Large Nonlinear Optical Activity of a Near-infrared-absorbing Bithiophene-based Polymer with a Head-to-head Linkage

Although the production of near-infrared (NIR)-absorbing organic polymers with an excellent nonlinear optical (NLO) response is vital for various optoelectronic devices and photodynamic therapy, the molecular design and relevant photophysical investigation still remain challenging. In this work, large NLO activity is observed for an NIR-absorbing bithiophene-based polymer with a unique head-to-head linkage in the NIR region. The saturable absorption coefficient and modulation depth of the polymer are determined as ∼−3.5×10⁵ cm GW⁻¹ and ∼32.43%, respectively. Notably, the polymer exhibits an intrinsic nonlinear refraction index up to ∼−9.36 cm² GW⁻¹, which is six orders of magnitude larger than that of CS₂. The maximum molar-mass normalized two-photon absorption cross-section (σ₂/M) of this polymer can be up to ∼14 GM at 1200 nm. Femtosecond transient absorption measurements reveal significant spectral overlap between the 2PA and excited state absorption in the 1000–1400 nm wavelength range and an efficient triplet quantum yield of ∼36.7%. The results of this study imply that this NIR-absorbing polymer is promising for relevant applications.     

An Iridium Complex as an AIE-active Photosensitizer for Image-guided Photodynamic Therapy

Image-guided photodynamic therapy (PDT) has received growing attention due to its non-invasiveness and precise controllability. However, the PDT efficiency of most photosensitizers are decreased in living system due to the aggregation-caused singlet oxygen (¹O₂) generation decreasing. Herein, we present an Iridium (III) pyridylpyrrole complex (Ir-1) featuring of aggregation-induced emission (AIE) and ¹O₂ generation characteristics for image-guided PDT of cancer. Ir-1 aqueous solution exhibits bright red phosphorescence peaked at 630 nm, large Stokes shift of 227 nm, and good ¹O₂ generation ability. The ¹O₂ generating rate of Ir-1 in EtOH/water mixture solution is 2.3 times higher than that of Rose Bengal. In vitro experimental results revealed that Ir-1 has better biocompatibility and higher phototoxicity compared with clinically used photosensitizers (Rose Bengal and Ce6), suggesting that Ir-1 can serve as a photosensitizer for image-guided PDT of cancer.     

Facile Surfactant-, Reductant-, and Ag Salt-free Growth of Ag Nanoparticles with Controllable Size from 35 to 660 nm on Bulk Ag Materials

Morphologically and dimensionally controlled growth of Ag nanocrystals has long been plagued by surfactants or capping agents that complicate downstream applications, unstable Ag salts that impaired the reproducibility, and multistep seed injection that is troublesome and time-consuming. Here, we report a one-pot electro-chemical method to fast (∼2 min) produce Ag nanoparticles from commercial bulk Ag materials in a nitric acid solution, eliminating any need for surfactants or capping agents. Their size can be easily manipulated in an unprecedentedly wide range from 35 to 660 nm. Furthermore, the Ag nanoparticles are directly grown on the Ag substrate, highly desirable for promising applications such as catalysis and plasmonics. The mechanistic studies reveal that the concentration of Ag⁺ in the diffusion layer nearby the surface, controlled by the magnitude and duration of voltage, is critical in governing the nanoparticle formation (<1.3 mM) and its dimensional adjustability.     

Simultaneous Removal of Antibiotics and Heavy Metals with Poly(Aspartic Acid)-Based Fenton Micromotors

The discharge of diverse pollutants has led to a complex water environment and posed a huge health threat to humans and animals. Self-propelled micromotors have recently attracted considerable attention for efficient water remediation due to their strong localized mass transfer effect. However, a single functionalized component is difficult to tackle with multiple contaminants and requires to combine different decontamination effects together. Here, we introduced a multifunctional micromotor to implement the adsorption and degradation roles simultaneously by integrating the poly(aspartic acid) (PASP) adsorbent with a MnO₂-based catalyst. The as-prepared micromotors are well propelled in contaminated waters by MnO₂ catalyzing hydrogen peroxide. In addition, the catalytic ramsdellite MnO₂(R-MnO₂) inner layer is decorated with Fe₂O₃ nanoparticles to improve their catalytic performance, contributing to an excellent degradation ability with 90% tetracycline (TC) removal in 50 minutes by enhanced Fenton-like reactions. Combining the attractive adsorption capability of poly (aspartic acid) (PASP), the composite micromotors offer an efficient removal of heavy metal ions in short time. Moreover, the designed micromotors are able to simultaneously remove antibiotic and heavy metals in mixed contaminants circumstance just in single treatment. This multifunctional micromotor with distinctive decontamination ability exhibits a promising prospective in treating multiple pollutants in the future.     

Catalytic enantioselective synthesis of macrodiolides and their application in chiral recognition

New types of C₂-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.

An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex.     

Presodiation Strategies for the Promotion of Sodium-Based Energy Storage Systems

Nowadays sodium-based energy storage systems (Na-based ESSs) have been widely researched as it possesses the possibility to replace traditional energy storage media to become next generation energy storage system. However, due to the irreversible loss of sodium ions in the first cycle, development of Na-based ESSs is limited. Presodiation, as a strategy of adding excess sodium ions to the system in advance, accomplishes the enhancement of electrochemical performance. In this minireview, different presodiation strategies applied in sodium-based energy storage systems will be summarized in detail, their functions and corresponding mechanisms will be discussed as well. Furthermore, the current novel application of presodiation method in other aspects of Na-based ESSs will be mentioned additionally. At last, in the view of present research status of presodiation, issues that can be mitigated are put forward and guidelines are given on how to deliberate in-depth presodiation technology in the future, dedicating to promote the further development of Na-based ESSs.     

BirA*-protein A fusion protein based BioEnhancer amplifies western blot immunosignal

Western blot (protein immunoblot) is a widely used analytical technique in molecular biology. Utilizing the specific recognizing primary antibody, proteins immobilized on various matrix are investigated by subsequent visualization steps, for example, by the horse radish peroxidase conjugated secondary antibody incubation. Methods to improve the sensitivity in protein identification or quantification are appreciated by biochemists. Herein, we report a new strategy to amplify Western blot signals by constructing a probe with proximal labeling and IgG targeting abilities. The R118G mutation attenuated the biotin-AMP binding affinity of the bacterial biotin ligase BirA*, offering a proximity-dependent labeling ability, which could be used as a signal amplifier. We built a BirA*-protein A fusion protein (BioEnhancer) that specifically binds to IgG and adds biotin tags to its proximal amine groups, enhancing the immunosignal of target proteins. In our experiments, the BioEnhancer system amplified the immunosignal by tenfold compared to the standard western blot. Additionally, our strategy could couple with other signal enhancement methods to further increase the western blot sensitivity.     

Rate sensitivity and deformation mechanism of semi-crystalline polymers during instrumented indentation

Instrumented indentation tests using both constant loading rate (CLR) and continuous stiffness measurement (CSM) operation modes were performed to investigate the deformation mechanism and their sensitivity to the deformation rate in semi-crystalline polymers through the quantitative analysis of load-depth loading and unloading curves. The strain rate was constant during the CSM tests, while the strain rate decreased with the increasing of loading time in CLR tests. The mechanical response mechanism of the semi-crystalline polymers to these tests was very complicated because of the combined effects of strain-hardening in the crystal phase and strain-softening in the amorphous phase. Results show that the loading index m reflects the strain-hardening or strain-softening response during indentation. When m > 2, the mechanical response was due to the strain-hardening, and when m < 2, the response was due to strain-softening. A method based on the measured contact hardness was proposed to obtain the unloading stiffness, and the other mechanical parameters could then be determined according to the unloading stiffness.     

Potential Role of Melatonin as an Adjuvant for Atherosclerotic Carotid Arterial Stenosis

Carotid artery stenosis (CAS) is an atherosclerotic disease characterized by a narrowing of the artery lumen and a high risk of ischemic stroke. Risk factors of atherosclerosis, including smoking, hypertension, hyperglycemia, hyperlipidemia, aging, and disrupted circadian rhythm, may potentiate atherosclerosis in the carotid artery and further reduce the arterial lumen. Ischemic stroke due to severe CAS and cerebral ischemic/reperfusion (I/R) injury after the revascularization of CAS also adversely affect clinical outcomes. Melatonin is a pluripotent agent with potent anti-inflammatory, anti-oxidative, and neuroprotective properties. Although there is a shortage of direct clinical evidence demonstrating the benefits of melatonin in CAS patients, previous studies have shown that melatonin may be beneficial for patients with CAS in terms of reducing endothelial damage, stabilizing arterial plaque, mitigating the harm from CAS-related ischemic stroke and cerebral I/R injury, and alleviating the adverse effects of the related risk factors. Additional pre-clinical and clinical are required to confirm this speculation.     

Filling the Charge–Discharge Voltage Gap in Flexible Hybrid Zinc-Based Batteries by Utilizing a Pseudocapacitive Material

The high charge–discharge voltage gap is one of the main bottlenecks of zinc–air batteries (ZABs) because of the kinetically sluggish oxygen reduction/evolution reactions (ORR/OER) on the oxygen electrode side. Thus, an efficient bifunctional catalyst for ORR and OER is highly desired. Herein, honeycomb-like MnCo₂O_4.5 spheres were used as an efficient bifunctional electrocatalyst. It was demonstrated that both ORR and OER catalytic activity are promoted by Mn^IV-induced oxygen vacancy defects and multiple active sites. Importantly, the multivalent ions present in the material and its defect structure endow stable pseudocapacitance within the inactive region of ORR and OER; as a result, a low charge–discharge voltage gap (0.43 V at 10 mA cm⁻²) was achieved when it was employed in a flexible hybrid Zn-based battery. This mechanism provides unprecedented and valuable insights for the development of next-generation metal–air batteries.