S-Shaped Helical Singlet Diradicaloid and Its Transformation to Circumchrysene via a Two-Stage Cyclization.

Polycyclic hydrocarbons with diradical and polyradical characters usually display unique reactivities in ring-cyclization reactions. However, such reactions are rarely used to construct π-extended polycyclic aromatic hydrocarbons. Here, we describe the synthesis of an S-shaped doubly helical singlet diradicaloid compound and its facile transformation into an unprecedented circumchrysene via a two-stage ring cyclization, which includes: (1) an eletrocylization from diradicaloid precursor and (2) a Scholl reaction. The reaction mechanism was investigated through in situ spectroscopic studies, assisted by theoretical calculations. This reaction sequence yields an optically resolved π-extended [5]helicene derivative with a fluorescence quantum yield up to 85% and a circularly polarized luminescence brightness up to 6.05 M-1 cm-1 in the far-red to near-infrared regions. This sequence also yielded a highly delocalized circumchrysene molecule, exhibiting large electron delocalization, moderate fluorescence quantum yield, and multistage redox properties.

Bioinspired Hierarchical Multi-Protective Membrane for Extreme Environments via Co-Electrospinning-Electrospray Strategy.

Extreme environments can cause severe harm to human health, and even threaten life safety. Lightweight, breathable clothing with multi-protective functions would be of great application value. However, integrating multi-protective functions into nanofibers in a facile way remains a great challenge. Here, a one-step co-electrospinning-electrospray strategy is developed to fabricate a superhydrophobic multi-protective membrane (S-MPM). The water contact angle of S-MPM can reach up to 164.3°. More importantly, S-MPM can resist the skin temperature drop (11.2 °C) or increase (17.2 °C) caused by 0 °C cold or 70 °C hot compared with pure electrospun membrane. In the cold climate (-5 °C), the anti-icing time of the S-MPM is extended by 2.52 times, while the deicing time is only 1.45 s due to the great photothermal effect. In a fire disaster situation, the total heat release and peak heat release rate values of flame retarded S-MPM drop sharply by 24.2% and 69.3%, respectively. The S-MPM will serve as the last line of defense for the human body and has the potential to trigger a revolution in the practical application of next-generation functional clothing.

Perforating cutaneous vessels: A key feature of acupoints - Anatomical evidence from five-Shu acupoints in the upper limbs.

Acupuncture has been proven an effective clinical treatment for numerous pathological conditions and malfunctions. However, substantial anatomical evidence for acupuncture points (APs) and meridians is still lacking, so the location of APs is relatively subjective and understanding of the biological mechanisms of acupuncture is limited. All these problems hinder the clinical applications and worldwide acceptance of acupuncture. Our long-term microsurgery experience has indicated that Perforating Cutaneous Vessels (PCVs) are highly relevant to APs but the anatomical evidence is insufficient. To address this lack, two specimens of fresh adult human upper limbs were dissected using an advanced vascular perfusion-fixation method and then examined. The results show that all 30 five-Shu APs in the upper limbs have corresponding PCVs. Both specimens showed a 100% coincidence rate between APs and PCVs, indicating that PCVs could be critical anatomical features of APs. This study also provides an anatomical basis for locating APs objectively via preliminary detection of PCVs. The findings could lead to a better theoretical understanding of mechanisms of acupuncture and the essence of meridians.

Second Near-Infrared (NIR-II) Window for Imaging-Navigated Modulation of Brain Structure and Function.

For a long time, optical imaging of the deep brain with high resolution has been a challenge. Recently, with the advance in second near-infrared (NIR-II) bioimaging techniques and imaging contrast agents, NIR-II window bioimaging has attracted great attention to monitoring deeper biological or pathophysiological processes with high signal-to-noise ratio (SNR) and spatiotemporal resolution. Assisted with NIR-II bioimaging, the modulation of structure and function of brain is promising to be noninvasive and more precise. Herein, in this review, first the advantage of NIR-II light in brain imaging from the interaction between NIR-II and tissue is elaborated. Then, several specific NIR-II bioimaging technologies are introduced, including NIR-II fluorescence imaging, multiphoton fluorescence imaging, and photoacoustic imaging. Furthermore, the corresponding contrast agents are summarized. Next, the application of various NIR-II bioimaging technologies in visualizing the characteristics of cerebrovascular network and monitoring the changes of the pathology signals will be presented. After that, the modulation of brain structure and function based on NIR-II bioimaging will be discussed, including treatment of glioblastoma, guidance of cell transplantation, and neuromodulation. In the end, future perspectives that would help improve the clinical translation of NIR-II light are proposed.

Super low-frequency electric field measurement based on Rydberg atoms.

We demonstrate the measurement of super low-frequency electric field using Rydberg atoms in an atomic vapor cell with inside parallel electrodes, thus overcoming the low-frequency electric-field-screening effect at frequencies below a few kHz. Rydberg electromagnetically induced transparency (EIT) spectra involving 52D5/2 state is employed to measure the signal electric field. An auxiliary DC field is applied to improve the sensitivity. A DC Stark map is demonstrated, where the utilized 52D5/2 exhibits mj = 1/2, 3/2, 5/2 Stark shifts and splittings. The mj = 1/2 state is employed to detect the signal field because of its larger polarizability than that of mj = 3/2, 5/2. Also, we show that the strength of the spectrum is dependent on the angle between the laser polarizations and the electric field. With optimization of the applied DC field to shift the mj = 1/2 Rydberg energy level to a high sensitivity region and the laser polarizations to obtain the maximum mj = 1/2 signal, we achieve the detection of the signal electric field with a frequency of 100 Hz down to 214.8 µV/cm with a sensitivity of 67.9 µV cm-1Hz-1/2, and the linear dynamic range is over 37 dB. Our work extends the measurement frequency of Rydberg sensors to super low frequency with high sensitivity, which has the advantages of high sensitivity and miniaturization for receiving super low frequency.

Rational Construction of a Triple-Phase Reaction Zone Using CuO-Based Heterostructure Nanoarrays for Enhanced Water Oxidation Reaction.

The development of high-efficiency oxygen evolution reaction (OER) electrocatalysts for the production and conversion of clean energy is paramount yet also full of challenges. Herein, we proposed a simple and universal method to precisely fabricate the hierarchically structured CuO/TMOs loaded on Cu foil (CuO/TMOs/CF) (TMO represents Mn3O4, NiO, CoO, and CuO) nanorod-array electrodes as a highly active and stable OER electrocatalyst, employing Cu(OH)2/CF as a self-sacrificing template by the subsequent H2O2-induced chemical deposition (HiCD) and pyrolysis process. Taking CuO/Mn3O4/CF as an example, we systematically investigated its structure-performance relationship via experimental and theoretical explorations. The enhanced OER activity can be ascribed to the rational design of the nanoarray with multiple synergistic effects of abundant active sites, excellent electronic conductivity of the metallic Cu foil substrate, strong interface charge transfer, and quasi-superhydrophilic/superaerophobic property. Consequently, the optimal CuO/Mn3O4/CF presents an overpotential of 293 mV to achieve a current density of 20 mA cm-2 in 1.0 M KOH media, comparable to that of commercial RuO2 (282 mV), delivering excellent durability by the electrolysis of water at a potential of around 1.60 V [vs reversible hydrogen electrode (RHE)] without evident degeneration. This work might offer a feasible scheme for developing a hybrid nanoarray OER electrocatalyst via regulating electron transportation and mass transfer.

Accuracy analysis of traditional acupoint location and the coincidence of cutaneous arterial perforators and acupoints.

Several reports have shown a coincidence relationship between perforators and acupoints. However, there have been few previous reports of objective experimental methods to verify the reliability of the accuracy of acupoint location (APL) with nearby perforators. This research aimed to determine the internal agreement of the APL of five acupuncturists and to analyze the coincidence rate of acupoints with nearby perforators. Three two healthy volunteers were recruited with the inclusion and exclusion criteria. Three TCM clinical physicians determined acupoints in areas of the lower limb of participants. Two microsurgeons sketched corresponding regions based on the most common skin flap operation sites, located bone markers, and drew the skin flap axis. Doppler ultrasound was used to mark the perforator point and the distances measured for both points. There is no significant difference in the distance between the acupoints and perforators localization in different groups, and there are significant differences between the angle formed by acupoints and penetrators in all groups. All the points located by the traditional Chinese medicine (TCM) therapists are distributed around the dot. The distance between the coordinate point (A-B) of Wenliu (LI7) localization is the largest, reaching 16.6 mm. The accuracy of the acupoint location of each physician is limited by the clinical experience of physicians, and the difference among them is significant. There is a certain correspondence between the location of acupoints and perforators, which needs further studies to confirm.

Biodegradable Dual-Network Cellulosic Composite Bioplastic Metafilm for Plastic Substitute.

With the escalating environmental and health concerns over petroleum-based plastics, sustainable and biodegradable cellulosic materials are a promising alternative to plastics, yet remain unsatisfied properties such as fragility, inflammability and water sensitivity for practical usage. Herein, we present a novel dual-network design strategy to address these limitations and fabricate a high-performance cellulosic composite bioplastic metafilm with the exceptional mechanical toughness (23.5 MJ m-3 ), flame retardance, and solvent resistance by in situ growth of cyclotriphosphazene-bridged organosilica network within bacterial cellulose matrix. The phosphorus, nitrogen-containing organosilica network, verified by the experimental and theoretical results, plays a triple action on significantly enhancing tensile strength, toughness, flame retardance and water resistance of composite bioplastic metafilm. Furthermore, cellulosic bioplastic composite metafilm demonstrates a higher maximum usage temperature (245 °C), lower thermal expansion coefficient (15.19 ppm °C-1 ), and better solvent resistance than traditional plastics, good biocompatibility and natural biodegradation. Moreover, the composite bioplastic metafilm have a good transparency of average 74 % and a high haze over 80 %, which can serve as an outstanding substrate substitute for commercial polyethylene terephthalate film to address the demand of flexible ITO films. This work paves a creative way to design and manufacture the competitive bioplastic composite to replace daily-used plastics.

Stable Crystalline Nanohoop Radical and Its Self-Association Promoted by van der Waals Interactions.

A stable nanohoop radical (OR3) combining the structures of cycloparaphenylene and an olympicenyl radical is synthesized and isolated in the crystalline state. X-ray crystallographic analysis reveals that OR3 forms a unique head-to-tail dimer that further aggregates into a one-dimensional chain in the solid state. Variable-temperature NMR and concentration-dependent absorption measurements indicate that the π-dimer is not formed in solution. An energy decomposition analysis indicates that van der Waals interactions are the driving force for the self-association process, in contrast with other olympicenyl derivatives that favor π-dimerization. The physical properties in solution phase have been studied, and the stable cationic species obtained by one-electron chemical oxidation. This study offers a new molecular design to modulate the self-association of organic radicals for overcoming the spin-Peierls transition, and to prepare novel nanohoop compounds with spin-related properties.

Symmetry-Broken Intermolecular Charge Separation of Cationic Radicals.

A quadrupolar compound Pyr-BA with two pyrrole-type nitrogen atoms doped externally was prepared in this work. In high contrast with other π ionic radicals, its cationic radical Pyr-BA⋅+ undergoes unusual symmetry-broken charge separation (SB-CS), generating the mixed valence complex of Pyr-BA+1-q ⋅⋅⋅Pyr-BA+1+q , where q is the degree of charge transfer. Variable-temperature (VT) single-crystal analysis, absorption and EPR experiments all confirmed that aggregation and lower temperature would help to facilitate this SB-CS process. Gibbs energy calculations and gauge-including magnetically induced current simulation both validate that, for Pyr-BA⋅+ , SB-CS behavior is more favorable than the conventional dimerization mode. To the best of our knowledge, this is the first study that shows solid single-crystal evidence for spontaneous SB-CS between identical ionic radicals. Such a unique phenomenon is of great significance both in terms of fundamental aspects and uncharted material science.

π-Extended Doublet Open-Shell Graphene Fragments Exhibiting One-Dimensional Chain Stacking.

The hitherto elusive benzo[c]anthanthrenyl radical derivatives composed of seven fused six-membered rings are synthesized and isolated in the crystalline form, representing a laterally π-extended doublet open-shell graphene fragment compared to the phenalenyl and olympicenyl radical structures. X-ray crystallographic analysis revealed one-dimensional chain stacking with relatively close intermolecular contacts, which is an important precondition for achieving single-component conductors. The magnetic, optical, and redox properties are investigated in the solution phase. In combination with the good stability, such open-shell molecular systems have potentials as functional electronic materials.

Rydberg atom-based AM receiver with a weak continuous frequency carrier.

We demonstrate an atom-based amplitude-modulation (AM) receiver for digital communication with a weak continuous frequency carrier using a Rydberg AC Stark effect in a vapor cell and achieve the operating carrier frequency continuously from 0.1 GHz to 5 GHz at a single Rydberg state. A strong local oscillator (LO) field ELO acts as a gain to shift the Rydberg level to a high sensitivity region, and a weak carrier field ECarr keeps the same frequency with the LO field. The digital baseband signals are encoded onto the ECarr using the amplitude modulation technique with the different modulation frequency. The response of Rydberg atom to the baseband signal is probed via a Rydberg electromagnetically induced transparency (EIT). The measured instantaneous bandwidth of the system is about 230 kHz. To demonstrate the performance of our system for an actual communication, we consider a color image as an example, the received image displays that the bit error rate (BER) is less than 5% when the maximum data transfer rate is about 238 kbps. Meanwhile, our system shows the weak carrier field of ECarr ≥ 13.52 µV/cm can be used for the practical communication with BER less than 5%. Our works break the limitation that EIT-AT based atomic receivers only operate at the near resonant frequencies of the Rydberg transitions, making this emerging of quantum technology close to the practical application with high sensitivity and broad bandwidth.

Fiber-in-Tube Design of Co9 S8 -Carbon/Co9 S8 : Enabling Efficient Sodium Storage.

The sodium-ion battery is a promising battery technology owing to its low price and high abundance of sodium. However, the sluggish kinetics of sodium ion makes it hard to achieve high-rate performance, therefore impairing the power density. In this work, a fiber-in-tube Co9 S8 -carbon(C)/Co9 S8 is designed with fast sodiation kinetics. The experimental and simulation analysis show that the dominating capacitance mechanism for the high Na-ion storage performance is due to abundant grain boundaries, three exposed layer interfaces, and carbon wiring in the design. As a result, the fiber-in-tube hybrid anode shows a high specific capacity of 616 mAh g-1 after 150 cycles at 0.5 A g-1 . At 1 A g-1 , a capacity of ca. 451 mAh g-1 can be achieved after 500 cycles. More importantly, a high energy density of 779 Wh kg-1 and power density of 7793 W kg-1 can be obtained simultaneously.

Self-fitting shape memory polymer foam inducing bone regeneration: A rabbit femoral defect study.

Although tissue engineering has been attracted greatly for healing of critical-sized bone defects, great efforts for improvement are still being made in scaffold design. In particular, bone regeneration would be enhanced if a scaffold precisely matches the contour of bone defects, especially if it could be implanted into the human body conveniently and safely. In this study, polyurethane/hydroxyapatite-based shape memory polymer (SMP) foam was fabricated as a scaffold substrate to facilitate bone regeneration. The minimally invasive delivery and the self-fitting behavior of the SMP foam were systematically evaluated to demonstrate its feasibility in the treatment of bone defects in vivo. Results showed that the SMP foam could be conveniently implanted into bone defects with a compact shape. Subsequently, it self-matched the boundary of bone defects upon shape-recovery activation in vivo. Micro-computed tomography determined that bone ingrowth initiated at the periphery of the SMP foam with a constant decrease towards the inside. Successful vascularization and bone remodeling were also demonstrated by histological analysis. Thus, our results indicate that the SMP foam demonstrated great potential for bone regeneration.

Dual-channel extraordinary ultraviolet transmission through an aluminum nanohole array.

Ultraviolet (UV) surface plasmon (SP) has distinct applications in UV filters, high-density optical storage, spectral enhancement, optical detectors, and nanolithography, which are closely related to plasmon-induced extraordinary optical transmission (EOT). However, such EOT in the UV region has not been the subject of detailed research. We report UV transmission based on theoretical research using the finite-difference time-domain method, by modulating the Al thickness, hole size, array periodicity, and SiO2 overlayer thickness. It is notable that we can obtain dual-channel UV transmission peaks with excellent qualities such as high transmissivity, zero cross-talk, narrow bandwidth, and perfect symmetry, by optimizing the parameters. The UV transmission peaks have been discovered to non-monotonously shift with increasing hole size. Although array periodicity has great influence on the transmission peak position, the peak energy in the UV region is much less than the value predicted by the well-known periodicity-related surface plasmon polariton (SPP) wavelength equation; the energy discrepancy in the UV region can reach above 20%, which is much larger than the value (typically 4%) in the visible-infrared region. Furthermore, the SiO2 overlayer may significantly modify the transmission properties. The Al nanohole arrays have also been found to exhibit distinct multi-band UV electric field enhancement properties with special interface effect and size effect. Such extraordinary dual-channel UV transmission with zero cross-talk, based on a very simple Al nanohole array, has promising application in dual-channel UV filters, high-density optical storage, and plasmon-enhanced fluorescence/Raman spectroscopy, which generally involves two wavebands (writing/reading storage or exciting/emission wavelengths). This study is expected to broaden our fundamental understanding of the UV EOT phenomenon, and provide references for experimental research and application of deep-UV and near-UV-related dual-band plasmonic devices.

Interband π plasmon of graphene: strong small-size and field-enhancement effects.

The interband π plasmon of graphene has energy corresponding to the ultraviolet (UV) wave band, and hence is promising for UV nanophotonics and nanooptoelectronics. However, its special size effect and electric field-enhancement effect have not been well understood. Here, we have investigated the far-field optical extinction and near-field enhancement features of the interband π plasmon in a graphene nanodisk using discrete dipole approximation and finite-difference time-domain methods. Very interestingly, it has been found that the in-plane (transverse mode) optical extinction peak of monolayer graphene firstly significantly red shifts with increasing diameter, but then tends to a saturation value when the diameter is above 20 nm, showing a strong small-size-sensitive effect. Furthermore, the transverse mode optical extinction peak obviously blue shifts with increasing thickness when the thickness is relatively small. Significantly, the corresponding local electric field enhancement factor produced by the plasmon, which can be found to be as large as several tens, firstly increases with the increase of the size and then reaches a maximum value at only several nanometers in size. Such an ultrasmall-size-sensitive plasmon in the UV region endows graphene dots with new promising potential uses in ultrasmall photo-electric devices and nanoantennas, and in UV enhancers.

Hydrogen-bonding interactions in hard segments of shape memory polyurethane: toluene diisocyanates and 1,6-hexamethylene diisocyanate. A theoretical and comparative study.

In this study, the hydrogen-bonding interactions of three widely used diisocyanate-based hard-segment (HS) models in polyurethane, 2,4-toluenediisocyanate-methanol (2,4-TDI-MeOH), 2,6-toluenediisocyanate-methanol (2,6-TDI-MeOH), and 1,6-hexamethylenediisocyanate-methanol (HDI-MeOH), were investigated theoretically by density functional theory (DFT). The B3LYP/6-31G* method was used to calculate the equilibrium structures, Mulliken charges, hydrogen-bonding energies, and infrared (IR) spectra, in good agreement with previous experimental data. The HS models with benzene ring have much longer hydrogen bonds (HB), due to steric hindrance of benzene ring, whereas the aliphatic model forms much shorter hydrogen bonds. Different positions of the methyl group on the benzene ring for 2,4-TDI-MeOH and 2,6-TDI-MeOH result in different types of hydrogen bonds with various strengths. The style of hydrogen bonding for HDI-MeOH is more flexible due to simple aliphatic chemical structure without the benzene ring. The charge transfer on atoms N, H, and O involved in hydrogen bonding occurs with the forming of a hydrogen bond. The hydrogen bonding of 2,4-TDI-MeOH is much stronger than the others, and 2,6-TDI-MeOH froms the weakest hydrogen bonds. This study can supply guidance for the selection of a hard segment in the design of polyurethane and in-depth understanding of the hydrogen-bonding mechanism in the hard segments of polyurethane.

Fluid Unidirectional Transport Induced by Structure and Ambient Elements across Porous Materials: From Principles to Applications.

Spontaneous or nonspontaneous unidirectional fluid transport across multidimension can occur under specific structural designs and ambient elements for porous materials. While existing reviews have extensively summarized unidirectional fluid transport on surfaces, there is an absence of literature summarizing fluid's unidirectional transport across porous materials. This review introduces wetting phenomena observed on natural biological surfaces or porous structures. Subsequently, it offers an overview of diverse principles and potential applications in this field, emphasizing various physical and chemical structural designs (surface energy, capillary size, topographic curvature) and ambient elements (underwater, under oil, pressure, and solar energy). Applications encompass moisture-wicking fabric, sensors, skincare, fog collection, oil-water separation, electrochemistry, liquid-based gating, and solar evaporators. Additionally, significant principles and formulas from various studies are compelled to offer readers valuable references. Simultaneously, potential advantages and challenges are critically assessed in these applications and the perspectives are presented.

Efficacy of knee osteoarthritis by use of laser acupuncture: A systematic review and meta-analysis.

BACKGROUND: Previous studies need to be aggregated and updated. We aim to assess the efficacy of laser acupuncture (LA) in knee osteoarthritis (OA) through a meta-analysis. METHODS: Electronic databases were searched for studies investigating laser acupuncture's efficacy in managing OA. Data were collected from the beginning of each database to 2022 (up to March). The "WOMAC total score," "WOMAC stiffness score," "WOMAC pain score," "WOMAC physical function score," and "VAS score" were the key outcomes of interest. The Der Simonian-Laird method for random effects was used. RESULTS: Twenty-five randomized controlled clinical trials met our criteria and were included (2075 patients). Comparisons of interest is the LA versus Sham LA (efficacy), LA versus. A (Acupuncture) (comparative effectiveness), LA combined with A versus A (effectiveness as an adjunct), and any other research used LA in their treatment. Laser irradiation is effective in patients with Knee OA. LA is also effective and has almost the same outcome as laser irradiation. LA can achieve almost the same effect as manual acupuncture, even better than acupuncture in some studies. CONCLUSION: Laser acupuncture is more or less effective in patients with OA; better efficacy will be achieved under appropriate laser parameters (810 nm, 785 nm) in the LA versus Sham LA group. Many studies have diverse results, possibly due to unstaged analysis of patients' disease, inappropriate selection of acupoints, lack of remote combined acupoints, and unreasonable laser parameters. Furthermore, a combination of acupoints was found to be more effective, which aligns with the combined-acupoints application of traditional Chinese medicine.

Recent advances of electrospun strategies in topical products encompassing skincare and dermatological treatments.

As the potential applications of electrospinning in healthcare continue to be explored, along with advancements in industrial-scale solutions and the emergence of portable electrospinning devices, some researchers have explored electrospinning technology in topical products, including its application in skincare, such as facial masks, beauty patches, sunscreen, and dermatological treatments for conditions like atopic dermatitis, psoriasis, acne, skin cancer, etc. In this review, we first outline the fundamental principles of electrospinning and provide an overview of existing solutions for large-scale production and the components and functionalities of portable spinning devices. Based on the essential functionalities required for skincare products and the mechanisms and treatment methods for the aforementioned dermatological diseases, we summarize the potential advantages of electrospinning technology in these areas, including encapsulation, sustained release, large surface area, and biocompatibility, among others. Furthermore, considering the further commercialization and clinical development of electrospinning technology, we offer our insights on current challenges and future perspectives in these areas, including issues such as ingredients, functionality, residue concerns, environmental impact, and efficiency issues.