qMAP enabled microanatomical mapping of human skin aging.

Aging is a major driver of diseases in humans. Identifying features associated with aging is essential for designing robust intervention strategies and discovering novel biomarkers of aging. Extensive studies at both the molecular and organ/whole-body physiological scales have helped determined features associated with aging. However, the lack of meso-scale studies, particularly at the tissue level, limits the ability to translate findings made at molecular scale to impaired tissue functions associated with aging. In this work, we established a tissue image analysis workflow - quantitative micro-anatomical phenotyping (qMAP) - that leverages deep learning and machine vision to fully label tissue and cellular compartments in tissue sections. The fully mapped tissue images address the challenges of finding an interpretable feature set to quantitatively profile age-related microanatomic changes. We optimized qMAP for skin tissues and applied it to a cohort of 99 donors aged 14 to 92. We extracted 914 microanatomic features and found that a broad spectrum of these features, represented by 10 cores processes, are strongly associated with aging. Our analysis shows that microanatomical features of the skin can predict aging with a mean absolute error (MAE) of 7.7 years, comparable to state-of-the-art epigenetic clocks. Our study demonstrates that tissue-level architectural changes are strongly associated with aging and represent a novel category of aging biomarkers that complement molecular markers. Our results highlight the complex and underexplored multi-scale relationship between molecular and tissue microanatomic scales.

Diameter-selective extraction of single-walled carbon nanotubes by interlocking with Cu-tethered square nanobrackets.

We have been working with carbon nanotube separation through host-guest chemistry. Herein, a new macrocyclic host molecule, Cu-tethered square nanobrackets, is designed, synthesized and applied to single-walled carbon nanotubes (SWNTs) for their diameter-based separation. The complexation between copper ions and dipyrrin moieties of the nanobracket gives Cu-tethered square nanobrackets, which is confirmed by absorption, Raman and MALDI-TOF mass spectra. Upon extraction of SWNTs with the nanobracket and copper(II), in situ-formed square Cu-nanobrackets are found to interlock SWNTs to disperse them in 2-propanol. The interlocking is confirmed by Raman spectroscopy after thorough washing of the extracted SWNTs. Pristine SWNTs were recovered through demetalation of the interlocked ones along with the nanobracket. Raman and absorption spectroscopies of the extracted SWNTs reveals the diameter enrichment of only several kinds of SWNTs in the diameter range from 0.94 to 1.10 nm among ≈20 kinds of SWNTs from 0.76 to 1.20 nm in their diameter range. The diameter selectivity is supported by the theoretical calculations with the GFN2-xTB method, indicating that the most preferred SWNT diameter for the square Cu-nanobrackets is 1.04 nm.

Effects of biochar application methods on greenhouse gas emission and nitrogen use efficiency in paddy fields.

Biochar application in rice production reduces nitrogen loss and greenhouse gases. We conducted in situ experiments for 3 years, with N210B0 (210 kg N ha-1) as the control. Two biochar application methods (B1:15 t ha-1 biochar applied once and B2: biochar applied three times at 5 t ha-1 yr-1) combined with two nitrogen levels (N210: 210 kg N ha-1 and N168: 168 kg N ha-1) were used. Soil physicochemical properties, CH4 and N2O emissions, functional gene abundance, rice yield, and nitrogen use efficiency were analyzed. Both methods improved the physicochemical properties of the soil, however, B1 was less effective than B2 in increasing soil pH, bulk density, organic carbon, total nitrogen, and microbial biomass nitrogen in year 3. B1 had a higher CH4 emission mitigation effect than B2 in 3 consecutive years, mainly due to the higher pmoA gene abundance. B1 showed a higher reduction effect of N2O emissions compared to B2 in year 1, but the opposite was observed in years 2 and 3. B2 had a higher abundance of AOB, nirK, and nosZ genes compared to B1 in year 3. Compared with N210B0, rice yields were increased by 9.1 %, 9.6 %, and 3.6 % with N210B1, N210B2, and N168B2, respectively, over 3 years, while N168B1 improved yields in the previous 2 years. Biochar improved nitrogen use efficiency over 3 consecutive years directly due to increased use efficiency of panicle fertilizer; the effect of B1 was greater than that of B2 during years 1 and 2, while the opposite was observed in year 3. Both Biochar applied once and three times appeared to be promising practices to increase yield and mitigate GHGs. From the GHGI perspective, the biochar applied once combined with 168 kg N ha-1 can further improve nitrogen use efficiency, and reduce GHGs without hindering improvements in rice yield.

Interlocking of Single-Walled Carbon Nanotubes with Metal-Tethered Tetragonal Nanobrackets to Enrich a Few Hundredths of a Nanometer Range in Their Diameters.

We have separated carbon nanotubes through host-guest complexation using host molecules named "nanotweezers" and "nanocalipers". In this work, a host molecule named tetragonal "M-nanobrackets", consisting of a pair of dipyrrin nanocalipers corresponding to two brackets "[" and "]" tethered by two metals (M), is designed, synthesized, and employed to separate single-walled carbon nanotubes (SWNTs). A facile three-step process including one-pot Suzuki coupling is developed to synthesize M-nanobrackets in a 37% total yield (M = Cu). Upon extraction of SWNTs with a square nanobracket and Cu(II), in situ formed tetragonal M-nanobrackets are found to interlock SWNTs to disperse them in 2-propanol. The interlocking is confirmed by absorption and Raman spectroscopy as well as transmission electron and atomic force microscopy. Especially, Raman spectroscopy is utilized to prove the interlocking of SWNTs; Cu-nanobrackets are found to show inherent resonance Raman signals and affect the SWNT signals, or a radial breathing vibration, due to the rigid rectangular structure of Cu-nanobrackets. The interlocking is facilely and thoroughly released through demetalation to recover the pristine SWNTs as well as the square nanobracket. Such chemically controlled locking and unlocking for SWNTs are one of the characteristics of our separation process. This enables a precise evaluation by Raman, photoluminescence, and absorption spectroscopy of the diameter selectivity to SWNTs, revealing the diameter enrichment of only three kinds of SWNTs, (7,6), (9,4), and (8,5), in the 0.02 nm diameter range from 0.90 to 0.92 nm among ∼20 kinds of SWNTs from 0.76 to 1.17 nm in their diameter range.

Effects of cadmium sulfide nanoparticles on sulfate bioreduction and oxidative stress in Desulfovibrio desulfuricans.

Sulfate-containing wastewater has a serious threat to the environment and human health. Microbial technology has great potential for the treatment of sulfate-containing wastewater. It was found that nano-photocatalysts could be used as extracellular electron donors to promote the growth and metabolic activity of non-photosynthetic microorganisms. However, nano-photocatalysts could also induce oxidative stress and damage cells. Therefore, the interaction mechanism between photosynthetic nanocatalysts and non-photosynthetic microorganisms is crucial to determine the regulatory strategies for microbial wastewater treatment technologies. In this paper, the mechanism and regulation strategy of cadmium sulfide nanoparticles (CdS NPs) on the growth of sulfate-reducing bacteria and the sulfate reduction process were investigated. The results showed that the sulfate reduction efficiency could be increased by 6.4% through CdS NPs under light conditions. However, the growth of Desulfovibrio desulfuricans C09 was seriously inhibited by 55% due to the oxidative stress induced by CdS NPs on cells. The biomass and sulfate reduction efficiency could be enhanced by 6.8% and 5.9%, respectively, through external addition of humic acid (HA). At the same time, the mechanism of the CdS NPs strengthening the sulfate reduction process by sulfate bacteria was also studied which can provide important theoretical guidance and technical support for the development of microbial technology combined with extracellular electron transfer (EET) for the treatment of sulfate-containing wastewater.

Effect of Protein Corona on Mitochondrial Targeting Ability and Cytotoxicity of Triphenylphosphonium Conjugated with Polyglycerol-Functionalized Nanodiamond.

Functionalization of nanoparticles (NPs) with targeting moieties has a high potential to advance precision nanomedicine. However, the targeting moieties on a NP surface are known to be masked by a protein corona in biofluids, lowering the targeting efficiency. Although it has been demonstrated at the cellular level, little is known about the influence of the protein corona on the subcellular targeting. Herein, we adopted triphenylphosphonium (TPP) as a mitochondrial targeting moiety and investigated the effects of protein coronas from fetal bovine serum and human plasma on its targeting ability and cytotoxicity. Specifically, we introduced TPP in low (l) and high (h) densities on the surface of nanodiamond (ND) functionalized with polyglycerol (PG). Despite the "corona-free" PG interface, we found that the TPP moiety attracted proteins to form a corona layer with clear linearity between the TPP density and the protein amount. By performing investigations on human cervix epithelium (HeLa) and human lung epithelial carcinoma (A549) cells, we further demonstrated that (1) the protein corona alleviated the cytotoxicity of both ND-PG-TPP-l and -h, (2) a smaller amount of proteins on the surface of ND-PG-TPP-l did not affect its mitochondrial targeting ability, and (3) a larger amount of proteins on the surface of ND-PG-TPP-h diminished its targeting specificity by restricting the NDs inside the endosome and lysosome compartments. Our findings will provide in-depth insights into the design of NPs with active targeting moiety for more precise and safer delivery at the subcellular level.

A new turn-on fluorescent probe for sensing 4-methylbenzenethiol in real water samples.

A new fluorescent probe (MBT) for the detection of 4-methylbenzenethiol (p-MePhSH) was developed by using 4-(benzo[d]thiazol-2-yl)-3-methoxyphenol as the fluorophore and 2,4-dinitrophenyl ether as the sensing moiety. Probe MBT displayed good selectivity toward p-MePhSH in DMSO/PBS buffer (5/5, v/v) solution and anti-interference over other competitive species via nucleophilic aromatic substitution. The fluorescence intensities of the probe responded p-MePhSH showed a 22-fold enhancement and good linearity with p-MePhSH concentration collected in the range of 0-15 µM. Moreover, the probe is sensitive to p-MePhSH and the limit of detection is 45 nM. The sensing mechanism of probe MBT was verified by high-resolution mass spectrometry and fluorescence lifetime. Furthermore, the probe was used to the detection of p-MePhSH in real water samples.

[Contribution of Emissions from the Iron and Steel Industry to Air Quality in China].

Based on the data from a continuous emission monitoring systems network in 2015, this study analyzed the compliance rates of exhaust gas in the processes of China's iron and steel industry, and established a high-resolution steel plant emission inventory for China (HSEC, 2015), based on the bottom-up method. The contribution of emissions from the iron and steel industry to regional air quality was quantitatively simulated using a CAMx model. The results showed that in 2015, the total emissions of SO2, NOx, PM10, PM2.5, PCDD/Fs, VOCs, CO, BC, OC, EC, and F were 374800 t, 720500 t, 334800 t, 150300 t, 1.91 kg, 842900 t, 34788500 t, 6400 t, 8300 t, 800 t, and 7700 t, respectively. From a regional perspective, the iron and steel industry in Shanghai and Tianjin has the highest emission intensity per unit area and contributes a high proportion to regional air pollution. From a process perspective, in 2015, the exhaust concentration of flue gas in the main process gradually decreased, with a high compliance rate, and the emission factor significantly decreased to lower than that in the existing research results. From a species perspective, in 2015, NOx emission from the steel industry contributed the most to regional air quality, and there is therefore a great emission reduction potential for NOx.

Efficient All-Inorganic Perovskite Light-Emitting Diodes with Improved Operation Stability.

Stability is becoming a main issue for perovskite light-emitting diodes (PeLEDs), as their external quantum efficiency (EQE) has been boosted to above 20%. An all-inorganic perovskite, cesium lead iodide (CsPbI3), has better stability than organic-inorganic hybrid perovskites but suffers from a transition to yellow δ-CsPbI3 phase at room temperature. Herein, we report stabilization of the α-CsPbI3 phase by in situ formation of perovskite nanocrystals (NCs). By incorporation of a proper ratio of bulky organoammonium halides, 4-fluoro-phenylmethylammonium iodide (4-F-PMAI), stable α-CsPbI3 films with nanometer-sized crystals can be obtained using a one-step spin-coating approach. The PeLEDs using α-CsPbI3 NC films as emitters show a pure red emission at 692 nm and a high EQE of 14.8%. The EQE is further boosted to 18.6% using CsPbI2.8Br0.2 as the emissive layer. Furthermore, the PeLEDs show a very decent half-lifetime of over 1200 min and a shelf stability of over 2 months, much longer than that of hybrid PeLEDs.