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Nowadays, a considerable progress in the syngas-to-olefins (STO) reaction has been made by physically mixed oxide-zeolite catalysts; however, contradictions concerning the reaction mechanism still ...

Human pluripotent stem cells hold great promise for improving regenerative medicine. However, a risk for tumor formation and difficulties in generating large amounts of subtype derivatives remain the major obstacles for clinical applications of stem cells. Here, we discovered that zinc finger E-box–binding homeobox 1 (ZEB1) is highly expressed upon differentiation of human embryonic stem cells (hESCs) into neuronal precursors. CRISPR/Cas9-mediated ZEB1 depletion did not impede neural fate commitment, but prevented hESC-derived neural precursors from differentiating into neurons, indicating that ZEB1 is required for neuronal differentiation. ZEB1 overexpression not only expedited neural differentiation and neuronal maturation, which ensured safer neural cell transplantation, but also facilitated the generation of excitatory cortical neurons, which were valuable for managing certain neurological disorders, such as Parkinson's disease (PD) and amyotrophic lateral sclerosis (ALS). Our study provides useful information on how human neural cells are generated, which may help in forming strategies for developing and improving replacement therapies for treating patients with neurological diseases.

Memory T cells exhibit considerable diversity that determines their ability to be protective and their durability. Here, we examined whether changes in T cell heterogeneity contribute to the age-associated failure of immune memory. By screening for age-dependent T cell surface markers, we have identified CD4 and CD8 memory T cell subsets that are unrelated to previously defined subsets of central and effector memory cells. Memory T cells expressing the ecto-5’-nucleotidase CD73 constitute a functionally distinct subset of memory T cells that declines with age. They exhibit many features favorable for immune protection, including longevity and polyfunctionality. They have a low turnover, but are poised to display effector functions and to develop into cells resembling tissue-resident memory T cells (TRM). Upstream regulators of differential chromatin accessibility and transcriptomes include transcription factors that are characteristic for conferring these superior memory features as well as facilitating CD73 expression. CD73 is not just a surrogate marker of these regulatory networks but is directly involved in T cell survival and TRM differentiation Interventions preventing the decline of this T cell subset or increasing CD73 expression have the potential to improve immune memory in older adults.

BACKGROUND: The mechanism of portal vein tumor thrombus (PVTT) in hepatocellular carcinoma (HCC) has been widely studied, and numerous diagnostic and prognostic biomarkers for HCC with PVTT have been identified. We aimed to evaluate the extent to which these biomarkers may aid the personalized precision therapy of HCC with PVTT. METHODS: Matched tissue specimens [primary HCC tumor (PT), adjacent normal (N) liver, and PVTT tissues] were acquired from 3 Chinese HCC patients who underwent surgery at Sun Yat-sen University Cancer Centre between 2019 and 2020. Ribonucleic acid (RNA) sequencing was performed on the 9 tissue samples. GFOLD (generalized fold change) algorithm was used to analyze the differently expressed genes (DEGs) between the PVTT, PT, and normal tissues from each patient. Genes with a P1 were identified as having significantly different expression. RESULTS: In total, 3,543, 32,472, and 12,901 tumorigenesis-associated genes, and 2,919, 17,679, and 14,825 metastasis-associated genes, were detected in Patient 1 (P1), Patient 2 (P2), and Patient 3 (P3), respectively. We analyzed the expression levels of genes associated with hypoxia, macrophage recruitment and cancer stem cells (CSCs). The results showed that hypoxia and CSCs may have contributed to tumorigenesis but not to metastasis in P1. We also found the hypoxia microenvironment played an important role in tumorigenesis and metastasis in P2, and CSCs may have contributed to metastasis. Additionally, we found that CSCs played critical roles in metastasis but not in tumorigenesis in P3. The results also showed that the long non-coding RNA (lncRNA) Metastasis-Associated Lung Adenocarcinoma Transcript 1 (MALAT1) was greatly overexpressed in the PTs and PVTT in all 3 patients, and Heart and Neural Crest Derivatives Expressed 2-antisense RNA 1 (HAND2-AS1) was downregulated in PVTT compared with PTs in all 3 patients. Thus, MALAT1 and HAND2-AS1 may be robust biomarkers for metastasis in HCC patients with PVTT. CONCLUSIONS: Tumor-associated macrophages (TAMs)-targeted immunotherapy is a promising therapy for HCC patients with PVTT. LncRNAs MALAT1, and HAND2-AS1 may be promising targets for HCC therapy.

The present work investigated the effect of Polylactic acid (PLA) fibers produced by centrifugal spinning with incorporated BaTiO3 particles to improve their bacteriostatic behavior. The PLA matrix and three composites, presenting three different amounts of fillers, were subjected to UV/O3 treatment monitoring the possible modifications that occurred over time. The morphological and physical properties of the surfaces were characterized by different microscopic techniques, contact angle, and surface potential measurements. Subsequently, the samples were tested in vitro with human dermal fibroblasts (HDF) to verify the cytotoxicity of the substrates. No significant differences between the PLA matrix and composites emerged, the high hydrophobicity of the fibers, derived by the polymer structure, represented an obstacle limiting the fibroblast attachment. Samples underwent bacterial exposure (Staphylococcus epidermidis) for 12 and 24 h. Increasing the concentration of BT, the number of living bacteria and their distribution decreased in comparison with the PLA matrix suggesting an effect of the inorganic filler, which generates a neutralization effect leading to reactive oxygen species (ROS) generation and subsequently to bacterial damages. These results suggest that the barium titanate (BT) fillers clearly improve the antibacterial properties of PLA fibers after aging tests made before bacterial exposure, representing a potential candidate in the creation of composites for medical applications.

The recent increase of the number of unidentified cadavers has become a serious problem throughout the world. As a simple and objective method for age estimation, we attempted to utilize Raman spectrometry for forensic identification. Raman spectroscopy is an optical-based vibrational spectroscopic technique that provides detailed information regarding a sample’s molecular composition and structures. Building upon our previous proof-of-concept study, we measured the Raman spectra of abdominal skin samples from 132 autopsy cases and the protein-folding intensity ratio, RPF, defined as the ratio between the Raman signals from a random coil an α-helix. There was a strong negative correlation between age and RPF with a Pearson correlation coefficient of r = 0.878. Four models, based on linear (RPF), squared (RPF2), sex, and RPF by sex interaction terms, were examined. The results of cross validation suggested that the second model including linear and squared terms was the best model with the lowest root mean squared error (11.3 years of age) and the highest coefficient of determination (0.743). Our results indicate that the there was a high correlation between the age and RPF and the Raman biological clock of protein folding can be used as a simple and objective forensic age estimation method for unidentified cadavers.

Surface inactivation of human microbial pathogens has a long history. The Smith Papyrus (2600 ~ 2200 B.C.) described the use of copper surfaces to sterilize chest wounds and drinking water. Brass and bronze on doorknobs can discourage microbial spread in hospitals, and metal-base surface coatings are used in hygiene-sensitive environments, both as inactivators and modulators of cellular immunity. A limitation of these approaches is that the reactive oxygen radicals (ROS) generated at metal surfaces also damage human cells by oxidizing their proteins and lipids. Silicon nitride (Si3N4) is a non-oxide ceramic compound with known surface bacterial resistance. We show here that off-stoichiometric reactions at Si3N4 surfaces are also capable of inactivating different types of single-stranded RNA (ssRNA) viruses independent of whether their structure presents an envelop or not. The antiviral property of Si3N4 derives from a hydrolysis reaction at its surface and the subsequent formation of reactive nitrogen species (RNS) in doses that could be metabolized by mammalian cells but are lethal to pathogens. Real-time reverse transcription (RT)-polymerase chain reaction (PCR) tests of viral RNA and in situ Raman spectroscopy suggested that the products of Si3N4 hydrolysis directly react with viral proteins and RNA. Si3N4 may have a role in controlling human epidemics related to ssRNA mutant viruses.

Osteosarcoma cell viability, proliferation, and differentiation into osteoblasts on a silicon nitride bioceramic were examined as a function of chemical modifications of its as-fired surface. Biological and spectroscopic analyses showed that (i) postsintering annealing in N2 gas significantly improved apatite formation from human osteosarcoma (SaOS-2) cells; (ii) in situ Raman spectroscopic monitoring revealed new metabolic details of the SaOS-2 cells, including fine differences in intracellular RNA and membrane phospholipids; and (iii) the enhanced apatite formation originated from a high density of positively charged surface groups, including both nitrogen vacancies (VN3+) and nitrogen N–N bonds (N4+) formed during annealing in N2 gas. At homeostatic pH, these positive surface charges promoted binding of proteins onto an otherwise negatively charged surface of deprotonated silanols (SiO–). A dipole-like electric-charge, which includes VN3+/N4+ and SiO– defective sites, is proposed as a mechanism to expl...

Memory T cells exhibit considerable diversity that determines their ability to be protective and their durability. Here, we examined whether changes in T cell heterogeneity contribute to the age-associated failure of immune memory. By screening for age-dependent T cell surface markers, we have identified CD4 and CD8 memory T cell subsets that are unrelated to previously defined subsets of central and effector memory cells. Memory T cells expressing the e cto-5ʹ-nucleotidase CD73 constitute a functionally distinct subset of memory T cells that declines with age. They exhibit many features favorable for immune protection, including longevity and polyfunctionality. They have a low turnover, but are poised to display effector functions and to develop into cells resembling tissue-resident memory T cells (TRM). Upstream regulators of differential chromatin accessibility and transcriptomes include transcription factors that are characteristic for conferring these superior memory features as well as facilitating CD73 expression. CD73 is not just a surrogate marker of these regulatory networks but is directly involved in T cell survival and T RM differentiation Interventions preventing the decline of this T cell subset or increasing CD73 expression have the potential to improve immune memory in older adults.

The recent increase of the number of unidentified cadavers has become a serious problem in the world. As a simple and objective method for age estimation, we attempted to utilize Raman spectrometry for forensic identification. Raman spectroscopy is an optical-based vibrational spectroscopic technique that provides detailed information about molecular composition and structure. Building upon our previous proof-of-concept study, Raman spectra of abdominal skin sample were measured in 132 autopsy cases and protein-folding intensity ratio (RPF) was calculated. There was a strong negative correlation between age and RPF with a Pearson correlation coefficient r = 0.878. The results of cross validation suggested that Model 2 (the square of RPF) is the best model with lowest mean squared error (127.9) and highest coefficient of determination (0.743) among the four models. Our results indicate that the there is a high correlation between the age and RPF. The Raman biological clock of protein folding can be used as a simple and objective forensic age estimation method of unidentified cadavers.

The performance, durability, and bio-integration of functional biomedical coatings can be enhanced by changing or improving their substrate properties. In this study, we applied silicon nitride powder-based laser claddings to various substrates and undertook an in vitro assessment of their osteoconductive and antibacterial properties. The substrates included common arthroplasty materials: polyethylene, titanium, zirconia-toughened alumina, and zirconia. Multiple analytical techniques were used to characterize the physical and chemical structure of the claddings after deposition. Partial decomposition of the silicon nitride powders occurred during the cladding process, resulting in nitrogen loss during intermetallic formation phases under some substrate and treatment conditions. The osteoconductive capabilities of various laser-cladded substrates were evaluated in a SaOS-2 osteosarcoma cell culture by measuring the amount of bone formation on the coated surface. Antibacterial testing was performed using Gram-positive Staphylococcus epidermidis at 24 and 48 h of incubation. Silicon nitride coating enhanced both osteoconductive and antibacterial properties.

Poly-caprolactone is one of the most promising biocompatible polymers on the market, in particular for temporary devices that are not subjected to high physiological loads. Even if completely resorbable in various biological environments, poly-caprolactione does not play any specific biological role in supporting tissue regeneration and for this reason has a limited range of possible applications. In this preliminary work, for the first time l-dopa and fibroin have been combined with electrospun poly-caprolactone fibers in order to induce bioactive effects and, in particular, stimulate the proliferation, adhesion and osteoconduction of the polymeric fibers. Results showed that addition of low-molecular weight fibroin reduces the mechanical strength of the fibers while promoting the formation of mineralized deposits, when tested in vitro with KUSA-A1 mesenchymal cells. l-dopa, on the other hand, improved the mechanical properties and stimulated the formation of agglomerates of mineralized deposits containing calcium and phosphorous with high specific volume. The combination of the two substances resulted in good mechanical properties and higher amounts of mineralized deposits formed in vitro.

With the increased scientific interest in green technologies, many researches have been focused on the production of polymeric composites containing naturally occurring reinforcing particles. Apart from increasing mechanical properties, these additions can have a wide range of interesting effects, such as increasing the resistance to bacterial and fungal colonization. In this work, different amounts of two different natural products, namely neem and turmeric, were added to polyethylene to act as a natural antibacterial and antifungal product for food packaging applications. Microscopic and spectroscopic characterization showed that fractions of up to 5% of these products could be dispersed into low-molecular weight polyethylene, while higher amounts could not be properly dispersed and resulted in an inhomogeneous, fragile composite. In vitro testing conducted with Escherichia coli, Staphylococcus aureus, and Candida albicans showed a reduced proliferation of pathogens when compared to the polyethylene references. In particular, turmeric resulted in being more effective against E. coli when compared to neem, while they had similar performances against S. aureus. Against C. albicans, only neem was able to show a good antifungal behavior, at high concentrations. Tensile testing showed that the addition of reinforcing particles reduced the mechanical properties of polyethylene, and in the case of turmeric, it was further reduced by UV irradiation.

Tooth loss impairs mastication, deglutition and esthetics and affects systemic health through nutritional deficiency, weight loss, muscle weakness, delayed wound healing, and bone fragility. Approximately 90% of tooth loss is due to dental caries and periodontal disease. Accordingly, early treatment of dental caries is essential to maintaining quality of life. To date, the clinical diagnosis of dental caries has been based on each dentist&rsquo, s subjective assessment, but this visual method lacks objectivity. To improve diagnostic ability, highly sensitive quantitative methods have been developed for the diagnosis and prevention of dental caries and are gradually becoming a mandatory item in modern dentistry. High-resolution Raman spectroscopy is a suitable tool for recognizing the subtle structural changes that occur in dental enamel in already developed or, more importantly, incipient dental caries. Raman analysis could soon emerge as a breakthrough in dentistry because of its high diagnostic sensitivity. In this study, we build upon our previous findings in a new analysis of dental caries using Raman spectroscopy imaging and discuss the possibility of using Raman photonic imaging in support of objective diagnostics in dentistry. Our findings support the Raman method of caries detection in comparison with other conventional or new approaches.

Previous studies using gram-positive and -negative bacteria demonstrated that hydrolysis of silicon nitride (Si

Surface roughness, bioactivity, and antibacterial properties are desirable in skeletal implants. We hot-pressed a mix of particulate sodium chloride (NaCl) salt and silicon nitride (β-Si3N4) onto the surface of bulk PEEK. NaCl grains were removed by leaching in water, resulting in a porous PEEK surface embedded with sim15 vol% β-Si3N4 particles. This functionalized surface showed the osteogenic and antibacterial properties previously reported in bulk silicon nitride implants. Surface enhancement of PEEK with β-Si3N4 could improve the performance of spinal fusion cages, by facilitating arthrodesis and resisting bacteria.

The myelinating activity of living Schwann cells in coculture with neuronal cells was examined

Early detection of dental caries and variations in composition/structure of both enamel and dentin represents an important issue in modern dentistry. Demineralization has been associated to teeth discoloration, development of caries, and formation of cavities. Objective In this study, we systematically monitored the processes of demineralization/remineralization in dentin samples by means of three different spectroscopic techniques, namely, Raman spectroscopy, X-Ray Photo-electron spectroscopy (XPS), and X-Ray Diffractometry (XRD). Methods Bovine dentin samples were first exposed to acidic solutions and their structure systematically monitored as a function of time and pH. Then, the samples were rinsed in artificial saliva to simulate remineralization. Results The above three spectroscopic techniques provided quantitative structural information spanning from the nanometer to the millimeter scale of sample penetration depth. An irreversible level of demineralization was reached when dentin was exposed to pH 2 beyond a time threshold of 6 h, successive treatments with artificial saliva being unable to restore the mineral fraction. On the other hand, short-term treatments at pH 5 and long-term treatments at pH 6 could partially or completely recover the dentin structure within one week of remineralization treatment. Significance Two specific Raman parameters, namely, the bandwidth of the symmetric phosphate-stretching signal and the mineral-to-matrix intensity ratio, showed strong correlations with XPS and XRD data, and matched laser microscopy observations. Such correlations open the path to apply Raman spectroscopy in monitoring dentin demineralization in vivo and provide quantitative working algorithms for the prevention of oral caries.

IntroductionViral disease spread by contaminated commonly touched surfaces is a global concern. Silicon nitride, an industrial ceramic that is also used as an implant in spine surgery, has known antibacterial activity. The mechanism of antibacterial action relates to the hydrolytic release of surface disinfectants. It is hypothesized that silicon nitride can also inactivate the coronavirus SARS-CoV-2.MethodsSARS-CoV-2 virions were exposed to 15 wt.% aqueous suspensions of silicon nitride, aluminum nitride, and copper particles. The virus was titrated by the TCD50method using VeroE6/TMPRSS2 cells, while viral RNA was evaluated by real-time RT-PCR. Immunostaining and Raman spectroscopy were used as additional probes to investigate the cellular responses to virions exposed to the respective materials.ResultsAll three tested materials showed >99% viral inactivation at one and ten minutes of exposure. Degradation of viral RNA was also observed with all materials. Immunofluorescence testing showed that silicon nitride-treated virus failed to infect VeroE6/TMPRSS2 cells without damaging them. In contrast, the copper-treated virus suspension severely damaged the cells due to copper ion toxicity. Raman spectroscopy indicated differential biochemical cellular changes due to infection and metal toxicity for two of the three materials tested.ConclusionsSilicon nitride successfully inactivated the SARS-CoV-2 in this study. The mechanism of action was the hydrolysis-mediated surface release of nitrogen-containing disinfectants. Both aluminum nitride and copper were also effective in the inactivation of the virus. However, while the former compound affected the cells, the latter compound had a cytopathic effect. Further studies are needed to validate these findings and investigate whether silicon nitride can be incorporated into personal protective equipment and commonly touched surfaces, as a strategy to discourage viral persistence and disease spread.

In the modern information warfare, the evaluation of the reconnaissance efficiency of the radar countermeasure equipment is fundamental to response timely and master the development of equipment. In this paper, according to the basic tasks of the radar countermeasures reconnaissance, the evaluation model of the reconnaissance efficiency is constructed based on the DHGF algorithm. Firstly, Delphi algorithm is adopted to construct the multi-index evaluation system. Secondly, the weight of each index is calculated by AHP algorithm. Afterwards, the grade of the reconnaissance efficiency is evaluated by grey correlation analysis and the fuzzy evaluation. Finally, the grade of evaluation object is analyzed and verified by an example. Thus, the validity of the DHGF algorithm is verified, which provides the basis for equipment efficiency evaluation.

In view of the real-time effect of radar interference, an online evaluation method based on entropy-topsis's radar interference effect is proposed, which is based on the comparison of the threat level of the radar target of some kind of interference strategy, and the effectiveness of the radar interference effect is judged. This method is proved to be feasible by the problem of typical pattern.

Zirconia is the most common ceramic used in dental implants. Even if it possesses both mechanical strength and esthetics, its intrinsic bio-inertness often results in a lack of biological integration. On the other hand, Si3N4 has been proved to be bio-active and to be able to easily osteointegrate. In this work, a Si3N4 powder-based laser-cladding process has been developed in order to improve the biological response to biomedical zirconia. The process resulted in the formation of a composite coating with Si3N4 particles dispersed in nano-crystalline/amorphous silicon. Microscopic observation showed that the layer is adherent to the substrate. The application of the laser cladding treatment resulted in an increase of the roughness, further enhancing the probability of interaction with biological tissues and consequently the bioactivity. Testing with human osteosarcoma cell lines resulted in the formation of bone tissue with high collagen maturity, high carbonate to phosphate ratios and good tissue mineralization, but lower cell proliferation when compared to stoichiometric Si3N4. The bone tissue quality parameters, as measured by Raman spectroscopy, resulted to be comparable to healthy human bone tissue and suggest that laser-cladded Si3N4 treatments might be able to improve the stability of zirconia implants.

The purpose of the present study was to compare the wear behavior of ceramic-on-vitamin-E-diffused crosslinked polyethylene (Vit-E XLPE) hip bearings employing the gold standard oxide ceramic, zirconia (ZrO2)-toughened alumina (Al2O3) (ZTA, BIOLOX&reg, delta) and a new non-oxide ceramic, silicon nitride (Si3N4, MC2&reg, ). In vitro wear test was performed using a 12-station hip joint simulator. The test was carried out by applying the kinematic inputs and outputs as recommended by ISO 14242-1:2012. Vitamin-E-diffused crosslinked polyethylene (Vit-E XLPE) acetabular liners (E1&reg, ) were coupled with &Oslash, 28-mm ZTA and Si3N4 femoral heads. XLPE liner weight loss over 5 million cycles (Mc) of testing was compared between the two different bearing couples. Surface topography, phase contents, and residual stresses were analyzed by contact profilometer and Raman microspectroscopy. Vit-E XLPE liners coupled with Si3N4 heads produced slightly lower wear rates than identical liners with ZTA heads. The mean wear rates (corrected for fluid absorption) of liners coupled with ZTA and Si3N4 heads were 0.53 &plusmn, 0.24 and 0.49 &plusmn, 0.23 mg/Mc after 5 Mc of simulated gait, respectively. However, after wear testing, the ZTA heads retained a smoother topography and showed fewer surface stresses than the Si3N4 ones. Note that no statistically significant differences were found in the above comparisons. This study suggests that the tribochemically formed soft silica layer on the Si3N4 heads may have reduced friction and slightly lowered the wear of the Vit-E XLPE liners. Considering also that the toughness of Si3N4 is superior to ZTA, the present wear data represent positive news in the future development of long-lasting hip components.

Functional coatings are commonly applied to biomaterials in order to improve their properties. In this work, polyethylene was coated with a silicon nitride (Si3N4) powder using a pulsed laser source in a nitrogen gas atmosphere. Several analytical techniques were used to characterize the functionalized surface of the polymer, including Raman spectroscopy, laser microscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Antibacterial properties were tested in vitro against Staphylococcus epidermidis. The Si3N4 coating sensibly reduced the amount of living bacteria when compared to the uncoated polymer. Osteoconductivity was also tested in vitro using SaOS-2 osteosarcoma cells. The presence of Si3N4 coating resulted in an increased amount of hydroxyapatite. Coating of polyethylene with silicon nitride may lead to improved performance of indwelling orthopaedic or less invasive medical devices.

Zirconia-toughened alumina (ZTA) currently represents the bioceramic gold standard for load-bearing components in artificial hip joints. ZTA is long known for its high flexural strength and fracture toughness, both properties arising from a microscopic crack-tip shielding mechanism due to the stress-induced tetragonal-to-monoclinic (t&rarr, m) polymorphic transformation of zirconia. However, there have been concerns over the years regarding the long-term structural performance of ZTA since the t&rarr, m transformation also spontaneously occurs at the material&rsquo, s surface under low-temperature environmental conditions with a concomitant degradation of mechanical properties. Spontaneous surface degradation has been extensively studied in vitro, but predictive algorithms have underestimated the extent of in vivo degradation observed in retrievals. The present research focused on burst-strength assessments of &Oslash, 28 mm ZTA femoral before and after long-term in vitro hydrothermal ageing according to ISO 7206-10. An average burst strength of 52 kN was measured for pristine femoral heads. This value was ~36% lower than results obtained under the same standard conditions by other authors. A further loss of burst strength (~13% in ultimate load) was observed after hydrothermal ageing, with increased surface monoclinic content ranging from ~6% to &gt, 50%. Nevertheless, the repetitively stressed and hydrothermally treated ZTA heads exceeded the minimum burst strength stipulated by the US Food and Drug Administration (FDA) despite severe test conditions. Lastly, Raman spectroscopic assessments of phase transformation and residual stresses on the fracture surface of the femoral heads were used to clarify burst-strength fluctuations and the effect of hydrothermal ageing on the material&rsquo, s overall strength degradation.

Diamond-like carbon films/coatings (DLC) can be employed in a wide range of applications, but the film quality and performance are strongly dependent on the deposition conditions. In this paper, we attempted to clarify the structural and compositional alterations induced by substrate bias voltage (SBV) variation in DLC films by employing different spectroscopic analyses and to correlate them with the variations of two important film properties, hardness and adhesion energy. A series of DLC films fabricated by unbalanced magnetron sputtering with changing substrate bias voltage were investigated by Raman, FTIR and X-ray photoelectron spectroscopies. The results revealed the presence of sp2 and sp3 carbon chains and rings and various types of hydrocarbon in the tetrahedral amorphous carbon films due to incorporation of hydrogen and oxygen. The reduction in hydrogen content together with a generation of sp2 hydrocarbon rings in response to SBV increase were responsible for increases in Young's modulus and hardness, and, concurrently, for a decrease in film adhesion energy.

Acrylic acid (AA) and its ester, methyl acrylate (MA), were produced by a green one-step aldol condensation reaction of dimethoxymethane and methyl acetate. The reaction was conducted over ZSM-35 zeolites with different concentrations of Bronsted acid, which were prepared by the sodium ion-exchange process with H-form zeolite. The acidic property of HZSM-35 was studied in detail through infrared experiments. About 51% of all bridging OH groups were distributed in cages, while 23% and 26%, respectively, were distributed in 10- and 8-ring channels. The catalytic performance was enhanced by a high concentration of Bronsted acid, indicating that Bronsted acid is an active site for the aldol condensation reaction. The ZSM-35 zeolite possessing a concentration of Bronsted acid as high as 0.049 mmol/g demonstrated excellent performance with a MA+AA selectivity of up to 73%.

Despite being the most used ceramic biomaterial in hip joint prosthesis, Zirconia Toughened Alumina (ZTA) is liable to undergo several degradation mechanisms in vivo, which might drastically affect its structural performance over time. Our standing point in this investigation was that neither in vitro tests nor finite elements simulations are yet capable to fully reproduce the complexity of the in vivo conditions. Through accurate analyses of retrievals, we attempt to add more pieces to the puzzle of in vivo loading history and to obtain better insight into the ZTA degradation mechanisms. For doing so, we applied a previously established automated scanning protocol to investigate the coupling between a ZTA femoral head and its metal stem counterpart in a short-term (20 months) retrieved hip implant. Metal contamination on the ZTA surface was severe and polymorphic transformation widespread on the whole surface of the taper, though reaching different values depending on the specific zone of the taper. Clear signs of third body abrasive wear and fatigue crack initiation could be found by means of laser and electron microscopies, and X-ray spectroscopy. Highly resolved mapping by Raman micro-spectroscopy revealed very high monoclinic fractions and pronounced residual stress magnitudes despite the relatively short in-vivo lifetime. Keywords: Zirconia-toughened alumina, Confocal Raman spectroscopy, Phase transformation, Metal contamination, 3D-CAD

A series of hierarchical HY zeolites were prepared by using sequential acid (H4EDTA) and alkaline (NaOH and NH4OH) solution treatments. The nitrogen adsorption-desorption analysis proved that the mesoporous structure was definitely formed with the pore diameter at about 3.5 and 17.5 nm, and the external surface area and mesopore volume significantly increased. The XRD, XRF, and NH3-TPD characterization results disclosed that the relative crystallinity, crystalline sizes, and acidity of as-treated HY zeolites decreased as compared with parent HY although their Si/Al ratios were higher. The zeolites were conducted in vapor phase carbonylation of dimethoxymethane (DMM) to methoxyacetate (MMAc) at 5.0 MPa and different temperatures. As compared with reference HY, the DMM conversion and MMAc selectivity obviously increased from 50.41% to 90.91% and from 34.79% to 84.57% at 383 K, respectively. The DMM conversion were closely related to the medium-strong acid amount and greater amount of medium-strong acid sites resulted in higher DMM conversion. The catalytic stability of HY-DAl0.11-DSiNaOH0.05 was carried out at 393 K and 5.0 MPa for 100 h. The DMM conversion (about 97%) and products selectivity (MMAc: 84%) kept unchanged during the whole carbonylation process, exhibiting excellent catalytic stability, which was also supported by the TG-DTA analysis that the carbon deposition was effectively suppressed. In a word, as-treated HY zeolites with larger external surface area and mesopore volume that contributed to promoting the mass transfer efficiency exhibited much higher DMM conversion, MMAc selectivity and excellent catalytic stability than parent HY.

Summary: Differentiation of human pluripotent stem cells (hPSCs) into striatal medium spiny neurons (MSNs) promises a cell-based therapy for Huntington's disease. However, clinical-grade MSNs remain unavailable. Here, we developed a chemical recipe named XLSBA to generate clinical-grade MSNs from embryonic stem cells (ESCs). We introduced the γ-secretase inhibitor DAPT into the recipe to accelerate neural differentiation, and replaced protein components with small molecules. Using this optimized protocol we could efficiently direct regular human ESCs (hESCs) as well as clinical-grade hESCs to lateral ganglionic eminence (LGE)-like progenitors and striatal MSNs within less than half of the time than previous protocols (within 14 days and 21 days, respectively). These striatal cells expressed appropriate MSN markers and electrophysiologically acted like authentic MSNs. Upon transplantation into brains of neonatal mice or mouse model of Huntington's disease, they exhibited sufficient safety and reasonable efficacy. Therefore, this quick and highly efficient derivation of MSNs offers unprecedented access to clinical application. : In this article, Wu and colleagues showed that a cocktail of small molecules could induce clinical-grade hESCs into clinically compatible striatal LGE-like progenitors and GABAergic MSNs rapidly and efficiently. Keywords: clinical-grade hESCs, differentiation, striatal medium spiny neurons, small molecules

How trehalose has exceptional property in helping biomolecules preserve their native structures remains a subject of active research. Running molecular dynamics simulations on a model protein in low-concentrated trehalose solution and pure water, respectively, the present study verifies the ability of trehalose in stabilizing protein native structure and provides a comprehensive atomic-level picture of the molecular interactions among protein, trehalose, and water in their mixed solution. Trehalose directly interacts to and meanwhile affects the interactions between the other species via hydrogen bonding: 1) trehalose molecules are clustered through inter-molecular hydrogen bonding interaction; 2) trehalose forms hydrogen bond with water which influences the strength of water-water hydrogen bonding network but does not impair protein-water hydrogen bonding; 3) trehalose is accessible to form hydrogen bonds towards protein and simultaneously replace water molecules around protein which reduces the hydrogen bonding possibility from water to protein, in accordance with “water replacement” scenario.

The conversion of methanol into aromatics over unmodified H-ZSM-5 zeolite is generally not high because the hydrogen transfer reaction results in alkane formation. Now circa 80 % aromatics selectivity for the coupling reaction of methanol and carbon monoxide over H-ZSM-5 is reported. Carbonyl compounds and methyl-2-cyclopenten-1-ones (MCPOs), which were detected in the products and catalysts, respectively, are considered as intermediates. The latter species can be synthesized from the former species and olefins. 13 C isotope tracing and 13 C liquid-state NMR results confirmed that the carbon atoms of CO molecules were incorporated into MCPOs and aromatic rings. A new aromatization mechanism that involves the formation of the above intermediates and co-occurs with a dramatically decreased hydrogen transfer reaction is proposed. A portion of the carbons in CO molecules are incorporated into aromatic, which is of great significance for industrial applications.

Transformation of greenhouse gas CO2 and renewable H2 into fuels and commodity chemicals is recognized as a promising route to store fluctuating renewable energy. Although several C1 chemicals, olefins, and gasoline have been successfully synthesized by CO2 hydrogenation, selective conversion of CO2 and H2 into aromatics is still challenging due to the high unsaturation degree and complex structures of aromatics. Here we report a composite catalyst of ZnAlOx and H-ZSM-5 which yields high aromatics selectivity (73.9%) with extremely low CH4 selectivity (0.4%) among the carbon products without CO. Methanol and dimethyl ether, which are synthesized by hydrogenation of formate species formed on ZnAlOx surface, are transmitted to H-ZSM-5 and subsequently converted into olefins and finally aromatics. Furthermore, 58.1% p-xylene in xylenes is achieved over the composite catalyst containing Si-H-ZSM-5. ZnAlOx&H-ZSM-5 suggests a promising application in manufacturing aromatics from CO2 and H2., Selective conversion of CO2 and H2 into aromatics remains challenging due to the high unsaturation degree and complex structure of aromatics. Here the authors report a composite catalyst of ZnAlOx and H-ZSM-5 which promotes the formation of aromatics with high selectivity while inhibiting CO and CH4 formation in CO2 hydrogenation reactions.

Recent developments in Raman imaging at the microscopic scale were exploited here with the specific purpose of locating spectral fingerprints of individual membrane lipids and deoxynucleoside triphosphates during neuronal cell networking and separation. After carefully screening the Raman spectra of isolated lipid components, we located an in situ mapped specific Raman fingerprints from individual phospholipids at the micrometric level in comparison with the total lipid distribution within single living cells. We concurrently examined silent zones of lipid emissions and exploited those peculiar spectral ranges for mapping both abundance and localization of individual DNA nucleoside triphosphates. This work represents a first step toward label-free/molecular-selective Raman patterning with high spectral resolution of the relevant chemical species involved with the functionality of neuronal cells.

Human pluripotent stem cells (hPSCs) promise a foreseeing future for regeneration medicine and cell replacement therapy with their abilities to produce almost any types of somatic cells of the body. The complicated immunogenicity of hPSC derivatives and context dependent responses in variable transplantations greatly hurdle the practical application of hPSCs in clinic. Especially for applications of hPSCs, induction of immune tolerance at the same time increases the risks of tumorigenesis. Over the past few years, thanks to the progress in immunology and practices in organ transplantation, endeavors on exploring strategies to induce long term protection of allogeneic transplants have shed light on overcoming this barrier. Novel genetic engineering techniques also allow to precisely cradle the immune response of transplantation. Here we reviewed the current understanding on immunogenicity, and efforts have been attempted on inducing immune tolerance for hPSC derivatives, with extra focus on modifying the graft cells. We also glimpse on employing cutting-edge genome editing technologies for this purpose, which will potentially endow hPSC derivatives with the nature of wide spectrum drugs for therapy.

The purposes of this study were to document novel Raman spectroscopic findings in femoral heads affected by osteonecrosis and to identify molecular structure differences based on aetiology.We obtained 13 femoral heads with osteonecrosis from 13 different patients who underwent total hip arthroplasty. Comparisons were made between the viable zones of each femoral head examined. The samples were scanned with X-ray micro-CT for structural mapping and a central coronal section slab was prepared for Raman spectroscopy and histological analyses. Raman spectra were collected at different locations, including the viable and necrotic zones of the femoral head, using a highly spectrally resolved Raman microprobe.Significant alterations in the spectral morphology in the high wavenumber region were found, with a pronounced inhibition of peculiar lipid signals in the frequency interval 2851 ~ 2890 cmWe systematically found a decrease in Raman intensity for sphingomyelin and phenylalanine fingerprint bands in the necrotic zones, and these differences may be related to the etiology of osteonecrosis.

In this work, kelp-like structured NiCo2S4-C-MoS2 composite electrode materials for supercapacitors were successfully synthesized by a facile hydrothermal and solvothermal method. Due to the synergistic effect of the mixture of graphene-like MoS2 nanosheets, highly conductive carbon and NiCo2S4, the composite materials exhibited superior electrochemical performance: specific capacitance of 1601 F/g at a current density of 0.5 A/g, and rate performance of 61% at 10 A/g. Furthermore, an asymmetric supercapacitor (ASC), fabricated by using the NiCo2S4-C-MoS2 composite and activated carbon (AC) as positive and negative electrodes, respectively, showed a high energy density of 27.7 Wh/kg at a power density of 400 W/kg (it retained 14.4 Wh/kg at power density up to 8 kW/kg). After 1000 charge-discharge cycles at 2 A/g, the ASC device still maintained 60% of its initial capacitance. The outstanding performance of the NiCo2S4-C-MoS2 composite indicates its great potential for applications in high-performance energy storage systems.

Methyl methoxyacetate (MMAc), which is an important fine chemical, can be used as an intermediate to produce ethylene glycol from syngas. For the reported vapor-phase carbonylation of dimethoxymethane (DMM), the reaction was conducted under a higher (>100) CO/DMM molar ratio with a lower CO conversion (

The metabolic response of Gram-positive Staphylococcus epidermidis (S. epidermidis) bacteria to bioceramic substrates was probed by means of Fourier transform infrared spectroscopy (FTIR). Oxide zirconia-toughened alumina (ZTA) and non-oxide silicon nitride (Si3N4) substrates were tested. Bacteria exposed to silica glass substrates were used as a control. S. epidermidis, a major cause of periprosthetic infections, was screened to obtain a precise time-lapse knowledge of its molecular composition and to mechanistically understand its interaction with different substrates. At the molecular level, the structure of proteins, lipids, nucleic acid, and aromatic amino acids evolved with time in response to different substrates. In combination with statistical validation and local pH measurements, a chemical lysis mechanism was spectroscopically observed in situ on the Si3N4 substrates. Utilization of FTIR in this study avoided fluorescence noise which occurred while probing the ZTA samples with Raman spectroscopy in a companion paper. The substrate-driven dynamics of polysaccharide and peptide variations in the bacterial cell wall, peculiar to Si3N4 bioceramics, are elucidated.

Zirconia containing bioceramics suffer from low temperature degradation in biological and hydrothermal environments, and the presence of transition metal contamination has been shown to greatly affect the zirconia stability in different materials. In this paper, X-ray photoelectron spectroscopy was used to investigate the compositional and structural variations of different zirconia containing hip-joint bioceramics with and without transition metal stains in hydrothermal environments. Non-stained and stainless-steel-stained femoral head samples of 3 mol% Y2O3 doped tetragonal zirconia polycrystals (3Y-TZP) and zirconia-toughened alumina (ZTA) subjected to isothermal treatments in water vapor were investigated with quantifying their respective compositional XP lines. The outputs of these spectroscopic experiments revealed a significant difference in the off-stoichiometric reactions taking place at the surface of zirconia-containing ceramics in the presence and absence of transition metal contamination. The complex off-stoichiometric chemistry that occurred in the presence of metal contaminants could be interpreted in terms of defect-related chemical reactions among metal, water vapor, and oxide lattice, with a crucial contribution of the alumina phase in the transformation kinetics of ZTA.

Commercial precipitated iron catalysts suffer from severe fragmentation when applied in the Fischer–Tropsch to lower olefins reaction (FTO). Herein, sintered precipitated iron catalysts for FTO are prepared by varying the calcination temperature from 800 to 1400 °C to enhance their fragmentation-resistance ability. Compared with traditional precipitated iron catalysts, sintered precipitated iron catalysts require higher reduction temperatures to maintain high and stable activity and shift the production of hydrocarbons towards lower olefins. Spent sintered precipitated iron catalysts show bulk morphologies with less fragmentation than the fragmented and aggregated morphologies of spent traditional precipitated iron catalysts. The amount of coke inside the spent catalysts decreases from 41.8 to 12.5% as the calcination temperature increases from 500 to 1200 °C, and simultaneously, the chain length of soluble coke decreases from C32 to C21. The lower amount of coke and shorter chain length of soluble coke of the sintered precipitated iron catalysts come from the stronger mechanical strength-induced less space for coke accumulation during FTO, which further enhance the fragmentation-resistance ability of the catalysts.

The multiple mutations of the severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) virus have created variants with structural differences in both their spike and nucleocapsid proteins. While the functional relevance of these mutations is under continuous scrutiny, current findings have documented their detrimental impact in terms of affinity with host receptors, antibody resistance, and diagnostic sensitivity. Raman spectra collected on two British variant sub‐types found in Japan (QK002 and QHN001) are compared with that of the original Japanese isolate (JPN/TY/WK‐521), and found bold vibrational differences. These included: i) fractions of sulfur‐containing amino acid rotamers, ii) hydrophobic interactions of tyrosine phenol ring, iii) apparent fractions of RNA purines and pyrimidines, and iv) protein secondary structures. Building upon molecular scale results and their statistical validations, the authors propose to represent virus variants with a barcode specially tailored on Raman spectrum. Raman spectroscopy enables fast identification of virus variants, while the Raman barcode facilitates electronic recordkeeping and translates molecular characteristics into information rapidly accessible by users., Raman measurements clearly discriminate between SARS‐CoV‐2 variants and original isolate by resolving in times of tens of seconds conclusive differences in conformational isomerism of spike proteins. Key molecular information encrypted in the Raman spectrum is represented with a barcode locating the variant and decryptable into readable information through appropriate apps. The Raman barcode can support on‐site Coronavirus Disease 2019 (COVID‐19) virology diagnostics.

Purpose To explore the cause of functional changes of tumor necrosis factor alpha (TNF-α) in development of gastric cancer through the structural changes of each site in TNF-α before and after mutation. Methods Three typical mutant sites (TNF-α-308G/A, 857C/T and 863C/A of TNF-α) were chosen and methods like ab initio modeling was adopted for 3D modeling of TNF-α before and after mutation, besides, the structural changes were also analyzed. Results Mutation of TNF-α-308G/A led to the production of multiple helical structures and that of 863C/A caused the production of one helical structure in its adjacent region. Mutation of 857C/T, however, did not cause the change in the basic structure of TNF-α. Conclusions Structural changes of TNF-α may have a significant effect on development of gastric cancer.

Raman spectroscopy was applied to characterize at the molecular scale the nutritional quality of the Japanese Koshihikari rice cultivar in comparison with other renowned rice cultivars including Carnaroli from Italy, Calrose from the USA, Jasmine rice from Thailand, and Basmati from both India and Pakistan. For comparison, two glutinous (mochigome) cultivars were also investigated. Calibrated and validated Raman analytical algorithms allowed quantitative determinations of: (i) amylopectin and amylose concentrations, (ii) fractions of aromatic amino acids, and (iii) protein content and secondary structure. The Raman assessments non-destructively linked the molecular composition of grains to key nutritional parameters and revealed a complex intertwine of chemical properties. The Koshihikari cultivar was rich in proteins (but with low statistical relevance as compared to other investigated cultivars) and aromatic amino acids. However, it also induced a clearly higher glycemic impact as compared to long-grain cultivars from Asian countries. Complementary to genomics and wet-chemistry analyses, Raman spectroscopy makes non-destructively available factual and data-driven information on rice nutritional characteristics, thus providing customers, dietitian nutritionists, and producers with a solid science-consolidated platform.