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Constant oxidative stress and lactate accumulation are two main causes of tumor immunosuppression, their concurrent reduction plays a dominant role in effective antitumor immunity, but remains challenging. Herein, reactive oxygen species (ROS) responsive prodrug nanoparticles (designed as DHCRJ) are constructed for metabolic amplified chemo-immunotherapy against triple-negative breast cancer (TNBC) by modulating oxidative state and hyperglycolysis. Specifically, DHCRJ is prepared by the self-assembly of DOX prodrug-tethered ROS consuming bond-bridged copolymers with the loading of bromodomain-containing protein 4 inhibitor (BRD4i) JQ1. Interestingly, the nanoparticle polymer network could reduce ROS to relieve tumor hypoxia and realize the dense-to-loose structure inversion arising from ROS-triggered network collapse, which favors JQ1 release and hyaluronidase (Hyal)-activatable DOX prodrugs generation. More importantly, disruption of oxidative stress decreases glucose uptake and assists JQ1 to down-regulate oncogene c-Myc driven tumor glycolysis for blocking the source of lactate and reshaping immunosuppressive tumor microenvironment (ITME). Meanwhile, benefiting from the synergistic effect of DOX prodrugs and JQ1, DHCRJ is able to facilitate tumor immunogenicity and potentiate systemic immune responses through antigen processing and presentation pathway. In this manner, DHCRJ significantly suppresses tumor growth and metastasis with prolonged survival. Collectively, this study represents a proof of concept antioxidant-enhanced chemo-immunometabolic therapy strategy using ROS-reducing nanoparticles for efficient synergistic therapeutic modality of TNBC. [Display omitted] [ABSTRACT FROM AUTHOR]

Simple Summary: Cancer metastasis is a critical event in the progression of solid tumors and is invariably associated with adverse outcomes and mortality. Understanding novel mechanisms or molecules that promote cancer metastasis will facilitate the development of new strategies for cancer treatment. Recently, MARCKS has been studied extensively in several cancers and has been implicated in tumor progression and metastasis. This review summarizes recent advances in the understanding of MARCKS on cancer metastasis, stemness, and therapeutic resistance and provides prospects on targeting MARCKS therapeutically. Specifically, we review the molecular mechanisms and multiple signaling pathways by which MARCKS contributes to the progression and metastasis in solid tumors. The myristoylated alanine-rich C-kinase substrate (MARCKS) is a membrane-associated protein kinase C (PKC) substrate ubiquitously expressed in eukaryotic cells. MARCKS plays important roles in multiple cellular processes, including cell adhesion and motility, mucin secretion, exocytosis, and inflammatory response. Aberrant MARCKS signaling has been observed in the development and progression of multiple cancer types. In addition, MARCKS facilitates cancer metastasis through modulating cancer cell migration and invasion. Moreover, MARCKS contributes to treatment resistance, likely by promoting cancer stem cell renewal as well as immunosuppression. In this review, we describe MARCKS protein structure, cellular localization, and biological functions. We then discuss the role of MARCKS in cancer metastasis as well as its mechanisms of action in solid tumors. Finally, we review recent advances in targeting MARCKS as a new therapeutic strategy in cancer management. [ABSTRACT FROM AUTHOR]

• A process to make P containing Y zeolite more stable. • P is incorporated into the framework by P for Si(4Al) isomorphous substitution. • Si(4Al) becomes the more stable site P(4Al) in the Y zeolite framework. • The P species in DPY zeolite are more difficult to loss than usual P modify. • The distribution of P species in DPY zeolite is more uniform. It's a dream to make zeolites more stable so as to keep the activity and stability of the catalyst. Phosphorus modification is an effective method, however, the known post-modification predominantly presents as non-framework P, and the P-loss is a big trouble in application. We have discovered that in the reaction of PCl 3 or SiCl 4 + PCl 3 with NaY zeolite, a portion of P enters the framework of the zeolite, forming a PO 4 -AlO 4 structure. Further investigations revealed that P cannot be incorporated into the framework through P for Al isomorphous substitution, but rather through isomorphous substitution with Si(4Al). PCl 3 exhibits two effects in reaction: at lower quantities, it mainly undergoes isomorphous substitution with Si(4Al); at higher quantities, it leads to zeolite dealumination generating aluminum vacancies, which disrupt the zeolite framework or promotes Si for Al isomorphous substitution. After hydrothermal aging at 800 °C for 4 h, the stable presence of framework PO 4 -AlO 4 implies that the weakest site Si(4Al) becomes the more stable site P(4Al) in the Y zeolite framework. Compared with the JPY (prepared by impregnating (NH 4) 2 HPO 4 solution to high silica Y zeolite) sample, after 10 cycles of hydrothermal and water washing treatment, the P 2 O 5 loss rate of DPY (prepared by SiCl 4 + PCl 3 with NaY) zeolite ranged from 0.4 % to 3.5 %, significantly lower compared to the range of 18.7 % to 25.9 % observed in the JPY sample. This indicates that in DPY zeolite, the interaction between P and the zeolite is stronger and less prone to loss. Moreover, P is more uniformly distributed on the surface and bulk phase of DPY than JPY sample. [ABSTRACT FROM AUTHOR]

A fundamental challenge in probiotic therapy is effective delivery and rapid colonization of probiotics; however, the physiological structure of probiotic spores provides an interesting idea to address this problem. Herein, the spore coat is innovatively prepared into a type of versatile spore coat nanomaterial (CN) which is subsequently anchored to the surface of probiotics to form CN‐coated probiotics. The CN retains the characteristics of high resistance and natural affinity of spore coats, which serve as the "armor" for the enhancement of the probiotics delivery. Moreover, CN is beneficial for the explosive proliferation and competitive colonization of probiotics. Notably, it is found that not only CN used solely has good anti‐inflammatory effect, but also it can significantly improve the functions of probiotics such as microbiome regulation, gut barrier integrity and tumor prevention. This work provides a simple and universal strategy that may guide the development of nanomaterial and material‐based microecological agents. [ABSTRACT FROM AUTHOR]

Despite the potential of drug‐loaded scaffolds for tumor recurrence and metastasis (TRM) postoperation, their therapeutic benefits are limited by marked immunosuppressive tumor microenvironment (ITME) and drug‐related untargeted toxicity. Herein, an innovative implantable bioresponsive nanoarray is developed to overcome the above limitations. Chemotherapeutics doxorubicin (DOX) and the epigenetic modulator JQ1 are coloaded into tumor‐targeting nanoparticles (HP‐DOX/JQ1 NPs), which are then linked up through a bio‐responsive linker to construct the nanoarray loading with another part of JQ1 (DOX/JQ1‐IBRN). Under high level of H2O2 in TME, the implanted DOX/JQ1‐IBRN disaggregates and release JQ1 while generating small‐sized HP‐DOX/JQ1 NPs for realizing ITME modulation and tumor‐targeting therapy. JQ1 selectively blocks programmed death‐ligand 1 (PD‐L1) mediated immune evasion and reduces regulatory T cells (Tregs)/‐disruptive effect to facilitate immunopositivity. HP‐DOX/JQ1 NPs destroy residual tumor precisely and trigger gasdermin E (GSDME)‐dependent pyroptosis, further enhancing the number and functions of tumor‐infiltrating T lymphocytes for antitumor immunity. It is demonstrated that DOX/JQ1‐IBRN prevents post‐surgical TRM and prolongs survival in multiple murine tumor models with negligible toxicity. This cooperation in tumor accurate pyroptosis and ITME conversion through the implantable nanoarray (a simple, valid, and safe scaffold) is expected to provide crucial insights for post‐surgical treatment. [ABSTRACT FROM AUTHOR]

The effects of photodynamic therapy (PDT) are limited by the hypoxic tumor microenvironment (TME). In this paper, a new type of biocompatible multifunctional photosensitizer delivery system was fabricated to relieve tumor hypoxia and improve the efficacy of PDT. The photosensitizer hematoporphyrin monomethyl ether (HMME) and catalase (CAT) were encapsulated in the pores of mesoporous graphitic-phase carbon nitride nanosheets (mpg-C 3 N 4 ). Next, hyaluronic (HA) was coated on the surface of the mpg-C 3 N 4 via an amide linkage to construct the tumor-targeting HAase/CAT dual activatable and mpg-C 3 N 4 /HMME response photosensitizer delivery system (HA@mpg-C 3 N 4 -HMME/CAT). Upon intravenous injection, HA@mpg-C 3 N 4 -HMME/CAT shows high tumor accumulation owing to the tumor-targeting HA coating. Meanwhile, CAT within mpg-C 3 N 4 could trigger decomposition of endogenic TME H 2 O 2 to increase oxygen supply in-situ to relieve tumor hypoxia. This effect together with mpg-C 3 N 4 /HMME dual response is able to dramatically improve PDT efficiency. The hypoxia status of tumors was evaluated in vivo to demonstrate the success of the O 2 -supplying. And the in vitro and in vivo results showed the excellent therapeutic effect of the HA@mpg-C 3 N 4 -HMME/CAT photosensitizer delivery system. O 2 -supplying PDT may enable the enhancement of traditional PDT and future PDT design. [ABSTRACT FROM AUTHOR]

Although antibacterial activities of graphene oxide (GO) and its derivatives have been investigated comprehensively, their antifungal properties are still less reported. Yet, fungal contamination seriously threatens the public health. Herein, we present a design of graphene oxide-borneol (GOB) composite, and report its great antifungal effect. This GOB composite is prepared by esterification of borneol with thiomalic-acid-modified GO sheets, where the linker molecule is used to increase surface carboxyl groups. As a result, the antifungal activity displays a dramatically conversion from no activity of GO and its derivatives to distinct antifungal adhesion and growth inhibition of the GOB. Under microscopy, few spores can be found on the GOB surface, while large numbers of sporangia and spores adhere and grow on the control groups. It is also worth noting that on the GOB sample the fallen spore does not germinate even after 5 days, demonstrating a long-term antifungal effect of the GOB composite. Further studies confirm that carbon stereochemistry rather than wettability plays a crucial role on the antifungal adhesion properties. This study not only highlights a promising GOB composite as a candidate of graphene-based antifungal agent, but also provides us with in-depth understanding of the interactions between fungi and graphene-based materials. [ABSTRACT FROM AUTHOR]

MET plays an important role in the development and progression of papillary renal cell carcinoma (pRCC). Evaluation of efficacy of MET inhibitors against pRCC has been hampered by limited preclinical models depicting MET abnormalities. We established a new patient-derived xenograft (PDX) model of pRCC carrying an activating mutation of MET and tested the ability of cabozantinib, an inhibitor of receptor tyrosine kinases including MET, to inhibit tumor growth and metastasis. Precision-cut, thin tissue slices from a pRCC specimen obtained by nephrectomy were implanted under the renal capsule of RAG2−/−γC−/−mice to establish first generation TSG-RCC-030. Histologic and genetic fidelity and metastatic potential of this model were characterized by immunohistochemistry, direct DNA sequencing and quantitative polymerase chain reaction (qPCR). The effect of cabozantinib on tumor growth and metastasis was evaluated. Whether measurements of circulating tumor DNA (ctDNA) by allele-specific qPCR could be used as a biomarker of tumor growth and response to therapy was determined. Subrenal and subcutaneous tumor grafts showed high take rates and metastasized to the lung. Both primary tumors and metastases expressed typical markers of pRCC and carried the same activating MET mutation as the parental tumor. Cabozantinib treatment caused striking tumor regression and inhibited lung metastasis in TSG-RCC-030. Plasma ctDNA levels correlated with tumor volume in control mice and changed in response to cabozantinib treatment. TSG-RCC-030 provides a realistic preclinical model to better understand the development and progression of pRCC with MET mutation and accelerate the development of new therapies for pRCC. [ABSTRACT FROM PUBLISHER]

Traditional cotton water dyeing has a considerable ecological impact because of the use of water, but the available anhydrous cotton dyeing technologies cannot balance low recyclable energy consumption and excellent dyeing effects. In this study, a recyclable anhydrous cotton dyeing technology was designed and implemented by mixing supercritical carbon dioxide, dimethyl sulfoxide, and ethanol for the first time. Compared to the existing anhydrous cotton dyeing technologies, the novel technology could simultaneously obtain low recyclable energy consumption and excellent dyeing effects, such as dye penetration, washing and crocking fastness, levelness, color depth control and color matching. The dye fixations of reactive dyes in the novel technology are 5.1%–26.4% higher than those in traditional water dyeing. Meanwhile, the energy consumption of the novel technology is only 70% of that of traditional water dyeing, and the comprehensive cost of materials and energy of the novel technology is only 56% of that of traditional water dyeing. It is a new green option with low energy consumption for cotton dyeing. [Display omitted] • No water involves in SC-CO 2 /EtOH/DMSO multi-medium dyeing. • All dyeing media of SC-CO 2 /EtOH/DMSO multi-medium dyeing are recyclable. • SC-CO 2 /EtOH/DMSO multi-medium dyeing is a low-energy process. • SC-CO 2 /EtOH/DMSO multi-medium dyeing has excellent dyeing effects. [ABSTRACT FROM AUTHOR]

Sialic acids have been implicated in cancer initiation, progression, and immune evasion in diverse human malignancies. Sialylation of terminal glycans on cell surface and secreted glycoproteins is a long-recognized feature of cancer cells. Recently, immune checkpoint inhibitor immunotherapy has tremendously improved the outcomes of patients with various cancers. However, available immunotherapy approaches have had limited efficacy in metastatic castration-resistant prostate cancer. Sialic acid modified glycoproteins in prostate cancers and their interaction with Siglec receptors on tumor infiltrating immune cells might underlie immunosuppressive signaling in prostate cancer. Here, we summarize the function of sialic acids and relevant glycosynthetic enzymes in cancer initiation and progression. We also discuss the possible uses of sialic acids as biomarkers in prostate cancer and the potential methods for targeting Siglec-sialic acid interactions for prostate cancer treatment. [Display omitted] [ABSTRACT FROM AUTHOR]

Androgen receptor (AR) is expressed in normal murine and human kidneys of both genders, but its physiologic role is uncertain. Several studies showed loss of AR in renal cell carcinoma (RCC) in conjunction with increasing clinical stage and pathological grade, but others found that higher AR expression correlated with worse outcomes. Limited functional studies with renal cell lines suggested tumor-promoting activity of AR. In this study, we queried transcriptomic, proteomic, epigenetic and survival data from The Cancer Genome Atlas (TCGA) to evaluate AR expression and its association with overall survival in three subtypes of RCC (clear cell [ccRCC], papillary [pRCC], and chromophobe [chRCC]). We found that although there was no significant difference in AR mRNA expression in ccRCC of males vs. females, AR protein expression in ccRCC was significantly higher in male compared to female patients. More importantly, higher expression of AR at both transcript and protein levels was associated with improved overall survival in both genders with ccRCC, but did not predict survival of either gender with pRCC or chRCC. Genes whose transcript levels were associated with AR mRNA levels significantly overlapped between ccRCC and pRCC, but not with chRCC, suggesting a similar transcriptional program mediated by AR in ccRCC and pRCC. Ingenuity pathway analysis also identified overlapping pathways and upstream regulators enriched in AR-associated genes in ccRCC and pRCC. Hypermethylation of CpG sites located in the promoter and first exon of AR was associated with loss of AR expression and poor overall survival. Our findings support a tumor suppressor role for AR in both genders that might be exploited to decrease the incidence or progression of ccRCC. [ABSTRACT FROM AUTHOR]

Induced pluripotent stem (iPS) cells are a valuable resource for discovery of epigenetic changes critical to cell type-specific differentiation. Although iPS cells have been generated from other terminally differentiated cells, the reprogramming of normal adult human basal prostatic epithelial (E-PZ) cells to a pluripotent state has not been reported. Here, we attempted to reprogram E-PZ cells by forced expression of Oct4, Sox2, c-Myc, and Klf4 using lentiviral vectors and obtained embryonic stem cell (ESC)-like colonies at a frequency of 0.01%. These E-PZ-iPS-like cells with normal karyotype gained expression of pluripotent genes typical of iPS cells (Tra-1-81, SSEA-3, Nanog, Sox2, and Oct4) and lost gene expression characteristic of basal prostatic epithelial cells (CK5, CK14, and p63). E-PZ-iPS-like cells demonstrated pluripotency by differentiating into ectodermal, mesodermal, and endodermal cells in vitro, although lack of teratoma formation in vivo and incomplete demethylation of pluripotency genes suggested only partial reprogramming. Importantly, E-PZ-iPS-like cells re-expressed basal epithelial cell markers (CD44, p63, MAO-A) in response to prostate-specific medium in spheroid culture. Androgen induced expression of androgen receptor (AR), and co-culture with rat urogenital sinus further induced expression of prostate-specific antigen (PSA), a hallmark of secretory cells, suggesting that E-PZ-iPS-like cells have the capacity to differentiate into prostatic basal and secretory epithelial cells. Finally, when injected into mice, E-PZ-iPS-like cells expressed basal epithelial cell markers including CD44 and p63. When co-injected with rat urogenital mesenchyme, E-PZ-iPS-like cells expressed AR and expression of p63 and CD44 was repressed. DNA methylation profiling identified epigenetic changes in key pathways and genes involved in prostatic differentiation as E-PZ-iPS-like cells converted to differentiated AR- and PSA-expressing cells. Our results suggest that iPS-like cells derived from prostatic epithelial cells are pluripotent and capable of prostatic differentiation; therefore, provide a novel model for investigating epigenetic changes involved in prostate cell lineage specification. [ABSTRACT FROM AUTHOR]

Abstract: Unique and remarkable interferences were observed when dried blood spot (DBS) sampling was used in conjunction with liquid chromatography/mass spectrometry (LC/MS) assays. In particular, chromatographic retention time shifting and chromatographic peak shape distortion were observed, along with a severe suppression of MS signal intensity. The type of DBS cards, and chromatographic conditions were investigated using the same set of test compounds to gain insight into these interferences. It was determined that a constituent of the DBS cards, primarily sodium dodecyl sulfate (SDS), was responsible for the interferences by means of an ion-pairing mechanism. SDS formed ion pairs with compounds containing basic amine groups, which resulted in increased retention on a C18 stationary phase, peak shape distortion and ion suppression. These interferences were greatly alleviated and/or completely overcome with non-acidic mobile phases and/or DBS cards with no SDS coating. To the best of the authors’ knowledge, this is the first in-depth report of interferences induced by DBS cards. [Copyright &y& Elsevier]

Abstract: Using flux variability analysis of a genome scale metabolic network of Streptomyces coelicolor, a series of reactions were identified, from disparate pathways that could be combined into an actinorhodin-generating mini-network. Candidate process feed nutrients that might be expected to influence this network were used in process simulations and in silico predictions compared to experimental findings. Ranking potential process feeds by flux balance analysis optimisation, using either growth or antibiotic production as objective function, did not correlate with experimental actinorhodin yields in fed processes. However, the effect of the feeds on glucose assimilation rate (using glucose uptake as objective function) ranked them in the same order as in vivo antibiotic production efficiency, consistent with results of a robustness analysis of the effect of glucose assimilation on actinorhodin production. [Copyright &y& Elsevier]

Abstract: NaY/kaolin composite microspheres were synthesized by an in situ method using calcined kaolin microspheres as raw material. By mixing the modified NaY/kaolin composite microspheres and additive microspheres containing ZSM-5, a novel fluid catalytic cracking (FCC) catalyst for maximizing propylene yield in FCC unit was prepared. The catalyst was characterized by X-ray diffraction (XRD), temperature-programmed desorption of ammonium (NH3-TPD), and N2 adsorption–desorption techniques and tested in a bench FCC unit. The characterization results indicated that the catalyst has more meso- and macro-pores and more acid sites than the reference catalyst and thus can increase propylene yield by 1.27%. [Copyright &y& Elsevier]

To obtain a comprehensive view of the transcriptional programs in prostatic stromal cells of different histological/pathological origin, we profiled 18 adult human stromal cell cultures from normal transition zone (TZ), normal peripheral zone (PZ), benign prostatic hyperplasia (BPH), and prostate cancer (CA) using cDNA microarrays. A hierarchical clustering analysis of 714 named unique genes whose expression varied at least threefold from the overall mean abundance in at least three samples in all 18 samples demonstrated that cells of different origin displayed distinct gene expression profiles. Many of the differentially expressed genes are involved in biological processes known to be important in the development of prostatic diseases including cell proliferation and apoptosis, cell adhesion, and immune response. Significance Analysis of Microarrays (SAM) analysis identified genes that showed differential expression with statistical significance including 24 genes between cells from TZ versus BPH, 34 between BPH versus CA, and 101 between PZ versus CA. S100A4 and SULF1, the most up- and downregulated genes in BPH versus TZ, respectively, showed expression at the protein level consistent with microarray analysis. In addition, sulfatase assay showed that BPH cells have lower SULF1 activity compared to TZ cells. Quantitative real-time polymerase chain reaction (qRT-PCR) analysis confirmed differential expression of ENPP2/autotoxin and six other genes between PZ versus CA, as well as differential expression of six genes between BPH versus CA. Our results support the hypothesis that prostatic stromal cells of different origin have unique transcriptional programs and point towards genes involved in actions of stromal cells in BPH and CA. J. Cell. Physiol. 210: 111–121, 2007. © 2006 Wiley-Liss, Inc. [ABSTRACT FROM AUTHOR]

Abstract: Fifteen putative Streptomyces spp. isolated from soil were selected to be analysed using Fourier transform infrared (FT-IR) spectroscopy and 16S rRNA gene sequencing. Four colour groupings (groups 1–4) were obtained and described according to the colour of their substrate mycelia, aerial mycelia, spore mass and pigmentation. The dendrogram constructed using unsupervised cluster analysis of the FT-IR data was in good congruence with the four colour groups and the neighbour-joining phylogenetic tree for 16S rDNA sequencing. In particular, those isolates having 100% 16S rDNA similarities which are supposed to be from the same species can be separated from each other using FT-IR analysis. This high throughput method only takes 1–10s to collect a FT-IR spectrum from each sample, and both 96- and 384-well microplates are available for automated analysis. FT-IR therefore presents itself as a rapid, whole-organism fingerprinting approach which can be used for preliminary differentiation of Streptomyces spp. at sub-species or strain level. [Copyright &y& Elsevier]

• A new antimicrobial material, borneol-modified chitosan (BMC), was prepared. • BMC displayed good antibacterial and antifungal adhesion properties. • Guinea pig experiments were performed for skin flora evaluation. • BMC resisted pathogens but did not harm skin flora. • Stereochemical strategies are crucial for managing and controlling microbes. Antimicrobial modifications of chitosan usually endow the products with strong bactericidal activities. However, if the products come into direct contact with human skin, the skin flora, which is beneficial to human health, may be damaged. To address this issue, we developed a stereochemical antimicrobial strategy by grafting borneol 4-formylbenzoate to chitosan using a stable Schiff base bond; this process yielded borneol-modified chitosan (BMC) as a novel antimicrobial material. This material was challenged with gram-negative Escherichia coli , gram-positive Bacillus subtilis , and Aspergillus niger. All tests showed excellent antimicrobial adhesive properties. Guinea pig skin experiments further demonstrated that BMC did not damage the skin flora. Owing to the antimicrobial mechanism of borneol stereochemistry, BMC successfully defended against pathogens and protected the skin flora. Thus, this material may have excellent potential applications in multifunctional textiles, healthcare, and flexible skin electronics. [ABSTRACT FROM AUTHOR]

The failure of any phase in continuous multi-link immune response process can cause unsatisfactory outcomes, which might be improved by all-cancer-immunity-cycle boosted strategy. Herein, a nanoplatform Mn/CaCO 3 @PL/SLC is developed, which is based on palmitoyl ascorbate (PA)-liposome (PL) loaded with Mn-doped CaCO 3 nanoparticles (Mn/CaCO 3 NPs) and carbonic anhydrase (CAIX) inhibitor SLC-0111. The nanoplatform comprehensively amplifies all immune stages including tumor-associated antigens (TAAs) release and presentation, T cells activation and infiltration, as well as tumor cells destruction. In detail, Mn-triggered lipid peroxidation facilitates TAAs release and subsequent T cells activation to initiate immunity cycle. Additionally, SLC-0111 and PA amplify the infiltration and tumor killing activity of these effector T cells. The former polarizes the immunosuppressive tumor microenvironment to an immune-active phenotype and the latter enhances the function of tumor-infiltrating T lymphocytes. Importantly, Mn augments the all-immunity-cycle by promoting cGAS-STING pathway activation. In summary, the Mn/CaCO 3 @PL/SLC nanoplatform is verified to boost anti-tumor immunity and achieve outstanding immunotherapeutic effects in eradicating tumor and preventing tumor metastasis. Such an all-cancer-immunity-cycle boosted strategy is meaningful for antitumor immunotherapy. The schematic diagram of Mn/CaCO 3 @PL/SLC NPs, which augments the all-immunity-cycle by inducing immunogenic cell death of tumor cells, polarizing the immunosuppresive tumor microenvironment and increasing the vitality of tumor-infiltrating T lymphocytes. [Display omitted] [ABSTRACT FROM AUTHOR]

Glycoproteins in urine have the potential to provide a rich class of informative molecules for studying human health and disease. Despite this promise, the urine glycoproteome has been largely uncharacterized. Here, we present the analysis of glycoproteins in human urine using LC–MS/MS-based intact glycopeptide analysis, providing both the identification of protein glycosites and characterization of the glycan composition at specific glycosites. Gene enrichment analysis reveals differences in biological processes, cellular components, and molecular functions in the urine glycoproteome versus the urine proteome, as well as differences based on the major glycan class observed on proteins. Meta-heterogeneity of glycosylation is examined on proteins to determine the variation in glycosylation across multiple sites of a given protein with specific examples of individual sites differing from the glycosylation trends in the overall protein. Taken together, this dataset represents a potentially valuable resource as a baseline characterization of glycoproteins in human urine for future urine glycoproteomics studies. [ABSTRACT FROM AUTHOR]

The biological barriers have seriously restricted the efficacious responses of oral delivery system in diseases treatment. Utilizing a carrier based on the single construction means is hard to overcome these obstacles simultaneously because the complex gastrointestinal tract environment requires carrier to have different or even contradictory properties. Interestingly, spore capsid (SC) integrates many unique biological characteristics, such as high resistance, good stability etc. This fact offers a boundless source of inspiration for the construction of multi-functional oral nanoplatform based on SC without further modification. Herein, we develop a type of biomimetic spore nanoplatform (SC@DS NPs) to successively overcome oral biological barriers. Firstly, doxorubicin (DOX) and sorafenib (SOR) are self-assembled to form carrier-free nanoparticles (DS NPs). Subsequently, SC is effectively separated from probiotic spores and served as a functional vehicle for delivering DS NPs. As expect, SC@DS NPs can efficaciously pass through the rugged stomach environment after oral administration and further be transported to the intestine. Surprisingly, we find that SC@DS NPs exhibit a significant improvement in the aspects of mucus penetration and transepithelial transport, which is related to the protein species of SC. This study demonstrates that SC@DS NPs can efficiently overcome multiple biological barriers and improve the therapeutic effect. [ABSTRACT FROM AUTHOR]

PURPOSE: Accurately distinguishing renal cell carcinoma (RCC) from normal kidney tissue is critical for identifying positive surgical margins (PSMs) during partial and radical nephrectomy, which remains the primary intervention for localized RCC. Techniques that detect PSM with higher accuracy and faster turnaround time than intraoperative frozen section (IFS) analysis can help decrease reoperation rates, relieve patient anxiety and costs, and potentially improve patient outcomes. MATERIALS AND METHODS: Here, we extended our combined desorption electrospray ionization mass spectrometry imaging (DESI-MSI) and machine learning methodology to identify metabolite and lipid species from tissue surfaces that can distinguish normal tissues from clear cell RCC (ccRCC), papillary RCC (pRCC), and chromophobe RCC (chRCC) tissues. RESULTS: From 24 normal and 40 renal cancer (23 ccRCC, 13 pRCC, and 4 chRCC) tissues, we developed a multinomial lasso classifier that selects 281 total analytes from over 27,000 detected molecular species that distinguishes all histological subtypes of RCC from normal kidney tissues with 84.5% accuracy. On the basis of independent test data reflecting distinct patient populations, the classifier achieves 85.4% and 91.2% accuracy on a Stanford test set (20 normal and 28 RCC) and a Baylor-UT Austin test set (16 normal and 41 RCC), respectively. The majority of the model's selected features show consistent trends across data sets affirming its stable performance, where the suppression of arachidonic acid metabolism is identified as a shared molecular feature of ccRCC and pRCC. CONCLUSION: Together, these results indicate that signatures derived from DESI-MSI combined with machine learning may be used to rapidly determine surgical margin status with accuracies that meet or exceed those reported for IFS. Combining mass spectrometry imaging and machine learning enables successful diagnosis of renal cell carcinoma from normal kidney tissues. [ABSTRACT FROM AUTHOR]

Abstract: Objective: Discovery of curative therapies for renal cell carcinoma (RCC) is hampered by lack of authentic preclinical models. Tumorgrafts, generated by direct implantation of patient-derived tissues into mice, have demonstrated superior ability to predict therapeutic response. We evaluated “tissue slice grafts” (TSGs) as an improved tumorgraft model of RCC. Materials and methods: Cores of fresh RCC were precision-cut at 300µm and implanted under the renal capsule of RAG2−/−γC−/− mice. Engraftment rate, histology, biomarker expression, genetic fidelity, and metastatic potential were evaluated. Magnetic resonance imaging (MRI) was tested as a noninvasive method to measure tumor volume, and response to a targeted therapy was determined. Results: All 13 cases of RCC engrafted and displayed characteristic histology and biomarkers. TSG volume quantified noninvasively by MRI highly correlated with graft weights, providing a unique tool for monitoring orthotopic growth. Moreover, in 2 cases, cancer cells from TSGs metastasized to clinically relevant sites, including bone. Microarray analysis and DNA sequencing demonstrated a high degree of correlation of global gene expression and von Hippel-Lindau (VHL) status between TSGs and parental tumors. Treatment of TSGs with sunitinib significantly decreased graft weight and mean vessel density compared with controls. Conclusion: The TSG model of RCC faithfully recapitulates tumor pathology, gene expression, genetic mutation, and drug response. The high engraftment rate and metastatic potential of this authentic model, in conjunction with the ability to generate large first-generation animal cohorts and to quantitate tumor volume at the orthotopic site by MRI, proffer significant advantages compared with other preclinical platforms. [Copyright &y& Elsevier]

Increased expression of NUSAP1 has been identified as a robust prognostic biomarker in prostate cancer and other malignancies. We have previously shown that NUSAP1 is positively regulated by E2F1 and promotes cancer invasion and metastasis. To further understand the biological function of NUSAP1, we used affinity purification and mass spectrometry proteomic analysis to identify NUSAP1 interactors. We identified 85 unique proteins in the NUSAP1 interactome, including ILF2, DHX9, and other RNA-binding proteins. Using proteomic approaches, we uncovered a function for NUSAP1 in maintaining R-loops and in DNA damage response through its interaction with ILF2. Co-immunoprecipitation and colocalization using confocal microscopy verified the interactions of NUSAP1 with ILF2 and DHX9, and RNA/DNA hybrids. We showed that the microtubule and charged helical domains of NUSAP1 were necessary for the protein-protein interactions. Depletion of ILF2 alone further increased camptothecin-induced R-loop accumulation and DNA damage, and NUSAP1 depletion abolished this effect. In human prostate adenocarcinoma, NUSAP1 and ILF2 mRNA expression levels are positively correlated, elevated, and associated with poor clinical outcomes. Our study identifies a novel role for NUSAP1 in regulating R-loop formation and accumulation in response to DNA damage through its interactions with ILF2 and hence provides a potential therapeutic target. [ABSTRACT FROM AUTHOR]

Background: Effective eradication of high-risk primary prostate cancer (HRPCa) could significantly decrease mortality from prostate cancer. However, the discovery of curative therapies for HRPCa is hampered by the lack of authentic preclinical models.Methods: We improved upon tumorgraft models that have been shown to predict drug response in other cancer types by implanting thin, precision-cut slices of HRPCa under the renal capsule of immunodeficient mice. Tissue slice grafts (TSGs) from 6 cases of HRPCa were established in mice. Following androgen deprivation by castration, TSGs were recovered and the presence and phenotype of cancer cells were evaluated.Results: High-grade cancer in TSGs generated from HRPCa displayed characteristic Gleason patterns and biomarker expression. Response to androgen deprivation therapy (ADT) was as in humans, with some cases exhibiting complete pathologic regression and others showing resistance to castration. As in humans, ADT decreased cell proliferation and prostate-specific antigen expression in TSGs. Adverse pathological features of parent HRPCa were associated with lack of regression of cancer in corresponding TSGs after ADT. Castration-resistant cancer cells remaining in TSGs showed upregulated expression of androgen receptor target genes, as occurs in castration-resistant prostate cancer (CRPC) in humans. Finally, a rare subset of castration-resistant cancer cells in TSGs underwent epithelial-mesenchymal transition, a process also observed in CRPC in humans.Conclusions: Our study demonstrates the feasibility of generating TSGs from multiple patients and of generating a relatively large number of TSGs from the same HRPCa specimen with similar cell composition and histology among control and experimental samples in an in vivo setting. The authentic response of TSGs to ADT, which has been extensively characterized in humans, suggests that TSGs can serve as a surrogate model for clinical trials to achieve rapid and less expensive screening of therapeutics for HRPCa and primary CRPC. [ABSTRACT FROM AUTHOR]

[Display omitted] • Great differences in coordination structures of Mg were found in Mg- and Mg/ZSM-5. • Mg well modulate the location of the framework Al in Mg-ZSM-5 zeolites. • Mg-ZSM-5 has more single Al and framework Al in straight and sinusoidal channels. • Propylene yields were improved markedly by inhibiting hydride transfer process. Al distribution engineering is an effective way to tune the catalytic performance of ZSM-5 zeolite. In the present work, a series of [Al, Mg]-ZSM-5 with different Mg contents were obtained by hydrothermal synthesis method. For comparison, Mg/ZSM-5 with a comparable Mg content were also prepared using the conventional impregnation method. Characterizations of XPS-sputtering, H 2 -TPR and Py-IR indicated the distribution and coordination structures of Mg in the samples obtained by the two preparation methods were quite different. Besides, the introduction of magnesium by hydrothermal synthesis well regulates the location of framework Al, which is not possible by the impregnation method. 27Al MAS NMR and UV–vis-DRS of Co2+-exchanged zeolites demonstrated [Al,1.0 Mg]-ZSM-5 has less aluminum in the channel intersections compared to conventional HZSM-5. Finally, the significantly lower content of "Al pairs" in [Al,1.0 Mg]-ZSM-5 inhibits the hydride transfer process, resulting in higher yields of propylene in n -octane and crude oil catalytic cracking reactions. [ABSTRACT FROM AUTHOR]

Abstract: In this study, the association between MH-DAB gene polymorphism and disease resistance was evaluated by challenging grass carp (Ctenopharyngodon idellus) with Flavobacterium columnare. Eight genotypes and six alleles were found, and named by common nomenclature. The genotypes AA, BB, EE, and DE, and the alleles Ctid-DAB1*0101, Ctid-DAB1*0201 and Ctid-DAB1*0401 were more preponderant in fish. The genotype BB was associated with higher resistance to F. columnare, as well as two alleles Ctid-DAB*0101 and Ctid-DAB*0201. Allele Ctid-DAB*0102 has decreased resistance to F. columnare. The expression of MH-DAB gene was decreased in the liver, kidney, and intestine but not in the spleen, gill, and skin at 2days post infection (dpi), versus to that in the control group. MH-DAB gene expression was up-regulated in most tissues but remained at normal levels in the intestine at 15days post infection. Our data suggested that MH-DAB polymorphism can be used as a potential genetic marker for disease resistance breeding of grass carp in the future. [Copyright &y& Elsevier]

• Changes of absorbances and melting points were not related to color differences. • Changes in solubilities and affinities were fundamental reason for color differences. • Degree of esterification had greatest effect on disperse red 167:1′s color difference. [Display omitted] The reason of color differences caused by different degree of esterification disperse dyes were investigated by disperse orange 30, disperse red 167:1, disperse blue 79:1 with different degree of esterification. The results showed that the changes of light absorbance abilities and melting points caused by ester groups had no obvious correlation with the color differences caused by ester groups. The changes in the solubilities and affinities caused by the ester groups were the fundamental reason for the changes in the dyeing properties of disperse orange 30, disperse red 167:1 and disperse blue 79:1. As a joint result of the decrease in solubilities and affinities, the dye sorption in polyethylene terephthalate of unesterified disperse orange 30, unesterified disperse red 167:1 and unesterified disperse blue 79:1 were reduced by 37.7%, 83.6% and 54.6%, respectively, compared with those of the corresponding completely esterified dyes. [ABSTRACT FROM AUTHOR]

[Display omitted] • Versatile nanoparticles for MMP2-triggered enhanced photo-immunotherapy. • Targeting tumor with HA-AuNR arouses ICD and activates antitumor immune response. • M2pep reverses immunosuppression by selectively depleting M2-TAMs. • This study provides a strategy to increase antitumor efficacy. Despite the potential of immunotherapy in various solid tumors, the efficiency of immunotherapy is limited by little tumor-infiltrating lymphocytes (TILs) and abundant immunosuppressive M2-type tumor-associated macrophages (M2-TAMs) in the tumor microenvironment (TME). Herein, we design a versatile photo-immunotherapy nanoparticle (termed as HA-AuNR/M-M2pep NP) to conquer above challenges. The HA-AuNR/M-M2pep NP is composed of hyaluronic acid modified gold nanorod (HA-AuNR) surface-modified with matrix metalloproteinase-2 (MMP2)-responsive M2pep fusion peptides (M-M2pep). Upon tumor site, the fabricated HA-AuNR/M-M2pep NP releases M2pep through the cleavage of MMP2-sensitive peptide to selectively deplete M2-TAMs and improve immunoactivity of TME. Meanwhile, HA-AuNR could target to tumor cells and realize precise tumor photothermal therapy (PTT) under near infrared light irradiation, which further triggers immunogenic cell death (ICD) of tumor cells and elicits antitumor immunity. In vivo antitumor studies reveal that HA-AuNR/M-M2pep NPs-mediated PTT and M2-TAMs depletion recruit TILs, activate effector T lymphocytes, secrete antitumor cytokines (e.g. IFN-γ, TNF-α), and effectively inhibit the growth of tumor. Collectively, HA-AuNR/M-M2pep NP-mediated photo-immunotherapy based on dual targeted delivery and bio-responsive drug release holds tremendous promise to enhance antitumor efficacy. [ABSTRACT FROM AUTHOR]

Several fluorescent probes have been designed to detect ClO− in biological systems based on the isomerization mechanism of C = N bonds. Particularly, fluorescein has emerged as an important fluorophore for detecting ClO− because of its unique properties. Previously, we introduced the fluorescein analog F-1 with an active aldehyde group. In this study, two ClO− fluorescent sensors (F-2 and F-3) with imine groups were designed and synthesized using diaminomaleonitrile and 2-hydrazylbenzothiazole as amines. The electron cloud distribution of F-2 and F-3 in ground and excited states was explored via Gaussian calculations, reasonably explaining their photophysical properties. The fluorescence detection of ClO− in solution using the two probes (F-2 and F-3) was realized based on the mechanism of imine deprotection with ClO−. NaClO concentration titration demonstrated that the colorimetric detection of ClO− with the naked eye could be achieved using both F-2 and F-3. However, after adding ClO−, the fluorescence intensity of probe F-2 increased, whereas that of probe F-3 first decreased and then increased. Probes F-2 and F-3 exhibited good selectivity, anti-interference capability, and sensitivity, with the detection limits of 169.95 and 37.30 µM, respectively. Owing to their low cell toxicity, probes F-2 and F-3 can be applied to detect ClO− in vivo. The design approach adopted in this study will further advance the future development of ClO− chemical probes through the removal of C = N bond isomerization. [ABSTRACT FROM AUTHOR]

Highlights • Tumor-derived exosomes as a novel liquid biopsy biomarker for cancer diagnosis. • MUC-1 is over-expressed on the surface of adenocarcinomas, in particular MCF-7 cells. • MUC-1 is also highly expressed on the surface of exosomes secreted by MCF-7 cells. • MUC-1 aptasensor of “on-off”-type specific detection of tumor exosomes in the blood. Abstract Numerous studies have demonstrated tumor-derived exosomes (TEX) as an ideal biomarker for cancer. However, most present exosome detection methods were cumbersome and expensive, simple and specific detection of TEX in the blood still remained a challenging task. To solve the above problem, we found firstly that MUC1 was highly expressed on the surface of exosomes secreted by MCF-7 cells compared to other cells. Here, we designed an “on-off”-type aptasensor based on MUC1 activation on TEX. In the absence of TEX, the aptasensor was “off” state. Once in the presence of TEX, the aptasensor recognized the MUC1 on TEX and then turned “on” state, resulting in emitting a fluorescence signal. We used the aptasensor to detect exosomes derived from MCF-7, MCF-7/ADR, A549, MGC-803 and Hs578Bst cells and blood serum from breast cancer patients and healthy donors. The fluorescence signal value of exosomes from serum in breast cancer patients was markedly higher than healthy donors, which were a significant difference between the two groups (P < 0.05). Consequently, the method based on exosomes with high sensitivity, specificity and small amount sample were very likely to be used for breast cancer diagnosis. More importantly, this method can be universally applicable for other tumor diagnosis by changing the aptamer. [ABSTRACT FROM AUTHOR]

Abstract Combination therapy with multiple drugs or/and multiple assistant treatments has become a hot spot in cancer therapy. In this study, a new type of core-shell structured dual-drug delivery system based on poly (lactic- co -glycolic acid) (PLGA, inner cores) and hyaluronic acid (HA, outer shells) was constructed. Firstly, HA was conjugated to PLGA for preparation of HA-PLGA block copolymer. Secondly, 5-amino levulinic acid (ALA) was connected to PLGA through a pH-sensitive hydrazone bond for synthesization of PLGA-HBA-ALA. Finally, the core-shell structured nanoparticles (HA-PLGA@ART/ALA NPs) were constructed by self-assembled method for artemisinin (ART) loading in PLGA cores. In this co-delivery system, ALA and ART can be released in a manner of procedural controlled release. ALA was released from the NPs at first though the pH sensitive hydrazone bond cleavage in order to generate protoporphyrin IX (PpIX) for heme formation. And the increase of heme can effectively improve the curative effect of the subsequent released ART. Furthermore, this system has also shown obvious sonodynaimc activity which can be used for cancer sonodynamic combination therapy. The in vitro and in vivo anticancer results demonstrate that HA-PLGA@ART/ALA delivery system could provide a prospective comprehensive treatment strategy for cancer therapy. Graphical abstract A tumor-targeting drug delivery system based on the PLGA nanoparticles for ART and ALA dual-drug delivery and sonodynamic combination cancer therapy. Unlabelled Image Highlights • The dual drug delivery system has drug procedural controlled release function. • 5-amino levulinic acid can generate protoporphyrin IX for heme formation. • The increase of heme can effectively improve the curative effect of artemisinin. • The delivery system can be used for cancer sonodynamic combination therapy. [ABSTRACT FROM AUTHOR]

As one of the most important coumarin-like dyes, disperse fluorescent Yellow 82 exhibits exceptionally large two-photon effects. Here, it was firstly introduced into the supercritical CO dyeing polyester fabrics in this work. Results of the present work showed that the dyeing parameters such as the dyeing time, pressure and temperature had remarkable influences on the color strength of fabrics. The optimized dyeing condition in supercritical CO dyeing has been proposed that the dyeing time was 60 min; the pressure was 25 MPa and the temperature was 120 °C. As a result, acceptable products were obtained with the wash and rub fastness rating at 5 or 4-5. The polyester fabrics dyed with fluorescent dyes can be satisfied for the requirement of manufacturing warning clothing. Importantly, the confocal microscopy imaging technology was successfully introduced into textile fields to observe the distribution and fluorescence intensity of disperse fluorescent Yellow 82 on polyester fabrics. As far as we know, this is the first report about supercritical CO dyeing polyester fabrics based on disperse fluorescent dyes. It will be very helpful for the further design of new fluorescent functional dyes suitable for supercritical CO dyeing technique. [ABSTRACT FROM AUTHOR]

Connectivity of mesopores in zeolites, which is a key factor for the high efficiency catalyst design, is still a challenge to be generated without using organic template. Herein, a hierarchical porous Y zeolite (USY B ) was synthesized by introducing catalytic amounts of boron into the framework of NaY, followed by steaming. The introduction of framework boron promoted the hydrolysis of the surrounding Si O Al and Si O B bonds in steaming treatment. When the boron was dislocated from framework, it could further create more mesopores by steaming. It was deemed that boron played catalytic like role for leading to generate well interconnected mesoporosity. As a result, the mesopore volume of the zeolite increased by 46% relatively. The influence of the generated interconnected mesoporosity on the higher activity was evidenced in both iso -octane (i.e. 2,2,4-trimethylpentane) and 1,3,5-triisopropylbenzene (TIPB) cracking over USY B zeolite. Compared with conventional USY zeolite, there would be 2.1% increase in the yield of gasoline for the cracking of heavy oil over USY B catalyst. [ABSTRACT FROM AUTHOR]

The investigation on the construction strategy, relationship between the structure and photophysical properties of fluorescein analogs plays an important role in the rational design of specific fluorescent dyes. In this work, a fluorescein analog Fc-1 , containing a reactive aldehyde group was prepared using 2′, 7′-dichlorofluorescein (DCF) as the raw material and Vilsmeier–Haack reaction mechanism. Meanwhile, two more fluorescein analogs Fc-2 and Fc-3 were synthesized based on Fc-1 and the Knoevenagel reaction mechanism. The results of Fc-1 indicated that the yield of Fc-1 was higher than 95% after a step of the low-temperature hydrolysis (40 °C) from an intermediate imine salt DCF-3. The fluorescence quantum yield (Φ) of Fc-1 was relatively high in polar protic solvents, even in H 2 O (Φ = 0.25). Fc-1 had large Stokes shifts in different solvents (≧ 123 nm), which was indentified by the Gaussian calculation of Fc-1. Meanwhile, Fc-1 was also used as a ratio and colorimetric fluorescent probe for H 2 S in vitro , and the dianion ([Fc-1-2H] 2- ) mechanism for detecting H 2 S was proposed by nuclear magnetic resonance (NMR), pH titration, and Gaussian calculation. Additionally, Fc-1 can be used in leukocyte classification because of its relatively high Φ in water, cell permeability, and cytotoxicity. All the data of dyes Fc-2 and Fc-3 indicated that the derivatization of the carboxyl group for Fc-2 did not affect the photophysical properties of Fc-2. Both of them had relatively large Stokes shifts and long emission wavelengths. The large Stokes shift of Fc-2 and Fc-3 was due to the distribution of electron clouds in the excited states of Fc-2 and Fc-3. The results of pH titration proved that dyes Fc-2 and Fc-3 were sensitive to the changes in pH and exhibited their potentials as pH probes. Thus, the strategy of constructing fluorescent dyes based on Vilsmeier–Haack and Knoevenagel reactions and the relationship between structure and properties will be beneficial to developing more dyes with large Stokes shift. In this work, three fluorescein analogs (Fc-1 , Fc-2 , and Fc-3) using DCF as raw material were designed and successfully synthesized by the Vilsmeier–Haack and Knoevenagel reaction mechanisms. Dye Fc-1 with reactive aldehyde group was obtained in high yield from the low-temperature hydrolysis. The photophysical results showed that Fc-1 had relatively high fluorescence quantum yields in polar proton solvents and large Stokes shifts in different solvents. The Gaussian calculation proved and explained the reason for the large Stokes shift of Fc-1. Meanwhile, it was found that Fc-1 could detect H 2 S in ratio and colorimetric assay. The mechanism of detecting H 2 S with Fc-1 was rationally proposed by combining the results of NMR, pH titrations, and Gaussian calculation. Additionally, Fc-1 realized the five-classification detection of leukocytes because of its good water solubility, cell permeability, and cytotoxicity. Further, the photophysical properties of dyes Fc-2 and Fc-3 were studied, which showed that both dyes exhibited large Stokes shifts and long emission wavelengths. The derivatization of the carboxyl group on the benzene ring did not affect the photophysical properties of Fc-2. Similarly, the Gaussian calculation method was used to explain the reason for the large Stokes shift. The spectral changes of two dyes at different pH values proved that dyes Fc-2 and Fc-3 had potential applications in pH fluorescent probes. The strategy of constructing fluorescent dyes with excellent photophysical properties was recommended on the basis of Vilsmeier–Haack and Knoevenagel reactions and it will be beneficial to developing more dyes. [Display omitted] • Three fluorescein analogs were constructed based on Vilsmeier-Haack and Knoevenagel condensation reactions. • The fluorescent dye Fc-1 can realize the detection of H 2 S and pH simultaneously. • The constructing strategy of fluorescent dyes based on Vilsmeier-Haack and Knoevenagel reactions will be beneficial to developing dyes with large Stokes shifts. Synopsis: Three fluorescein analogs with relatively good photophysical properties were synthesized and their relationships between structure and properties were investigated. [ABSTRACT FROM AUTHOR]

To elucidate the migration process of cerium-cations and the resulting chemical diversification in cerium-NaY (Ce-NaY) ion-exchange processes, three calcination atmospheres (N 2 -atmosphere, O 2 -oxidation, N 2 -atmosphere followed by O 2 -oxidation) were adopted to study the influence of variable valence (III to IV) on ion migration, thermal stability, and catalytic activity. The results indicated that under N 2 -protection, significant amounts of Ce-(III) ions moved into the sodalite cage and increased the thermal stability of Ce-NaY. Under O 2 -oxidation, most Ce-(III) were converted to Ce-(IV) and remained inside the supercage. Ce-(IV) promoted water polarization and exhibited a unique hydroxyl group at 3582 cm −1 in the infrared spectra. Ce ion-exchanged ultrastable Y zeolite (CeUSY O2 ) exhibited the highest amount of Brønsted acid due to the location of the Ce ions. Compared to CeUSY N2 , CeUSY O2 increased light oil selectivity in vacuum gas oil catalytic cracking due to its higher Brønsted acidity. [ABSTRACT FROM AUTHOR]

Supercritical carbon dioxide (scCO 2) is commonly used as an excellent solvent in chemical reactions and dyeing fields because of its advantages. In this work, three coumarin and 1,8-naphthalimide fluorescent dyes (DAMC , NP-NH , and NP-dimethyl) were successfully constructed on the basis of the Au/titanium dioxide (Au/TiO 2) catalytic reduction of nitro in scCO 2 instead of SnCl 2 /hydrochloric acid solution, and their structures were confirmed correctly by mass spectrometry (MS) and nuclear magnetic resonance (NMR). The cleaner synthesis and dyeing polyester fabrics of coumarin derivative (DAMC) in the presence or absence of N-methyl-pyrrolidone (NMP) were first studied by employing stepwise and synchronous methods. All results for DAMC indicated that the synchronous synthesis and dyeing method is more beneficial. Here, the synchronous synthesis and dyeing polyester fabrics of 1,8-naphthalimide derivatives (NP–NH and NP-dimethyl) in scCO 2 were also investigated. Through the comprehensive analysis of color strength (K/S) value and fixation rate, the optimal temperatures and pressures of synthesis and dyeing for NP-NH and NP-dimethyl were obtained in the absence or presence of NMP. The dyed fabrics with NP-NH and NP-dimethyl exhibited yellow or yellowish-brown in daylight and bright fluorescent yellowish-green in ultraviolet light. All results showed that the clean production of fluorescent dyes (DAMC , NP-NH , and NP-dimethyl) can be realized by the hydrogenation of nitro with efficient Au/TiO 2 catalyst in scCO 2 , meanwhile, the synchronous synthesis and dyeing method was proposed for the synthesized dyes. The realization of synchronous synthesis and dyeing fabrics for fluorescent dyes in scCO 2 is an effective way to prevent environment pollution brought by the processes of synthesis and dyeing. Thus, the constructing and dyeing strategy of fluorescent dyes will be beneficial to the sustainable development of environment. In this study, three coumarin and 1,8-naphthalimide fluorescent dyes (DAMC , NP-NH , and NP-dimethyl) were successfully constructed on the basis of the Au/titanium dioxide (Au/TiO 2) catalytic reduction of nitro in scCO 2 , and their structures were confirmed correctly by mass spectrometry (MS) and nuclear magnetic resonance (NMR). The cleaner synthesis and dyeing polyester fabrics of coumarin derivative (DAMC) in the presence or absence of N-methyl-pyrrolidone (NMP) were first studied by employing stepwise and synchronous methods. All results for DAMC indicated that the synchronous synthesis and dyeing method is more beneficial. Here, the synchronous synthesis and dyeing polyester fabrics of 1,8-naphthalimide derivatives (NP–NH and NP-dimethyl) in scCO 2 were also investigated. Through the comprehensive analysis of color strength (K/S) value and fixation rate, the optimal temperatures and pressures of synthesis and dyeing for NP-NH and NP-dimethyl were obtained in the absence or presence of NMP. The dyed fabrics with NP-NH and NP-dimethyl exhibited yellow or yellowish-brown in daylight and bright fluorescent yellowish-green in ultraviolet light.Synopsis: The synchronous synthesis and dyeing polyester fabrics of coumarin and 1,8-naphthalimide dyes in scCO 2 were also investigated. [Display omitted] • Three coumarin and 1,8-naphthalimide fluorescent dyes were constructed in scCO 2 media. • The synchronous synthesis and dyeing method was proposed for the synthesized dyes in scCO 2. • The constructing and dyeing strategy of fluorescent dyes is beneficial for the sustainable development of environment. [ABSTRACT FROM AUTHOR]

Realumination of dealuminated HZSM-5 zeolites by acid treatment has always been controversial and puzzling. Through characterizations of XRD, nitrogen adsorption, NH 3 -TPD, IR, XPS and 27Al MAS NMR, this work confirmed realumination of dealuminated HZSM-5 zeolites could indeed be achieved after treated with HCl solution. And it was found mainly a portion of the penta-coordinated extra-framework aluminia (EFAl) were reinserted into the framework during the process of realumination. Moreover, the characterizations of ICP-AES and UV–Vis-DRS of Co2+-exchanged zeolites indicated the realumination capacity was closely related to the distribution of framework Al (Al F). Realumination was more likely achieved when there was lower content of Al pairs and less Al F located in the channel intersections in HZSM-5. Finally, realuminated zeolites exhibited a higher conversion of n -octane due to its more Brønsted acid sites than dealuminated HZSM-5 in catalytic cracking reaction. The significantly lower content of Al pairs in realuminated zeolites compared to parent HZSM-5 inhibits the hydride transfer process to a certain extent, resulting in a higher selectivity of propylene. [Display omitted] • Realumination of dealuminated HZSM-5 zeolites achieved by treatment with the aq HCl solution. • A portion of the penta-coordinated EFAl reinserted into the framework during realumination. • Realumination capacity is strongly dependent on the distribution of Al F in HZSM-5 zeolites. • Fewer Al pairs and more Al F located in the straight and sinusoidal channels are easier for realumination. [ABSTRACT FROM AUTHOR]

Tunable mesoporosity was successfully generated by introducing Fe cations into the framework of NaY as starting points, and then by sequential ammonium ion exchange and steaming deferrization–dealumination treatment. Accordingly, the pore diameter and volume of mesopores depended on the content of framework Fe. The zeolite products were characterized by a complementary combination of X-ray diffraction (XRD), N 2 physisorption, TEM, DSC, Py-IR, and 27 Al MAS NMR. The results show that the mesopore volumes of the Fe-induced mesoporous ultra-stable Y (USY Fe ) zeolites, which prepared via sequential deferrization-dealumination by steaming, are all higher than 0.21 cm 3 g −1 with an additional thermal stability. The highest one reaches 0.23 cm 3 g −1 , over 53% of enhancement compared to USY (0.15 cm 3 g −1 ) without deteriorating acidity. Furthermore, the most probable mesopore distributions can be finely tuned, typically in the range of 9–17 nm. In addition, it is found that large mesopores (8–50 nm) are surprisingly boosted with the increase in the Fe content used for the preparation of USY Fe samples. In the catalytic cracking of adsorbate molecule of 1,3,5-triisopropylbenzene, the mesopores-enriched zeolites exhibit higher activity and lower deactivation tendency than USY with time on stream. The results demonstrated that the mesoporous material originating from the modification of zeolite with the pre-set Fe sites aided the diffusion into and out of the micropores via mesopores, and thus produced a positive influence on the catalytic performance. [ABSTRACT FROM AUTHOR]

Abstract: Mesoporous ultra-stable Y zeolite with outstanding performance for heavy oil cracking was prepared through the combination of desilication and dealumination. Atomic removal of silicon atoms from the starting NaY zeolite framework during desilication was reported. Nucleation and propagation of mesopores in the following dealumination process was studied. Si(0Al) and Si(1Al) atoms are selectively removed from zeolite framework by desilication. Consequently, silanol nests and unique hydroxyl nests with framework associated Al-OH were created in the framework of the desilicated zeolite. The artificial defects effect the initiation of mesopores in crystal parts where used to be rich in framework silicon and unfavorable for mesopore formation and promote the propagation and coalescence of mesopores. Catalytic studies revealed improved activity and lifetime in the crack of 1,3,5-triisopropylbenzene and showed increased gasoline and light cycle oil selectivity when the conversion of a heavy oil was compared. [Copyright &y& Elsevier]

Abstract: Study on the rare earth exchange performance was carried out with high silica, normal silica and low silica NaY zeolites with framework SiO2/Al2O3 ratios of 5.8, 4.8 and 4.6, respectively. It is found that the silicon content of the starting NaY zeolite is one of the significant factors in determining the ion exchange efficiency. The higher the framework SiO2/Al2O3 ratio is, the less selective to the rare earth ions the zeolite will be. However, the efficiency of the use of rare earth ions are comparable to each other when the concentration of rare earth in the ion exchange solution is less than 6wt.%, no matter the level of the framework SiO2/Al2O3 ratio of the starting zeolites. Comparison of the hydrothermal stability of the rare earth and ammonium exchanged zeolites (REHY) indicates that the REHY sample prepared from the high silica NaY and with the lowest rare earth loading (2.9wt.%) exhibits the best hydrothermal stability. The reaction studies indicate that the catalyst containing this REHY zeolite shows much better activity and product selectivity in the catalytic conversion of heavy oil than another REHY zeolite prepared from the normal silica NaY zeolite and having a rare earth loading as high as 6.6wt.%, which is highly probably due to the superior hydrothermal stability of the former zeolite. It is suggested that the REHY zeolite with a low level of rare earth loading prepared from the high silica NaY can be considered as an alternative catalyst for the catalytic conversion of gas oil. [Copyright &y& Elsevier]

Abstract: Deletion of either of the genes (zwf), coding for glucose-6-phosphate dehydrogenase isoforms in Streptomyces coelicolor, resulted in an increase in in vitro determined glucose-6-phosphate dehydrogenase activity in the surviving isoform. Mutants carrying either one of these deletions exhibited significantly increased actinorhodin biosynthesis, an effect that was not predicted by simple flux balance simulation. The flux variability distribution, obtained using experimental measured variables as constraints, was examined. The reactions whose flux variabilities were most significantly affected, as a result of the increased actinorhodin production and changes in nutrient uptake rates, included reactions from a number of different pathways. These could be connected together to form an actinorhodin-generating network. They included glutamate synthesising and catabolising reactions. Subsequent experiments, in which glutamate was fed to steady state cultures, resulted in increased actinorhodin production and the in silico model predicted the importance of the same reactions that were amplified in the zwf model. Introduction of a constitutively expressed copy of actII-orf4, the pathway-specific activator of the actinorhodin pathway genes, on the integrating plasmid pIJ8714 resulted in a switch from growth dissociated (typical secondary metabolite) to growth associated antibiotic production. [Copyright &y& Elsevier]

Analogues of the marine natural product (−)-laulimalide were prepared by total synthesis and evaluated in vitro for anticancer activity. [Copyright &y& Elsevier]

Technology of supercritical carbon dioxide (scCO 2) dyeing has been used in dyeing synthetic and natural fibers. It is important to understand the scCO 2 dyeing mechanism owing to the possibility of using this knowledge to design dyes that are suitable for scCO 2 dyeing. Here, using the N-site and 4-site modification of 1,8-naphthalimide matrix, six fluorescent dyes (1 , 2 , 3 , 4 , 5 , and 6) with fluorescent properties were synthesized; dyeing performance and fluorescent images indicate that all the synthesized dyes can be utilized for scCO 2 dyeing wool fibers. Therefore, the dyed wool fibers possess not only conventional dyeing characteristics but also luminescent properties. Especially, the dyed wool fibers with solid free fluorescent dye 2 exhibit strong yellow-green fluorescence. Owing to the lack of proper fixation process, the fixation rate of these six fluorescent dyes on wool fibers was not relatively high. Thus, the dye 7 with an active group N-hydroxysuccinimide (NHS) was synthesized to improve the binding force between dyes and wool fibers and it can react with the –NH 2 group in wools, which results in that the fixation rate of the synthesized dye 7 reaches approximately 91% through chemical combination. Mass spectra prove that the byproduct of 7 reacting with the amino group of wool fibers is not corrosive to dyeing equipment, which realizes the eco-friendly fluorescent dyeing of wool fibers in scCO 2. Our results proved that the fluorescent dyes with conjugated system can overcome the problem of fluorescence quenching in natural fibers. Meanwhile, our strategy of constructing fluorescent dyes and the proposed dyeing mechanism will be helpful to develop reactive disperse dyes that are suitable for scCO 2 dyeing. [Display omitted] • The dyed wool fibers with solid free fluorescent dye 2 showed strong yellow-green fluorescence. • Photophysical properties and dyeing mechanism of dyes suitable for the scCO 2 dyeing wool fibers were investigated. • The fixation rate of new reactive disperse dye 7 reached approximately 91% through chemical combination. [ABSTRACT FROM AUTHOR]

Hydrogen sulfide (H 2 S), as the third multifunctional signaling biomolecule, it acts as a neuromodulator in the human brain and is recognized as an important gas transmitter in human physiology. The abnormal concentrations of H 2 S in human cells can result in several common diseases. Therefore, accurate, fast, and reliable methodologies are required for measuring the in vitro and in vivo concentrations of H 2 S to further investigate its function. In this study, a novel DR–SO 2 N 3 fluorescent probe containing the fluorophore Disperse Red 277 and a sulfonyl azide group was developed and exploited based on the structural characteristic of Disperse Red 277 that contains the active site easily can be attacked by HS−. Therefore, this probe featured two reaction sites that involved the reduction and Michael addition of H 2 S and exhibited rapid ratiometric fluorescence changes and high selectivity towards H 2 S with a 619-fold enhancement factor. Further, the density functional theory (DFT)/time-dependent density functional theory (TDDFT) studies are conducted to understand the photophysical properties of DR–SO 2 N 3 and the final product DRHS–SO 2 NH 2 , which makes the proposed mechanism more reasonable. Furthermore, the probe was successfully applied for the ratiometric fluorescence imaging of exogenous H 2 S in living cells. A novel DR–SO 2 N 3 fluorescent probe containing the fluorophore Disperse Red 277 and a sulfonyl azide group was developed and exploited for the ratiometric detection of hydrogen sulfide (H 2 S). This probe featured two reaction sites that involved the reduction and Michael addition of H 2 S and exhibited rapid ratiometric fluorescence changes and high selectivity with a 619-fold enhancement factor. Further, the density functional theory (DFT)/time-dependent density functional theory (TDDFT) studies are conducted to understand the photophysical properties of DR–SO 2 N 3 and the final product DRHS–SO 2 NH 2. Furthermore, the probe was successfully applied for the ratiometric fluorescence imaging of exogenous H 2 S in living cells. Unlabelled Image • DR–SO 2 N 3 probe containing Disperse Red 277 and a sulfonyl azide group was developed. • Probe featured two reaction sites that involved the reduction and Michael addition of H 2 S. • It exhibits rapid ratiometric fluorescence changes and high selectivity towards H 2 S. [ABSTRACT FROM AUTHOR]

Desorption electrospray ionization mass spectrometry (DESI-MS) is an emerging analytical tool for rapid in situ assessment of metabolomic profiles on tissue sections without tissue pretreatment or labeling. We applied DESI-MS to identify candidate metabolic biomarkers associated with kidney injury at the early stage. DESI-MS was performed on sections of kidneys from 80 mice over a time course following unilateral ureteral obstruction (UUO) and compared to sham controls. A predictive model of renal damage was constructed using the LASSO (least absolute shrinkage and selection operator) method. Levels of lipid and small metabolites were significantly altered and glycerophospholipids comprised a significant fraction of altered species. These changes correlate with altered expression of lipid metabolic genes, with most genes showing decreased expression. However, rapid upregulation of PG(22:6/22:6) level appeared to be a hitherto unknown feature of the metabolic shift observed in UUO. Using LASSO and SAM (significance analysis of microarrays), we identified a set of well-measured metabolites that accurately predicted UUO-induced renal damage that was detectable by 12 h after UUO, prior to apparent histological changes. Thus, DESI-MS could serve as a useful adjunct to histology in identifying renal damage and demonstrates early and broad changes in membrane associated lipids. [ABSTRACT FROM AUTHOR]