Efficient separation of monobromotoluene isomers by nonporous adaptive perbromoethylated pillar[5]arene crystals.

Herein we report an efficient adsorptive separation approach for monobromotoluene isomers using nonporous adaptive crystals of perbromoethylated pillar[5]arene (BrP5). The purity of separated m-bromotoluene from an equal volume mixture of m-bromotoluene and o-bromotoluene reaches 96.6% in one cycle and the adsorbent BrP5 can be reused without losing separation performance.

Pillararene incorporated metal-organic frameworks for supramolecular recognition and selective separation.

Crystalline frameworks containing incorporated flexible macrocycle units can afford new opportunities in molecular recognition and selective separation. However, such functionalized frameworks are difficult to prepare and challenging to characterize due to the flexible nature of macrocycles, which limits the development of macrocycle-based crystalline frameworks. Herein, we report the design and synthesis of a set of metal-organic frameworks (MOFs) containing pillar[5]arene units. The pillar[5]arene units were uniformly embedded in the periodic frameworks. Single crystal X-ray diffraction analysis revealed an interpenetrated network that appears to hinder the rotation of the pillar[5]arene repeating units in the frameworks, and it therefore resulted in the successful determination of the precise pillar[5]arene host structure in a MOF crystal. These MOFs can recognize paraquat and 1,2,4,5-tetracyanobenzene in solution and selectively remove trace pyridine from toluene with relative ease. The work presented here represents a critical step towards the synthesis of macrocycle-incorporated crystalline frameworks with well-defined structures and functional utility.

Substrate-Responsive Pillar[5]arene-Based Organic Room-Temperature Phosphorescence.

Room-temperature phosphorescence (RTP) is a photophysical phenomenon typically associated with a long-lived emission that can be detected by the unaided eye. Several natural proteins display RTP, as do certain artificial polymers. In both cases, the RTP is ascribed to effective intramolecular through-space electronic communication. However, small molecules with internal electronic communication that enable RTP are relatively rare. Herein, we describe an alkyl halide-responsive RTP system consisting of a meta-formylphenyl-bearing pillar[5]arene derivative that supports effective through-space charge transfer (TSCT) within the pillararene cavity. Treatment with bromoethane, a heavy atom-containing guest for the pillar[5]arene host, serves to enhance the emission. An isomeric para-formylphenyl-bearing pillar[5]arene system proved ineffective in producing an RTP effect. Quantum chemical calculations based on single-crystal X-ray diffraction analyses provided insights into the structural determinants governing TSCT between the 1,4-dimethoxybenzene donor units and the formylphenyl groups of the pillar[5]arene, as well as the associated energy gaps and intersystem crossing channels. We believe that the present system and the associated mechanistic analysis provide the foundation for design of new small molecule with tunable RTP features.

Estimating individualized treatment effects using a risk-modeling approach: an application to epidural steroid injections for lumbar spinal stenosis.

ABSTRACT: Conventional "1-variable-at-a-time" analyses to identify treatment effect modifiers are often underpowered and prone to false-positive results. This study used a "risk-modeling" approach guided by the Predictive Approaches to Treatment effect Heterogeneity (PATH) Statement framework: (1) developing and validating a multivariable model to estimate predicted future back-related functional limitations as measured by the Roland-Morris Disability Questionnaire (RMDQ) and (2) stratifying patients from a randomized controlled trial (RCT) of lumbar epidural steroid injections (LESIs) for the treatment of lumbar spinal stenosis into subgroups with different individualized treatment effects on RMDQ scores at the 3-week follow-up. Model development and validation were conducted in a cohort (n = 3259) randomly split into training and testing sets in a 4:1 ratio. The model was developed in the testing set using linear regression with least absolute shrinkage and selection regularization and 5-fold cross-validation. The model was then applied in the testing set and subsequently in patients receiving the control treatment in the RCT of LESI. R2 values in the training set, testing set, and RCT were 0.38, 0.32, and 0.34, respectively. There was statistically significant modification ( P = 0.03) of the LESI treatment effect according to predicted risk quartile, with clinically relevant LESI treatment effect point estimates in the 2 quartiles with greatest predicted risk (-3.7 and -3.3 RMDQ points) and no effect in the lowest 2 quartiles. A multivariable risk-modeling approach identified subgroups of patients with lumbar spinal stenosis with a clinically relevant treatment effect of LESI on back-related functional limitations.

Efficient Purification of 2,6-Lutidine by Nonporous Adaptive Crystals of Pillararenes.

2,6-Lutidine (2,6-LT) is a very important raw material in the chemical industry, but the impurities of 3-picoline (3-PC) and 4-picoline (4-PC) existing in 2,6-LT seriously affect its quality. Considering different molecular sizes of these three compounds, herein, we exploit nonporous adaptive crystals (NACs) of pillararenes as purifying agents for removal of 3-PC and 4-PC in 2,6-LT. We find that per-ethylated pillar[5]arene (EtP5) can selectively adsorb 3-PC and 4-PC, while negligible capture of 2,6-LT is observed, resulting in improvement of the purity of 2,6-LT up to 94.9%. Single-crystal structures indicate that the excellent selectivity originates from the size match and complexation stability differences among different host/guest pairs. After purification, NACs of EtP5 can be easily regenerated and used in the next run without a significant performance degradation.

Separation of pyrrolidine from tetrahydrofuran by using pillar[6]arene-based nonporous adaptive crystals.

Pyrrolidine, an important feedstock in the chemical industry, is commonly produced via vapor-phase catalytic ammoniation of tetrahydrofuran (THF). Obtaining pyrrolidine with high purity and low energy cost has extremely high economic and environmental values. Here we offer a rapid and energy-saving method for adsorptive separation of pyrrolidine and THF by using nonporous adaptive crystals of per-ethyl pillar[6]arene (EtP6). EtP6 crystals show a superior preference towards pyrrolidine in 50 : 50 (v/v) pyrrolidine/THF mixture vapor, resulting in rapid separation. The purity of pyrrolidine reaches 95% in 15 min of separation, and after 2 h, the purity is found to be 99.9%. Single-crystal structures demonstrate that the selectivity is based on the stability difference of host-guest structures after uptake of THF or pyrrolidine and non-covalent interactions in the crystals. Besides, EtP6 crystals can be recycled efficiently after the separation process owing to reversible transformations between the guest-free and guest-loaded EtP6.

Pillararene-Induced Intramolecular Through-Space Charge Transfer and Single-Molecule White-Light Emission.

The fabrication of single-molecule white-light emission (SMWLE) materials has become a highly studied topic in recent years and through-space charge transfer (TSCT) is emerging as an important concept in this field. However, the preparation of ideal TSCT-based SMWLE materials is still a big challenge. Herein, we report a bifunctional pillar[5]arene (TPCN-P5-TPA) with a linear donor-spacer-acceptor structure and aggregation-induced emission (AIE) property. The bulky pillar[5]arene between the donor and acceptor induces a twisted conformation and a non-conjugated structure, resulting in intramolecular TSCT. In addition, the AIE feature and pillar[5]arene cavity endow TPCN-P5-TPA with responsiveness to viscosity and polar guests, by which the TSCT emission is triggered. The combination of blue locally-excited state emission and yellow TSCT emission of TPCN-P5-TPA generates SMWLE. Therefore, we provide a new and versatile strategy for the construction of TSCT-based SMWLE materials.

Comparative iTRAQ proteomics identified proteins associated with sperm maturation between yak and cattleyak epididymis.

BACKGROUND: During maturation, spermatozoa acquire motility and fertilizing capacity as they transit through the epididymis. In recent years, two-dimensional gel electrophoresis has been employed in proteomics studies conducted in rat, boar and human. However, there has not been a complete information regarding the proteins associated with sperm maturation in the epididymis. In this study, we employed iTRAQ proteomics to investigate proteins associated with sperm maturation between yak and cattleyak epididymis. RESULTS: After a successful sampling and protein extraction, the iTRAQ coupled with LC-MS/MS mass spectrometry and bioinformatics analysis were performed. We identified 288 differentially abundant proteins (DAPs) between yak and cattleyak epididymis; 151 were up-regulated while 137 were down-regulated in cattleyak relative to yak. Gene Ontology analysis identified that down-regulated DAPs in cattleyak were mostly enriched in the acetylation of protein component, along with negative and positive regulatory activities. iTRAQ proteomics data showed that the top up-regulated DAPs were mainly enriched in cell communication, cell adhesion, cytoskeleton organization, stress response, post-translational modifications and metabolic functions while the down-regulated DAPs were predominantly associated with sperm maturation, long-term sperm storage, sperm forward motility, sperm-oocyte fusion and regulatory functions. CONCLUSION: These results provide insight into the molecular mechanisms underlying male cattleyak sterility.

Chemoresponsive Supramolecular Polypseudorotaxanes with Infinite Switching Capability.

Chemoresponsive supramolecular systems with infinite switching capability are important for applications in recycled materials and intelligent devices. To attain this objective, here a chemoresponsive polypseudorotaxane is reported on the basis of a bis(p-phenylene)-34-crown-10 macrocycle (H) and a cyano-substituted viologen guest (G). H and G form a [2]pseudorotaxane (H⊃G) both in solution and in the solid state. Upon addition of AgSF6 , a polypseudorotaxane (denoted as [H⋅G⋅Ag]n ) forms as synergistically driven by host-guest complexation and metal-coordination interactions. [H⋅G⋅Ag]n depolymerizes into a [3]pseudorotaxane (denoted as H2 ⋅G⋅Ag2 ⋅acetone2 ) upon addition of H and AgSF6 , while it reforms with successive addition of G. The transformations between [H⋅G⋅Ag]n and H2 ⋅G⋅Ag2 ⋅acetone2 can be switched for infinite cycles, superior to the conventional chemoresponsive supramolecular polymeric systems with limited switching capability.

A novel approach to diagnose sleep apnea using enhanced frequency extraction network.

Sleep apnea-hypopnea syndrome (SAHS), as a widespread respiratory sleep disorder, if left untreated, can lead to a series of pathological changes. By using Polysomnography (PSG), traditional SAHS diagnosis tends to be complex and costly. Nasal airflow (NA) is the most direct reflection of the severity of SAHS. Therefore, we try to take advantage of NA signals that can be easily recorded by wearable devices. In this paper, we present an automatic detection approach of SAH events based on single-channel signal. Through this approach, an enhanced frequency extraction network is designed, which factorizes the mixed feature maps by their frequencies. And the spatial resolution of low-frequency components is reduced so as to save spending. Besides, in our research, the vanilla convolution block of the high-frequency components are replaced by residual blocks and smaller groups of filters with bigger size kernels. And we use the spatial attention module to facilitate feature extraction. Compared with state-of-the-art networks in this field, the promising results reveal that the proposed network for SAH events multiclass classification shows outstanding performance with accuracy of 91.23%, sensitivity of 90.81% and specificity of 90.59%. Thus, we believe that our approach, as a low-cost and high-efficiency solution, shows a great potential for detecting SAH events.

Deep Learning for Diagnosis and Classification of Obstructive Sleep Apnea: A Nasal Airflow-Based Multi-Resolution Residual Network.

PURPOSE: This study evaluated a novel approach for diagnosis and classification of obstructive sleep apnea (OSA), called Obstructive Sleep Apnea Smart System (OSASS), using residual networks and single-channel nasal pressure airflow signals. METHODS: Data were collected from the sleep center of the First Affiliated Hospital, Sun Yat-sen University, and the Integrative Department of Guangdong Province Traditional Chinese Medical Hospital. We developed a new model called the multi-resolution residual network (Mr-ResNet) based on a residual network to detect nasal pressure airflow signals recorded by polysomnography (PSG) automatically. The performance of the model was assessed by its sensitivity, specificity, accuracy, and F1-score. We built OSASS based on Mr-ResNet to estimate the apnea‒hypopnea index (AHI) and to classify the severity of OSA, and compared the agreement between OSASS output and the registered polysomnographic technologist (RPSGT) score, assessed by two technologists. RESULTS: In the primary test set, the sensitivity, specificity, accuracy, and F1-score of Mr-ResNet were 90.8%, 90.5%, 91.2%, and 90.5%, respectively. In the independent test set, the Spearman correlation for AHI between OSASS and the RPSGT score determined by two technologists was 0.94 (p < 0.001) and 0.96 (p < 0.001), respectively. Cohen's Kappa scores for classification between OSASS and the two technologists' scores were 0.81 and 0.84, respectively. CONCLUSION: Our results indicated that OSASS can automatically diagnose and classify OSA using signals from a single-channel nasal pressure airflow, which is consistent with polysomnographic technologists' findings. Thus, OSASS holds promise for clinical application.

Comparative rna-seq analysis of region-specific miRNA expression in the epididymis of cattleyak.

The epididymis is the site of post-testicular sperm maturation, which constitutes the acquisition of sperm motility and the ability to recognize and fertilize oocytes. The role of miRNA in male reproductive system, including the control of different steps leading to proper fertilization such as gametogenesis, sperm maturation and maintenance of male fertility where the deletion of Dicer in mouse germ cells led to infertility, has been demonstrated. The identification of miRNA expression in a region-specific manner will therefore provide valuable insight into the functional differences between the regions of the epididymis. In this study, we employed RNA-seq technology to explore the expression pattern of miRNAs and establish some miRNAs of significant interest with regard to epididymal sperm maturation in the CY epididymis. We identified a total of 431 DE known miRNAs; 119, 185 and 127 DE miRNAs were detected for caput versus corpus, corpus versus cauda and caput versus cauda region pairs, respectively. Our results demonstrate region-specific miRNA expression in the CY epididymis. The GO and KEGG enrichment for the predicted target genes indicated the functional values of miRNAs. Furthermore, we observed that the expression of miR-200a was downregulated in the caput, compared with cauda. Since the family of miR-200 has previously been suggested to contribute to the distinct physiological function of sperm maturation in epididymis of adult rat, we speculate that the downregulation of miR-200a in CY caput epididymis may play an important role of sperm maturation in the epididymis of CY. Therefore, our findings may not only increase our understanding of the molecular mechanisms regulated by the miRNA functions in region-specific miRNA expression in the CY epididymis, it could provide a valuable information to understand the mechanism of male infertility of CY.

Preserving Minority Structures in Graph Sampling.

Sampling is a widely used graph reduction technique to accelerate graph computations and simplify graph visualizations. By comprehensively analyzing the literature on graph sampling, we assume that existing algorithms cannot effectively preserve minority structures that are rare and small in a graph but are very important in graph analysis. In this work, we initially conduct a pilot user study to investigate representative minority structures that are most appealing to human viewers. We then perform an experimental study to evaluate the performance of existing graph sampling algorithms regarding minority structure preservation. Results confirm our assumption and suggest key points for designing a new graph sampling approach named mino-centric graph sampling (MCGS). In this approach, a triangle-based algorithm and a cut-point-based algorithm are proposed to efficiently identify minority structures. A set of importance assessment criteria are designed to guide the preservation of important minority structures. Three optimization objectives are introduced into a greedy strategy to balance the preservation between minority and majority structures and suppress the generation of new minority structures. A series of experiments and case studies are conducted to evaluate the effectiveness of the proposed MCGS.

Selective Separation of Methylfuran and Dimethylfuran by Nonporous Adaptive Crystals of Pillararenes.

The separation of 2-methylfuran (MeF) and 2,5-dimethylfuran (DMeF) mixtures is very important in the chemical industry. Herein, we offer a novel strategy for the separation of MeF and DMeF using nonporous adaptive crystals (NACs) of perethylated pillar[5]arene (EtP5), perethylated pillar[6]arene (EtP6), perbromoethylated pillar[5]arene (BrP5), and perbromoethylated pillar[6]arene (BrP6). We find that the crystals of EtP6 and BrP5 show remarkable selectivities for MeF in a 50:50 (v/v) MeF:DMeF mixture vapor, yielding purities of 94.0 and 96.3%, respectively. Single-crystal structures reveal that these different selectivities come from the different thermodynamic stabilities and binding modes of the host-guest complexes. Cycling experiments demonstrate that these crystals can be reused more than five cycles without loss of performance.

Rationally Designed Self-Immolative Rotaxane Sensor Based on Pillar[5]arene for Fluoride Sensing.

We develop a self-immolative rotaxane sensor for fluoride sensing based on host-guest interactions between pillar[5]arene and fluoride-promoted cleavage of Si-O bond. Because of the selective and fast reaction between silane and fluoride, the rotaxane sensor shows anion selectivity and rapid response. The self-immolative nature of the rotaxane improve its sensitivity. Moreover, a fluoride sensing test paper based on the rotaxane sensor is made, which shows the practicable application of the rotaxane sensor.

Clinical outcome of standardized oxygen therapy nursing strategy in COVID-19.

BACKGROUND: Novel coronavirus pneumonia (COVID-19) has become a global pandemic. However, a technical standard for oxygen therapy nursing, as well as how this would improve clinical outcomes and symptoms, is yet to be explored. METHODS: From February 9, 2020, to March 31, 2020, 58 patients of confirmed COVID-19 were admitted to the 20th ward of the Eastern Branch, Renmin Hospital of Wuhan University. Fifteen patients who did not receive oxygen therapy and 13 patients who were transferred from other hospitals were excluded. The rest of the 30 patients that received standardized oxygen therapy in our unit were included in the study. Baseline characteristics, symptoms, and finger pulse oxygen saturation were collected during hospitalization. RESULTS: Clinical outcomes of the 30 patients were as follows: 27 patients (90.00%) were cured and discharged; 3 patients (10.00%) who continued to stay in hospital were stabilized with symptoms relieved. The fingertip oxygen saturation was 94.80%±3.49% at ICU admission and 97.8%±1.27% when transferred out of ICU after standardized oxygen therapy (P<0.005). The symptoms of dyspnea, fatigue, and muscle aches of the patients were improved when transferred out of ICU, compared with their condition when admitted to ICU (P<0.05). CONCLUSIONS: The standardized oxygen therapy nursing strategy for patients with COVID-19 emphasizes the nursing measurement, which focuses on the patient's oxygenation. It is led by nurses and starts oxygen therapy at an earlier stage. It not only improves the clinical outcomes of critical patients but also effectively reduces the infection risk of medical staff while emphasizing nursing quality management.

Pillararene Host-Guest Complexation Induced Chirality Amplification: A New Way to Detect Cryptochiral Compounds.

The contradiction between the rising demands of optical chirality sensing and the failure in chiral detection of cryptochiral compounds encourages researchers to find new methods for chirality amplification. Inspired by planar chirality and the host-guest recognition of pillararenes, we establish a new concept for amplifying CD signals of cryptochiral molecules by pillararene host-guest complexation induced chirality amplification. The planar chirality of pillararenes is induced and stabilized in the presence of the chiral guest, which makes the cryptochiral molecule detectable by CD spectroscopy. Several chiral guests are selected in these experiments and the mechanism of chiral amplification is studied with a non-rotatable pillararene derivative and density functional theory calculations. We believe this work affords deeper understanding of chirality and provides a new perspective for chiral sensing.

On-chip optical narrowband reflector based on anti-symmetric Bragg grating.

We propose an on-chip optical narrowband reflector (NBR) based on two cascaded Bragg gratings (BGs). A π phase shifted anti-symmetric Bragg grating (π-PS-ASBG) and a rear uniform Bragg grating (UBG), are in-line connected. The π-PS-ASBG provides a hybrid mode resonance between the even- and odd TE (TE0 and TE1) modes, while the UBG is used as a rear reflector to reflect the TE0 mode that transmitted from the π-PS-ASBG. Different from traditional UBG, the reflection bandwidth decreases when the coupling coefficient increases. The calculated 3-dB bandwidth is 0.16 nm when the whole grating length is 400 µm. The proposed NBR can be applied in the cases requiring narrow reflection such as narrow linewidth semiconductor lasers.

Transverse modal control of wide-stripe high power semiconductor lasers using sampled grating.

A transverse Bragg resonance (TBR) waveguide semiconductor laser with sampled grating is proposed and analyzed. The transverse phase shift in the middle of the grating is realized by shifting half of the sampling period, resulting in a good single transverse mode resonance. The characteristics such as the modal gain, the electric field distribution, the near and far field beam patterns are theoretically studied. Since the sampled grating is designed by combining a uniform basic grating with a micrometer scale sampling pattern, it can be easily fabricated by holographic exposure and conventional photolithography with low cost. Therefore, the proposed method would be beneficial to volume fabrication of wide-stripe high power semiconductor lasers.