requires exogenous contrast agents with high sensitivity, spatial-temporal resolution, and high penetration depth for the accurate diagnosis and surveillance of cancer. Herein, we design a highly efficient fluorescent and magnetic multimodal probe by doping fluorescent molecule 2-(4-bromophenyl)-3-(4-(4-(diphenylamino)styryl)phenyl)fumaronitrile (TB) with near-infrared (NIR) fluorescent emission (714 nm) and superparamagnetic iron oxide (SPIO) into a polystyrene-polyethylene glycol (PS-PEG) matrix to form TB/SPIO@PS-PEG nanoparticles (TSP NPs). The as-prepared TSP NPs exhibit red aggregation-induced emission (AIE) with a maximum wavelength at 655 nm and high fluorescence quantum yield (QY) of 14.6%, facilitating the improvement of sensitivity and signal-to-background ratio for fluorescence molecular imaging (FMI). Phase behavior investigation of the TB/SPIO@PS-PEG probe system by Flory-Huggins lattice theory elucidates the highly efficient fluorescence of the multimodal probe, originating from the poor miscibility between TB and SPIO. Meanwhile, the TSP NPs possess good superparamagnetism and relaxivity and can thus be used as appropriate magnetic contrast agents for magnetic resonance imaging (MRI) and magnetic particle imaging (MPI). In addition, the good biocompatibility and photostability of the TSP NPs make them suitable for long-term monitoring. In vivo fluorescence imaging results indicate that the TSP NPs can facilitate monitoring of subcutaneous tumor growth for more than 24 days in a real-time manner. Multimodal imaging consisting of FMI, MRI, and MPI reveals that TSP NPs can monitor a liver tumor in situ with almost unlimited depth in tissues and high temporal-spatial resolution. As a multimodal probe, the TSP NPs manifest obvious synergistic advantages of long-term monitoring and high penetration depth and hold great prospects in tumor imaging.

Highly sensitive determination of copper in HeLa cell using capillary electrophoresis combined with a simple cell extraction treatment.

A new separation system of capillary electrophoresis (CE1) for the highly sensitive determination of copper was established by using ethylenediaminetetraacetic acid (EDTA) as a complexing agent and employing cetyltrimethylammonium chloride (CTAC) as a capillary inner wall modifier. Benefitted from the combination of field-enhanced sample injection (FESI) method, a limit of detection (LOD) of 2.7 nM was obtained, which was much lower than that of the conventional methods. This made it possible to determine trace copper in HeLa cell only by a simple cell extraction (CE2) treatment. Two copper-extraction methods-acid-hydrolysis and freeze-thaw-were compared. Limited by the requirement of low ion strength in FESI, only the extract using freeze-thaw could be successfully applied in the determination. The effectiveness assessment of this CE(2)-FESI method was adopted by inductively coupled plasma-atomic emission spectrometry (ICP-AES) as a gold standard.

A novel electrochemical chiral sensor for 3,4-dihydroxyphenylalanine based on the combination of single-walled carbon nanotubes, sulfuric acid and square wave voltammetry.

We demonstrate, for the first time, an electrochemical sensor that provides antipodal signals upon application of square wave voltammetry (SWV), for enantioselective recognition of 3,4-dihydroxyphenylalanine based on chiral single-walled carbon nanotubes (SWCNTs) in the presence of sulphuric acid. Interestingly, the enantioselectivity was not observed using the common method of cyclic voltammetry (CV) but the SWV peak currents of enantiomers were found to be quite different and hence the enantiomers could be successfully recognized. Moreover, the antipodal signals provided by two SWV scan modes offer the possibility for results to be confirmed mutually, showing a great practical value and analytical application prospects.

Comparison of vertebroplasty and kyphoplasty in the treatment of osteoporotic vertebral compression fractures with intravertebral clefts.

BACKGROUND: Few studies have compared the surgical outcomes of vertebroplasty (VP) and kyphoplasty (KP) in the treatment of osteoporotic vertebral compression fractures (VCFs) with intravertebral clefts. METHODS: A retrospective study was conducted to review patients with a single-level osteoporotic VCF treated by VP or KP. Intravertebral clefts were assessed by preoperative computed tomography (CT) and magnetic resonance scans. All enrolled patients were followed up for 12 months. Clinical outcomes, radiological findings and complications were evaluated. RESULTS: A total of 53 patients were available for data analysis. Most of the fractures (75.5 %) occurred in the region of the thoracolumbar junction (T10-L2). Twenty-four patients received VP and 29 patients received KP. Patients in both group had significant pain relief after surgery (P < 0.01). Compared with VP group, there was a significant lower visual analogue scale (VAS) score in KP group at the 6- (P = 0.04) and 12-month follow-up (P = 0.02), but the decreased values of VAS score had no significant correlation with the magnitude of deformity correction. Restoration of vertebral body height and reduction in kyphotic angle were achieved in both groups, and the magnitude of correction was more significant in KP group (P < 0.01). Cement leakage rate in VP group (66.7 %) was higher than that in KP group (20.7 %), and there was a significant difference (P < 0.01). CONCLUSIONS: Intravertebral clefts occur primarily at the thoracolumbar junction and can be detected easily by CT and magnetic resonance imaging scans. Both VP and KP are effective in the treatment of clefts, but patients in KP group tend to have a better pain relief at the medium and long-term follow-up. However, the better pain relief effect of KP cannot be attributed to the higher magnitude of deformity correction.

Evaluation of conservative treatment and timing of surgical intervention for mild forms of cervical spondylotic myelopathy.

The optimal management approach for patients with mild forms of cervical spondylotic myelopathy (MCSM) has not been well established. The aim of the present study was to investigate the outcome of conservative treatment, identify prognostic factors and provide evidence for the timing of surgical intervention. A total of 90 patients with MCSM attending hospital between February 2007 and January 2009 were prospectively enrolled. Initially, all patients received conservative treatment and were followed up periodically. When a deterioration in myelopathy was clearly identified, surgical treatment was conducted. Clinical and radiological factors correlating with the deterioration were examined, and final clinical outcomes were evaluated using the Japanese Orthopedic Association (JOA) score. At the end of January 2012, follow-ups of >3 years were completed. Seventy-eight patients were available for data analysis. Only 21 patients (26.9%) deteriorated and underwent surgery thereafter (group A), while the remaining 57 patients (73.1%) were treated conservatively throughout (group B). Statistical analysis revealed that segmental instability and cervical spinal stenosis were adverse factors for the prognosis of conservative treatment. Although the JOA scores of the patients in group A declined initially, following surgical intervention, no significant differences were identified in JOA scores between the two groups at the time of the final follow-up (P=0.46). In summary, conservative treatment is effective in MCSM patients. Patients with segmental instability and cervical spinal stenosis have a tendency to deteriorate, but conservative treatment remains the recommendation for the first action. If the myelopathy deteriorates during conservative treatment, timely surgical intervention is effective.

A chiral electrochemical sensor for propranolol based on multi-walled carbon nanotubes/ionic liquids nanocomposite.

A novel chiral electrochemical sensor based on multi-walled carbon nanotubes (MWCNTs)/ionic liquids (ILs) nanocomposite was developed and applied to the enantiomeric recognition of propranolol (PRO). Mechanisms for chiral sensing were discussed in terms of the formation of an efficient chiral nanospace originating from the weak interactions between quasi-chiral MWCNTs and versatile ILs. This work provided new evidence that the electro-oxidation of PRO should result from its hydroxyl group. Herein the ratio of oxidation peak currents, instead of the commonest shift of peak potential, was used to sense the enantiomeric fraction (EF) of (R)-PRO with a linear correlation coefficient of 0.9936. This simple and reliable sensor was successfully applied in an accurate determination of the enantiomeric purity of reagent, as well as the evaluation of waste water treatment efficiency.

A CE-LIF method to monitor autophagy by directly detecting LC3 proteins in HeLa cells.

A fast, simple and quantitative approach was established for monitoring autophagy in HeLa cells by directly detecting the conversion of green fluorescent protein (GFP) labelled autophagy markers, GFP-LC3-I to GFP-LC3-II, in crude cellular extract using capillary electrophoresis (CE) with laser-induced fluorescence (LIF). Compared with the traditional methods, this proposed method is simpler and more reliable. Moreover, high sensitivity, with a limit of detection (LOD) of 0.48 ppt (bovine serum albumin as standard protein), was obtained by an in-capillary derivatization method coupled with a field-enhanced sample injection (FESI) technique, this may allow the success of this technique in the detection of endogenous markers of autophagy in cells.

Simultaneous and sensitive capillary electrophoretic enantioseparation of three ß-blockers with the combination of achiral ionic liquid and dual CD derivatives.

Successful simultaneous enantioseparation and sensitive determination of three ß-blockers (PIN, OX and PRO), have been achieved by capillary electrophoresis using an achiral ionic liquid, [GTMA]Cl, as a modifier to cooperate with dual CDs containing DM-ß-CD and TM-ß-CD. The influence of aIL was investigated in details, including various aILs, the concentration of aIL and molar ratio of aIL to CD. The ratio of DM-ß-CD to TM-ß-CD in dual CDs was also discussed. DM-ß-CD and TM-ß-CD favor the enantioseparations of PIN/OX and PRO, respectively. Meanwhile, the presence of [GTMA]Cl was found to play a key role in enantioseparations, and it widened the scope of application of DM-ß-CD and TM-ß-CD. Furthermore, FESI as an effective on-line sample enrichment technique was developed to improve the detection sensitivity. Under the optimum conditions, the detection limits of the three pairs of enantiomers range from 0.10 to 0.65 nM, which are much lower than those in the conventional methods. Eventually, the proposed method was successfully applied to the analysis of spiked urine sample with good recoveries.

Highly sensitive detection of melamine and its derivatives by capillary electrophoresis coupled with online preconcentration techniques.

Two kinds of online preconcentration techniques including large-volume sample stacking-sweeping and selective-exhaustive injection-sweeping (SEI-S) were employed in CE to develop a rapid, simple and sensitive method for determination of melamine (MM) and its derivatives such as ammeline (AMN), ammelide (AMD) and cyanuric acid (CA) in liquid milk products. Though the sensitivity of large-volume sample stacking-sweeping is not particularly high, it can be used to detect all the four compounds simultaneously. However, it is very difficult to improve the sensitivity of these four compounds by using single SEI-S method directly, owing to their completely different extents of protonation or deprotonation. Grouping can solve this problem perfectly. After the four compounds are divided into two groups (MM/AMN and AMD/CA), cation-SEI-S or anion-SEI-S can be applied for their online stacking. In cation-SEI-S, the detection limits for MM and AMN were both 0.01 ng/mL based on the signal-to-noise ratio of 3. In anion-SEI-S, the detection limits were 0.05 and 0.02 ng/mL for CA and AMD, respectively. Results of this study show a great potential for the SEI-S method to be a useful tool for the rapid and sensitive determination of MM and its derivatives in liquid milk products.