Polyalkenamers as Drop-In Additives for Ring-Opening Metathesis Polymerization: A Promising Upcycling Paradigm.

We report a distinct strategy to upcycle waste polyalkenamers such as polybutadiene into new, performance-advantaged materials by using them as drop-in additives for ring-opening metathesis polymerization (ROMP). The polyalkenamers serve as competent chain-transfer agents in ROMPs of common classes of cyclic olefin monomers, facilitating good molecular weight control, allowing low Ru catalyst loadings, and enabling efficient incorporation of the polyalkenamer into the synthesized polymeric material. We successfully demonstrate ROMP using model polyalkenamers and translate these learnings to leverage commercial polybutadiene and acrylonitrile butadiene styrene (ABS) as chain transfer agents for ROMP copolymerizations. Critically, our strategy is shown to be highly efficient and operationally simple, quantitatively incorporating the polyalkenamer and inheriting aspects of its thermomechanical performance. Our results highlight a promising pathway for the upcycling of polyalkenamers and provide an alternative to existing deconstruction and functional upcycling strategies.

Chiral Third-Harmonic Metasurface for Multiplexed Holograms.

Chiral nonlinear metasurfaces could natively synergize nonlinear wavefront manipulation and circular dichroism, offering enhanced capacity for multifunctional and multiplexed nonlinear metasurfaces. However, it is still quite challenging to simultaneously enable strong chiral response, precise wavefront control, high nonlinear conversion efficiency, and independent functions on spins and chirality. Here, we propose and experimentally demonstrate multiplexed third-harmonic (TH) holograms with four channels based on a chiral Au-ZnO hybrid metasurface. Specifically, the left- and right-handed circularly polarized (LCP and RCP) components of the TH holographic images can be designed independently under the excitation of an LCP (or RCP) fundamental beam. In addition, the TH conversion efficiency is measured to be as large as 10-5, which is 8.6 times stronger than that of a bare ZnO film with the same thickness. Thus, our work provides a promising platform for realizing efficient and multifunctional nonlinear nanodevices.

Variations in the toxicity and condition index of five bivalve species throughout a red tide event caused by Alexandrium catenella: A field study.

Harmful red tides in China have caused paralytic shellfish toxins (PSTs) pollution and led to severe socioeconomic effects in shellfish aquaculture. Although shellfish can survive harmful algal blooms, the effects on their Condition Index (CI) have been underestimated. This study sought to evaluate the effects of the profiles and levels of paralytic shellfish toxins on variations in the CI in bivalves under natural blooming conditions. We observed clear soft tissue lesions to varying degrees except in Mytilus galloprovincialis after toxin exposure. Among the five species of shellfish exposed in situ, only M. galloprovincialis accumulated PSTs content above the maximum permitted level (800 µg STX di-HCl eq./kg). The highest toxin content in all sample tissues was observed in Patinopecten yessoensis. Significant interspecies differences in PSTs accumulation among the five bivalve species were observed in the hepatopancreas. A total of nine PSTs components and four new C-11 hydroxyl metabolites (so-called M-toxins) toxins were detected, and detoxification diversity was observed among bivalves. We observed a higher proportion of M-toxin in early stages, and the proportions changed only slightly over time in M. galloprovincialis and Magallana gigas, thus accounting for the significantly higher metabolism rate. Notably, the CI in M. gigas and Argopecten irradians was positively correlated with lowest toxin accumulation of PSTs content, but significantly inhibited. In conclusion, our results revealed a significant inhibitory effect on the CI in shellfish, in a species specific manner, with distinct levels of inhibition correlated with different toxin metabolites. Our study revealed the toxin content of different bivalves exposed to a natural red tide environment and the consequent effects on growth, thus building a foundation for research on the mechanisms underlying the effects of PSTs on growth. These data establish the ecological and economic significance of the effects of harmful algal blooms on bivalves.

Target Localization in Wireless Sensor Networks Based on Received Signal Strength and Convex Relaxation.

A new positioning algorithm based on RSS measurement is proposed. The algorithm adopts maximum likelihood estimation and semi-definite programming. The received signal strength model is transformed to a non-convex estimator for the positioning of the target using the maximum likelihood estimation. The non-convex estimator is then transformed into a convex estimator by semi-definite programming, and the global minimum of the target location estimation is obtained. This algorithm aims at the L0 known problem and then extends its application to the case of L0 unknown. The simulations and experimental results show that the proposed algorithm has better accuracy than the existing positioning algorithms.

Highly Active Heterogeneous Catalyst for Ethylene Dimerization Prepared by Selectively Doping Ni on the Surface of a Zeolitic Imidazolate Framework.

The production of 1-butene by ethylene dimerization is an important chemical industrial process currently implemented using homogeneous catalysts. Here, we describe a highly active heterogeneous catalyst (Ni-ZIF-8) for ethylene dimerization, which consists of isolating Ni-active sites selectively located on the crystal surface of a zeolitic imidazolate framework. Ni-ZIF-8 can be easily prepared by a simple one-pot synthesis method in which site-specific anchoring of Ni is achieved spontaneously because of the incompatibility between the d8 electronic configuration of Ni2+ and the three-dimensional framework of ZIF-8. The full exposure and square-planar coordination of the Ni sites accounts for the high catalytic activity of Ni-ZIF-8. It exhibits an average ethylene turnover frequency greater than 1 000 000 h-1 (1-butene selectivity >85%) at 35 °C and 50 bar, far exceeding the activities of previously reported heterogeneous catalysts and many homogeneous catalysts under similar conditions. Moreover, compared to molecular Ni complexes used as homogeneous catalysts for ethylene dimerization, Ni-ZIF-8 has significantly higher stability and shows constant activity during 4 h of continuous reaction. Isotopic labeling experiments indicate that ethylene dimerization over Ni-ZIF-8 follows the Cossee-Arlman mechanism, and detailed characterizations combined with density functional theory calculations rationalize this observed high activity.

BMSC-derived exosomes ameliorate sulfur mustard-induced acute lung injury by regulating the GPRC5A-YAP axis.

Sulfur mustard (SM) is a highly toxic chemical warfare agent that causes acute lung injury (ALI) and/or acute respiratory distress syndrome (ARDS). There are no effective therapeutic treatments or antidotes available currently to counteract its toxic effects. Our previous study shows that bone marrow-derived mesenchymal stromal cells (BMSCs) could exert therapeutic effects against SM-induced lung injury. In this study, we explored the therapeutic potential of BMSC-derived exosomes (BMSC-Exs) against ALI and the underlying mechanisms. ALI was induced in mice by injection of SM (30 mg/kg, sc) at their medial and dorsal surfaces. BMSC-Exs (20 µg/kg in 200 µL PBS, iv) were injected for a 5-day period after SM exposure. We showed that BMSC-Exs administration caused a protective effect against pulmonary edema. Using a lung epithelial cell barrier model, BMSC-Exs (10, 20, 40 µg) dose-dependently inhibited SM-induced cell apoptosis and promoted the recovery of epithelial barrier function by facilitating the expression and relocalization of junction proteins (E-cadherin, claudin-1, occludin, and ZO-1). We further demonstrated that BMSC-Exs protected against apoptosis and promoted the restoration of barrier function against SM through upregulating G protein-coupled receptor family C group 5 type A (GPRC5A), a retinoic acid target gene predominately expressed in the epithelial cells of the lung. Knockdown of GPRC5A reduced the antiapoptotic and barrier regeneration abilities of BMSC-Exs and diminished their therapeutic effects in vitro and in vivo. BMSC-Exs-caused upregulation of GPRC5A promoted the expression of Bcl-2 and junction proteins via regulating the YAP pathway. In summary, BMSC-Exs treatment exerts protective effects against SM-induced ALI by promoting alveolar epithelial barrier repair and may be an alternative approach to stem cell-based therapy.

Catamenial pneumothorax with bubbling up on the diaphragmatic defects: a case report.

BACKGROUND: Catamenial pneumothorax is characterized by spontaneous recurring pneumothorax during menstruation, which is a common clinical manifestation of thoracic endometriosis syndrome. There are still controversies about its pathogenesis. CASE PRESENTATION: A 43-year-old woman with a history of endometriosis came to our hospital due to recurring pneumothorax during menstruation. Uniportal Video-assisted Thoracoscopic Surgery (VATS) exploration was performed on the eve of menstruating. We thoroughly explored the diaphragm, visceral and parietal pleura: The lung surface was scattered with yellowish-brown implants; no bullae were found; multiple diaphragmatic defects were found on the dome. And surprisingly, we caught a fascinating phenomenon: Bubbles were slipping into pleural cavity through diaphragmatic defects. We excised the diaphragmatic lesions and wedge resected the right upper lung lesion; cleared the deposits and flushed the thoracic cavity with pure iodophor. Diaphragmatic lesions confirmed the presence of endometriosis, and interestingly enough, microscopically, endometrial cells were shedding with impending menses. After a series of intraoperative operations and postoperative endocrine therapy, the disease did not recur after a period of follow-up. CONCLUSION: We have witnessed the typical signs of catamenial pneumothorax at the accurate timing: Not only observed the process of gas migration macroscopically, but also obtained pathological evidence of diaphragmatic periodic perforation microscopically, which is especially precious and confirms the existing theory that retrograde menstruation leads to diaphragmatic endometriosis, and the diaphragmatic fenestration is obtained due to the periodic activities of ectopic endometrium.

Structural analysis of transient reaction intermediate in formic acid dehydrogenation catalysis using two-dimensional IR spectroscopy.

The molecular structure of a catalytically active key intermediate is determined in solution by employing 2D IR spectroscopy measuring vibrational cross-angles. The formate intermediate (2) in the formic acid dehydrogenation reaction catalyzed by a phosphorus-nitrogen PN3P-Ru catalyst is elucidated. Our spectroscopic studies show that the complex features a formate ion directly attached to the Ru center as a ligand, and a proton added to the imine arm of the dearomatized PN3P* ligand. During the catalytic process, the imine arms are not only reversibly protonated and deprotonated, but also interacting with the protic substrate molecules, effectively serving as the local proton buffer to offer remarkable stability with a turnover number (TON) over one million.

Super terahertz phase shifter achieving high transmission and large modulation depth.

We propose an industrial-grade liquid-crystal-based terahertz (THz) 2π-phase shifter with predictable ultra-high amplitude transmittance. The phase retardation reaches 360.5° at 1.68 THz by analyzing the birefringence of liquid crystal (LC), and the amplitude transmittance in 0.3-1.5 THz is over 83%. More than 91.5% transmittance can be reached by decreasing the scattering of the THz wave in the dynamic deflection process of LC molecules, and that is close to the transmittance limit of quartz-based devices. This millimeter-thick phase shifter reaches full phase modulation and ultra-high transmittance in a broad THz band, is easy to be integrated in a quasi-optical system with a compact size and can be utilized as a wave plate, even an element in a THz phased array.

High-precision processing method for an aluminum mirror assisted with a femtosecond laser.

At present, aluminum-based optical payloads are widely used in the aviation and aerospace field, and the demand for aluminum mirrors has become increasingly urgent in the visible light region. The main processing of an aluminum alloy mirror involves single-point diamond turning followed by a combined polishing process. Among these processes, magnetorheological finishing (MRF) is an important method for improving a surface figure. During the MRF process, excessive impurity contaminants are introduced into the surface of the aluminum mirror, thereby reducing surface reflectivity. In this paper, theoretical analysis and time-of-flight secondary ion mass spectrometry depth profiling were used to obtain the cause of pollution, and the process scheme of femtosecond laser cleaning was proposed. After verifying the feasibility, a new, to the best of our knowledge, process route was implemented on a Φ50mm aluminum mirror. Finally, the surface figure of RMS 0.022λ and the surface roughness of Ra 3.24 nm were obtained. In addition, reflectance in the visible light and near-infrared bands has increased by about 50%.

Study on the surface crystallization mechanism and inhibition method in the CMP process of aluminum alloy mirrors.

Owing to its material properties, aluminum-based optical loads are widely used in the aerospace field. At present, the main processing of an aluminum alloy mirror is single-point diamond turning followed by the combined polishing process. The surface will generate some white crystals during the chemical mechanical polishing process (CMP). These crystals can affect the improvement of surface quality and seriously reduce the processing efficiency of the whole process. In view of the above problems, four main factors of crystallization are obtained by interface theoretical analysis, Visual MINTEQ simulation of chemical morphological distribution, and experimental analysis. They are temperature, PH value of polishing fluid, solid-liquid contact angle, and impurity content of aluminum alloy. The crystallization phenomenon in the polishing process is successfully suppressed by improving the polishing process and selecting new materials. The experimental results showed that the surface roughness decreased from 7.21 to 2.98 nm without crystallization using the new method.

The Effect of AtHKT1;1 or AtSOS1 Mutation on the Expressions of Na⁺ or K⁺ Transporter Genes and Ion Homeostasis in Arabidopsis thaliana under Salt Stress.

HKT1 and SOS1 are two key Na⁺ transporters that modulate salt tolerance in plants. Although much is known about the respective functions of HKT1 and SOS1 under salt conditions, few studies have examined the effects of HKT1 and SOS1 mutations on the expression of other important Na⁺ and K⁺ transporter genes. This study investigated the physiological parameters and expression profiles of AtHKT1;1, AtSOS1, AtHAK5, AtAKT1, AtSKOR, AtNHX1, and AtAVP1 in wild-type (WT) and athkt1;1 and atsos1 mutants of Arabidopsis thaliana under 25 mM NaCl. We found that AtSOS1 mutation induced a significant decrease in transcripts of AtHKT1;1 (by 56⁻62% at 6⁻24 h), AtSKOR (by 36⁻78% at 6⁻24 h), and AtAKT1 (by 31⁻53% at 6⁻24 h) in the roots compared with WT. This led to an increase in Na⁺ accumulation in the roots, a decrease in K⁺ uptake and transportation, and finally resulted in suppression of plant growth. AtHKT1;1 loss induced a 39⁻76% (6⁻24 h) decrease and a 27⁻32% (6⁻24 h) increase in transcripts of AtSKOR and AtHAK5, respectively, in the roots compared with WT. At the same time, 25 mM NaCl decreased the net selective transport capacity for K⁺ over Na⁺ by 92% in the athkt1;1 roots compared with the WT roots. Consequently, Na⁺ was loaded into the xylem and delivered to the shoots, whereas K⁺ transport was restricted. The results indicate that AtHKT1;1 and AtSOS1 not only mediate Na⁺ transport but also control ion uptake and the spatial distribution of Na⁺ and K⁺ by cooperatively regulating the expression levels of relevant Na⁺ and K⁺ transporter genes, ultimately regulating plant growth under salt stress.

Fringe discretization and manufacturing analysis of a computer-generated hologram in a null test of the freeform surface.

A computer-generated hologram (CGH) is the core component for an aspheric surface test. According to fabrication demands, it is necessary to convert the designed CGH phase compensation function into the processed pattern, that is, the fringe discretization process. In this paper, we propose a new discretization method for a CGH in a test of the freeform surface, and realized the encoding of processed fringes by MATLAB software. Furthermore, we designed the experiment to verify the accuracy of the new discretization method and compared the calculation efficiency between the new algorithm and the reported algorithm. Finally, based on the testing requirement of a freeform mirror in a camera optical system, we completed the design, encoding, and fabrication of the CGH sample, and analyzed the influence of various errors on wavefront accuracy of the CGH.

3D cone beam computed tomography reconstruction images in diagnosis of ameloblastomas of lower jaw: A case report and mini review.

Cone beam computed tomography (CBCT) has obvious advantages over regular radiography in diagnosis of complex diseases. Objective of this study is to report a case of a mandibular jaw ameloblastoma recurring cyst, which represents a benign tumor of odontogenic epithelium, using CBCT imaging technology. CBCT examination of the patient suffering with recurrent lower jaw cyst (relapsing four years after surgery) showed a decrease in irregular bone density and appearance of a honeycomb pattern (3.5 cm×2.5 cm×1.8 cm) in the right lower jaw. This suggests that the lesion is more likely to be an ameloblastoma. Preoperative tissue biopsy and pathological examination of surgical sample confirmed the diagnosis. Surgical resection of the diseased tissue and autogenous bone grafting in the mandible was performed. Postoperative CBCT examination showed that the bone defect healed well, without recurrence of the tumor 22 months postoperatively. In conclusion, the rotated 3D CBCT images clearly displays the exact size, location, borders and internal changes of the tumor in the jaw cyst itself and the adjacent tissues. Thus, the dental CBCT allows clinicians to better evaluate lesions, leading to better treatment outcomes.

Dehydrogenation of Formic Acid Catalyzed by a Ruthenium Complex with an N,N'-Diimine Ligand.

We report a ruthenium complex containing an N,N'-diimine ligand for the selective decomposition of formic acid to H2 and CO2 in water in the absence of any organic additives. A turnover frequency of 12 000 h-1 and a turnover number of 350 000 at 90 °C were achieved in the HCOOH/HCOONa aqueous solution. Efficient production of high-pressure H2 and CO2 (24.0 MPa (3480 psi)) was achieved through the decomposition of formic acid with no formation of CO. Mechanistic studies by NMR and DFT calculations indicate that there may be two competitive pathways for the key hydride transfer rate-determining step in the catalytic process.

Association of Matrix Metalloproteinase-1 and Matrix Metalloproteinase-3 Gene Variants with Ischemic Stroke and Its Subtype.

BACKGROUND: Genetic variations in the genes of matrix metalloproteinases (MMPs) may play an important role in the pathogenesis of ischemic stroke (IS). Here we investigate the association between MMP-1 -1607 1G/2G and MMP-3 -1171 5A/6A genetic polymorphisms and etiological subtypes of IS in the Han Chinese population. METHODS: A total of 640 eligible patients with IS and 637 age- and gender-matched apparently healthy volunteers were enrolled. Subtypes of IS were classified by Trial of Org 10172 in Acute Stroke Treatment criteria. MMP-1 (-1607 1G/2G) and MMP-3 (-1171 5A/6A) polymorphisms were evaluated using polymerase chain reaction-restriction fragment length polymorphism. RESULTS: The frequencies of the 5A/6A + 5A/5A genotypes and 5A allele were significantly higher in patients with IS than in controls (P <.001, P <.001, respectively). No association was found between MMP-1 1G/2G polymorphism and overall IS. In subgroup analyses, MMP-1 1G/2G and 2G/2G genotypes increased the risk of small-artery occlusion (SAO) subtype (multivariate-adjusted, P <.001, P = .002, respectively), and MMP-3 5A/6A + 5A/5A genotypes were related with large-artery atherosclerosis (LAA) subtype (multivariate-adjusted, P <.001). Haplotype analyses indicated that 2G-6A and 1G-5A increased the risk of SAO (multivariate-adjusted, P = .029) and LAA (multivariate-adjusted, P <.001), respectively. CONCLUSIONS: MMP-1 (-1607 1G/2G) and MMP-3 (-1171 5A/6A) polymorphisms may contribute to different subtypes of IS susceptibility.

Impact of 5A/6A polymorphism of matrix metalloproteinase-3 on recurrent atherosclerotic ischemic stroke in Chinese.

Little is known about the impact of the 5A/6A polymorphism of matrix metalloproteinase-3 (MMP-3) on recurrence of atherosclerotic ischemic stroke in Chinese. The aim of this study was to investigate the association of MMP-3 serum level and 5A/6A genetic polymorphism with the recurrence of atherosclerotic ischemic stroke in the Chinese Han population. We analyzed 106 large artery atherosclerosis (LAA) recurrent ischemic stroke patients and 545 LAA first onset ischemic stroke patients from January 2009 to June 2014. Serum MMP-3 concentrations were measured with an enzyme-linked immunosorbent assay. The genotypes of MMP-3 promoter polymorphism (-1171 5A/6A) were determined using polymerase chain reaction-restriction fragment length polymorphism. The frequencies of MMP-3 5A/6A+5A/5A (32.08% vs. 21.47%, p = 0.02) genotype and 5A (16.98% vs. 11.01%, p = 0.01) allele in the recurrent group was significantly higher than those in the first onset group. After adjustment for vascular risk factors, multivariate logistic regression analysis suggested that the MMP-3 5A/6A+5A/5A genotype was an independent risk factor for LAA recurrent ischemic stroke (odds ratio [OR], 1.74; 95% confidence interval [CI], 1.09-2.79, p = 0.021). No significant difference was observed for the MMP-3 serum concentrations between the recurrent group and the first onset group (22.23 ± 8.31 vs. 21.49 ± 7.89 ng/ul, t = 0.88, p = 0.38). The MMP-3 (-1171 5A/6A) polymorphism may contribute to LAA recurrent ischemic stroke susceptibility. Analysis of 5A/6A polymorphism in MMP-3 may identify patients at higher risk for LAA ischemic stroke recurrence, who may be selected for intensive preventive therapy.

Accelerated Fmoc solid-phase synthesis of peptides with aggregation-disrupting backbones.

In this work, we describe an accelerated solid-phase synthetic protocol for ordinary or difficult peptides involving air-bath heating and amide protection. For the Hmsb-based backbone amide protection, an optimized acyl shift condition using 1,4-dioxane was discovered. The efficiency and robustness of the protocol was validated in the course of preparation of classical difficult peptides and ubiquitin protein segments.

Quantitative assessment of the influence of common variations (rs8034191 and rs1051730) at 15q25 and lung cancer risk.

Several genome-wide association studies on lung cancer (LC) have reported similar findings of a new susceptibility locus, 15q25. After that, a number of studies reported that rs8034191 and rs1051730 polymorphisms at chromosome 15q25 have been implicated in LC risk. However, studies have yielded contradictory results. To derive a more precise estimation of the relationship, a meta-analysis of 43,742 LC cases and 58,967 controls from 17 published case-control studies was performed. Overall, significantly elevated LC risk was associated with rs8034191-C (OR = 1.26, 95% CI 1.22-1.31, P < 10(-5)) and rs105173-A variant (OR = 1.28, 95% CI 1.20-1.36, P < 10(-5)) when all studies were pooled into the meta-analysis. In the subgroup analysis by ethnicity, significantly increased risks were found for rs8034191 and rs105173 polymorphisms among Caucasians and African American, while no significant associations were observed for the two polymorphisms in East Asians. In addition, we found that rs8034191 and rs105173 confer risk, for both adenocarcinoma and squamous cell carcinoma when stratified by histological types of LC. Furthermore, our results on stratified analysis according to smoking status showed an increased LC risk in ever-smokers, while no associations were detected among never-smokers for the two polymorphisms. In conclusion, this meta-analysis demonstrated that the two common variations (rs8034191 and rs1051730) at 15q25 are a risk factor associated with increased LC susceptibility, but these associations vary in different ethnic populations.

Prediction of Fuhrman pathological grade of renal clear cell carcinoma based on CT texture analysis.

OBJECTIVE: To study the predictive performance of the imaging model based on the texture analysis of CT plain scan in distinguishing between low (grade I and II) and high (grade III and IV) of Fuhrman pathological grade of renal clear cell carcinoma. METHODS: The clinical data of 94 patients with ccRCC who underwent CT scan and were confirmed by biopsy or surgery in TCGA-KIRC public database were retrospectively analyzed. There were 32 cases of low-grade ccRCC and 62 cases of high-grade ccRCC. The patients were randomly divided into training set and verification set according to the proportion of 7:3 by stratified sampling method. The imaging characteristics of ccRCC were calculated in the plain CT images. Lasso regression was used to reduce the dimensionality of the imaging characteristics of the training set, and binary logistic regression was used to construct the prediction model. Bootstrap method was used to verify the training set model and the validation set model, and the area under the receiver operating characteristic (ROC) curve (AUC) was calculated respectively. RESULTS: Binary logistic regression showed that only imaging features were independent risk factors for predicting the Furhman classification of ccRCC. The predictive model was y = 1/[1 + exp (-z)], z = 1.274 × imaging risk score + 0.072. The results of bootstrap internal validation showed that the AUC of the training group was 0.961 (95% CI: 0.900-0.913). The Hosmer-Lemeshow goodness of fit test showed that the prediction model had a good calibration in the training group (P = 0.416). The AUC of prediction model in validation group was 0.731 (95% CI: 0.500-1.000). The Hosmer-Lemeshow goodness of fit test results showed that the prediction model had a good calibration in the validation group (P = 0.592). CONCLUSION: The model based on CT texture analysis has a good predictive effect in differentiating low-grade and high-grade ccRCC and can provide reference for the treatment and prognosis of patients.