Wastewater Treatment Using High-Performance In Situ Formed Double-Heterojunction Janus Photocatalyst Microparticles Shaped via a Microfluidic Device.

In this work, a heterogeneous photocatalysis system is fabricated for treating wastewater containing organic dyes and pharmaceutical substances. Double-heterojunction Janus photocatalysts are formed on the surface of size-tunable polydimethylsiloxane (PDMS) microparticles shaped via simple and low-cost coflow microfluidic devices. Ag0/Ag0-TiO2/TiO2 Janus-like photocatalysts are synthesized on the surface of porous PDMS microparticles as the support in which the metal-semiconductor heterojunction of Ag0/Ag0-TiO2 and the second heterojunction of Ag0-TiO2/TiO2 are created in situ, leading to the formation of Ag0/Ag0-TiO2/TiO2@PDMS photocatalysis systems. To form the heterojunctions on the PDMS surface, the polymer chain etching method is employed as a desired strategy to have half of the TiO2 nanoparticles on the surface of microparticles, which are treated by a Ag source. Using salt additives and the etching method, PDMS microparticles are made porous, providing more surface area for photoreactions. Surprisingly, the highest decomposition efficiencies of 94.4 and 91.1% are achieved for rhodamine B(RhB) and tetracycline (TC), respectively, under visible light for 60 min pH 11, a light source at a distance of 2 cm, 5 mM AgNO3, 10 wt % TiO2, 7 wt % NaCl, and 20 gm/L photocatalyst, which are conditions that result in the best performance for RhB degradation. Regarding the stability of the photocatalysts, no significant change is observed in the performance after five cycles.

Design and analysis of 2D one-way splitter waveguide based on topological photonics.

We present a new high-efficiency splitter waveguide design based on photonic topological insulators. The system's robust edge states allow electromagnetic waves to propagate in the 2D waveguide without backscattering, resulting in almost 100% transmission in the outputs. We also study resonating modes in the structure and show that introducing specific defects can create such modes. We consider four domains with rods of varying magneto-optical properties to provide edge modes in the system. By eliminating rows and columns of rods, we calculate the transmission at the outputs, revealing resonating modes in the middle of the structure with spatial symmetry. Our calculations indicate that the most promising resonating mode occurs when two rods and two columns are eliminated, with a quality factor Q = 1.02 × 106 at frequency f = 8.23 GHz and almost zero transmission at this frequency to the outputs. We further confirm our results using the transmission line resonator model as a semi-analytical model, which agrees well with our findings.

Metastructure Engineering with Ruddlesden-Popper 2D Perovskites: Stability, Flexibility, and Quality Factor Trade-Offs.

In this study, we investigate the opto-electro-mechanical properties, thermodynamic stability, and moisture stability of the Ruddlesden-Popper (RP) two-dimensional perovskites of L2PbI4 (L = PEA, FPEA, BA, and BZA) using density functional theory. The goal is to explore their potential application in metastructures. The results show that the stability of FPEA2PbI4 is better than that of PEA2PbI4, BA2PbI4, and BZA2PbI4 due to the replacement of a hydrogen atom with a fluorine atom. On the other hand, BA2PbI4 is more flexible than other materials because it lacks an aromatic ring in its spacer cation, but it is less stable. We introduce a new kind of metastructure composed of an RP perovskite film and conduct an extensive investigation of the quasi-bound states in the continuum (q-BIC) characteristics by near-field analysis and multipole decomposition calculations. The q-BIC resonances in BZA2PBI4 have a greater quality factor due to its larger refractive index in comparison to other materials. Therefore, based on these results, the perovskite materials can be selected for the metastructures from different aspects of stability, flexibility, and refractive index.

Mucin-Inspired Polymeric Fibers for Herpes Simplex Virus Type 1 Inhibition.

Mucus lines the epithelial cells at the biological interface and is the first line of defense against multiple viral infections. Mucins, the gel-forming components of mucus, are high molecular weight glycoproteins and crucial for preventing infections by binding pathogens. Consequently, mimicking mucins is a promising strategy for new synthetic virus inhibitors. In this work, synthetic mucin-inspired polymers (MIPs) as potential inhibitors of herpes simplex virus 1 (HSV-1) are investigated. By using a telechelic reversible addition-fragmentation chain-transfer (RAFT) polymerization technique, a new dendronized polysulfate p(G1AAm-OSO3)PDS with an amide-backbone similar to the native mucin glycoproteins is synthesized. p(G1AAm-OSO3)PDS shows mucin-like elongated fiber structure, as revealed in cryo-electron microscopy (cryo-EM) imaging, and its HSV-1 inhibition activity together with its previously reported methacrylate analogue p(G1MA-OSO3)PDS is tested. Both of the sulfated MIPs show strong HSV-1 inhibition in plaque reduction assays with IC50 values in lower nanomolar range (<3 × 10-9 m) and demonstrate a high cell compatibility (CC50 > 1.0 mg mL-1) with lower anticoagulant activity than heparin. In addition, the prophylactic and therapeutic activity of both MIPs is assessed in pre- and post-infection inhibition assays and clearly visualize their high potential for application using fluorescent microscopy imaging of infected cells.

Primary aortoduodenal fistula: As a first presentation of brucellosis; a case report.

INTRODUCTION: The etiologies of primary aortoenteric fistula include aneurysm (most common), foreign body, tumor, radiation therapy, and infection (e.g., tuberculosis, syphilis). Brucellosis is a rare cause of primary aortoenteric fistula. PRESENTATION OF CASE: In this study, we reported the case ofa 55-years-old male with an aortoenteric fistula and a positive brucellosis test. DISCUSSION: In regions where brucellosis is endemic, the coexistence of aortitis and aneurysm should prompt consideration of brucella infection as a relatively uncommon cause of aortoenteric fistula. CONCLUSION: While aortitis due to brucellosis is rare, it can lead to life-threatening manifestations such as aortoduodenal fistula. Therefore, we recommend the use of Wright, Coombs Wright, and 2ME tests in similar cases.

Recent advances in heterogeneous catalysis of solar-driven carbon dioxide conversion.

Solar-driven carbon dioxide (CO2) conversion including photocatalytic (PC), photoelectrochemical (PEC), photovoltaic plus electrochemical (PV/EC) systems, offers a renewable and scalable way to produce fuels and high-value chemicals for environment and energy sustainability. This review summarizes the basic fundament and the recent advances in the field of solar-driven CO2 conversion. Expanding the visible-light absorption is an important strategy to improve solar energy conversion efficiency. The separation and migration of photogenerated charges carriers to surface sites and the surface catalytic processes also determine the photocatalytic performance. Surface engineering including co-catalyst loading, defect engineering, morphology control, surface modification, surface phase junction, and Z-scheme photocatalytic system construction, have become fundamental strategies to obtain high-efficiency photocatalysts. Similar to photocatalysis, these strategies have been applied to improve the conversion efficiency and Faradaic efficiency of typical PEC systems. In PV/EC systems, the electrode surface structure and morphology, electrolyte effects, and mass transport conditions affect the activity and selectivity of electrochemical CO2 reduction. Finally, the challenges and prospects are addressed for the development of solar-driven CO2 conversion system with high energy conversion efficiency, high product selectivity and stability.

Design and analysis of a flexible Ruddlesden-Popper 2D perovskite metastructure based on symmetry-protected THz-bound states in the continuum.

A Ruddlesden-Popper 2D perovskite PEA2PbX4 (X = I, Br, and Cl) is proposed for metasurface applications. Density functional theory is used to analyze the optical, electrical, mechanical properties, moisture and thermodynamic stability of PEA2PbX4. The refractive index of PEA2PbX4 varies with the halides, resulting in 2.131, 1.901, and 1.842 for X = I, Br, and Cl, respectively. Mechanical properties with Voigt-Reuss-Hill approximations indicate that all three materials are flexible and ductile. Based on the calculations of formation energy and adsorption of water molecules, PEA2PbI4 has superior thermodynamic and moisture stability. We present a novel metasurface based on 2D-PEA2PbI4 and analyze symmetry protected-bound states in the continuum (sp-BIC) excitation. The proposed structure can excite multiple Fano quasi-BICs (q-BICs) with exceptionally high Q-factors. We verify the group theoretical analysis and explore the near-field distribution and far-field scattering of q-BICs. The findings indicate that x-polarized incident waves can excite magnetic toroidal dipole-electromagnetic-induced transparency-BIC and magnetic quadrupole-BIC, while y-polarized incident waves can excite electric toroidal dipole-BIC and electric quadrupole-BIC. The influence of meta-atom and substrate losses, array size limitations, and fabrication tolerances are also discussed. The proposed structure can be employed for applications in the THz region, such as polarization-dependent filters, bidirectional optical switches, and wearable photonic devices.

Quasi-BIC based all-dielectric metasurfaces for ultra-sensitive refractive index and temperature sensing.

In this paper, an all-dielectric metasurface that measures refractive index and temperature using silicon disks is presented. It can simultaneously produce three resonances excited by a magnetic toroidal dipole, magnetic toroidal quadrupole, and electric toroidal dipole, in the THz region. Asymmetric structures are used to generate two quasi-bound states in the continuum (BIC) resonances with ultra-high-quality factors driven by magnetic and electric toroidal dipoles. We numerically study and show the dominant electromagnetic excitations in the three resonances through near-field analysis and cartesian multipole decomposition. The effects of geometric parameters, scaling properties, polarization angles, incident angles, and silicon losses are also investigated. The proposed metasurface is an excellent candidate for sensing due to the extremely high-quality factor of the quasi-BICs. The results demonstrate that the sensitivities for liquid and gas detection are Sl = 569.1 GHz/RIU and Sg = 529 GHz/RIU for magnetic toroidal dipole, and Sl = 532 GHz/RIU and Sg = 498.3 GHz/RIU for electric toroidal dipole, respectively. Furthermore, the sensitivity for temperature monitoring can reach up to 20.24 nm/°C. This work presents a valuable reference for developing applications in the THz region such as optical modulators, multi-channel biochemical sensing, and optical switches.

Analytical study of gold-DNA nano core-shell cloaking characteristics for drug delivery and cancer therapy.

The cloaking characteristics of biocells can be considered as a factor to determine drug absorption by the tissues. The metal-organic core-shell structure can act as a cloak around the molecules of tissue and can be used as a nanomachine for drug delivery. Thus, we define a ratio of drug absorption based on frequency red-shift and the effective permittivity in the optical spectrum. Here, a cylinder of molecules coated by plasmonic nano core-shells is proposed for measuring the cloaking characteristics of biocells. The overall bandwidth of the proposed cloak for reflectance less than -10 dB is 36%. We check the effect of the filling factors of nanoparticles on the reflection and the frequency response of the tissue. Besides the frequency red-shift and change in the level of reflection, the phase and impedance are extracted. We could obtain the normalized scattering cross-section of 5 dB lower than the cylinder without cloak for the cylinder with a gold-DNA core-shell cloak. Here, we modify the Maxwell-Garnett equation for a cylindrical structure to obtain the effective value of the permittivity for cancer and normal tissues. The results show that obtained permittivity from the simulation has a good match with the calculated permittivity from the Maxwell-Garnet equation. Therefore, this approach can be considered as an efficient method for drug absorption and diagnosis of cancer cells from normal cells.

Mucin-Inspired Single-Chain Polymer (MIP) Fibers as Potent SARS-CoV-2 Inhibitors.

Mucins are the key component of the defensive mucus barrier. They are extended fibers of very high molecular weight with diverse biological functions depending strongly on their specific structural parameters. Here, we present a mucin-inspired nanostructure, produced via a synthetic methodology to prepare methacrylate-based dendronized polysulfates (MIP-1) on a multi gram-scale with high molecular weight (MW=450 kDa) and thiol end-functionalized mucin-inspired polymer (MIP) via RAFT polymerization. Cryo-electron tomography (Cryo-ET) analysis of MIP-1 confirmed a mucin-mimetic wormlike single-chain fiber structure (length=144±59 nm) in aqueous solution. This biocompatible fiber showed promising activity against SARS-CoV-2 and its mutant strain, with a remarkable low half maximal (IC50 ) inhibitory concentration (IC50 =10.0 nM). Additionally, we investigate the impact of fiber length on SARS-CoV-2 inhibition by testing other functional polymers (MIPs) of varying fiber lengths.

Biomedical Applications of Microfluidic Devices: A Review.

Both passive and active microfluidic chips are used in many biomedical and chemical applications to support fluid mixing, particle manipulations, and signal detection. Passive microfluidic devices are geometry-dependent, and their uses are rather limited. Active microfluidic devices include sensors or detectors that transduce chemical, biological, and physical changes into electrical or optical signals. Also, they are transduction devices that detect biological and chemical changes in biomedical applications, and they are highly versatile microfluidic tools for disease diagnosis and organ modeling. This review provides a comprehensive overview of the significant advances that have been made in the development of microfluidics devices. We will discuss the function of microfluidic devices as micromixers or as sorters of cells and substances (e.g., microfiltration, flow or displacement, and trapping). Microfluidic devices are fabricated using a range of techniques, including molding, etching, three-dimensional printing, and nanofabrication. Their broad utility lies in the detection of diagnostic biomarkers and organ-on-chip approaches that permit disease modeling in cancer, as well as uses in neurological, cardiovascular, hepatic, and pulmonary diseases. Biosensor applications allow for point-of-care testing, using assays based on enzymes, nanozymes, antibodies, or nucleic acids (DNA or RNA). An anticipated development in the field includes the optimization of techniques for the fabrication of microfluidic devices using biocompatible materials. These developments will increase biomedical versatility, reduce diagnostic costs, and accelerate diagnosis time of microfluidics technology.

DNA sequencing by Förster resonant energy transfer.

We propose a new DNA sequencing concept based on nonradiative Förster resonant energy transfer (FRET) from a donor quantum dot (QD) to an acceptor molecule. The FRET mechanism combined with the nanopore-based DNA translocation is suggested as a novel concept for sequencing DNA molecules. A recently-developed hybrid quantum/classical method is employed, which uses time-dependent density functional theory and quasistatic finite difference time domain calculations. Due to the significant absorbance of DNA bases for photon energies higher than 4 eV, biocompatibility, and stability, we use Zinc-Oxide (ZnO) QD as a donor in the FRET mechanism. The most sensitivity for the proposed method to DNA is achieved for the Hoechst fluorescent-dye acceptor and 1 nm ZnO-QD. Results show that the insertion of each type of DNA nucleobases between the donor and acceptor changes the frequency of the emitted light from the acceptor molecule between 0.25 to 1.6 eV. The noise analysis shows that the method can determine any unknown DNA nucleobases if the signal-to-noise ratio is larger than 5 dB. The proposed concept and excellent results shed light on a new promising class of DNA sequencers.

Thermoresponsive and antibacterial two-dimensional polyglycerol-interlocked-polynipam for targeted drug delivery.

Two-dimensional polymeric networks are a new class of polymers with interesting physicochemical and biological properties. They promise a wide range of future biomedical applications including pathogen interactions, drug delivery, bioimaging, photothermal, and photodynamic therapy, owing to their unique features, such as high surface area and multivalent interactions at nano-biointerfaces. In this work, a thermosensitive two-dimensional polymeric network consisting poly(N-isopropylacrylamide) (pNIPAM) chains that are mechanically interlocked by a polyglycerol platform was synthesized and used for bacteria incapacitation. Two-dimensional hyperbranched polyglycerol (2D-hPG) was synthesized by a graphene-assisted strategy and used for encapsulation of azobisisobutyronitrile (AIBN). Radical polymerization of N-isopropylacrylamide by encapsulated AIBN resulted in thermoresponsive platforms with ~ 500 nm lateral size and 20-50 nm thickness. Due to its porous structure, 2D-PNPG was able to efficiently load antibiotics, such as tetracycline (TC) and amoxicillin (AMX). The rate of release of antibiotics from 2D-PNPG and the antibacterial activity of the system correlated with the variation of temperature as a result of the thermosensitivity of 2D-PNPG. This study shows that two-dimensional polymers are efficient platforms for future biomedical applications including drug delivery and bacteria incapacitation. Graphical abstract: Thermoresponsive two-dimensional nanomaterials with the ability of loading therapeutic agents and antibacterial activity are synthesized and characterized.

A fast open-source Fiji-macro to quantify virus infection and transfection on single-cell level by fluorescence microscopy.

The ability to automatically analyze large quantities of image data is a valuable tool for many biochemical assays, as it rapidly provides reliable data. Here, we describe a fast and robust Fiji macro for the analysis of cellular fluorescence microscopy images with single-cell resolution. The macro presented here was validated by successful reconstruction of fluorescent and non-fluorescent cell mixing ratios (for fluorescence fractions ranging between 0 and 100%) and applied to quantify the efficiency of transfection and virus infection inhibition. It performed well compared with manually obtained image quantification data. Its use is not limited to the cases shown here but is applicable for most monolayered cellular assays with nuclei staining. We provide a detailed description of how the macro works and how it is applied to image data. It can be downloaded free of charge and may be used by and modified according to the needs of the user. • Rapid, simple, and reproducible segmentation of eukaryotic cells in confluent cellular assays • Open-source software for use without technical or computational expertise • Single-cell analysis allows identification and quantification of virus infected cell populations and infection inhibition.

First-principles study of lead-free Ge-based 2D Ruddlesden-Popper hybrid perovskites for solar cell applications.

Recently, 2D halide perovskites have attracted attention because they are excellent photo absorbing materials for perovskite solar cells. To date, the majority of 2D perovskite-based devices have been made of Pb, a material with toxic properties and environmental concerns. Thus, lead-free alternatives are essential to enable the expansion of photovoltaic systems based on perovskites. Herein, we examine the structural, electronic, optical and stability properties of Pb-free 2D Ruddlesden-Popper (RP) perovskites (BA)2(MA)n-1GenI3n+1 (BA = CH3(CH2)3NH3+; MA = CH3NH3+; n = 1-5, and ∝) by using DFT calculations and comparing the results to their Pb-based counterparts (BA)2(MA)n-1PbnI3n+1 (n = 1-5, and ∝). Theoretical analysis indicates that Pb and Ge-based 2D perovskites are significantly more thermodynamically stable than their corresponding 3D materials. A more accurate bandgap is achieved using the HSE06 + SOC scheme and compared to the findings of the PBE and PBE + SOC. These materials are direct bandgap semiconductors. Due to spin-orbit coupling, Pb-based perovskite displays higher Rashba energy splitting than Ge-based ones. The bandgap changes from 2.37 eV (n = 1) to 1.79 eV (n = 5), and from 1.92 eV (n = 1) to 1.56 eV (n = 5) for Pb and Ge-based perovskites, respectively. The bandgap of all Ge-based perovskites is lower than their corresponding Pb-based ones. We show that the 2D perovskites could serve as hole-transporting materials when they are alongside 3D perovskites. The trade-off between thermodynamic stability and absorption coefficient of the considered compounds indicates that 2D RP perovskites BA2MA4Ge5I16 are promising Pb-free halide semiconductors for solar cell applications.

Chemical Approaches to Synthetic Drug Delivery Systems for Systemic Applications.

Poor water solubility and low bioavailability of active pharmaceutical ingredients (APIs) are major causes of friction in the pharmaceutical industry and represent a formidable hurdle for pharmaceutical drug development. Drug delivery remains the major challenge for the application of new small-molecule drugs as well as biopharmaceuticals. The three challenges for synthetic delivery systems are: (i) controlling drug distribution and clearance in the blood; (ii) solubilizing poorly water-soluble agents, and (iii) selectively targeting specific tissues. Although several polymer-based systems have addressed the first two demands and have been translated into clinical practice, no targeted synthetic drug delivery system has reached the market. This Review is designed to provide a background on the challenges and requirements for the design and translation of new polymer-based delivery systems. This report will focus on chemical approaches to drug delivery for systemic applications.

Enhancing the efficiency and stability of perovskite solar cells based on moisture-resistant dopant free hole transport materials by using a 2D-BA2PbI4 interfacial layer.

In this work, the photovoltaic performance and stability of perovskite solar cells (PSCs) based on a dopant-free hole transport layer (HTL) are efficiently improved by inserting a two-dimensional (2D) interfacial layer. The benzyl ammonium lead iodide (BA2PbI4) 2D perovskite is used as an interfacial layer between the 3D CH3NH3PbI3 perovskite and two moisture-resistant dopant-free HTLs including poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] (TQ1) and poly(3-hexylthiophene) (P3HT). TQ1 with a facile synthesis procedure has a higher moisture resistivity compared to P3HT which can improve the stability of PSCs. The 2D BA2PbI4 perovskite with a less-volatile bulkier organic cation efficiently passivates the defects at the perovskite/HTL interface, leading to 11.95% and 15.04% efficiency for the modified TQ1 and P3HT based cells, respectively. For a better understanding, the structural, optical, and electrical properties of PSCs comprising P3HT and TQ1 HTLs with and without interface modification are studied. The interface modified PSCs show slower open-circuit voltage decay and longer carrier lifetimes compared to unmodified cells. In addition, impedance spectroscopy reveals lower charge transport resistance and higher recombination resistance for the modified devices, which could be associated with the modification of the interface between the 3D CH3NH3PbI3 perovskite and HTL caused by the 2D interfacial layer. Also after aging under ambient conditions for about 800 hours, the modified PCSs retain more than 80% of their initial PCEs. These results give us the hope of achieving simpler, cheaper, and more stable PSCs with dopant-free HTLs through 2D interfacial layers, which have great potential for commercialization.

Interband plasmon-enhanced optical absorption of DNA nucleobases through the graphene nanopore.

We propose a novel, to the best of our knowledge, plasmonic-based methodology for the purpose of fast DNA sequencing. The interband surface plasmon resonance and field-enhancement properties of graphene nanopore in the presence of the DNA nucleobases are investigated using a hybrid quantum/classical method (HQCM), which employs time-dependent density functional theory and a quasistatic finite difference time domain approach. In the strong plasmonic-molecular coupling regime where the plasmon and DNA absorption frequencies are degenerated, the optical response of DNA molecule in the vicinity of the nanopore is enhanced. In contrast, when the plasmon and nucleobases resonances are detuned the distinct peaks and broadening of the molecular resonances represent the inherent properties of the nucleobase. Due to the different optical properties of DNA nucleobases in the ultraviolet (UV) region of light, the signal corresponding to the replacement of nucleobases in a DNA block can be determined by considering the differential absorbance. Results show the promising capability of the present mechanism for practical DNA sequencing.

One-pot gram-scale synthesis of virucidal heparin-mimicking polymers as HSV-1 inhibitors.

A straightforward and gram-scale synthesis method was developed to engineer highly sulfated hyperbranched polyglycerol bearing sulfated alkyl chains. The compounds with shorter alkyl chains showed multivalent virustatic inhibition against herpes simplex virus type 1 (HSV-1), similar to heparin. In contrast, the compound with the longest alkyl chains irreversibly inhibited the virus.

Highly sensitive crumpled 2D material-based plasmonic biosensors.

We propose surface plasmon resonance biosensors based on crumpled graphene and molybdenum disulphide (MoS2) flakes supported on stretchable polydimethylsiloxane (PDMS) or silicon substrates. Accumulation of specific biomarkers resulting in measurable shifts in the resonance wavelength of the plasmon modes of two-dimensional (2D) material structures, with crumpled structures demonstrating large refractive index shifts. Using theoretical calculations based on the semiclassical Drude model, combined with the finite element method, we demonstrate that the interaction between the surface plasmons of crumpled graphene/MoS2 layers and the surrounding analyte results in high sensitivity to biomarker driven refractive index shifts, up to 7499 nm/RIU for structures supported on silicon substrates. We can achieve a high figure of merit (FOM), defined as the ratio of the refractive index sensitivity to the full width at half maximum of the resonant peak, of approximately 62.5 RIU-1. Furthermore, the sensing properties of the device can be tuned by varying crumple period and aspect ratio through simple stretching and integrating material interlayers. By stacking multiple 2D materials in heterostructures supported on the PDMS layer, we produced hybrid plasmon resonances detuned from the PDMS absorbance region allowing higher sensitivity and FOM compared to pure crumpled graphene structures on the PDMS substrates. The high sensitivity and broad mechanical tunability of these crumpled 2D material biosensors considerable advantages over traditional refractive index sensors, providing a new platform for ultrasensitive biosensing.