Underestimated contribution of fugitive emission to VOCs in pharmaceutical industry based on pollution characteristics, odorous activity and health risk assessment.

Fugitive emission has been becoming an important source of volatile organic compounds (VOCs) in pharmaceutical industry, but the exact contribution of fugitive emission remains incompletely understood. In present study, pollution characteristics, odorous activity and health risk of stack and fugitive emissions of VOCs from four functional units (e.g., workshop, sewage treatment station, raw material storage and hazardous waste storage) of three representative pharmaceutical factories were investigated. Workshop was the dominant contributor to VOCs of fugitive emission in comparison with other functional units. Extreme high concentration of VOCs from fugitive emission in unsealed workshop (94.87 mg/m3) was observed relative to sealed one (1.18 mg/m3), accounting for 31% and 5% of total VOCs, respectively. Fugitive emission of VOCs in the unsealed workshop mainly consisted of n-hexane, 1-hexene and dichloromethane. Odorous activity indexes and non-cancer hazard ratios of these VOCs from fugitive emission in the unsealed workshop were as high as that from stack exhaust. Furthermore, cancer risk of dichloromethane from fugitive emission and stack exhaust was up to (1.6-1.8) × 10-5. Odorous activity or health risk index of the VOCs from fugitive emission was up to 13 or 11 times of the corresponding threshold value, posing remarkable health threat on pharmaceutical workers. Our findings highlighted the possibly underestimated contribution of fugitive emission on VOCs in the pharmaceutical industry.

Oxygen Isotope Tracing Study to Directly Reveal the Role of O2 and H2O in the Photocatalytic Oxidation Mechanism of Gaseous Monoaromatics.

O2 and H2O influence the photocatalytic oxidation mechanism of gaseous monoaromatics, but still in an unclear manner, due to the lack of direct evidence. Tracing an oxygen atom from 16O2 and H218O to intermediates can clarify their roles. The low H218O content suppressed the formation of benzenedicarboxaldehydes during the oxidation of xylenes and 16O2 greatly affected the yield of total intermediates, while neither of them altered the percentage order of the products. Methylbenzaldehydes, methylbenzyl alcohols, and benzenedicarboxaldehydes possessed greater 16O percentage (≥69.49%), while higher 18O distribution was observed in methylbenzoic acids and phthalide (≥59.51%). Together with the interconversion results of the products revealed, 16O2 determined the transformation of xylenes initially to methylbenzaldehydes and then to methylbenzyl alcohols or benzenedicarboxaldehydes, while H218O mainly contributed to conversion of methylbenzaldehydes to methylbenzoic acids or phthalide. Further interaction sites of xylene and its products with H2O and O2 were confirmed by molecular dynamics calculations. The same roles of 16O2 and H218O in the degradation of toluene, ethylbenzene, 1,2,4-trimethylbenzene, and 1,3,5-trimethylbenzene were also verified. This is the first report that provides direct evidence for the roles of O2 and H2O in the photocatalytic oxidation mechanism of gaseous monoaromatics. These findings are helpful to achieve controllable product formation from the oxidation of monoaromatics and predict their migration process in the atmospheric environment.

Superoxide radical enhanced photocatalytic performance of styrene alters its degradation mechanism and intermediate health risk on TiO2/graphene surface.

Enhancement of reactive oxygen species (ROS) on semiconductor coupled by carbon material promotes photocatalytic performance toward aromatic hydrocarbons, while the contribution to their degradation mechanism and health risk is not well understood. Herein, photocatalytic degradation of styrene on TiO2 and TiO2/reduced graphene oxide (TiO2/rGO) surface is compared under dry air condition to investigate the role of ·O2- in styrene degradation. TiO2/rGO shows 4.8 times higher degradation efficiency than that of TiO2, resulting in 16% reduced production of intermediates with identical composition. The improved formation of ·O2- on TiO2/rGO is confirmed responsible for these variations. Theoretical calculation further reveals the enhancement of ·O2- thermodynamically favoring conversion of styrene to acetophenone, turning the most dominant intermediate from benzoic acid on TiO2 to acetophenone on TiO2/rGO. The accumulated formation of acetophenone on TiO2/rGO poses increased acute threat to human beings. Our findings proclaim that ROS promoted photocatalytic performance of semiconductor after carbon material composition ultimately changes the priority order of degradation pathways to form by-product with higher threat toward human beings. And more attentions are advised focusing on the relevance with degradation efficiency, intermediate and toxicity of aromatic hydrocarbons on carbon material based photocatalyst.

Revelation of contributing mechanism of reactive oxygen species in photocatalytic ozonation heterocyclization of gaseous hexane isomers.

The reactive oxygen species (ROS) involved photocatalytic ozonation of gaseous n-hexane to heterocyclic compounds has been recently reported. However, whether such heterocyclization reaction happens on other alkanes and what is the contributing mechanism of ROS to the heterocyclic compound formation are still unclear. In present study, photocatalytic ozonation of three n-hexane's isomers (i.e. 2-methypentane, 3-methylpentane and 2,3-dimethylbutane) on Cu2O-CuO/TiO2-foam ceramic was investigated. Within reaction period, 2-methylpentane and 3-methylpentane not only showed higher average degradation efficiency than 2,3-dimethylbutane, but also separately converted to interfacial heterocyclic compounds of 5,5-dimethyldihydro-2(3H)-furanone and 4,5-dimethyl-4,5-dihydro-2(3H)-furanone. Enough reaction time, optimum experimental atmosphere and shorter light wavelength benefited the formation of heterocyclization products. None of O3, 1O2, electron and hole directly contributed to the heterocyclic compound formation. While •O2- dominated the production of the heterocyclic compound under the dry reaction atmosphere and •OH showed more important role than •O2- in the heterocyclic compound formation under the moist reaction atmosphere. Theoretical calculation confirmed that •OH or •O2- induced heterocyclization reaction of alkane was exothermic, while the former reaction released 0.47 eV higher energy than the later reaction. The findings provide a comprehensive understanding of contributing roles of ROS in heterocyclization reaction of alkanes, and are helpful for effective elimination of industrial alkanes by advanced oxidation methods.

Laser-assisted failure recovery for dielectric elastomer actuators in aerial robots.

Insects maintain remarkable agility after incurring severe injuries or wounds. Although robots driven by rigid actuators have demonstrated agile locomotion and manipulation, most of them lack animal-like robustness against unexpected damage. Dielectric elastomer actuators (DEAs) are a class of muscle-like soft transducers that have enabled nimble aerial, terrestrial, and aquatic robotic locomotion comparable to that of rigid actuators. However, unlike muscles, DEAs suffer local dielectric breakdowns that often cause global device failure. These local defects severely limit DEA performance, lifetime, and size scalability. We developed DEAs that can endure more than 100 punctures while maintaining high bandwidth (>400 hertz) and power density (>700 watt per kilogram)-sufficient for supporting energetically expensive locomotion such as flight. We fabricated electroluminescent DEAs for visualizing electrode connectivity under actuator damage. When the DEA suffered severe dielectric breakdowns that caused device failure, we demonstrated a laser-assisted repair method for isolating the critical defects and recovering performance. These results culminate in an aerial robot that can endure critical actuator and wing damage while maintaining similar accuracy in hovering flight. Our work highlights that soft robotic systems can embody animal-like agility and resilience-a critical biomimetic capability for future robots to interact with challenging environments.

On-site growth of perovskite nanocrystal arrays for integrated nanodevices.

Despite remarkable progress in the development of halide perovskite materials and devices, their integration into nanoscale optoelectronics has been hindered by a lack of control over nanoscale patterning. Owing to their tendency to degrade rapidly, perovskites suffer from chemical incompatibility with conventional lithographic processes. Here, we present an alternative, bottom-up approach for precise and scalable formation of perovskite nanocrystal arrays with deterministic control over size, number, and position. In our approach, localized growth and positioning is guided using topographical templates of controlled surface wettability through which nanoscale forces are engineered to achieve sub-lithographic resolutions. With this technique, we demonstrate deterministic arrays of CsPbBr3 nanocrystals with tunable dimensions down to <50 nm and positional accuracy <50 nm. Versatile, scalable, and compatible with device integration processes, we then use our technique to demonstrate arrays of nanoscale light-emitting diodes, highlighting the new opportunities that this platform offers for perovskites' integration into on-chip nanodevices.

Multifunctional microelectronic fibers enable wireless modulation of gut and brain neural circuits.

Progress in understanding brain-viscera interoceptive signaling is hindered by a dearth of implantable devices suitable for probing both brain and peripheral organ neurophysiology during behavior. Here we describe multifunctional neural interfaces that combine the scalability and mechanical versatility of thermally drawn polymer-based fibers with the sophistication of microelectronic chips for organs as diverse as the brain and the gut. Our approach uses meters-long continuous fibers that can integrate light sources, electrodes, thermal sensors and microfluidic channels in a miniature footprint. Paired with custom-fabricated control modules, the fibers wirelessly deliver light for optogenetics and transfer data for physiological recording. We validate this technology by modulating the mesolimbic reward pathway in the mouse brain. We then apply the fibers in the anatomically challenging intestinal lumen and demonstrate wireless control of sensory epithelial cells that guide feeding behaviors. Finally, we show that optogenetic stimulation of vagal afferents from the intestinal lumen is sufficient to evoke a reward phenotype in untethered mice.

Atomic-level insight into effect of substrate concentration and relative humidity on photocatalytic degradation mechanism of gaseous styrene.

Substrate concentration and relative humidity (RH) impact the photocatalytic efficiency of industrial aromatic hydrocarbons, but how they influence intermediate formation and degradation pathway remains unclear. With the help of oxygen isotope tracing method, the effects of these two environmental parameters on degradation mechanism of styrene were revealed at atomic level. Increasing styrene concentration favored product formation, which was however inhibited by RH elevation. Gaseous products were not directly formed in gaseous phase, but originated from desorption of interfacial intermediates. The volatile aldehydes and furans further exchanged their 16O with 18O in H218O. Increase of RH showed higher enhancement on 18O distribution in all products and pathways than that of substrate concentration. Low RH preferred high generation of 16O2•- and (16)1O2, dominating reaction to form 1-phenyl-1,2-ethandiol, 2-hydroxy-1-phenyl-ethanon and phenylglyoxal monohydrate in sequence. Successive production of benzyl alcohol, benzaldehyde and benzoic acid through the reaction of styrene with promoted •18OH by increasing RH became predominant. Hydration was firstly observed and confirmed as an important gaseous transformation step of aldehyde and furan products. Our findings provide a deep insight into photocatalytic degradation mechanism of aromatic hydrocarbons regulated by environmental parameters to further improve their industrial purification efficiency, and are helpful predicting environmental geochemistry fate of organics and preventing their negative impact on natural environment.

A High-Lift Micro-Aerial-Robot Powered by Low-Voltage and Long-Endurance Dielectric Elastomer Actuators.

Dielectric elastomer actuators (DEAs) are a special class of artificial muscles that have been used to construct animal-like soft robotic systems. However, compared with state-of-the-art rigid actuators such as piezoelectric bimorphs and electromagnetic motors, most DEAs require higher driving voltages, and their power density and lifetime remain substantially lower. These limitations pose significant challenges for developing agile and powered autonomous soft robots. Here, a low-voltage, high-endurance, and power-dense DEA based on novel multiple-layering techniques and electrode-material optimization, is reported. When operated at 400 Hz, the 143 mg DEA generates forces of 0.36 N and displacements of 1.15 mm. This DEA is incorporated into an aerial robot to demonstrate high performance. The robot achieves a high lift-to-weight ratio of 3.7, a low hovering voltage of 500 V, and a long lifetime that exceeds 2 million actuation cycles. With 20 s of hovering time, and position and attitude error smaller than 2.5 cm and 2°, respectively, the robot demonstrates the longest and best-performing flight among existing sub-gram aerial robots. This important milestone demonstrates that soft robots can outperform their state-of-the-art rigid counterparts, and it provides an important step toward realizing power autonomy in soft robotic flights.

Nanoparticle contact printing with interfacial engineering for deterministic integration into functional structures.

Deterministic, pristine, and scalable integration of individual nanoparticles onto arbitrary surfaces is an ongoing challenge, yet essential for harnessing their unique properties for functional nanoscale devices. To address this challenge, we present a versatile technique where spatially arranged nanoparticles assembled in a topographical template are printed onto diverse surfaces, through a single contact-and-release step, with >95% transfer yield and <50-nanometer placement accuracy. Through engineering of interfacial interactions, our approach uniquely promotes high-yield transfer of individual particles without needing solvents, surface treatments, and polymer sacrificial layers, which are conventionally inevitable. By avoiding these mediation steps, surfaces can remain damage and contamination free and accessible to integrate into functional structures. We demonstrate this in a particle-on-mirror model system, where >2000 precisely defined nanocavities display a consistent plasmonic response with minimized interstructure variability. Through fabricating arrays of emitter-coupled nanocavities, we further highlight the integration opportunities offered by our contact printing.

Role of Multivalent Interactions in Dynamic-Template-Directed Assembly of Conjugated Polymers.

Dynamic-template-directed assembly is a promising method to enhance molecular ordering and electronic properties of solution-coated polymer semiconductor thin films over a large area. In this work, we establish that multicomponent dynamic templates of complementary chemistries can promote polymer crystallization through cooperative multivalent interactions. We investigate this phenomenon using a combination of templating substrates including a fluoropolymer, a hydrogen-bonded liquid, and an ionic liquid (IL). Template-dependent multiscale morphology is studied by a comprehensive set of characterization techniques to understand how introducing diverse chemical moieties modulates polymer assembly. Our results clearly confirm synergistic effects between components of complementary chemistries constituting the dynamic template. The relative degree of crystallinity is improved by 50-150% for films deposited on multicomponent dynamic templates compared to their neat constituents. In addition, macroscopic alignment is increased significantly (2-5 times) compared to single-component templates. As a result, highly anisotropic charge transport is observed with apparent hole mobilities up to 3.6 cm2 V-1 s-1. In contrast, such a synergistic effect is not observed when using a multicomponent dynamic template of comparable chemistries (i.e., IL and polymerized IL). We elucidate the origin of this synergistic effect by using attenuated total reflectance Fourier transform infrared spectroscopy and isothermal titration calorimetry. When the dynamic template comprises two or more components interacting with complementary binding sites on the conjugated polymer (CP) (esp. backbone vs side chain), the template-polymer interactions is significantly enhanced compared to the sum of single component contributions. These results provide valuable insights into surface-directed CP crystallization during large-area solution coating. Template dynamics is rarely studied and represents a new opportunity for guiding assembly of soft functional matter.

Large Modulation of Charge Carrier Mobility in Doped Nanoporous Organic Transistors.

Molecular doping of organic electronics has shown promise to sensitively modulate important device metrics. One critical challenge is the disruption of structure order upon doping of highly crystalline organic semiconductors, which significantly reduces the charge carrier mobility. This paper demonstrates a new method to achieve large modulation of charge carrier mobility via channel doping without disrupting the molecular ordering. Central to the method is the introduction of nanopores into the organic semiconductor thin films via a simple and robust templated meniscus-guided coating method. Using this method, the charge carrier mobility of C8 -benzothieno[3,2-b]benzothiophene transistors is boosted by almost sevenfold. This paper further demonstrates enhanced electron transport by close to an order of magnitude in a diketopyrrolopyrrole-based donor-acceptor polymer. Combining spectroscopic measurements, density functional theory calculations, and electrical characterizations, the doping mechanism is identified as partial-charge-transfer induced trap filling. The nanopores serve to enhance the dopant/organic semiconductor charge transfer reaction by exposing the π-electrons to the pore wall.

The Anti-Inflammatory Effects of a Yin Zhi Huang Soup in an Experimental Autoimmune Prostatitis Rat Model.

The present study aimed to investigate the therapeutic effects of the Chinese herbal medicine Yin Zhi Huang soup (YZS) in an experimental autoimmune prostatitis (EAP) rat model. In total, 48 rats were randomly divided into the following four groups (n = 12/group): saline group, pathological model group, Qianlietai group, and YZS group. We determined the average wet weight of the prostate tissue, the ratio of the wet weight of the prostate tissue to body weight, tumor necrosis factor-alpha (TNF-α) levels in the blood serum, the expression of inducible nitric oxide synthase (iNOS) in the rats' prostate tissues, and the pathological changes in the prostate tissue using light microscopy. YZS reduced the rats' prostate wet weight, the ratio of the prostate wet weight to body weight, and TNF-α levels in the blood serum and inhibited the expression of iNOS in the rats' prostate tissues (P < 0.05). Following YZS treatment, the pathological changes in the rats' prostates were improved compared with those in the model group (P < 0.05). Furthermore, YZS treatment reduced inflammatory changes in the prostate tissue. It also significantly suppressed proinflammatory cytokines, such as TNF-α, and chemokines, such as iNOS, in the rat model of EAP.