Metasurface-assisted amorphous germanium-tin waveguide bolometer for mid-infrared photodetection.

An amorphous germanium-tin (a-Ge0.83Sn0.17) waveguide bolometer featuring a one-dimension (1D) metasurface absorber is proposed for mid-infrared photodetection at room-temperature. The device is based on the germanium-on-silicon (GOS) photonic platform. The impacts of the 1D metasurface on the performances of the waveguide bolometer are investigated. The responsivity of the a-Ge0.83Sn0.17 waveguide bolometer could be significantly enhanced by the metasurface. A responsivity of around -3.17%/µW within the 4.1 ∼ 4.3 µm wavelength range is achieved. In addition, a 3-dB roll-off frequency higher than 10 kHz is obtained.

Design of a Long-Acting Rivastigmine Transdermal Delivery System: Based on Computational Simulation.

The purpose of our study was using a computational simulation to develop a long-acting patch of rivastigmine (RVS). A range of patch formulations were screened including pressure sensitive adhesive (PSA), pharmaceutical excipients, and controlled release membranes using transfer simulation based on a mathematical model. Diffusion dynamics parameters for simulated operations were acquired through in vitro release tests (IVRT) and in vitro skin permeation tests (IVPT). The mechanism of controlled release was studied by FTIR (Fourier transform infrared), DSC (differential scanning calorimeter) and molecular docking. Results of a rat in vitro permeation profile showed excellent correlation with the in vivo deconvolution profile (R2=0.998). Experiments testified to transfer of RVS at a relatively uniform speed with high skin permeation (2531.2±142.46 µg/cm2) in 72 h. Pharmacokinetic data obtained in vivo also confirmed stable plasma concentrations over 72 h for the optimized patch, and significant prolongation of both Tmax (11.20±1.79 h) and MRT0-t (33.91±5.33 h). Cmax was controlled with AUC0-t (267.34±24.46 h ng/ml), which was closely comparable to parameters of a commercial Exelon® Patch. The successful development of a long-acting patch of RVS thus underscores the potential of computer aided design in a context of promnesic transdermal delivery. Graphical abstract.

Association of Sex with Serum Potassium, Sodium, and Calcium Disorders after Hypertensive Intracerebral Hemorrhage.

OBJECTIVE: To determine the association of sex with serum potassium, sodium, and calcium disorders in patients with hypertensive intracerebral hemorrhage, and meanwhile investigate other risk factors. METHODS: A total of 516 patients with hypertensive intracerebral hemorrhage were retrospectively enrolled. The clinical characteristics were collected. Serum potassium, sodium, and calcium levels were measured. Multivariate analysis was performed to identify risk factors. RESULTS: Hypokalemia is the most common electrolyte disorder (50.2%) after hypertensive intracerebral hemorrhage, followed by hyponatremia (19.8%), hypocalcemia (13.8%), hypernatremia (12.0%), hyperkalemia (2.5%), and hypercalcemia (0.4%). Most of the electrolyte disorders occurred within 1 week after the onset of hypertensive intracerebral hemorrhage. The incidence rate of hypokalemia was higher in women than in men (61.7% vs. 42.3%, χ2 = 18.676; P < 0.001), but the incidence rates of hyponatremia, hypocalcemia, and hypernatremia were not statistically different between women and men (all P > 0.05). Sex was associated with hypokalemia with women having increased risk, whereas sex was not associated with hypernatremia, hypocalcemia, and hyponatremia. In addition, surgical treatment was a risk factor of hypokalemia, hyponatremia, hypocalcemia, and hypernatremia, both breaking into ventricle and age were risk factors of hyponatremia and hypocalcemia, and bleeding site was a risk factor of hypocalcemia and hypernatremia. CONCLUSIONS: In the treatment of female patients with hypertensive cerebral hemorrhage, the clinician should pay attention to potassium chloride supplementation and monitor its intensity. Within 1 week after intracerebral hemorrhage, individuals most prone to electrolyte disorders determined according to the identified risk factors should be monitored as early as possible, and the disorders should be promptly corrected.

Reduction of thrombotic and inflammatory complications of polystyrene-block-polyisoprene-block-polystyrene (SIS) with one-step electrospinning.

Polystyrene-block-polyisoprene-block-polystyrene (SIS) has been used as biomaterials due to its soft and stable properties under physiological conditions. However, the thrombotic and inflammatory complications caused by SIS restrain its application as blood-contacting implant. To overcome this problem, the hydrophilic core-shell structured SIS-based microfiber with antioxidant encapsulation is fabricated with one-step reactive electrospinning. We demonstrate that the phase separation of SIS and acylated Pluronic F127 (F127-DA) components and crosslinking during electrospinning renders the microfiber blood compatible and stable under physiological condition; the encapsulation of 2-O-d-glucopyranosyl-l-ascorbic acid (AA-2G) in microfiber and subsequent release of AA-2G detoxifies the excess reactive oxygen species (ROS). The microfibers are nontoxic to cells and promote the fast growth and proliferation of human umbilical vein endothelial cells (HUVECs) in the presence of ROS; the thrombotic and inflammatory complications are effectively reduced with implant evaluation in vivo. Therefore, our work paves a new way to improve the biocompatibility of SIS, making it a promising candidate for blood contact materials.

Elasto-Plastic Mechanical Properties and Failure Mechanism of Innovative Ti-(SiCf/Al3Ti) Laminated Composites for Sphere-Plane Contact at the Early Stage of Penetration Process.

A novel silicon carbide (SiC) continuous ceramic fiber-reinforced (CCFR) Ti/Al3Ti Metal-Intermetallic-Laminate (MIL) composite was fabricated. A high-efficiency semi-analytical model was proposed based on the numerical equivalent inclusion method (NEIM) for analyzing the small-strain elasto-plastic contact in the early stage of the penetration process. The microstructure and interface features were characterized by the scanning electron microscopy (SEM). Quasi-static compression tests were performed to determine the contact response and validate the proposed model. A group of in-depth parametric studies were carried out to quantify the influence of the microstructure. The comparison between results under the sphere-plane and plane-plane contact load indicates that, under the first sphere-plane, the compressive strength and failure strain are both lower and the SiC reinforcement effect on strength is very clear while the effect on ductility is not clear. The maximum plastic strain concentration (MPSC) in the Al3Ti layer is closest to the upper boundary of the central SiC fiber and then extends along the depth direction as the load increases, which are also the locations where cracks may initiate and extend. Moreover, the CCFR-MIL composite shows better mechanical properties when the center distance between adjacent SiC fibers is four times the fiber diameter and the volume fraction of Ti is 40%.

Facile Fabrication of Hierarchically Thermoresponsive Binary Polymer Pattern for Controlled Cell Adhesion.

A versatile platform allowing capture and detection of normal and dysfunctional cells on the same patterned surface is important for accessing the cellular mechanism, developing diagnostic assays, and implementing therapy. Here, an original and effective method for fabricating binary polymer brushes pattern is developed for controlled cell adhesion. The binary polymer brushes pattern, composed of poly(N-isopropylacrylamide) (PNIPAAm) and poly[poly(ethylene glycol) methyl ether methacrylate] (POEGMA) chains, is simply obtained via a combination of surface-initiated photopolymerization and surface-activated free radical polymerization. This method is unique in that it does not utilize any protecting groups or procedures of backfilling with immobilized initiator. It is demonstrated that the precise and well-defined binary polymer patterns with high resolution are fabricated using this facile method. PNIPAAm chains capture and release cells by thermoresponsiveness, while POEGMA chains possess high capability to capture dysfunctional cells specifically, inducing a switch of normal red blood cells (RBCs) arrays to hemolytic RBCs arrays on the pattern with temperature. This novel platform composed of binary polymer brush pattern is smart and versatile, which opens up pathways to potential applications as microsensors, biochips, and bioassays.

Multiple microarrays of non-adherent cells on a single 3D stimuli-responsive binary polymer-brush pattern.

We have developed a 3D smart binary polymer-brush pattern on the polymer substrate for inducing multiple cell microarrays aided by a lectin and temperature. The binary polymer-brush pattern composed of poly(N-isopropylacrylamide) (PNIPAM) and poly(d-gluconamidoethyl methacrylate) (PGAMA) brushes is fabricated by combining the photolithography technique with a surface-initiated photo-polymerization (SIPP) method. We demonstrate that well-defined binary polymer-brush patterns with high resolution are fabricated using this facile method. The patterned hierarchical PNIPAM brushes exhibit reversible switching to the adhesion of red blood cells (RBCs) induced by thermo-responsiveness. The PGAMA brush domains resist adhesion of RBCs but bind specifically with concanavalin A (Con A), forming a lectin pattern to capture RBCs in a site-specific manner. Therefore, multiple cell microarrays on a single platform are generated with the aid of Con A and temperature. This novel platform composed of a smart binary polymer-brush pattern is versatile and specific, which opens up pathways to potential applications such as microsensors, biochips and bioassays.

Guided protein/cell patterning on superhydrophilic polymer brushes functionalized with mussel-inspired polydopamine coatings.

A simple approach for preparing bicomponent polymer patterns was developed by coating polydopamine (PDA) on superhydrophilic poly(2-acryl-amido-2-methylpropane sulfonic acid) (PAMPS) brushes. Well-defined and versatile arrays of proteins and cells were achieved without harm to proteins and cells.

Unprecedentedly targeted customization of molecular energy levels with auxiliary-groups in organic solar cell sensitizers.

In dye-sensitized solar cells (DSSCs), the HOMO-LUMO energy gap of organic sensitizers should be large enough to enable efficient electron injection and dye regeneration. However, the LUMOs of most practical organic dyes are always too high, making energy "waste". In order to deepen the LUMOs, we focus on the targeted modulation of the molecular energy levels by embedding an electron donor or acceptor into the skeleton of a typical D-π-A model. The electron-rich group of 3,4-ethylenedioxythiophene (EDOT) lifts up the HOMO level with little influence on the LUMO, while the electron-deficient group of benzothiadiazole (BTD) or benzooxadiazole (BOD) mainly lowers the customized LUMO level. As a consequence, the auxiliary group change from EDOT (dye WS-53) to BOD (dye WS-55) brings forth a huge photoelectric conversion efficiency (PCE) increase by 38 fold from 0.24 to 9.46% based on an I-/I3- redox couple, and even reaching a high PCE of 10.14% with WS-55 under 0.3 sunlight irradiation.

Effect of grafted PEG chain conformation on albumin and lysozyme adsorption: A combined study using QCM-D and DPI.

In this study, elucidation of protein adsorption mechanism is performed using dual polarization interferometry (DPI) and quartz crystal microbalance with dissipation (QCM-D) to study adsorption behaviors of bovine serum albumin (BSA) and lysozyme (LYZ) on poly (ethylene glycol) (PEG) layers. From the analysis of DPI, PEG2000 and PEG5000 show tight and loose mushroom conformations, respectively. Small amount of LYZ could displace the interfacial water surrounding the tight mushroomed PEG2000 chains by hydrogen bond attraction, leading to protein adsorption. The loose mushroomed PEG5000 chains exhibit a more flexible conformation and high elastic repulsion energy that could prevent protein adsorption of all BSA and most of LYZ. From the analysis of QCM, PEG2000 and PEG5000 show tight and extended brush conformations. The LYZ adsorbed mass has critical regions of PEG2000 (0.19 chain/nm(2)) and PEG5000 (0.16 chain/nm(2)) graft density. When graft density of PEG is higher than the critical region (brush conformations), the attraction of hydrogen bonds between PEG and LYZ is the dominant factor. When graft density of PEG is lower than the critical region (mushroom conformations), elastic repulsion between PEG and proteins is driven by the high conformation entropy of PEG chains, which is the dominant force of steric repulsion in PEG-protein systems. Therefore, the adsorption of BSA is suppressed by the high elastic repulsion energy of PEG chains, whereas the adsorption of LYZ is balanced by the interactions between the repulsion of entropy elasticity and the attraction of hydrogen bonds.

Rational Molecular Engineering of Indoline-Based D-A-π-A Organic Sensitizers for Long-Wavelength-Responsive Dye-Sensitized Solar Cells.

Indoline-based D-A-π-A organic sensitizers are promising candidates for highly efficient and long-term stable dye-sensitized solar cells (DSSCs). In order to further broaden the spectral response of the known indoline dye WS-2, we rationally engineer the molecular structure through enhancing the electron donor and extending the π-bridge, resulting in two novel indoline-based D-A-π-A organic sensitizers WS-92 and WS-95. By replacing the 4-methylphenyl group on the indoline donor of WS-2 with a more electron-rich carbazole unit, the intramolecular charge transfer (ICT) absorption band of dye WS-92 is slightly red-shifted from 550 nm (WS-2) to 554 nm (WS-92). In comparison, the incorporation of a larger π-bridge of cyclopentadithiophene (CPDT) unit in dye WS-95 not only greatly bathochromatically tunes the absorption band to 574 nm but also largely enhances the molar extinction coefficients (ε), thus dramatically improving the light-harvesting capability. Under the standard global AM 1.5 solar light condition, the photovoltaic performances of both organic dyes have been evaluated in DSSCs on the basis of the iodide/triiodide electrolyte without any coadsorbent or cosensitizer. The DSSCs based on WS-95 display better device performance with power conversion efficiency (η) of 7.69%. The additional coadsorbent in the dye bath of WS-95 does not improve the photovoltaic performance, indicative of its negligible dye aggregation, which can be rationalized by the grafted dioctyl chains on the CPDT unit. The cosensitization of WS-95 with a short absorption wavelength dye S2 enhances the IPCE and improves the η to 9.18%. Our results indicate that extending the π-spacer is more rational than enhancing the electron donor in terms of broadening the spectral response of indoline-based D-A-π-A organic sensitizers.

Porphyrin cosensitization for a photovoltaic efficiency of 11.5%: a record for non-ruthenium solar cells based on iodine electrolyte.

Dye-sensitized solar cells (DSSCs) are promising for utilizing solar energy. To achieve high efficiencies, it is vital to synergistically improve the photocurrent (Jsc) and the photovoltage (Voc). In this respect, conjugation framework extension and cosensitization are effective for improving the absorption and the Jsc, which, however, is usually accompanied by undesirably decreased Voc. Herein, based on a rationally optimized porphyrin dye, we develop a targeted coadsorption/cosensitization approach for systematically improving the Voc from 645 to 727, 746, and 760 mV, with synergistical Jsc enhancement from 18.83 to 20.33 mA cm(-2). Thus, the efficiency has been dramatically enhanced to 11.5%, which keeps the record for nonruthenium DSSCs using the I2/I3(-) electrolyte. These results compose an alternative approach for developing highly efficient DSSCs with relatively high Voc using traditional iodine electrolyte.

Rational molecular engineering of cyclopentadithiophene-bridged D-A-π-A sensitizers combining high photovoltaic efficiency with rapid dye adsorption.

Dye-sensitized solar cell (DSSC) is considered as a feasible route to the clean and renewable energy conversion technique. The commercial application requires further enhancements on photovoltaic efficiency and simplification on the device fabrication. For avoiding the unpreferable trade-off between photocurrent (JSC) and photovoltage (VOC), here we report the molecular engineering and comprehensive photovoltaic characterization of three cyclopentadithiophene-bridged D-A-π-A motif sensitizers with a change in donor group. We make a careful choice on the donor and conjugation bridge for synergistically increasing JSC and VOC. Comparing with the reference dye WS-2, the photovoltaic efficiency with the single component dye of WS-51 increases by 18%, among one of the rare examples in pure metal-free organic dyes exceeding 10% in combination with traditional iodine redox couples. Moreover, WS-51 exhibits several prominent merits on potentially scale-up industrial application: i) facile synthetic route to target molecule, ii) simple dipping procedure without requirement of co-sensitization, and iii) rapid dye adsorption capability.

Immobilization of nattokinase-loaded red blood cells on the surface of superhydrophobic polypropylene targeting fibrinolytic performance.

A platform for capture and release of drug-loaded red blood cells (RBCs) is demonstrated by utilizing polymer grafted superhydrophobic polypropylene (PP). Combined with micro/nanobinary structures, thermoresponsive polymers, and lectin-saccharides recognition, this platform enables highly efficient capture and release of RBCs loaded with nattokinase, which endows PP with potent fibrinolytic ability.

Hemocompatible, antioxidative and antibacterial polypropylene prepared by attaching silver nanoparticles capped with TPGS.

Infections associated with medical devices cause significant costs, morbidity, and mortality. Medical devices with hemocompatibility, antioxidative stress, and antibacterial properties are difficult to fabricate. In this study, silver nanoparticles (Ag NPs) were synthesized for the first time in the presence of carboxylic d-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) as antibacterial agents. The Ag NPs were characterized by UV-visible spectroscopy, transmission electron microscopy, and zeta potential measurements. The results showed that Ag NPs had a good dispersion stability and uniform size distribution. The introduction of TPGS dispersed the Ag NPs in solution and provided active protection against Ag NP-induced free radical damage. N-Isopropylacrylamide (NIPAAm) and N-(3-aminopropyl) methacrylamide hydrochloride (APMA) were then co-grafted onto polypropylene (PP) membranes by ultraviolet grafting, which can provide antifouling properties. The modified PP surface can be used as a platform to load the Ag NPs capped with TPGS. The loading efficiency of Ag NPs was mediated by electrostatic interactions between the positively charged APMA and the negatively charged Ag NPs. The loaded TPGS can slow the lipid peroxidation of erythrocytes and fill the lipid bilayer of erythrocytes to prevent antioxidative stress and hemolysis. The bacteria adhesion, bacterial activity, and biofilm formation proved that the modified PP surfaces loaded with Ag NPs had excellent antibacterial and bactericidal properties. Therefore, our approach can serve as a basis for developing medical devices with excellent hemocompatibility, as well as simultaneous antioxidative and antibacterial properties, thereby providing a potential prevention measure of medical-device-associated infections.

Effect of a long alkyl group on cyclopentadithiophene as a conjugated bridge for D-A-π-A organic sensitizers: IPCE, electron diffusion length, and charge recombination.

The option of using conjugated π-linkers is critical for rational molecular design toward an energy-level strategy for organic sensitizers. To further optimize photovoltaic performance, methyl- and octyl-substituted 4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) are introduced into D-A-π-A featured sensitizers. Along with CPDT, instead of thiophene as conjugated bridge, WS-39 and WS-43 exhibit an extended spectral response due to the excellent conjugation and coplanarity of CPDT. Specifically, we focused on the critical effect of length of the alkyl group linked to the bridging carbon atoms of CPDT on the photovoltaic performances. Octyl-substituted WS-39 shows a broader IPCE onset with an enhanced photovoltage relative to the analogue WS-5. In contrast, WS-43, with methyl substituted on the CPDT moiety, presents a relatively low quantum conversion efficiency within the whole spectral response region, along with low photocurrent density. WS-43 displays a distinctly low IPCE platform, predominately arising from the short electron diffusion length with significant electron loss during the electron transport. The relative movement of the conduction band edge (E(CB)) and charge transfer resistance as well as lifetime of injected electrons are studied in detail. Under standard AM 1.5 conditions, WS-39-based solar cells show a promising photovoltaic efficiency of 9.07% (J(SC) = 16.61 mA cm(-2), V(OC) = 770 mV, FF = 0.71). The octyl chains attached on CPDT can provide dual protection and exhibit a high propensity to prevent binding of the iodide-triiodide redox couple, producing an efficient shielding effect to retard the charge recombination and resulting in improvement of V(OC). Our research paves the way to explore more efficient sensitizers through ingenious molecular engineering.

Stimuli-responsive polypropylene for the sustained delivery of TPGS and interaction with erythrocytes.

Hemocompatibility and oxidative stress are significant for blood-contacting devices. In this study, N-isopropylacrylamide (NIPAAm) and N-(3-aminopropyl)methacrylamide hydrochloride (APMA) were cografted on polypropylene (PP) membrane using ultraviolet grafting to load antioxidative d-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) and control the release of TPGS. The immobilization of NIPAAm and APMA onto PP membrane was confirmed by attenuated total reflectance Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. Combined with data from platelet adhesion, red blood cell (RBC) attachment, and hemolysis rate, the hemocompatibility of PP was significantly improved. An in-depth characterization using hemolysis rate test, scanning electron microscopy, atomic force microscopy, and confocal laser scanning microscopy was conducted to confirm that the mechanism of the release of TPGS interacted with RBCs was different at different stages. The release of TPGS from the loading PP membranes affected hemolysis at different stages. At the early stage of release, TPGS maintained the tiny (nanometer-sized) tubers on the membrane surface and enhanced the membrane permeabilization by generating nanosized pores on the cell membranes. Afterward, the incorporated TPGS slowed the lipid peroxidation of erythrocytes and filled in the lipid bilayer of erythrocyte to prevent hemolysis. Thus, the approach implemented to graft NIPAAm and APMA and load TPGS was suitable to develop medical device with excellent hemocompatibility and antioxidative property.

Fabricating antigen recognition and anti-bioadhesion polymeric surface via a photografting polymerization strategy.

A polymeric platform for immunodiagnostic bioassay was constructed based on biostable polymeric support and two functional monomers, low-fouling methacryloyloxyethyl phosphorylcholine (MPC) and acrylic acid (AAc), by a photografting polymerization approach. Covalent binding of antibody to pAAc chains was achieved by activating carboxyl with NHS/EDC partner. The resultant surface showed obvious suppression of nonspecific protein adsorption and platelet adhesion relative to the control sample, exhibiting good anti-bioadhesion performances. Based on the polymer-supported matrix, a highly sensitive antibody-antigen specific recognition was confirmed in both native plasma and diluted human plasma due to the enhanced antibody loading capacity and lowered bioadhesion as compared to the reference.

Fabrication of a detection platform with boronic-acid-containing zwitterionic polymer brush.

Development of technologies for biomedical detection platform is critical to meet the global challenges of various disease diagnoses, especially for point-of-use applications. Because of its natural simplicity, effectiveness, and easy repeatability, random covalent-binding technique is widely adopted in antibody immobilization. However, its antigen-binding capacity is relatively low when compared to site-specific immobilization of antibody. Herein, we report that a detection platform modified with boronic acid (BA)-containing sulfobetaine-based polymer brush. Mainly because of the advantage of oriented immobilization of antibody endowed with BA-containing three-dimensional polymer brush architecture, the platform had a high antigen-binding capacity. Notably, nonspecific protein adsorption was also suppressed by the zwitterionic pendants, thus greatly enhanced signal-to-noise (S/N) values for antigen recognition. Furthermore, antibodies captured by BA pendants could be released in dissociation media. This new platform is promising for potential applications in immunoassays.

Self-assembly of a diblock copolymer with pendant disulfide bonds and chromophore groups: a new platform for fast release.

An amphiphilic block copolymer comprising poly(ethylene glycol) (PEG) and poly(2-(methacryloyl)oxyethyl-2'-hydroxyethyl disulfide) (PMAOHD) blocks was synthesized by atom transfer radical polymerization (ATRP). Pyrenebutyric acid was conjugated to the block copolymer by esterification, and a block copolymer with pendant disulfide bonds and pyrenyl groups (PEG-b-P(MAOHD-g-Py)) was obtained. (1)H NMR and gel permeation chromatography (GPC) results demonstrated the successful synthesis of the block copolymer. The cleavage of the disulfide bonds and the degrafting of the pyrenyl groups were investigated in THF and a THF/methanol mixture. Fluorescence spectroscopy, GPC, and (1)H NMR results demonstrated fast cleavage of the disulfide bonds by Bu(3)P in THF. Fluorescence results showed the ratio of the intensity of the excimer peak to the monomer peak decreased rapidly within 20 min. GPC traces of the block copolymer moved to a long retention time region after addition of Bu(3)P, indicating the cleavage of the disulfide bonds and the degrafting of the pyrenyl groups. PEG-b-P(MAOHD-g-Py) can self-assemble into micelles with poly(MAOHD-g-Py) cores and PEG coronae in a mixture of methanol and THF (9:1 by volume). The dissociation of the micelles in the presence of Bu(3)P was investigated. After cleavage of the disulfide bonds in the micellar cores, a pyrene-containing small molecular compound and a block copolymer with pendant thiol groups were produced. Transmission electron microscopy (TEM), dynamic light scattering (DLS), and (1)H NMR were employed to track the dissociation of the polymeric micelles. All the techniques demonstrated the dissociation of the micelles and the fast release of pyrenyl groups from the micelles.