Intrinsic SERS Fingerprints of Aptamer-Peptide Conjugates for Direct High-Specific Profiling Abnormal Protein Levels in Cancer Patients.

Surface-enhanced Raman spectroscopy (SERS) with ultrasensitive vibrational fingerprints enables quick identification and trace detection of various kinds of molecules. But proteins usually have low Raman cross sections and are difficult to generate recognizable signals in direct SERS detection. Recently, nucleic acid-peptide conjugates are emerging with great potential in structuring, assembling, catalyzing, sensing, etc., and the coupling of aptamers further enables superior biological recognition and programmability. Here, we develop the aptamer-peptide conjugates as a new kind of SERS probe for direct high-specific profiling abnormal protein levels in cancer patients. The aptamer conjugated with glutathione (GSH) functions as both the recognition element and the SERS reporters that can simultaneously generate SERS fingerprints of both peptides and nucleic acids. This kind of biocompatible probe appears to have excellent performance in high-salt environments and realizes rapid, simple, and multisignal detection of thrombin (TB). Data-driven soft independent modeling of class analogy (DD-SIMCA) is used to distinguish SERS profiles of actual blood samples and realize the identification and classification of cancer patients. Furthermore, the effect of low-temperature storage time on blood samples is analyzed by tracking the changes of SERS profiles; the results hint that plasma samples stored under 4 °C for more than 2 days could generate false negative results due to TB hydrolysis, which has important implications for clinical sample analysis. This kind of nucleic acid-peptide conjugate provides new ideas for SERS sensing strategy in the future.

Antifreezing Hydroxyl Monolayer of Small Molecules on a Nanogold Surface.

The rational design of ice recrystallization inhibition (IRI) materials is challenging due to the poor understanding of the IRI mechanism at the molecular level. Here we report several new findings about IRI. (1) A dense hydroxyl monolayer of small molecules, e.g. 6-aza-2-thiothymine (ATT), adsorbed on a nanogold surface was demonstrated, for the first time, to have IRI activity. Five structural analogues adsorbed on groups nanogold with outward hydroxyl or methyl were created to evidence the origin of IRI activity. (2) Their IRI mechanism is closely related to the density of hydroxyls on a nanogold surface. However, the hydrophobic interaction in our model is not essential for macroscopic IRI activity. (3) A molecular dynamics simulation elucidates the hydroxyl density dependent IRI trajectories underlying the experimental observations, and the radial distribution function reveals that the methyl even slightly hinders the formation of hydrogen bonding due to a hydrophobic interaction. This work sheds more light on the IRI mechanism that should help in the customization of novel IRI materials.

One-Dimensional Co-Carbonate Hydroxide@Ni-MOFs Composite with Super Uniform Core-Shell Heterostructure for Ultrahigh Rate Performance Supercapacitor Electrode.

The insufficient contact between two phases in the heterostructure weakens the coupling interaction effect, which makes it difficult to effectively improve the electrochemical performance. Herein, a Co-carbonate hydroxide@ Ni-metal organic frameworks (Co-CH@Ni-MOFs) composite with super uniform core-shell heterostructure is fabricated by adopting 1D Co-CH nanowires as structuredirecting agents to induce the coating of Ni-MOFs. Both experimental and theoretical calculation results demonstrate that the heterostructure plays a vital role in the high performance of the as-prepared materials. On the one hand, the construction of super uniform core-shell heterostructure can create a large number of interfacial active sites and take advantages of the electrochemical characteristics of each component. On the other hand, the heterostructure can increase the adsorption energy of OH- ions and promote the electrochemical activity for improving the reversible redox reaction kinetics. Based on the aforementioned advantages, the as-fabricated Co-CH@Ni-MOFs electrode exhibits a high specific capacity of 173.1 mAh g-1 (1246 F g-1 ) at 1 A g-1 , an ultrahigh rate capability of 70.3% at 150 A g-1 and excellent cycling stability with 90.1% capacity retention after 10 000 cycles at 10 A g-1 . This study may offer a versatile design for fabricating a MOFs-based heterostructure as energy storage electrodes.

Recent Advances in Self-Assembly and Application of Para-Aramids.

Poly(p-phenylene terephthalamide) (PPTA) is one kind of lyotropic liquid crystal polymer. Kevlar fibers performed from PPTA are widely used in many fields due to their superior mechanical properties resulting from their highly oriented macromolecular structure. However, the "infusible and insoluble" characteristic of PPTA gives rise to its poor processability, which limits its scope of application. The strong interactions and orientation characteristic of aromatic amide segments make PPTA attractive in the field of self-assembly. Chemical derivation has proved an effective way to modify the molecular structure of PPTA to improve its solubility and amphiphilicity, which resulted in different liquid crystal behaviors or supramolecular aggregates, but the modification of PPTA is usually complex and difficult. Alternatively, higher-order all-PPTA structures have also been realized through the controllable hierarchical self-assembly of PPTA from the polymerization process to the formation of macroscopic products. This review briefly summarizes the self-assembly methods of PPTA-based materials in recent years, and focuses on the polymerization-induced PPTA nanofibers which can be further fabricated into different macroscopic architectures when other self-assembly methods are combined. This monomer-started hierarchical self-assembly strategy evokes the feasible processing of PPTA, and enriches the diversity of product, which is expected to be expanded to other liquid crystal polymers.

A twin enrichment method based on dispersive liquid-liquid microextraction and field-amplified sample injection for the simultaneous determination of sulfonamides.

A twin enrichment method based on offline dispersive liquid-liquid microextraction (DLLME) coupled with online field-amplified sample injection (FASI) was developed for the simultaneous determination of four sulfonamide (SA) antibiotics, including sulfamethazine (SMZ), sulfamerazine (SMR), sulfadizine (SDZ) and sulfacetamide (SFA), in different environmental waters, followed by capillary electrophoresis (CE). Various parameters that affected the separation performance of CE and the enrichment efficiencies of DLLME and FASI were optimized in detail, and excellent CE separation was attained within 6 min. The DLLME-FASI-CE offered high sensitivity enrichment factors of 206, 166, 185 and 150 for SMZ, SMR, SDZ and SFA, respectively. Highly sensitive detection was realized with low limits of detection (LODs), which ranged from 2.0-23.0, 2.2-26.0 and 4.3-63.0 ng mL-1 in tap water, lake water and seawater, respectively, as well as limits of quantification (LOQs) within 6.0-63.0, 7.4-96.0 and 14.0-201.0 ng mL-1, respectively. Satisfactory recoveries in the range of 91-108% were obtained with the three spiked environmental water samples, and the relative standard deviations were from 1.09-7.45%. The simple effective twin enrichment method provided promising perspective for CE determination of SAs in complicated aqueous matrices, with rapidity, sensitivity, and accuracy.

Flexible black phosphorus ambipolar transistors, circuits and AM demodulator.

High-mobility two-dimensional (2D) semiconductors are desirable for high-performance mechanically flexible nanoelectronics. In this work, we report the first flexible black phosphorus (BP) field-effect transistors (FETs) with electron and hole mobilities superior to what has been previously achieved with other more studied flexible layered semiconducting transistors such as MoS2 and WSe2. Encapsulated bottom-gated BP ambipolar FETs on flexible polyimide afforded maximum carrier mobility of about 310 cm(2)/V·s with field-effect current modulation exceeding 3 orders of magnitude. The device ambipolar functionality and high-mobility were employed to realize essential circuits of electronic systems for flexible technology including ambipolar digital inverter, frequency doubler, and analog amplifiers featuring voltage gain higher than other reported layered semiconductor flexible amplifiers. In addition, we demonstrate the first flexible BP amplitude-modulated (AM) demodulator, an active stage useful for radio receivers, based on a single ambipolar BP transistor, which results in audible signals when connected to a loudspeaker or earphone. Moreover, the BP transistors feature mechanical robustness up to 2% uniaxial tensile strain and up to 5000 bending cycles.

Solution Blow Spinning of the Benzimidazole-Containing Aramid Nanofibers for Separators of Lithium-Ion Batteries.

Nanofibers based on high-performance polymers are much highlighted in recent studies toward advanced lithium-ion batteries. Herein, we demonstrate one scalable poly(ethylene oxide) (PEO)-assisted solution blow spinning strategy for the preparation of heterocyclic aramid (HA) nanofibers of poly(p-phenylene-benzimidazole-terephthalamide). The incorporation of PEO is essential to improve the spinnability of the HA solution achieved directly through the low-temperature-solution copolymerization process. Additionally, the flexible PEO with a strong H-bonding affinity is also utilized as the molecular zipper to adjust the pore size of the nanofiber membrane during the post-treatment process. The obtained membrane combines the good wettability of PEO to the liquid electrolytes, with outstanding mechanical strength, modulus, toughness, and environmental resistance of HA. The nonwoven separator membranes with a porosity of 83.6% exhibited excellent comprehensive performance, which could be seen not only on the high tensile strength (68.2 MPa), modulus (3.0 GPa), and toughness but also on the high thermal stability (Td > 405 °C) and flame retardancy, as well as the high electrolyte uptake (302.4%). The ion conductivity of the porous separators reached 0.83 mS/cm, with the bulk resistance dropping to 1/4 of the reference polypropylene separator. In the assembly of the Li/LiFePO4 half battery, the HA separators displayed improved discharge specific capacity and high retention in both rate capability and cycling tests, providing the potential industrial preparation for advanced lithium-ion batteries.

Gauge factor and stretchability of silicon-on-polymer strain gauges.

Strain gauges are widely applied to measure mechanical deformation of structures and specimens. While metallic foil gauges usually have a gauge factor slightly over 2, single crystalline silicon demonstrates intrinsic gauge factors as high as 200. Although silicon is an intrinsically stiff and brittle material, flexible and even stretchable strain gauges have been achieved by integrating thin silicon strips on soft and deformable polymer substrates. To achieve a fundamental understanding of the large variance in gauge factor and stretchability of reported flexible/stretchable silicon-on-polymer strain gauges, finite element and analytically models are established to reveal the effects of the length of the silicon strip, and the thickness and modulus of the polymer substrate. Analytical results for two limiting cases, i.e., infinitely thick substrate and infinitely long strip, have found good agreement with FEM results. We have discovered that strains in silicon resistor can vary by orders of magnitude with different substrate materials whereas strip length or substrate thickness only affects the strain level mildly. While the average strain in silicon reflects the gauge factor, the maximum strain in silicon governs the stretchability of the system. The tradeoff between gauge factor and stretchability of silicon-on-polymer strain gauges has been proposed and discussed.

Quantified instant conjugation of peptides on a nanogold surface for tunable ice recrystallization inhibition.

The adverse effects of recrystallization limit the application of cryopreservation in many fields. Peptide-based materials play an essential role in the antifreezing area because of their excellent biocompatibility and abundant ice-binding sites. Peptide-gold nanoparticle conjugates can effectively reduce time and material costs through metal-thiol interactions, but controlled modification remains an outstanding issue, which makes it difficult to elucidate the antifreezing effects of antifreeze peptides at different densities and lengths. In this study, we developed an instant peptide capping on gold nanoparticles with butanol-assisted dehydration and provided a controllable quantitative coupling within a certain range. This chemical dehydration makes it possible to fabricate peptide-gold nanoparticle conjugates in large batches at minute levels. Based on this, the influence of the peptide density and sequence length on the antifreezing behaviors of the conjugates was investigated. The results evidenced that the antifreezing property of the flexible peptide conjugated on a rigid core is related to both the density and length of the peptide. In a certain range, the density is proportional to the antifreeze, while the length is negatively correlated with it. We proposed a rapidly controllable method for synthesizing peptide-gold nanoparticle conjugates, which may provide a universal approach for the development of subsequent recrystallization-inhibiting materials.

Synthesis of the Ni2P-Co Mott-Schottky Junction as an Electrocatalyst to Boost Sulfur Conversion Kinetics and Application in Separator Modification in Li-S Batteries.

To overcome the shuttling effect and sluggish conversion kinetics of polysulfides, a large number of catalysts have been designed for lithium-sulfur (Li-S) batteries. Herein, a Mott-Schottky junction catalyst composed of Co nanoparticles and Ni2P was designed to improve polysulfide kinetics. Our investigations reveal the rearrangement of charges at the Schottky junction interface and the construction of the built-in electric field are crucial for lowering the activation energy of the dissolved Li2Sn reduction and Li2S nucleation reaction. Furthermore, a series of experimental and electrochemical tests were performed to demonstrate that the Schottky catalytic effect enhanced the synergistic catalytic effect. With a Ni2P-Co@CNT catalyst, the battery exhibits an initial specific capacity of 874 mAh g-1 at a rate of 4.0 C, and the decay rate per cycle is 0.049% in 700 cycles. Meanwhile, the battery shows 0.118% decay rate per cycle at 0.5 C in 100 cycles at a high sulfur loading of 10 mg cm-2. The Schottky heterojunction structure proposed here has been shown to have a good catalytic effect on the reduction of Li2Sn and nucleation of Li2S, which provides a profound guidance for efficient and rational catalyst design.

The Aramid-Coating-on-Aramid Strategy toward Strong, Tough, and Foldable Polymer Aerogel Films.

Aerogel has been much highlighted as an emerging lightweight thermal insulation material, but problems such as fragility, low strength, liquid permeability, and lack of flexibility greatly limit further applications. In this work, a facile aramid-coating-on-aramid (ACoA) method is demonstrated to fabricate all-aramid aerogel composite films for thermal insulation. The method started from the bottom-up synthesis of polymerization-induced para-aramid nanofibers (PANF), which were easily transformed into aerogel films through the vacuum-assisted filtration followed by the freeze-drying techniques. Then, the heterocyclic aramid (HA) solution prepared through the low-temperature-solution polycondensation was used as the coating to be applied onto the PANF aerogel films, and composite films of HA/PANF aerogel were simply achieved with HA contributed to the dense and continuous surface layer. The bulk HA film is of superior mechanical and thermal properties to those of the PANF film. Moreover, reliable interfacial interlocking structures were developed beneath the outermost surface via the interpenetration of the infiltrated HA with PANF network. The comprehensive result was the 15 times enhanced tensile strength, 33 times enhanced fracture toughness, the high thermal decomposition temperature, and the additional flexibility for the foldable films of HA/PANF aerogel. The sealing of the surface macropores greatly suppressed the surface chalking and high water absorption. However, the survival of the tiny pores inside the composite maintained the low enough level of the thermal conductivity to provide effective protections against high temperature not only in air but also under wet or even liquid conditions, suggesting the broader applications for thermal insulation.

Nanosheet-assembled NiCo-LDH hollow spheres as high-performance electrodes for supercapacitors.

Layered double hydroxides (LDHs) have been considered as favorable pseudocapacitive electrode materials for supercapacitors due to their tunable layered structure/compositions and low cost. Here, we report the NiCo-LDH hollow spheres prepared with Co-glycerate as the sacrificial template and cobalt source. The hollow spheres are assembled with frizzy NiCo-LDH nanosheets, where the hollow structure can inhibit agglomeration of the LDH nanosheets to expose more active sites and shorten the diffusion path of electrolyte ions. The prepared NiCo-LDH hollow spheres show a high specific capacitance of 1962 F g-1 at 1 A g-1 and good capacitance retention rate of 66.4 % at 30 A g-1. The asymmetric supercapacitors fabricated using NiCo-LDH hollow spheres as positive electrode yields a large energy density 62.9 Wh kg-1 at the power density of 0.8 kW kg-1. This research may develop a facile synthesis way to prepare LDH hollow spheres for supercapacitors.

Strategies of dispersive liquid-liquid microextraction for coastal zone environmental pollutant determination.

Coastal zone means the interface of land and sea, and therefore, environmental pollutants steaming from land-based activities (like manufactories) and sea-based activities (like shipping) are all existing in coastal zone. These pollutants usually have characteristics of low residues, complicated matrices, easy accumulation and so on, causing difficulty to detect coastal pollutants quickly and sensitively. It is imperative to perform effective sample preparation prior to instrumental analysis. Dispersive liquid-liquid microextraction (DLLME) has attracted significant research interest for sample preparation, owing to its high enrichment ability, low reagent/sample consumption, and wide analyte/matrix applicability, as well as robustness, simplicity, rapidity and inexpensiveness. Herein, we comprehensively review the recent advancements of DLLME technology and its analytical parameters including enrichment principles, extraction modes, and practical application; the emphasis is on novel mode-construction and representative coastal-environmental pollutants extraction. Construction strategies are highlighted by classifying DLLME into five major modes, according to extractant's types, including normal ones, low density solvents, ionic liquids, deep eutectic solvents and others. The coupling of DLLME with other extraction techniques like solid-phase extraction is also briefly introduced. The strengths and weaknesses of each strategy and its rationality are also elaborated. In addition, some typical applications of the different DLLME modes for the determination of organic compounds and heavy metals in coastal water, sediment, soil, and biota are summarized. The increasingly concerned green aspects and instrumentation of DLLME are presented, and finally, the challenges and perspectives of the DLLME for environmental analysis are proposed.

Macroscopic-Scale Preparation of Aramid Nanofiber Aerogel by Modified Freezing-Drying Method.

Aerogel has been widely known as a low-density and highly porous material and is closely connected with the complex processing methods, such as freeze-drying or supercritical drying. In this work, using the polymerization-induced aramid nanofiber (PANF) as a building block, we put forward a modified freezing-drying method for the high-efficiency preparation of all-para-aromatic-amide aerogels. In the preparation process, PANF hydrogel is first frozen at -18 °C and then dried at 20-150 °C for the formation of PANF aerogel. The PANF framework formed during the freezing process is crucial for the formation of the PANF aerogel. Moreover, the space-occupying effect of ice crystals is also helpful for the formation of the macroscopic pore structure in the aerogel. Aerogels with large size or well-controlled shape could be successfully obtained by this method. Through the variation of PANF concentration in the hydrogel and drying temperature, aerogels with different densities (20-185 mg/cm3) could be achieved, and the lowest density is reached at 150 °C, with the PANF concentration of 0.7%. The low-density PANF aerogels show high specific compressive strengths and low thermal conductivities, which are comparable to those resulting from the freeze-drying or supercritical drying method. Furthermore, the shrinkage phenomenon in the drying process could be skillfully utilized for the preparation of PANF aerogel-coated objects. The PANF aerogels could be applied as a thermal insulating material or shock absorption material in practical applications.

MXenes induced formation of Ni-MOF microbelts for high-performance supercapacitors.

For the sake of developing new energy storage devices for satisfying the energy needs of the modern society, we herein report an innovative MXene-induced strategy to synthesize Ti3C2Tx MXenes/Ni based metal-organic framework composites (Ti3C2Tx/Ni-MOFs) for high-performance supercapacitors. The two-dimensional (2D) MXenes with oxygen-containing groups on the surface can be used as structure-directing agents to tune the Ni-MOFs into 2D microbelts. The presence of MXenes cannot only improve conductivity of the composite but also provide additional electric double layer capacitance and faradaic pseudocapacitance. The 2D Ni-MOF microbelts can offer rich activity sites for the faradaic redox reactions and shorten the ion transport path. Taking advantages of synergistic effects of Ni-MOF microbelts and Ti3C2Tx MXenes, the prepared Ti3C2Tx/Ni-MOFs electrode shows a good electrochemical performance with 1124 F g-1 at the current density of 1 A g -1 and 62% rate capability at 20 A g -1. This work can offer a new insight to design 2D MOF belts as high-performance electrode materials for supercapacitors.

Shape-controlled synthesis of Ni-based metal-organic frameworks with albizia flower-like spheres@nanosheets structure for high performance supercapacitors.

Metal organic frameworks (MOFs) are considered as very promising positive electrode materials for supercapacitors. To achieve good electrochemical performance, in this work, we report a mixed-ligand approach to prepare modified Ni-MOF by using trimesic acid (BTC) as the modulator to partially replace the terephthalic acid (PTA) ligands. The introduction of BTC can induce the formation of nanosheets with inserted albizia flower-like spheres, where the nanowires on the albizia flower-like spheres can provide rich redox reaction sites and the "spacer" spheres between the layers can hinder the aggregation of the 2D nanosheets to provide fast transport pathways. Moreover, adsorption simulation shows that the adsorption energy of OH- on the mixed organic ligands is increased after introducing the BTC ligands, which may improve the reversible redox reaction kinetics in the electrode materials. The as-obtained albizia flower-like spheres@nanosheets structured Ni-MOF with the optimized amount of BTC exhibits a high capacitance of 920 F g-1 at 1 A g-1, good rate capability of 61% at 20 A g-1, and an excellent cycling stability in 6 M KOH electrolyte. This work may provide helpful guidance for controlling the structure and surface property of MOFs to improve the electrochemical performance for supercapacitors.

Clinical outcomes for 61 cases of hypopharyngeal cancer with synchronous esophageal cancer.

The aim of this research was to provide data from a single-center study of the treatment of synchronous hypopharyngeal cancer (HPC) and esophageal cancer (EC) with different treatment modalities. A total of 61 patients with synchronous HPC and EC were included in this study. Patients were treated with radiotherapy/chemoradiotherapy (28 cases), surgery (9 cases), palliative radiotherapy and/or chemotherapy (17 cases), or supportive care (7 cases). The median radiotherapy doses for EC and HPC in the radiotherapy/chemoradiotherapy group were 64.5 Gy (range, 0-70) and 70 Gy (range, 60-75.2), respectively. Seven patients in the surgery group received pharyngoesophagectomy with gastric pull-up reconstruction, and two received esophagectomy followed by radiotherapy at the hypopharynx. Cox proportional hazard analysis revealed that the outcome of active treatments, including surgery and radiotherapy/chemoradiotherapy, was better than that of conservative care. In survival analysis, patients in the surgery group tended to have a better 3-year overall survival rate than those in the radiotherapy/chemoradiotherapy group (55.6% vs 30.9%); however, this difference was not statistically different (P = 0.493). The two groups had similar 3-year progression-free survival rates (30.6% and 33.3%, P = 0.420). The current study suggested that radiotherapy/chemoradiotherapy should be considered as an important treatment modality in addition to surgery for synchronous HPC and EC.

Stretchable Tattoo-Like Heater with On-Site Temperature Feedback Control.

Wearable tissue heaters can play many important roles in the medical field. They may be used for heat therapy, perioperative warming and controlled transdermal drug delivery, among other applications. State-of-the-art heaters are too bulky, rigid, or difficult to control to be able to maintain long-term wearability and safety. Recently, there has been progress in the development of stretchable heaters that may be attached directly to the skin surface, but they often use expensive materials or processes and take significant time to fabricate. Moreover, they lack continuously active, on-site, unobstructive temperature feedback control, which is critical for accommodating the dynamic temperatures required for most medical applications. We have developed, fabricated and tested a cost-effective, large area, ultra-thin and ultra-soft tattoo-like heater that has autonomous proportional-integral-derivative (PID) temperature control. The device comprises a stretchable aluminum heater and a stretchable gold resistance temperature detector (RTD) on a soft medical tape as fabricated using the cost and time effective "cut-and-paste" method. It can be noninvasively laminated onto human skin and can follow skin deformation during flexure without imposing any constraint. We demonstrate the device's ability to maintain a target temperature typical of medical uses over extended durations of time and to accurately adjust to a new set point in process. The cost of the device is low enough to justify disposable use.

Large-Area Monolayer MoS2 for Flexible Low-Power RF Nanoelectronics in the GHz Regime.

Flexible synthesized MoS2 transistors are advanced to perform at GHz speeds. An intrinsic cutoff frequency of 5.6 GHz is achieved and analog circuits are realized. Devices are mechanically robust for 10,000 bending cycles.

Electromechanical cardioplasty using a wrapped elasto-conductive epicardial mesh.

Heart failure remains a major public health concern with a 5-year mortality rate higher than that of most cancers. Myocardial disease in heart failure is frequently accompanied by impairment of the specialized electrical conduction system and myocardium. We introduce an epicardial mesh made of electrically conductive and mechanically elastic material, to resemble the innate cardiac tissue and confer cardiac conduction system function, to enable electromechanical cardioplasty. Our epicardium-like substrate mechanically integrated with the heart and acted as a structural element of cardiac chambers. The epicardial device was designed with elastic properties nearly identical to the epicardial tissue itself and was able to detect electrical signals reliably on the moving rat heart without impeding diastolic function 8 weeks after induced myocardial infarction. Synchronized electrical stimulation over the ventricles by the epicardial mesh with the high conductivity of 11,210 S/cm shortened total ventricular activation time, reduced inherent wall stress, and improved several measures of systolic function including increases of 51% in fractional shortening, ~90% in radial strain, and 42% in contractility. The epicardial mesh was also capable of delivering an electrical shock to terminate a ventricular tachyarrhythmia in rodents. Electromechanical cardioplasty using an epicardial mesh is a new pathway toward reconstruction of the cardiac tissue and its specialized functions.