Cellulose-Based Photothermal Coating: A Sustainable Solution for Seed Protection and Long-Term Grain Storage.

High-output modern agriculture based on synthetic chemicals (biocides, pesticides, and fertilizers) feeds the growing global population. To completely abandon the use of pesticides and fertilizers will undoubtedly cause a severe food crisis worldwide, and sustainable alternative solutions are urgently demanded to stop biocides and fertilizers overuse. Herein, a versatile and green strategy is proposed for seed protection and long-term storage of grains using a cellulose-based photothermal coating (PDA NPs@Cell-N+) that consists of photothermal polydopamine nanoparticles (PDA NPs) and a positive-charged cellulose derivative (Cell-N+) to eradicate seed-borne bacteria and fungi simply under infrared irradiation. In vitro and in vivo assays and the seedling-stage phenotypes of mung bean (Vigna radiata) suggest that pathogenic microbes, including the tough Aspergillus flavus (inhibition ratio >99%), can be efficiently eliminated by photothermal therapy. Thus, the seed-borne diseases of mung beans can finally be prevented. Owing to excellent solubility and biocompatibility, the PDA NPs@Cell-N+ coating can be washed off and recycled without food safety concerns. PDA NPs@Cell-N+ can be a nature-based solution for seed protection and long-term grain storage.

Accelerating Gas Escape in Anion Exchange Membrane Water Electrolysis by Gas Diffusion Layers with Hierarchical Grid Gradients.

At high current densities, gas bubble escape is the critical factor affecting the mass transport and performance of the electrolyzer. For tight assembly water electrolysis technologies, the gas diffusion layer (GDL) between the catalyst layer (CL) and the flow field plate plays a critical role in gas bubble removal. Herein, we demonstrate that the electrolyzer's mass transport and performance can be significantly improved by simply manipulating the structure of the GDL. Combined with 3D printing technology, ordered nickel GDLs with straight-through pores and adjustable grid sizes are systematically studied. Using an in situ high-speed camera, the gas bubble releasing size and resident time have been observed and analyzed upon the change of the GDL architecture. The results show that a suitable grid size of the GDL can significantly accelerate mass transport by reducing the gas bubble size and the bubble resident time. An adhesive force measurement has further revealed the underlying mechanism. We then proposed and fabricated a novel hierarchical GDL, reaching a current density of 2 A/cm2 at a cell voltage of 1.95 V and 80 °C, one of the highest single-cell performances in pure-water-fed anion exchange membrane water electrolysis (AEMWE).

Cellulose-Based Cryogel Microspheres with Nanoporous and Controllable Wrinkled Morphologies for Rapid Hemostasis.

First-aid hemostatic agents for acute bleeding can save lives in emergency situations. However, rapid hemostasis remains challenging when uncontrolled hemorrhage occurs on lethal noncompressible and irregular wounds. Herein, cellulose-based cryogel microspheres with deliberately customized micromorphologies for ultrafast water transportation and diffusion, including the shark skin riblet-inspired wrinkled surface with low fluid drag and the hydrophilic nanoporous 3D networks, are developed to deal with the acute noncompressible bleeding within seconds. These cryogel microspheres can rapidly absorb a large amount of blood over 6 times their own weight in 10 s and form a robust barrier to seal a bleeding wound without applying pressure. Remarkably, massive bleeding from a cardiac penetrating hole is effectively stopped using the microspheres within 20 s and no blood leakage is observed after 30 min. Additionally, these microspheres could be readily removed without rebleeding and capillary thrombus, which is highly favorable to rapid hemostasis in emergency rescue.

Anionic polymerization of nonaromatic maleimide to achieve full-color nonconventional luminescence.

Nonconventional or nonconjugated luminophore without polycyclic aromatics or extended π-conjugation is a rising star in the area of luminescent materials. However, continuously tuning the emission color within a broad visible region via rational molecular design remains quite challenging because the mechanism of nonconventional luminescence is not fully understood. Herein, we present a new class of nonconventional luminophores, poly(maleimide)s (PMs), with full-color emission that can be finely regulated by anionic polymerization even at ambient temperature. Interestingly, the general characteristics of nonconventional luminescence, cluster-triggered emission, e.g., concentration-enhanced emission, are not observed in PMs. Instead, PMs have features similar to aggregation-caused quenching due to boosted intra/inter-molecular charge transfer. Such a biocompatible luminescent material synthesized from a low-cost monomer shows great prospects in large-scale production and applications, including security printing, fingerprint identification, metal ion recognition, etc. It also provides a new platform of rational molecular design to achieve full-color nonconventional luminescence without any aromatics.

Bayesian Estimation of Supply Chain Innovation Path.

With the transformation of the supply chain from factor driven to investment driven and to innovation driven, supply chain innovation has attracted more and more attention. This paper obtains the Bayesian prior probability of innovation and studies the supply chain innovation path from the perspective of strategy and behavior. The model divides the overall innovation capability of the supply chain into specific node tasks and assets (Capability Set), and the innovation demand of the supply chain is expressed in the form of the conditional probability of market demand. Under the conditions of minimum risk, minimum cost, and rapid market response, it determines who should lead the supply chain innovation first and what type of supply chain innovation should be carried out first. Finally, taking the supply chain of the professional market in Zhejiang Province as an example, this paper verifies the theoretical model of supply chain innovation decision-making. The innovation of the supply chain of Zhejiang's specialized market is decomposed into the capability set of each enterprise node of the supply chain. This paper transforms the group innovation ability of the supply chain in the professional market into the individual innovation ability of a single enterprise node and reveals the starting point and intensity of the demand innovation of products/services in the supply chain.

Electrochemical process of early-stage corrosion detection based on N-doped carbon dots with superior Fe3+ responsiveness.

Iron corrosion is a subject of great technological importance and extensive public concern. However, the highly efficient detection of iron corrosion at early stage is still a challenging task. Herein, bright fluorescent carbon dots (CDs) with superior response to Fe3+ were prepared by simple solvothermal process based on citric acid and ammonia. The obtained CDs are able to rapidly, sensitively and selectively respond to Fe3+. The quantitative analysis showed that the CDs exhibited a linear response to Fe3+ in the range of 10 to 300 µM, with a detection limit of 0.9 µM. And the fluorescence quenching of CDs was obvious enough to be detected by the naked eyes. Such promising responsiveness of CDs offers a great opportunity for real-time and visual detection of Fe3+ during electrochemical corrosion process. In addition, due to the excellent stability and solubility of CDs, patterned papers and hydrogels have been fabricated utilizing cellulose and PVA as matrices. The as-prepared biocompatible, environmental-friendly and disposable CDs based fluorescent materials were successfully used for detecting the degree of iron corrosion. This could provide a simple and visual strategy for monitoring the safety of structural metal materials.

Cellulose nanosphere: Preparation and applications of the novel nanocellulose.

Over the past few years, cellulose nanosphere (CNS) has gained growing attention and rapid development. As a new type of nanocellulose materials, CNS can be prepared from native cellulose by using methods which have been adopted extensively to prepare the well-known nanocelluloses, i.e., cellulose nanofiber and cellulose nanocrystal. The particular interest is that the regenerated cellulose and mercerized cellulose can also be used as important feedstocks to produce CNS. In this review, the preparation methods of CNS are described and discussed, via both top-down processes, including chemical, mechanical, and enzymolysis ones, and bottom-up processes by using various cellulose I and II starting materials. This review also highlights the researches relative to cellulose composite nanospheres, and summarizes the applications of spherical cellulose-based nanoparticles. Finally, the future challenges and opportunities of CNS are prospected in this work.

Effect of GnRH immunocastration on immune function in male rats.

The present study aimed to reveal the effects of immunocastration on the development of the immune system in rats. Seventy rats were randomly assigned into two groups: Control (n = 35) and immunized (n = 35). Twenty-day-old rats were immunized with gonadotropin-releasing hormone (GnRH) and booster immunization was administered every two weeks (three immunizations in total). From 20-day-old rats, we collected samples every two weeks, including five immunized rats and five control rats (seven collections in total). We collected blood samples, testicles, thymuses, and spleens. The results showed that GnRH immunization increased the GnRH antibody titers and reduced the testosterone concentration (both P < 0.05). Compared with the control group, the number of CD4+CD8- cells, CD4-CD8+ cells, and CD4+CD8+ cells increased (P < 0.05) whereas the number of CD4-CD8- cells and CD4+CD25+ cells reduced in the immunized group (P < 0.05) over time. GnRH immunization also increased the relative weights of thymus and spleen (P < 0.05), serum concentrations of interleukin (IL)-2, IL-4, IL-6, IL-10, IL-17 and Interferon-γ (IFN-γ) over time (P < 0.05), and changed the mRNA levels of IL-2, IL-4, IL-6. IL-10, IL-17, IFN-γ, CD4, D8, CD19 GnRH, and GnRH receptor (GnRH-R) in thymus and spleen. Thus, GnRH immunization enhanced the immune markers in thymus, spleen, and blood immune cytokines in rats.

Spiropyran based recognitions of amines: UV-Vis spectra and mechanisms.

As one of the important photochromic molecules, spiropyran (SP) compounds are widely used as detectors and fluorescence probes in the environment and bio-imaging field. Although great achievements have been attained for various sophisticated spiropyrans in metal ion sensing, less success is achieved in sensing organic molecules due to the weak interaction between the spiropyran and the target of the organic molecule. In this study, a spiropyran derivative containing a hydroxyl group (SPOH) was employed for the recognition of four kinds of amines via ultraviolet-visible (UV-Vis) spectra. The aliphatic primary amines, aromatic primary amines, aliphatic secondary and tertiary amines, aromatic secondary and tertiary amines were successfully distinguished according to the shapes and trends of their UV-Vis absorption spectra. The chemical reaction between aliphatic, aromatic primary amines and SPOH as well as alkalinity are two vital interaction mechanisms for the recognition process which are testified by Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR). Although SP is generally water-insoluble, it is easy to achieve soluble by fixing SPOH inside micelle or vesicle and thus the results in this study is meaningful for amine recognition utility in environments and biological systems.

Cellulose-based fluorescent sensor for visual and versatile detection of amines and anions.

It is practical and challenging to construct ultrasensitive and multi-responsive sensors for visual and real-time monitoring of the environment. Herein, a cellulose-based multi-responsive fluorescent sensor (Phen-MDI-CA) is fabricated, and realizes a visual and ultrasensitive detection of not only various amines but also three anions based on the change of the fluorescence and/or visible colors. Once exposure to various amines in both the solution and vapor state, the Phen-MDI-CA solution and test paper exhibit different fluorescence colors, which can be used to distinguish triethylamine, ethylenediamine, methylamine, aniline, hydrazine and pyrrolidine from other amines. Moreover, via combining the Phen-MDI-CA with the Phen-MDI-CA/malachite green ratiometric system, phosphate (PO43-), carbonate (CO32-) and borate (B4O72-) can be visually and accurately recognized depending on the change of the visible and fluorescence colors. In fluorescent mode, the LOD for B4O72-, PO43- and CO32- ions is as low as 0.18 nmol, 0.69 nmol and 0.86 nmol, respectively. Significantly, the Phen-MDI-CA can readily make a qualitative and quantitative detection of B4O72-, PO43- and CO32- anions in the mixture of anions. The state-of-the-art responsive behavior of Phen-MDI-CA originates from the amplification effect of cellulose polymer chain and the differentiated interactions between the sensor and analytes.

Sunlight-Driven Wearable and Robust Antibacterial Coatings with Water-Soluble Cellulose-Based Photosensitizers.

Herein, a simple, effective, and general strategy is demonstrated to obtain a water-soluble and nontoxic cellulose-based photosensitizer (CPS) with enhanced photodynamic antibacterial activity through introducing protoporphyrin IX (PpIX) and quaternary ammonium salt (QAS) groups onto the cellulose backbone. The synergistic effect of the anchoring and diluting effect of the cellulose backbone and the electrostatic repulsion between QAS groups effectively inhibit the π-π stacking of PpIX groups, thus the as-prepared CPS exhibits markedly enhanced reactive oxygen species (ROS) yield. Meanwhile, the positively charged QAS groups endow the CPS with water-solubility and a strong attractive force to bacteria. As a result, the CPS can rapidly and efficiently kill drug-resistant bacteria strains, including E. coli and S. aureus, with a low light dose (2.4 J cm-2 ) and low concentration of PpIX groups (0.35 × 10-6 m). Benefiting from the excellent processability and formability, the CPS is readily applied as a sunlight-driven wearable and robust antibacterial coating by a spray coating and later crosslinking procedure.

Amine-responsive cellulose-based ratiometric fluorescent materials for real-time and visual detection of shrimp and crab freshness.

Herein, we design and prepare cellulose-based ratiometric fluorescent materials with superior amine-response, which offers the real-time and visual detection of seafood freshness. Through utilizing the reactive hydroxyl groups along cellulose chains, we covalently immobilize the fluorescein isothiocyanate (FITC) as indicator and protoporphyrin IX (PpIX) as internal reference onto cellulose acetate (CA), respectively. Subsequently, a series of dual-emission solid fluorescent materials are achieved by simply blending green emitting CA-FITC with red-emitting CA-PpIX with varying ratios. They exhibit a sensitive, color-responsive, rapid and linear response to ammonia in a wide range of 5.0 ppm to 2.5 × 104 ppm. Benefiting from the excellent solubility and processibility of cellulose derivatives, the as-prepared materials are readily processed into different material forms, including printing ink, coating, flexible film, and nanofibrous membrane. The electrospun nanofibrous membrane is successfully employed as a low-cost, high-contrasting, quick-responsive fluorescent trademark for visual monitoring the freshness of shrimp and crab.

Visual and Precise Detection of pH Values under Extreme Acidic and Strong Basic Environments by Cellulose-Based Superior Sensor.

Precise determination of pH values with an instrument-free mode is challenging and practical in industry processes, life science, and environmental monitoring. Here, taking advantage of the intramolecular charge transfer process, we construct a cellulose-based superior pH sensor, Phen-MDI-CA, which contains a highly sensitive, pH-responsive, and extended conjugation structure by combining phenanthroline moiety as a chromophore with urea group as a bridge. The resultant Phen-MDI-CA can precisely and visually determine pH values under extreme acidic and strong basic environments, depending on the different colors. In visible light mode, Phen-MDI-CA can readily discriminate the pH values of 14.0, 13.0, 12.0, and 11.0 and distinguish pH 2.0 from 1.0 by the naked eye. In fluorescent mode, Phen-MDI-CA can recognize more accurate pH values of pH 11.6-13.2 at a 0.2-0.4 pH interval by the high-contrasting color change. After addition of pH-irresponsive dyes as the reference, the corresponding ratiometric systems exhibit different colors at a 0.2-0.4 pH interval during the pH values of 11.0-14.0 and 1.0-2.0. Benefiting from the excellent formability, the Phen-MDI-CA was readily fabricated into pH test strips by coating method. To our knowledge, this is the first study to monitor extreme acidity and strong basicity in such precise pH values with an instrument-free mode.

Effect of active immunization using a novel GnRH vaccine on reproductive function in rats.

To investigate the effect of gonadotropin-releasing hormone 2-multiple antigen peptide (GnRH2-MAP) on reproductive function. In our study, 20-day-old male rats (n = 90) were randomly allocated to one of three treatment groups: GnRH2-MAP immunization, GnRH2 immunization, and non-immunized control groups. The immunized animals were administered three doses of GnRH2-MAP or GnRH2 vaccines from 0 to 6 weeks at 2-week intervals. The control group only received oil adjuvant. Blood and right testis samples were collected, and the left testis was weighed and its volume was measured at 0, 2, 4, 6, 8, 10 and 12 weeks after the first immunization. The serum antibody titer and testosterone concentration were determined by ELISA, and the right testis samples were collected for histological analysis. The results revealed that the serum of vaccinated rats elicited a significantly higher antibody titer and a lower T concentration compared with the control group two weeks after the first immunization (P < 0.05), but the highest antibody titer and lowest T concentration were found in animals treated with GnRH2-MAP (P < 0.05). The second immunization resulted in a significant decrease in testicular weight and volume (P < 0.05) in both immunized groups compared to the control, but these values were significantly lower in the GnRH2-MAP group than in the GnRH2 group. Furthermore, seminiferous tubules revealed more significant atrophy in the GnRH2-MAP group than in the GnRH2 group, and no sperm were observed in rats of the GnRH2-MAP group. Thus, GnRH2-MAP may be an effective antigen and a potential immunocastration vaccine with higher effectiveness.

Cellulose-Based Sensor Containing Phenanthroline for the Highly Selective and Rapid Detection of Fe2+ Ions with Naked Eye and Fluorescent Dual Modes.

Iron ions play a vital role in many biological processes, and their concentrations are responsible for human health. Therefore, it is essential to detect the concentration of iron ions by a rapid, accurate, highly selective, and practical method. Herein, we have synthesized a cellulose-based fluorescent sensor (Phen-MDI-CA) for the highly selective and rapid detection of Fe2+ ions via chemically bonding 1,10-phenanthroline-5-amine (Phen) onto cellulose acetate (CA) using 4,4'-methylene diphenyl diisocyanate (MDI) as a cross-linker. Benefiting from the anchoring and diluting effect of a cellulose skeleton, the resultant Phen-MDI-CA displays excellent fluorescence properties in both solution and solid state. More interestingly, a cellulose-based polymer chain significantly improves the sensitivity of phenanthroline to Fe2+ ions. Upon meeting Fe2+ ions, a red, insoluble, and nonfluorescent Fe-(Phen-MDI-CA) complex appears immediately; thus, Phen-MDI-CA can work as a multimode chromogenic sensor for the highly selective, sensitive, and rapid detection of Fe2+ ions. In the instrument-free visual mode, the detection limit for Fe2+ ions is 50 ppb, and in fluorescence mode, the detection limit is 2.6 ppb. To our knowledge, this is the first time that such a low detection limit for Fe2+ ions in aqueous media has been observed by the naked eye. In addition, Phen-MDI-CA has good solubility and processability in common organic solvents, which facilitates its use in different material forms, e.g., printing ink, coating, and film. Therefore, the Fe2+-responsive and chromogenic Phen-MDI-CA exhibits a huge potential in the detection and extraction of Fe2+ ions.

Synergy of different fluorescent enhancement effects on spiropyran appended onto cellulose.

An excellent fluorescent material derived from spiropyran species was facilely fabricated by appending spiropyran onto the cellulose matrix via a covalent link of an ester carbonyl group. The interior high-polar environment in the porous cellulose matrix can promote the concentration of the merocyanine form; the conformational constraint of cellulose cavities and the elimination of solvent influence can sufficiently develop the quantum yield of merocyanine. In contrast with other spiropyran materials, the synergy of the three different effects can significantly enhance the fluorescent intensity of the spiropyran compound by 1 order of magnitude approximately. These experimental results may bring about more promising applications of spiropyran species beyond their photochromic properties.

Comparative study on CdSe QDs synthesized from water and ethanol: Hydrogen bond induced particle agglomeration and enhancement on photoluminescence.

In this paper a comparative study is carried out on the CdSe QDs synthesized from water and ethanol. Our purpose is to present an insight understanding on how hydrogen bonds affect particle agglomeration and consequently photoluminescence (PL) behavior of the QDs. In comparison with those from water, the CdSe QDs from ethanol show super PL with high brightness. Detailed characterization gives the only difference of large agglomerates presented in the QDs from ethanol. The TEM and HRTEM observations reveal a tri-level microstructure for the QDs from ethanol while in the case of those from water it is bi-level. With these direct evidences weak hydrogen bond of TGA with ethanol is proposed to be responsible for these large agglomerates and consequently super PL behavior. Additional investigations on some other alcohols of methanol, n-propanol, and i-butanol yield positive results and confirm the truth of our proposal.