Microbial production of sulfur-containing amino acids using metabolically engineered Escherichia coli.

L-Cysteine and L-methionine, as the only two sulfur-containing amino acids among the canonical 20 amino acids, possess distinct characteristics and find wide-ranging industrial applications. The use of different organisms for fermentative production of L-cysteine and L-methionine is gaining increasing attention, with Escherichia coli being extensively studied as the preferred strain. This preference is due to its ability to grow rapidly in cost-effective media, its robustness for industrial processes, the well-characterized metabolism, and the availability of molecular tools for genetic engineering. This review focuses on the genetic and molecular mechanisms involved in the production of these sulfur-containing amino acids in E. coli. Additionally, we systematically summarize the metabolic engineering strategies employed to enhance their production, including the identification of new targets, modulation of metabolic fluxes, modification of transport systems, dynamic regulation strategies, and optimization of fermentation conditions. The strategies and design principles discussed in this review hold the potential to facilitate the development of strain and process engineering for direct fermentation of sulfur-containing amino acids.

An energy-free strategy to elevate anti-icing performance of superhydrophobic materials through interfacial airflow manipulation.

Superhydrophobic surfaces demonstrate excellent anti-icing performance under static conditions. However, they show a marked decrease in icing time under real flight conditions. Here we develop an anti-icing strategy using ubiquitous wind field to improve the anti-icing efficiency of superhydrophobic surfaces during flight. We find that the icing mass on hierarchical superhydrophobic surface with a microstructure angle of 30° is at least 40% lower than that on the conventional superhydrophobic plate, which is attributed to the combined effects of microdroplet flow upwelling induced by interfacial airflow and microdroplet ejection driven by superhydrophobic characteristic. Meanwhile, the disordered arrangement of water molecules induced by the specific 30° angle also raises the energy barriers required for nucleation, resulting in an inhibition of the nucleation process. This strategy of microdroplet movement manipulation induced by interfacial airflow is expected to break through the anti-icing limitation of conventional superhydrophobic materials in service conditions and can further reduce the risk of icing on the aircraft surface.

The roles of undercooling degree and materials surface configuration in the growth mechanism of ice layer caused by micro-droplets.

Effect mechanisms of the undercooling degree and the surface configuration on the ice growth characteristics were revealed under micro-droplets icing conditions. Preferential ice crystals appear firstly on the surfaces due to the randomness of icing, and obtain growth advantages to form protruding structures. Protruding structures block the incoming droplets from contacting the substrates, causing voids around the structures. The undercooling degree mainly affects the density and the growth rate of preferential ice crystals. With the increase of undercooling degree, the preferential ice crystals have higher density and growth rate, resulting in stronger growth advantage and higher porosity. The surface configuration affects the growth mode, and the ice layer grows with uniform mode, spreading mode and structure-induced mode on the aluminum, smooth Polytetrafluoroethylene (PTFE) and rough PTFE surface respectively, causing the needle-like, ridge-like and cluster-like ice crystals. The rough structures effectively improve the porosity of the ice layer, which is beneficial for optimizing the icephobic property of the materials. This paper provides important theoretical guidance for the design of subsequent icephobic materials.

Spontaneous Transport Mechanics of Water Droplets under a Synergistic Action of Designed Pattern and Non-Wetting Gradient.

The controllable spontaneous transport of water droplets on solid surfaces has a broad application background in daily life. Herein, a patterned surface with two different non-wetting characteristics was developed to control the droplet transport behavior. Consequently, the patterned surface exhibited great water-repellant properties in the superhydrophobic region, and the water contact angle reached 160° ± 0.2°. Meanwhile, the water contact angle on the wedge-shaped hydrophilic region dropped to 22° after UV irradiation treatment. On this basis, the maximum transport distance of water droplets could be observed on the sample surface with a small wedge angle of 5° (10.62 mm), and the maximum average transport velocity of droplets was obtained on the sample surface with a large wedge angle of 10° (218.01 mm/s). In terms of spontaneous droplet transport on an inclined surface (4°), both the 8 µL droplet and 50 µL droplet could move upward against gravity, which showed that the sample surface possessed an obvious driving force for droplet transport. Surface non-wetting gradient and the wedge-shaped pattern provided unbalanced surface tension to produce the driving forces in the process of droplet transport, and the Laplace pressure as well is produced inside the water droplet during this process. This work provides a new strategy to develop a patterned superhydrophobic surface for droplet transport.

Role of Molecular Chains Arrangement and Surface Energy State in the Low Ice Adhesion on Poly(tetrafluoroethylene).

The relation between polymer molecular chains arrangement and ice adhesion was studied at the molecular scale, and the energy states of water molecules on the poly(tetrafluoroethylene) surface were analyzed to explain the energy essence of ice adhesion. The ice adhesion on crystalline poly(tetrafluoroethylene) displayed a clear anisotropy phenomenon. Further research proved that the energy states of water molecules along the vertical direction of the molecular chains fluctuated regularly, and the water molecules in gaps between molecular chains were in the energy troughs, leading to the formation of energy traps. Water molecules needed more energy from outside to escape the energy traps, causing additional resistance to the ice movement and obvious increase of ice adhesion. Therefore, ice adhesion was closely related to the distribution of energy traps in the direction of ice removing, which mainly depended on the possibility of molecular chains perpendicularly arranged in the direction of ice removing.

Rationally Regulating the Mechanical Performance of Porous PDMS Coatings for the Enhanced Icephobicity toward Large-Scale Ice.

Ice accumulation on various surfaces in low-temperature and high-humidity environments is still a major challenge for several engineering applications. Herein, we fabricated a kind of PDMS coating with the introduction of porous structures under the surface by a two-step curing and phase separation method. The coatings with no further surface modification showed good hydrophobicity and icephobicity, and the typical ice adhesion strength was down to 40 kPa with a water contact angle of 116.5°. More than that, the porous PDMS coatings showed extraordinary icephobicity, especially toward large-scale ice (>10 cm2). In this case, the large-scale ice layer can be rapidly removed under a small external deicing force in a form of interface crack propagation rather than whole direct fracture. It was confirmed that by regulating the pore size and porosity of PDMS coatings properly, the stiffness mismatch between coatings and ice can be controlled to induce the initiation of interfacial cracks. On this basis, under the condition of a large-scale icing area, a small external deicing force can cause an increased surface stress concentration, and the formed interface cracks can propagate quickly, resulting in the ice layer falling off easily. In addition, under the influence of the size effect, ice can be removed without an additional force, and the minimum external force (per unit width) can be only 60 N/cm. This paper proposes that prefabricating a large number of microcracks at the interface can significantly weaken the bonding between ice and coatings, that is, reduce the fracture toughness. The new coatings have a remarkable effect toward large-scale icing.

Delayed initiation of radiation therapy is associated with inferior outcomes for breast cancer patients with hormone receptor-negative tumors after breast-conserving surgery.

BACKGROUND: To investigate whether the interval between adjuvant chemotherapy (CT) completion and postoperative radiation therapy initiation (ICR) after breast-conserving surgery (BCS) affects ipsilateral breast tumor recurrence (IBTR) or survival. METHODS: All women who were diagnosed with invasive breast cancer and underwent BCS between 2005 and 2014 were included. In total, 1,472 patients underwent adjuvant CT followed by postoperative radiation therapy (RT) (CT+), whereas 402 patients received postoperative RT alone (CT-). Analyses were stratified by ICR and the interval between surgery and the initiation of postoperative RT (ISR) in these two cohorts. The cutoff points for treatment delay were 47 days in the CT+ cohort and 69 days in the CT- cohort. IBTR, local-regional failure (LRF), disease-free survival (DFS), and overall survival (OS) were assessed through Kaplan-Meier (K-M) analysis. Univariate and multivariate regression analyses were performed to determine the prognostic factors of survival outcomes. RESULTS: The median follow-up duration was 56 months. There was an association between a delay in ICR and an increase in IBTR in the CT+ group (P=0.014 for intervals ≤47 vs. >47 days). This association was confirmed by multivariate analyses [hazard ratio (HR) of 2.766; P=0.046] in the hormone receptor-negative subgroup. The 5-year cumulative incidence rates of IBTR were 1.3% and 3.3% (≤47 vs. >47 days, respectively) in the CT+ cohort. For patients in the CT- cohort, a longer delay of initiation of postoperative RT (≤69 vs. >69 days) significantly decreased DFS (HR of 6.430; P=0.002). The 5-year cumulative incidence rates of disease recurrence were 3.0% for RT starting ≤69 days after surgery and 12.6% for RT starting >69 days after surgery. CONCLUSIONS: A high IBTR rate was related to an ICR beyond 47 days. Delay of RT after CT or surgery among patients who undergo BCS should be avoided, especially among patients in the hormone receptor-negative subgroup.

Clarifying the Correlation of Ice Adhesion Strength with Water Wettability and Surface Characteristics.

Although icephobic surfaces have been extensively investigated in the past decades, a controversy remains on the relationship between water repellency and ice repellency. Little insight has been truly obtained on the dependence of ice adhesion on the surface/interface characteristics because of the limited range of these characteristics that have been investigated in the past. In this study, we prepared 37 coatings with a wide range of surface characteristics. The measured ice adhesion strength was discussed in correlation with water wettability and surface topological parameters. It was verified that parameters related to water wettability, such as water contact angle, contact angle hysteresis, and an index of work of adhesion with water, (1 + cos θrec), do not have a simple correlation with ice adhesion strength. Thus, they should not be used as a design parameter for low icephobic surfaces. The current study points out that the study of surface texture should be carried out in conjunction with surface chemistry/energy consideration. Without control of the surface chemistry, the correlation between surface texture parameters will lead to inconsistent conclusions because of the uncertainty of the contact mode. Our investigation indicates that low ice adhesion strength (<50 kPa) is attainable with a smooth surface (root-mean-squared roughness < 50 nm) when a low surface energy (<15 mJ/m2) is maintained. This finding opens a new paradigm for the design of icephobic coatings away from the conventional practices of using superhydrophobic and oil-infused surfaces.

Spraying Preparation of Eco-Friendly Superhydrophobic Coatings with Ultralow Water Adhesion for Effective Anticorrosion and Antipollution.

Sustainability, eco-efficiency, and green chemistry guide the development of new materials in various fields. Herein, we designed and fabricated bio-based superhydrophobic coatings by means of a facile spraying synthesized method. The as-prepared superhydrophobic coatings exhibited high water repellency with higher water contact angle being up to 156.9 ± 2.7° and a lower sliding angle of only 4.3 ± 0.6°. Also, the water adhesion on the superhydrophobic coatings was as low as 11 µN, which was far less than that (346 µN) of the normal polyurethane surfaces. The superhydrophobic properties still retained high stability under the conditions of soaking in acid solution (pH = 1) and alkaline solution (pH = 13). Meanwhile, the as-prepared bio-based superhydrophobic coatings were verified for effective corrosion and pollution protection ability. The electrochemical measurements showed excellent corrosion resistance with a higher corrosion voltage of -204.7 mV and lower corrosion current of 1.494 × 10-5 A/cm2. The corrosion protection efficiency reached a value of 95.2%, and meantime, the superhydrophobic coatings displayed higher antipollution performance without any stains when they were removed from the polluted liquids. On this basis, the underlying physical-chemical mechanisms clearly revealed that the surface micro-nanostructures could capture the continuous and stable air layer to segregate the corrosion and pollution media.

Droplet Directional Movement on the Homogeneously Structured Superhydrophobic Surface with the Gradient Non-Wettability.

The surface with the gradient non-wettability intensely appeals to researchers because of its academic significance and applications for directional droplet movement. Herein, we developed a homogeneous structure superhydrophobic surface with the gradient non-wettability by a combination strategy of chemical etching and vapor diffusion modification. As a consequence, the as-prepared surface exhibits a remarkable gradient characteristic of water repellency, and the water contact angle is mainly located within the range of 162 ± 0.5 to 149 ± 0.4°. Meanwhile, the sliding angle also exhibits a corresponding change from 3 to 11°. On this basis, the gradient characteristic of non-wettability induces the distinguishing droplet adhesion on the surface, that is, from 19 µN for the most hydrophobic end to 57 µN for the opposite one. Because of the difference of the water adhesion force, droplets on the as-prepared surface can well roll alongside a specific direction (i.e., gradient direction of non-wettability). In terms of dynamic impact droplets, they can rapidly rebound off the sample surface with the short contact time of 12.8 ms, and the finally fallen droplets mainly deviate toward weaker regions because of water repellency. To analyze this phenomenon, it is found that the asymmetric mechanic behavior is mainly caused by the unbalanced retraction force between the both ends of the impact droplet. This work provides a novel strategy to construct the homogeneous structure superhydrophobic surface with the gradient non-wettability for the applications in the droplet movement control or transport.

Selective nucleation of ice crystals depending on the inclination angle of nanostructures.

Heterogeneous nucleation is decided by many factors, and surface morphology is one of the most important elements. This paper reports the selective ice nucleation and growth process on a series of nanorods with different inclinations, which were rarely mentioned in previous research studies. It is found that the nanorods with special inclinations can cause the selective nucleation of ice crystals because of the spatial geometry matching. On this basis, we can regulate the ice crystal types (mainly including cubic ice and hexagonal ice) accordingly and even improve the freezing efficiency via controlling the inclinations of surface nanorods. In particular, cubic ice occupies the dominant role in the ice crystal on the surface of 45°-inclination nanorods, yet 90°-inclination nanorods are more beneficial for the formation of hexagonal ice. The shape of the nanorods not only controls the type of ice crystal, but also changes the freezing efficiency because different ice crystals have an unequal nucleation energy barrier. There are no apparent differences in the freezing efficiency on nanostructures with 45°, 75° and 90° inclination nanorods, and 60°-inclination nanorods are more favorable for ice nucleation. Our studies can promote the understanding on the selective nucleation of ice crystals and provide a theoretical basis for achieving the regulation of freezing efficiency.

Statistically understanding the roles of nanostructure features in interfacial ice nucleation for enhancing icing delay performance.

Freezing is a spontaneous phase transformation process, which is mainly governed by heterogeneous ice nucleation. This work aims at the discussion of the roles of nanostructure geometrical features in interfacial ice nucleation. Two kinds of superhydrophobic nanostructures with sealed layered porous and open cone features were designed and fabricated by means of wet-chemical processing methods. Both the resultant surfaces exhibited a larger extent of improvement of non-wettability, especially in the aspect of droplet movement. Comparing with the sealed layered nanoporous structures, the open nanocone structures only induced a sliding angle of 1°. During the freezing process, the solid-liquid contact type highly determined the macroscopic freezing process, and resulted in a difference of icing delay time of ∼170 s (and freezing temperature of ∼3.7 °C) between both superhydrophobic nanostructures. Also, the precooling time, the period before the moment of a droplet instantaneously becoming turbid, occupied a dominant role (∼90%) in the entire freezing time. The ice nucleation behavior was analyzed in detail according to the statistical results of 500 cycles of freezing temperatures, demonstrating that the ice nucleation probability of nanocone structures is less than that of layered nanoporous structures. This is in line with the ice nucleation temperatures of both as-prepared superhydrophobic nanostructures. As a consequence, there was a greater distinction in the ice nucleation rate, especially in the solid-liquid interface nucleation rate, by two orders of magnitude.

Spraying Fabrication of Durable and Transparent Coatings for Anti-Icing Application: Dynamic Water Repellency, Icing Delay, and Ice Adhesion.

Anti-icing/icephobic coatings, typically applied in the form of surface functional materials, are considered to be an ideal selection to solve the icing issues faced by daily life and industrial production. However, the applications of anti-icing coatings are greatly limited by the two main challenges: bonding strength with substrates and stability of the high anti-icing performance. Here, we designed and fabricated a kind of high-performance superhydrophobic fluorinated silica (F-SiO2)@polydimethylsiloxane coatings and further emphasized the improvement of the bonding strength with substrates and the maintenance of high anti-icing performance. The resultant coatings exhibited excellent water repellency with a contact angle up to 155.3° and a very short contact time (∼10.2 ms) of impact droplets. At low temperatures, the coming droplets still rapidly rebounded off the coating surface, and the superhydrophobic coatings displayed a more than 50-fold increase of freezing time comparing with bare aluminum. The ice adhesion strength on the coatings was only 26.3 kPa, which was far less than that (821.9 kPa) of bare aluminum. Furthermore, the nanoporous structures constructed by anodic oxidation could tremendously enhance the bonding strength of the coatings with the substrate, which was evaluated through a standard method (ASTM D3359). The anti-icing properties still retained high stability under the conditions of 30 icing/deicing cycles, soaking, and scouring of acid solution (pH = 5.6). This work can effectively push the anti-icing coatings toward a real-world application.

One-Step Solvothermal Synthesis of Black TiO2 Films for Enhanced Visible Absorption.

An economic and facile solvothermal method was reported to prepare black TiO2 films on Ti foils that possessed the property of optical absorption in the visible region. The UV-vis spectra showed that the black TiO2 samples exhibited highly enhanced visible-light absorption from 400-600 nm. The black TiO2 films were compact and uniform, composed of nanoparticles and nanosheets. Moreover, a mixed structure of anatase and rutile was present in black TiO2 films. The electron paramagnetic resonance (EPR) spectra confirmed the presence of Ti3+ in samples, which accounted for longer wavelength optical absorption. The results showed that the TiO2 films had retained their black color upon storage in ambient atmosphere for more than one month. Therefore, it was supposed that the ethylene glycol in solvothermal reaction was the key factor for the extension of the absorption spectrum.

Rounded Cu2ZnSnS4 nanosheet networks as a cost-effective counter electrode for high-efficiency dye-sensitized solar cells.

Semi-transparent rounded Cu2ZnSnS4 (CZTS) nanosheet networks were in situ grown on a FTO glass substrate, via an effective solution method, without any post-treatments. An improved power conversion efficiency of 6.24% was obtained by applying CZTS nanosheet networks as a counter electrode for dye-sensitized solar cells. When assisted by a mirror reflection, the PCE increased to 7.12%.

Anti-icing potential of superhydrophobic Ti6Al4V surfaces: ice nucleation and growth.

On the basis of the icing-delay performance and ice adhesion strength, the anti-icing potential of the superhydrophobic surface has been well-investigated in the past few years. The present work mainly emphasized the investigations of ice nucleation and growth to fully explore the anti-icing potential of the superhydrophobic surface. We took the various surfaces ranging from hydrophilic to superhydrophobic as the research objects and, combining the classical nucleation theory, discussed the ice nucleation behaviors of the water droplets on these sample surfaces under the condition of supercooling. Meanwhile, the macroscopical growth processes of ice on these surfaces were analyzed on the basis of the growth mechanism of the ice nucleus. It was found that the superhydrophobic surface could greatly reduce the solid-liquid interface nucleation rate, owing to the extremely low actual solid-liquid contact area caused by the composite micro-nanoscale hierarchical structures trapping air pockets, leading to the bulk nucleation dominating the entire ice nucleation at the lower temperatures. Furthermore, ice on the superhydrophobic surface possessed a lower macroscopical growth velocity as a result of the less ice nucleation rate and the insulating action of the trapped air pockets.

Relationship between Wetting Hysteresis and Contact Time of a Bouncing Droplet on Hydrophobic Surfaces.

The contact time of impacting water droplets on superhydrophobic surfaces directly reflects the extent of thermal and energy conversions between the water droplet and the surface, which is also considered to be crucial to the practical applications. The purpose of this study was to reveal the relationship between the contact time and the wetting hysteresis. We designed and fabricated six classes of surfaces with different extent of hydrophobicity through modifying the microscale/nanoscale hierarchical textured titanium surfaces with 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, and we filmed the contact process of the water droplet impacting on these surfaces using a high-speed camera. It can be concluded that wetting hysteresis played a significant role in determining how long the impacting water droplet can bounce off the surface, based on the interfacial wetting mechanism and the work done against the resistance force generated by contact angle hysteresis during the dynamic process.

Nanostructures in superhydrophobic Ti6Al4V hierarchical surfaces control wetting state transitions.

This paper mainly reports the wetting state of liquid droplets on a Ti6Al4V micro-nanoscale hierarchical structured hydrophobic surface. In this work, the detailed action mechanism of the secondary nanostructure in the hierarchical structure on the wetting-state transition (from the Wenzel state to the Cassie state) was revealed and discussed. The variation of micro-morphology of the sample surface was observed using a field emission scanning electron microscope (FE-SEM). Furthermore, the apparent contact angle and sliding angle of the droplets on the surfaces were measured via a contact angle measurement instrument. The theoretical and experimental results indicated that the one-dimensional nanowire structure, which was planted on the microstructure surface by the hydrothermal method, effectively changed the wetting state of liquid droplets on the surface from the Wenzel state to the Cassie state owing to its good size synergies with microscale structure. This process not only increased the apparent contact angle of liquid droplets on the solid surface (to 161°), but also decreased the sliding angle significantly (to 3°) and contact angle hysteresis (to ∼2°), demonstrating the robust non-wetting property.