Exceptions to Fourier's Law at the Macroscale.

The usual basis to analyze heat transfer within materials is the equation formulated 200 years ago, Fourier's law, which is identical mathematically to the mass diffusion equation, Fick's law. Revisiting this assumption regarding heat transport within translucent materials, performing the experiments in vacuum to avoid air convection, we compare the model predictions to infrared-based measurements with nearly mK temperature resolution. After heat pulses, we find macroscale non-Gaussian tails in the surface temperature profile. At steady state, we find macroscale anomalous hot spots when the sample is topographically rough, and this is validated by using two additional independent methods to measure surface temperature. These discrepancies from Fourier's law for translucent materials suggest that internal radiation whose mean-free-path is millimeters interacts with defects to produce small heat sources that by secondary emission afford an additional, non-local mode of heat transport. For these polymer and inorganic glass materials, this suggests unique strategies of heat management design.

Multiple spatial scales of bacterial and fungal structural and functional traits affect carbon mineralization.

Studying the functional heterogeneity of soil microorganisms at different spatial scales and linking it to soil carbon mineralization is crucial for predicting the response of soil carbon stability to environmental changes and human disturbance. Here, a total of 429 soil samples were collected from typical paddy fields in China, and the bacterial and fungal communities as well as functional genes related to carbon mineralization in the soil were analysed using MiSeq sequencing and GeoChip gene microarray technology. We postulate that CO2 emissions resulting from bacterial and fungal carbon mineralization are contingent upon their respective carbon consumption strategies, which rely on the regulation of interactions between biodiversity and functional genes. Our results showed that the spatial turnover of the fungal community was 2-4 times that of the bacterial community from hundreds of meters to thousands of kilometres. The effect of spatial scale exerted a greater impact on the composition rather than the functional characteristics of the microbial community. Furthermore, based on the establishment of functional networks at different spatial scales, we observed that both bacteria and fungi within the top 10 taxa associated with carbon mineralization exhibited a prevalence of generalist species at the regional scale. This study emphasizes the significance of spatial scaling patterns in soil bacterial and fungal carbon degradation functions, deepening our understanding of how the relationship between microbial decomposers and soil heterogeneity impacts carbon mineralization and subsequent greenhouse gas emissions.

A dual-cycle regeneration to recover high-value and high-purity FePO4 from real wastewater for Li-battery application.

The recovery of high-purity and high-value FePO4 raw materials from wastewater has great prospects in LiFePO4 battery industry due to the huge demand for new energy vehicle. However, the conventional in-situ FePO4 precipitation, as well as ex-situ PO43- adsorption-alkali regeneration, was incapable of efficiently obtaining high-purity products. To solve these problems, a dual-cycle regeneration method of Fe-NH2-polyacrylonitrile (PAN) adsorbent and H2SO4 desorbing solution was proposed to ex-situ FePO4 recovery from wastewater for Li-battery application. Benefitted from coordination interaction and electrostatic attraction, the maximum PO43- adsorption capacity of Fe-NH2-PAN reached 73.1 ± 0.4 mg/g. The average PO43- removal rate of continuous flow devices were 88.5% and 91.3% when treating low-P-concentration (0.22 mg/L) municipal wastewater (MW) and high-P-concentration (48.9 mg/L) slaughterhouse wastewater (SW) respectively. Furthermore, high-purity FePO4 analyzed by XRD spectra was achieved from the desorption solution at pH ∼1.6, resulting in the ultrahigh P recovery efficiencies of 91.4 ± 3.2%-96.3 ± 2.5% for SW and 82.7 ± 3.5% for MW. Besides, the LiFePO4/C electrodes made of recycled FePO4 exhibited a better discharge capacity (37.3 - 55.8 mAh/g) than that of commercial FePO4 agent (32.2 - 35.1 mAh/g) from 80 to 132 cycles, which showed the promising feasibility of recovering FePO4 from wastewater for Li-battery application.

A Versatile Disorder-to-Order Technology to Upgrade Polymers into High-Performance Bioinspired Materials.

Biodegradable polymer as traditional material has been widely used in the medical and tissue engineering fields, but there is a great limitation as to its inferior mechanical performance for repairing load-bearing tissues. Thus, it is highly desirable to develop a novel technology to fabricate high-performance biodegradable polymers. Herein, inspired by the bone's superstructure, a versatile disorder-to-order technology (VDOT) is proposed to manufacture a high-strength and high-elastic modulus stereo-composite self-reinforced polymer fiber. The mean tensile strength (336.1 MPa) and elastic modulus (4.1 GPa) of the self-reinforced polylactic acid (PLA) fiber are 5.2 and 2.1 times their counterparts of the traditional PLA fiber prepared by the existing spinning method. Moreover, the polymer fibers have the best ability of strength retention during degradation. Interestingly, the fiber tensile strength is even higher than those of bone (200 MPa) and some medical metals (e.g., Al and Mg). Based on all-polymeric raw materials, the VDOT endows bioinspired polymers with improved strength, elastic modulus, and degradation-controlled mechanical maintenance, making it a versatile update technology for the massive industrial production of high-performance biomedical polymers.

Phosphorescent extensophores expose elastic nonuniformity in polymer networks.

Networks and gels are soft elastic solids of tremendous technological importance that consist of cross-linked polymers whose structure and connectivity at the molecular level are fundamentally nonuniform. Pre-failure local mechanical responses are not understood at the level of individual crosslinks, despite the enormous attention given to their macroscopic mechanical responses and to developing optical probes to detect their loci of mechanical failure. Here, introducing the extensophore concept to measure nondestructive forces using an optical probe with continuous force readout proportional to deformation, we show that the crosslinks in an elastic polymer network extend, fluctuate, and deform with a wide range of molecular individuality. Requiring little specialized equipment, this foundational single-molecule phosphorescence approach, applied here to polymer science and engineering, can be useful to a broad science and engineering community.

K. ZHENG ET AL.Gold-nanoparticle-based multistage drug delivery system for antitumor therapy.

Nanoparticles can promote the accumulation of drugs in tumors. However, they find limited clinical applications because they cannot easily penetrate the stroma of cancer tissues, and it is difficult to control drug release. We developed a multiresponse multistage drug-delivery nanogel with improved tumor permeability and responsiveness to the tumor microenvironment for the controlled delivery of anticancer agents. For this purpose, ∼100 nm multistage drug delivery nanogels with pH, redox, near-infrared stimulation, and enzyme responsiveness were grown in situ using 20 nm gold nanoparticles (AuNPs) via an emulsion-aiding crosslinking technique with cysteine crosslinker. An alginate cysteine AuNP (ACA) nanocarrier can efficiently load the cationic drug doxorubicin (DOX) to produce a multistage drug delivery nanocarrier (DOX@ACA). DOX@ACA can maintain the slow release of DOX and reduce its toxicity. In cancer tissues, the high pH and reductase microenvironment combined with the in vitro delivery of alginate and near-infrared light drove drug release. The developed nanoparticles effectively inhibited cancer cells, and in vivo evaluations showed that they effectively enhanced antitumor activity while having negligible in vivo toxicity to major organs.

Biopolymer Filament Entanglement Softens Then Hardens with Shear.

It is unsatisfactory that regarding the problem of entangled macromolecules driven out of equilibrium, experimentally based understanding is usually inferred from the ensemble average of polydisperse samples. Here, confronting with single-molecule imaging this common but poorly understood situation, over a wide range of shear rate we use single-molecule fluorescence imaging to track alignment and stretching of entangled aqueous filamentous actin filaments in a homebuilt rheo-microscope. With increasing shear rate, tube "softening" is followed by "hardening." Physically, this means that dynamical localization first weakens from molecular alignment, then strengthens from filament stretching, even for semiflexible biopolymers shorter than their persistence length.

Size-transformable gelatin/nanochitosan/doxorubicin nanoparticles with sequentially triggered drug release for anticancer therapy.

The translation of nanoparticles in cancer treatment is limited by their low drug-loading capacity, poor colloidal stability, insufficient tumor penetration, and uncontrolled drug release. Herein, gelatin/nanochitosan/doxorubicin nanoparticles (GND) are developed by crosslinking nanochitosan (NCT) with gelatin for doxorubicin delivery. The hydrophilicity and stability properties of GND allow it to be protected and have a long circulation time in blood. The GND formulation exhibited shedding and triggered release effects as well as improved colloidal stability. When reaching the tumor site, matrix metallopeptidase-2 (MMP-2) from the tumor environment degrades gelatin from 178-nm GND to release smaller 4 nm nanochitosan/doxorubicin (ND) nanoparticles for deep tumor penetration and efficient tumor cell endocytosis. Following endocytosis by tumor cells, the intracellular low pH and MMP-2 further trigger doxorubicin release, resulting in superior inhibitory capacity against cancer cells. Using a mouse tumor-bearing model, the superior anticancer activity and good in vivo biocompatibility of GND were verified. The rational design of tumor-penetrating GND enables MMP-2/pH sequentially triggered intelligent drug delivery, providing a practical approach for anticancer therapy.

Enhanced proteins and amino acids production based on ammonia nitrogen assimilation and sludge increment by the integration of bioadsorption with anaerobic-anoxic-oxic (AAO) process.

Poor effect of contaminants removal efficiency and low organic matter content of activated sludge are common in wastewater treatment plants (WWTPs) in China due to the low-strength wastewater. An anaerobic-anoxic-oxic (AAO) and an adsorption/AAO (A/AAO) combined system were established simultaneously to conduct a comparative study for realizing the conversion of carbon source in influent and the enrichment and recovery of proteins and amino acids through the assimilation of ammonia nitrogen. The experimental results showed that 63.5% of the organic matter in influent was adsorbed and flocculated in adsorption process, and the removal rates of chemical oxygen demand, total nitrogen and total phosphorus in A/AAO process were 88.7%, 77.1%, and 93.0% respectively, which were remarkably better than those in AAO process owing to the addition of improved carbon source. Ammonia assimilation rate of A/AAO process was 26.7% higher than that of AAO process, which implied that the ammonia used to synthesize sludge protein was prominently increased. Furthermore, intracellular proteins and amino acids in A/AAO process were 20% higher than those of AAO process, and the quality was equivalent with fish meal or soybean meal as feed. In addition, the microbial community analysis based on 16S rDNA was conducted. Dechloromonas, Zoogloea, Nitrospira, and Flavobacterium were the main genera, and played important roles in nutrient removal and ammonia nitrogen assimilation. The integration of adsorption process was significant to low-strength wastewater treatment and the improvement of excess sludge quality, which is a prospective inspiration for the resource recovery-based wastewater treatment process.

[Effects of Fertilization Strategies on the Cadmium Resistance of Paddy Soil Microorganisms].

Cadmium (Cd) is one of the commonly found heavy metal contaminants in soil and has a toxic effect on plants and humans. Understanding the Cd resistance of soil microorganisms under different fertilization regimes can provide a theoretical basis for controlling heavy metal pollution by organic fertilizers. In order to investigate the effects of inorganic and organic fertilizers on the Cd resistance level of soil microorganisms, paddy soil samples were taken in Changzhou, Shanggao, and Fuzhou. A functional gene array (GeoChip 5.0) was used to investigate the distribution of microbial Cd resistance genes. The results indicated that the content of available Cd in soil with organic fertilizer[(1.08±0.70) mg·kg-1] was significantly lower than that in soils with inorganic fertilizer[(3.75±1.22) mg·kg-1](P<0.05). A total of 639 Cd resistance genes were detected. The abundance of microbial Cd resistance gene in soil with organic fertilizer was higher than that of inorganic soil. The content of available Cd, moisture content, pH, and ammonium nitrogen were important environmental factors affecting the distribution of Cd resistant microorganisms. Analysis of the molecular ecological network of Cd resistant microorganisms showed that pH, moisture content, and the effective state of the Cd content were the main factors affecting the potential interaction of functional microorganisms with inorganic fertilizer, and the main factors were total potassium and moisture content with organic fertilizer. Compared with inorganic fertilizers, the application of organic fertilizers can improve the Cd resistance level of microorganisms in soil and promote positive relationships among Cd resistant soil microorganisms.

Distribution and diversity of filamentous bacteria in wastewater treatment plants exhibiting foaming of Taihu Lake Basin, China.

Foaming caused by filamentous bacteria in activated sludge (AS) is a common phenomenon in municipal wastewater treatment plants (WWTPs) in Taihu Lake Basin of South China. In this study, total bacterial and filamentous bacterial communities were comprehensively characterized in AS and foams from eight municipal WWTPs by high-throughput sequencing technology. Results showed that alpha diversities of total bacterial communities in foams were obviously lower than those in AS samples. The bacterial community structures were significantly different between WWTPs rather than sample types (AS vs. foam). For most WWTPs, the Actinobacteria phylum was highly enriched in foams and the most abundant genera in foams were common mycolata. Sixteen filamentous bacteria were identified against the improved bulking and foaming bacteria (BFB) database. Abundance and composition of BFB in different WWTPs and different sample types were significantly different. 'Nostocoida limicola' I Trichococcus and Microthrix were generally dominant in AS samples. The dominant BFB in foams were associated with Microthrix, Skermania, Gordonia, and Mycobacterium. A new Defluviicoccus spp. in cluster III was identified in severe and continuous foams. Moreover, dominant BFB in stable and continuous foams with light level in one typical WWTP were diverse, even, and dynamic. Bacterial co-occurrence network analysis implied that the bacterial community of AS was more sensitive to disturbance than that of foam.

Anomalous Diffusion Inside Soft Colloidal Suspensions Investigated by Variable Length Scale Fluorescence Correlation Spectroscopy.

The diffusion of molecules and particles inside the aqueous suspension of soft colloids (polymer microgels) is investigated using variable length scale fluorescence correlation spectroscopy (VLS-FCS). Carbopol 940 is chosen as the model matrix system, and two factors affecting diffusion are investigated: the spatial hindrance and the diffusant-matrix interaction. By studying diffusion of molecules and particles with different sizes inside the suspension, VLS-FCS reveals the restricted motion at a short length scale, that is, in the gaps between the microgels, and normal diffusion at a larger length scale. The information on the gap's length scale is also accessed. On the other hand, by tuning the pH value, the diffusant-matrix electrostatic attraction is adjusted and the results expose a short-time fast diffusion of probe molecules inside the gaps and a long-time restricted diffusion because of trapping inside the microgels. It is proved that VLS-FCS is a powerful method, investigating anomalous diffusion at different length scales and it is a promising approach to investigate diffusion in complex soft matter systems.

Tumor-mediated shape-transformable nanogels with pH/redox/enzymatic-sensitivity for anticancer therapy.

Lack of sufficient tumor penetration of the current nanomedicines is a major reason limiting their clinical success in cancer therapy. In this work, we aimed at the development of a novel biodegradable nanoplatform for the selective and controlled delivery of anticancer agents, with improved tumor permeability and the ability to release ultrasmall nanovesicles in the tumor microenvironment. To this end, positively charged nanogels were obtained through the double-crosslinking of chitosan with an ionic physical gelator and a disulfide-containing chemical crosslinker. After conjugation to an anionic oligomer, the cationic nanogels were transformed into negatively charged nanocarriers (CTCP), enabling effective encapsulation of the cationic anticancer agent doxorubicin (DOX) to generate a biodegradable nanomedicine (DOX@CTCP). DOX@CTCP could maintain sustained DOX release and decreased DOX toxicity. Upon arrival at the tumor tissue, the reductive and lysozyme-high microenvironment drives the cleavage of the nanomedicine to release DOX-carrying nanoblocks of smaller size, which together with their acidic-protonable feature achieves an effective therapeutic delivery into cancer cells. The nanomedicine described here showed excellent biocompatibility/biosafety and enhanced in vivo antitumor efficacy.

Full-scale membrane bioreactor process WWTPs in East Taihu basin: Wastewater characteristics, energy consumption and sustainability.

Based on the collection and analysis of essential data from wastewater treatment plants (WWTPs) in recent ten years, the work provides the wastewater characteristics and energy consumption performance in full-scale membrane bioreactor (MBR) process in East Taihu basin, China. High-quality effluent was achieved although the influent carbon source was not beneficial to total nitrogen and total phosphorus removal. The average specific energy consumption (SEC) was 0.52 kWh/m3, which was remarkably lower than that of full-scale MBR process in developed countries, however, the average SEC value was higher than that of conventional activated sludge (CAS) process in China. In addition, the SEC value was largely reduced in 2018, and the regulation of suction pump and aeration mode were considered as the main control methods. Energy consumption will increase along with the influent volume, while the elevation of COD and NH4+-N reduction will bring about relatively low energy consumption. Furthermore, sustainability index was established to comprehensively evaluate the performance of full-scale MBR process, meaning that with relatively low permeate ratio of effluent, full-scale MBR process presented to be inferior to CAS process in sustainability and not feasible to be applied in the upgradation and construction of WWTPs.

Promising carbon utilization for nitrogen recovery in low strength wastewater treatment: Ammonia nitrogen assimilation, protein production and microbial community structure.

Acetic acid and sodium acetate are generally supplied to wastewater treatment plants (WWTPs) in China to improve total nitrogen (TN) and total phosphorus (TP) removal, and the addition of carbon source also facilitates to increase sludge growth rate and further provides material basis for the extraction of proteins and amino acids from activated sludge. To recycle ammonia nitrogen resources, a system that combined adsorption and anaerobic-anoxic-oxic (A/AAO) process for treating low strength wastewater was established. Experimental results showed that by the addition of carbon substrate from a mixture of anaerobically fermented adsorption sludge, the average removal efficiency of chemical oxygen demand (COD), ammonia nitrogen, TN, and TP were 88%, 96.9%, 93.9%, and 92.1%, respectively, and the ratio of nitrogen assimilation to nitrogen dissimilation significantly increased by a factor of 2.5. Through energy analysis (based on adenosine triphosphate, ATP), sludge flocculation capacity and settling property, it was found that the AAO process sludge presented the logarithmic growth characteristics. The respective sludge protein and amino acids contents increased by over 11.4% and 40.3%, and the synthetic products of glutamic acid, alanine and aspartate increased through the assimilation of ammonia nitrogen, thereby indicating that replenishing the carbon substrate could markedly enhance protein and amino acids contents in AAO process sludge. Moreover, the diversity of the microbial community in adsorption process was relatively rich, the diversity in the adsorption process sludge was the highest, while the diversity of the AAO process sludge evidently decreased. The microbial community in each process was similarly based on 16S rDNA gene sequence analysis, microflora was prominent in the AAO process, with Dechloromonas, Flavobacterium, Zoogloea, Unclassified_Rhodocyclaceae and Thauera as the dominant species. Promising carbon utilization facilitates contaminants removal in low strength wastewater treatment and is conducive to protein production through ammonia nitrogen assimilation.

Innovative methods for random field establishment and statistical parameter inversion exemplified with 6082-T6 aluminum alloy.

This paper aims to eliminate the disharmony between simulation and experiment, and takes the mechanical properties of 6082-T6 Al alloy as an example. In order to obtain the equivalent distribution of material properties after considering the randomicity of materials, a new inversion method combining with stochastic finite element method (SFEM) is proposed. Besides, the discrete random field in SFEM is established by an innovative method to overcome some discretization difficulties in conventional methods. In summary, the generic methods proposed in this study can give a new solution for the correlation of meso-structure and macro-performance in computational materials science.

Charge evolution during the unfolding of a single DNA i-motif.

The effective charge and evolution of single chains of a DNA i-motif during its unfolding process are investigated at the single molecule level. Using fluorescence correlation spectroscopy and photon counting histograms, the single chain dimensions and electrical potential of cytosine-rich human telomeric oligonucleotides are monitored, during their unfolding from the i-motif to the random coil state. It is discovered that the effective charge density of the DNA chain is very sensitive to conformation changes and the results remarkably expose the existence of an intermediate state of the unfolding process. A huge difference in pH value exists in the vicinity of the DNA chain and the bulk solution, depending on the salt concentration, as reflected by a down-shift in the pH value of unfolding. The presence of an external salt in the solution helps to stabilize the i-motif structure at low pH values due to the reduction of the effective charge density. It can also destabilize the folded structure in the pH range of the conformation transition due to the elevation of the local pH value, encouraging the deprotonation of the cytosine groups. These results provide new information for understanding the structure and stability of i-motif DNA, and its biological function, as well as the building blocks for smart nanomaterials.

Covalent tethering of photo-responsive superficial layers on hydrogel surfaces for photo-controlled release.

The diffusion and transport of substances between a hydrogel and its environment have received tremendous research interest, due to the wide range of applications of hydrogel materials in fields related to drug carriers and drug delivery vehicles. To date, much research has been done to tailor the diffusion and transport of substances through hydrogels, where most efforts were focused on tuning the 3D network properties of the hydrogel including loop size, hydrophobicity of building blocks and the stimuli-responsive properties of backbones. These conventional strategies, however, usually suffer from complicated fabrication procedures and result in a homogeneous increase in hydrophobicity of the hydrogel network, leading to low efficiency control over the diffusion of substances through the hydrogel. Herein, a facile strategy that can functionalize the surfaces of hydrogels, while keeping the interior network unchanged, was reported, and is realized by quaternization reaction confined to the hydrogel/oil interface. Owing to the introduction of the photo-responsive molecule IBSP as a modifier, the surface wettability of the resulting hydrogel can be controlled by light both in air and underwater environments. Consequently, the diffusion rate of a substance through this modified hydrogel can be regulated by light, which brings convenience to the controlled release of hydrogels and other hydrogel-related fields.

Nine sesquiterpenes from Solanum torvum.

Three new sesquiterpenes, namely 3ß,11-dihydroxy-4,14-oxideenantioeudesmane (1), 1ß,10ß,12,14-tetrahydroxy-allo-aromadendrane (2) and 1ß,10ß,13,14-tetrahydroxy-allo-aromadendrane (3), along with six known sesquiterpenes (4-9), were isolated from the roots of Solanum torvum. Compound 4 and 5 are epimers, their main difference lies in the C-11 configulation. Normally, epimers do not make a huge difference in C NMR spectra, but in this kind of structure of A, B, C rings, and C ring is sterically strained structure, stericall effects influence strongly the (13)C NMR chemical shifts, when C-11 configulation changed, it makes a huge difference in the three ring of structure, such as C-6, C-7, C-11. New compound 2 and 3 are epimers and similar to compound 4 and 5, their just increase a hydroxy in C-1 and have a same regular pattern in C NMR spectra, otherwise, compound 5 was firstly confirmed by single-crystal X-ray diffraction.