Exploring PtAg onto silanized biogenic silica as an electrocatalyst for H2 evolution: A combined experimental and theoretical investigation.

The task of creating a remarkably stable and effective electrochemical catalyst for efficient hydrogen evolution is arduous, primarily due to the multitude of factors that need to be taken into account for the industrial utilization of Pt. In this work, hybrid formation through in-situ reduction of Pt onto biogenic porous silica (Pt-SiO2) is tested for its use as an efficient catalyst for hydrogen production. Exceptionally high electrocatalytic activity and excellent reusability of catalysts up to 200 cycles have been demonstrated. Pt-SiO2 with low Pt content of 0.48 to 0.82 at% with active catalytic sites exhibit superior catalytic activity with a Tafel slope of 22 mV dec-1 and an overpotential of 28 mV (vs. RHE at 10 mA cm-2) as compared to the Pt wire and previously reported bare Pt-SiO2 (0.65 at% and 0.48 at% of Pt), and hybrid (Pt/Ag) structures formed onto two different biogenic porous SiO2 substrates. The best catalytic performance of the Pt1Ag3 cluster, representing a low Pt concentration, has been validated by Density Functional Theory (DFT) calculations. Here, the high production from the Pt1Ag3 cluster is assigned to the mutual synergistic effect between Pt/Ag atoms. The Pt atoms transfer the excess charge to the nearest Ag neighbors inside the cluster, facilitating hydrogen diffusion on the activated sites. These important findings authenticate the superior hydrogen production at reduced Pt concentration on amine-functionalized biogenic porous silica.

Microalgae as a potential natural source for the green synthesis of nanoparticles.

The increasing global population is driving the development of alternative sources of food and energy, as well as better or new alternatives for health and environmental care, which represent key challenges in the field of biotechnology. Microalgae represent a very important source material to produce several high-value-added bioproducts. Due to the rapid changes in the modern world, there is a need to build new materials for use, including those in the nanometer size, although these developments may be chronological but often do not occur at a time. In the last few years, a new frontier has opened up at the interface of biotechnology and nanotechnology. This new frontier could help microalgae-based nanomaterials to possess new functions and abilities. Processes for the green synthesis of nanomaterials are being investigated, and the availability of biological resources such as microalgae is continuously being examined. The present review provides a concise overview of the recent advances in the synthesis, characterization, and applications of nanoparticles formed using a wide range of microalgae-based biosynthesis processes. Highlighting their innovative and sustainable potential in current research, our study contributes towards the in-depth understanding and provides latest updates on the alternatives offered by microalgae in the synthesis of nanomaterials.

Microsecond All-Optical Modulation by Biofunctionalized Porous Silicon Microcavity.

We successfully created a composite photonic structure out of porous silicon (PSi) microcavities doped by the photochromic protein, photoactive yellow protein (PYP). Massive incorporation of the protein molecules into the pores was substantiated by a 30 nm shift of the resonance dip upon functionalization, and light-induced reflectance changes of the device due to the protein photocycle were recorded. Model calculations for the photonic properties of the device were consistent with earlier results on the nonlinear optical properties of the protein, whose degree of incorporation into the PSi structure was also estimated. The successful proof-of-concept results are discussed in light of possible practical applications in the future.

Detection of organic pollutants, food additives and antibiotics using sustainable carbon dots.

The ecosystem across the globe has been adversely affected due to the adoption of unsustainable growth strategies. Overuse of organic pollutants such as dyes, pesticides, disinfectants, food additives and antibiotics, along with their release into the environment without proper treatment has severely affected the food chain and water bodies, hence ultimately the human race. As the organic contaminants, being non-biodegradable, persist in the environment for a long duration, a sustainable method for the detection of these harmful organic pollutants is essential. For food safety and restoration of ecological balance, simple, non-toxic, cost-effective and environmentally friendly green precursor derived carbon dots (CDs) are favorable as compared to inorganic nanoparticles (CdTe, CdS etc.) and chemically derived CDs. This review covers the summary of the studies devoted to the optical detection of organic pollutants, food additives and antibiotics through green precursor derived CDs, reported during the last few years. The upcoming studies of optical sensing systems with sustainable CDs provide powerful insight towards pollutant detection, as well as act as a future monitoring tool.

The identification of byproducts from the catalytic reduction reaction of 4-nitrophenol to 4-aminophenol: A systematic spectroscopic study.

Acetaminophenol, commonly recognized as paracetamol (considered safer than aspirin) is formed by nitration of phenol (4-nitrophenol (4-NP)) for its conversion to 4-aminophenol (4-AP), followed by the acetylation for the final product. As 4-NP is an intermediate product in acetaminophenol (paracetamol) production from phenol the dynamic analysis of acetylation of amine group is important. This study focuses on the feasibility of spectroscopic studies to monitor the removal of 4-NP using sodium borohydride (NaBH4) probe reaction in the presence of silver, gold, and bimetallic Ag/Au nanoparticles. UV-visible absorbance and fluorescence spectroscopy measurements reveal the formation of 1,4-benzoquinone (BQ), hydroquinone (HQ), and phenol (Ph) as the final products, in addition to the formation of typically reported 4-AP. The intermediates of NaBH4 seem to play a significant role in the formation of BQ, which converts to HQ in the basic medium followed by the formation of phenol in an acidic medium. Complete kinetic analysis with respect to spectroscopic studies of the standard compounds is presented. Similar results were obtained with 4-NP spiked river and seawater samples. The present findings may lead to catalytic benchmarking that can differ from most of the current practices and highlight the importance of adopting a holistic approach towards the fundamental understanding of 4-NP catalytic reduction that must take into account the concentration of NaBH4 and pH interdependencies.

Heavy metal ion detection using green precursor derived carbon dots.

The discovery of carbon dots (CDs) for environmental remediation has gained awareness because of the diverse economically viable and environmental friendly green precursors generated from biowastes and biomass compared to the toxic inorganic quantum dots and CDs prepared from chemical precursors. This review presents the recent progress in green CDs, including their synthesis methods and sensing applications for the detection of heavy metal ions such as Iron (III), Mercury (II), Copper (II), Chromium (VI), Lead (II), Arsenic (III), Cobalt (II), Aluminum (III), Silver (I), and Gold (III) which are prominent environmental pollutants. The comparison based on selectivity, sensitivity, quantum yield, detection limit, linear concentration range, and sensing mechanisms are also reported. This review also covers the performance of doped green CDs using heteroatoms, toward the detection of heavy metal ions. Apart from the future perspectives, this review provides a general guide to use such environmental friendly CDs to detect harmful pollutants.

Porous silicon pillar structures/photosynthetic reaction centre protein hybrid for bioelectronic applications.

Photosynthetic biomaterials have attracted considerable attention at different levels of the biological organisation, from molecules to the biosphere, due to a variety of artificial application possibilities. During photosynthesis, the first steps of the conversion of light energy into chemical energy take place in a pigment-protein complex, called reaction centre (RC). In our experiments photosynthetic reaction centre protein, purified from Rhodobacter sphaeroides R-26 purple bacteria, was bound to porous silicon pillars (PSiP) after the electropolymerisation of aniline onto the surface. This new type of biohybrid material showed remarkable photoactivity in terms of measured photocurrent under light excitation in an electrochemical cell. The photocurrent was found to increase considerably after the addition of ubiquinone (UQ-0), an e--acceptor mediator of the RC. The photoactivity of the complex was found to decrease by the addition of terbutryn, the chemical which inhibits the e--transport on the acceptor side of the RC. In addition to the generation of sizeable light-induced photocurrents, using the PSiP/RC photoactive hybrid nanocomposite material, the system was found to be sensitive towards RC inhibitors and herbicides. This highly ordered patterned 3D structure opens new solution for designing low-power (bio-)optoelectronic, biophotonic and biosensing devices.

Fluorescent films based on PVDF doped with carbon dots for evaluation of UVA protection of sunscreens and fabrication of cool white LEDs.

The ultraviolet-A (UVA) radiation from sunlight that reaches the earth's surface can induce premature aging, immunosuppression, and skin cancer. Commercial sunscreen products offer limited information regarding protection against UVA light. Therefore, proposing new and practical alternatives to evaluate the UVA protection capacity of commercial sunscreens is highly imperative. This work presents a novel methodology for evaluating the quality of sunscreens using polyvinylidene fluoride (PVDF) based films doped with plant derived photoluminescent carbon dots (CDs). The bluish white light emitting (under UVA exposure) PVDF/CD films were used to evaluate the UVA protection capacity of 8 different commercial sunscreens. The evaluation of UVA protection is based on the fluorescence attenuation observed with the films coated with sunscreens. In addition, visual evaluation of the UVA protection capacity of the sunscreens and commercial glasses, using the same films and a commercial UV lamp at 365 nm, has also been demonstrated. Two sunscreens with limited UVA protection were identified using the proposed simple evaluation mechanisms without conventionally used expensive instruments and complex methodologies. Additionally, the capacity of PVDF/CD material has been explored for the possible fabrication of WLEDs with cool light emission.

Nitrogen-Doped Carbon Dots Induced Enhancement in CO2 Sensing Response From ZnO-Porous Silicon Hybrid Structure.

In this study, we report a simple method for the fabrication of carbon dots sensitized zinc oxide-porous silicon (ZnO-pSi) hybrid structures for carbon dioxide (CO2) sensing. A micro-/nanostructured layer of ZnO is formed over electrochemically prepared pSi substrates using a simple chemical precipitation method. The hybrid structure was structurally and optically characterized using scanning electron microscopy, X-ray diffraction, fluorescence, and cathodoluminescence after the incorporation of hydrothermally prepared nitrogen-doped carbon dots (NCDs) by drop casting. With respect to the control sample, although all the devices show an enhancement in the sensing response in the presence of NCDs, the optimal concentration shows an increase of ~37% at an operating temperature of 200°C and a response time <30 s. The increment in the CO2-sensing response, upon the addition of NCDs, is attributed to an increase in CO2-oxygen species reactions on the ZnO surface due to an increment in the free electron density at the metal-semiconductor-type junction of NCD clusters and ZnO micro-/nanorods. A significant increase in the sensing response (~24%) at low operating temperature (100°C) opens the possibility of developing very large-scale integrable (VLSI), low operational cost gas sensors with easy fabrication methods and low-cost materials.

Porous Si-SiO2 based UV Microcavities.

Obtaining silicon-based photonic-structures in the ultraviolet range would expand the wavelength bandwidth of silicon technology, where it is normally forbidden. Herein, we fabricated porous silicon microcavities by electrochemical etching of alternating high and low refraction index layers; and were carefully subjected to two stages of dry oxidation at 350 °C for 30 minutes and 900 °C, with different oxidation times. In this way, we obtained oxidized porous silicon that induces a shift of a localized mode in the ultraviolet region. The presence of Si-O-Si bonds was made clear by FTIR absorbance spectra. High-quality oxidized microcavities were shown by SEM, where their mechanical stability was clearly visible. We used an effective medium model to predict the refractive index and optical properties of the microcavities. The model can use either two or three components (Si, SiO2, and air). The latter predicts that the microcavities are made almost completely of SiO2, implying less photon losses in the structure. The theoretical photonic-bandgap structure and localized photonic mode location showed that the experimental spectral peaks within the UV photonic bandgap are indeed localized modes. These results support that our oxidation process is very advantageous to obtain complex photonic structures in the UV region.

4-nitrophenol optical sensing with N doped oxidized carbon dots.

In this work, we report a facile strategy for 4-nitrophenol (4-NP) sensing using highly luminescent nitrogen-doped oxidized carbon dots. The quenching of fluorescence (turn OFF), with the addition of trace amounts of organic pollutant (4-NP) in NOCDs, has been attributed to the complete reduction of nitrogen-doped oxidized carbon dots (NOCDs) to reduced nitrogen-doped oxidized carbon dots (rNOCDs) and its formation was confirmed by infrared, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The chemical changes in oxygen-containing functional groups of NOCDs, in the presence of 4-NP, are elucidated and corresponding characterization through XPS reveals the changes in the peak intensities of CC (284.5 eV) and OCO (288.6 eV), indicating a decrement in hydroxyl groups that hinder its complete reduction to NOCDs. The sensitivity of NOCDs towards 4-NP has been tested in spiked tap water in the concentration range 2 µM to 2 mM with the minimum detection limit of 2 µM (linear detection range from 2 to 100 µM with regression coefficient R2 =0.99). The proposed simple sensing platform can be used to reduce NOCDs and simultaneously sense low concentrations of 4-NP. Finally, an effective treatment to improve the reduction of nitrogen-doped graphene oxide is proposed.

Nitrogen-Doped Graphene Oxide Dots-Based "Turn-OFF" H2O2, Au(III), and "Turn-OFF-ON" Hg(II) Sensors as Logic Gates and Molecular Keypad Locks.

Fluorescent nitrogen-doped graphene oxide dots (NGODs) have been demonstrated as an on-off nanosensor for the detection of Hg2+, Au3+, and H2O2. As compared to l-cystine, where the luminescence signal recovery results from the detachment of Hg2+ from the NGODs, signal recovery through l-ascorbic acid (turn-off-on model) has been attributed to the reduction of Hg2+ to Hg0. The sustainable recovery of the photoluminescence signal is demonstrated using common citrus fruits containing vitamin C (l-AA), suggesting a promising practical usage of this sensing system. Additionally, the sensitivity of NGOD- and AA-originated signal recovery from the Hg(II)-NGODs mixture has been successfully tested in Hg2+ ion-spiked tap water from three different places. Mimic devices were executed and verified on the basis of characteristic spectral changes, and the possible utility of this system in electronic security and memory element devices has also been demonstrated. Considering an easy synthesis process and excellent performance of NGODs, this investigation opens up new opportunities for preparing high-quality fluorescent NGODs to meet the requirements of many applications.

Persea americana seed extract mediated gold nanoparticles for mercury(ii)/iron(iii) sensing, 4-nitrophenol reduction, and organic dye degradation.

In this work, Persea americana (Avocado) seed extract mediated systematically optimized synthesis has been employed for the formation of small sized gold nanoparticles (Av-AuNPs) at different pH values. The size, shape and crystallinity of the as-prepared AuNPs have been studied using transmission electron microscopy and X-ray diffraction. The nanoparticles were found to be selective towards mercury(ii) upon the prior or subsequent addition of iron(iii), revealing a blue shift and an enhancement of the characteristic surface plasmon resonance (at 519 nm). Similar absorbance based selectivity has been observed towards Fe(iii) in the presence of Hg(ii). The high sensitivity and selectivity of Av-AuNPs towards Hg(ii) and Fe(iii) has been attributed to the formation of core-shell structures. From the UV-visible spectroscopic measurements, the limits of detection for Hg(ii) and Fe(iii) are found to be 50 nM and 30 nM (around one order of magnitude less than the Environment Protection Agency limit of 0.7 µM for Fe(iii) in drinking water) respectively, with an excellent linear dependence over a wide range of concentrations. Additionally, as-prepared Av-AuNPs have been demonstrated to be efficient in the reduction of organic pollutant 4-nitrophenol to 4-aminophenol and degradation of some organic dyes, such as Methylene Blue, Direct blue, Rhodamine 6G, Bromophenol blue and methyl orange. The use of the proposed Av-AuNPs for sensing and green catalysis can form the basis of high-performance analytical assays, effective multiplexed intracellular sensors, and sophisticated and sustainable probes/catalysts.

Biogenic porous silica and silicon sourced from Mexican Giant Horsetail (Equisetum myriochaetum) and their application as supports for enzyme immobilization.

Porous silica-based materials are attractive for biomedical applications due to their biocompatibility and biodegradable character. In addition, inorganic supports such as porous silicon are being developed due to integrated circuit chip compatibility and tunable properties leading to a wide range of multidisciplinary applications. In this contribution, biosilica extracted from a rarely studied plant material (Equisetum Myriochaetum), its conversion to silicon and the potential for both materials to be used as supports for enzyme immobilization are investigated. E. myriochaetum was subject to conventional acid digestion to extract biogenic silica with a% yield remarkably higher (up to 3 times) than for other Equisetum sp. (i.e. E. Arvense). The surface area of the isolated silica was ∼400 m2/g, suitable for biotechnological applications. Biogenic silicon was obtained by magnesiothermic reduction. The materials were characterized by SEM-EDX, XRD, FT-IR, ICP-OES, TGA and BET analysis and did not contain significant levels of class 1 heavy elements (such as Pb, Cd, Hg and As). Two commercial peroxidases, horseradish peroxidase (HRP) and Coprinus cinereus peroxidase (CiP) were immobilized onto the biogenic materials using three different functionalization routes: (A) carbodiimide, (B) amine + glutaraldehyde and (C) amine + carbodiimide. Although both biogenic silica and porous silicon could be used as supports differences in behaviour were observed for the two enzymes. For HRP, loading onto biogenic silica via the glutaraldehyde immobilization technique (route B) was most effective. The loading of CiP showed a much higher peroxidase activity onto porous silicon than silica functionalized by the carbodiimide method (route A). From the properties of the extracted materials obtained from Equisetum Myriochaetum and the immobilization results observed, these materials appear to be promising for industrial and biomedical applications.

Engineered Adhesion Peptides for Improved Silicon Adsorption.

Engineering peptides that present selective recognition and high affinity for a material is a major challenge for assembly-driven elaboration of complex systems with wide applications in the field of biomaterials, hard-tissue regeneration, and functional materials for therapeutics. Peptide-material interactions are of vital importance in natural processes but less exploited for the design of novel systems for practical applications because of our poor understanding of mechanisms underlying these interactions. Here, we present an approach based on the synthesis of several truncated peptides issued from a silicon-specific peptide recovered via phage display technology. We use the photonic response provided by porous silicon microcavities to evaluate the binding efficiency of 14 different peptide derivatives. We identify and engineer a short peptide sequence (SLVSHMQT), revealing the highest affinity for p(+)-Si. The molecular recognition behavior of the obtained peptide fragment can be revealed through mutations allowing identification of the preferential affinity of certain amino acids toward silicon. These results constitute an advance in both the engineering of peptides that reveal recognition properties for silicon and the understanding of biomolecule-material interactions.

Spectral barcodes by superposition of quasiperiodic refractive index profiles.

Averaging and shifting the refractive index profiles of quasiperiodic structure reveals the formation of several localized modes in the reflectivity spectrum and were used to generate different spectral barcodes. By associating the depth and wavelength of the observed resonant modes to the thickness and position of blackbars, respectively, the possibility to generate multiple codes has been shown. An experimental verification was carried out with multilayered dielectric porous silicon structures with reflectivity spectra revealing unique photonic fingerprints.

Controlled morphology and optical properties of n-type porous silicon: effect of magnetic field and electrode-assisted LEF.

Fabrication of photoluminescent n-type porous silicon (nPS), using electrode-assisted lateral electric field accompanied with a perpendicular magnetic field, is reported. The results have been compared with the porous structures fabricated by means of conventional anodization and electrode-assisted lateral electric field without magnetic field. The lateral electric field (LEF) applied across the silicon substrate leads to the formation of structural gradient in terms of density, dimension, and depth of the etched pores. Apart from the pore shape tunability, the simultaneous application of LEF and magnetic field (MF) contributes to a reduction of the dimension of the pores and promotes relatively more defined pore tips as well as a decreased side-branching in the pore walls of the macroporous structure. Additionally, when using magnetic field-assisted etching, within a certain range of LEF, an enhancement of the photoluminescence (PL) response was obtained.

Porous silicon functionalization for possible arsenic adsorption.

Thiol-functionalized porous silicon (PS) monolayer was evaluated for its possible application in As (III) adsorption. Dimercaptosuccinic acid (DMSA) attached to mesoporous silicon via amide bond linkages was used as a chelate for As (III). Two different aminosilanes namely 3-(aminopropyl) triethoxysilane (APTES) and 3-aminopropyl (diethoxy)-methylsilane (APDEMS) were tested as linkers to evaluate the relative response for DMSA attachment. The aminosilane-modified PS samples were attached to DMSA by wet impregnation followed by the adsorption of As (III). Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) have been used to identify the functional groups and to estimate the As (III) content, respectively. FTIR spectroscopy confirmed the covalent bonding of DMSA with amide and R-COOH groups on the nanostructured porous surface. XPS confirms the preferred arsenic adsorption on the surface of PS/DMSA samples as compared to the aminosilane-modified and bare PS substrates.

Optical characterization of porous silicon monolayers decorated with hydrogel microspheres.

The optical response of porous silicon (pSi) films, covered with a quasi-hexagonal array of hydrogel microspheres, to immersion in ethanol/water mixtures was investigated. For this study, pSi monolayers were fabricated by electrochemical etching, stabilized by thermal oxidation, and decorated with hydrogel microspheres using spin coating. Reflectance spectra of pSi samples with and without deposited hydrogel microspheres were taken at normal incidence. The employed hydrogel microspheres, composed of poly-N-isopropylacrylamide (polyNIPAM), are stimuli-responsive and change their size as well as their refractive index upon exposure to alcohol/water mixtures. Hence, distinct differences in the interference pattern of bare pSi films and pSi layers covered with polyNIPAM spheres could be observed upon their immersion in the respective solutions using reflective interferometric Fourier transform spectroscopy (RIFTS). Here, the amount of reflected light (fast Fourier transform (FFT) amplitude), which corresponds to the refractive index contrast and light scattering at the pSi film interfaces, showed distinct differences for the two fabricated samples. Whereas the FFT amplitude of the bare porous silicon film followed the changes in the refractive index of the surrounding medium, the FFT amplitude of the pSi/polyNIPAM structure depended on the swelling/shrinking of the attached hydrogel spheres and exhibited a minimum in ethanol-water mixtures with 20 wt% ethanol. At this value, the polyNIPAM microgel is collapsed to its minimum size. In contrast, the effective optical thickness, which reflects the effective refractive index of the porous layer, was not influenced by the attached hydrogel spheres. PACS: 81.05.Rm; 81.16.Dn; 83.80Kn; 42.79.Pw.