DNA Origami Plasmonic Nanoantenna for Programmable Biosensing of Multiple Cytokines in Cancer Immunotherapy.

Herein, we report a DNA origami plasmonic nanoantenna for the programmable surface-enhanced Raman scattering (SERS) detection of cytokine release syndrome (CRS)-associated cytokines (e.g., tumor necrosis factor-α (TNF-α) and interferon-γ (IFN-γ)) in cancer immunotherapy. Typically, the nanoantenna was made of self-assembled DNA origami nanotubes (diameter: ∼19 nm; length: ∼90 nm) attached to a silver nanoparticle-modified silicon wafer (AgNP/Si). Each DNA origami nanotube contains one miniature gold nanorod (AuNR) inside (e.g., length: ∼35 nm; width: ∼7 nm). Intriguingly, TNF-α and IFN-γ logically regulate the opening of the nanotubes and the dissociation of the AuNRs from the origami structure upon binding to their corresponding aptamers. On this basis, we constructed a complete set of Boolean logic gates that read cytokine molecules as inputs and return changes in Raman signals as outputs. Significantly, we demonstrated that the presented system enables the quantification of TNF-α and IFN-γ in the serum of tumor-bearing mice receiving different types of immunotherapies (e.g., PD1/PD-L1 complex inhibitors and STING agonists). The sensing results are consistent with those of the ELISA. This strategy fills a gap in the use of DNA origami for the detection of multiple cytokines in real systems.

Inactive Trojan Bacteria as Safe Drug Delivery Vehicles Crossing the Blood-Brain Barrier.

Escherichia coli K1 (EC-K1) can bypass the blood-brain barrier (BBB) and cause meningitis. Excitingly, we find the "dead EC-K1" can safely penetrate the BBB because they retain the intact structure and chemotaxis of the live EC-K1, while losing their pathogenicity. Based on this, we develop a safe "dead EC-K1"-based drug delivery system, in which EC-K1 engulf the maltodextrin (MD)-modified therapeutics through the bacteria-specific MD transporter pathway, followed by the inactivation via UV irradiation. We demonstrate that the dead bacteria could carry therapeutics (e.g., indocyanine green (ICG)) and together bypass the BBB after intravenous injection into the mice, delivering ∼3.0-fold higher doses into the brain than free ICG under the same conditions. What is more, all mice remain healthy even after 14 days of intravenous injection of ∼109 CFU of inactive bacteria. As a proof of concept, we demonstrate the developed strategy enables the therapy of bacterial meningitis and glioblastoma in mice.

CRISPR Cas12a-Powered Silicon Surface-Enhanced Raman Spectroscopy Ratiometric Chip for Sensitive and Reliable Quantification.

Sensitive and reliable clustered regularly interspaced short palindromic repeats (CRISPR) quantification without preamplification of the sample remains a challenge. Herein, we report a CRISPR Cas12a-powered silicon surface-enhanced Raman spectroscopy (SERS) ratiometric chip for sensitive and reliable quantification. As a proof-of-concept application, we select the platelet-derived growth factor-BB (PDGF-BB) as the target. We first develop a microfluidic synthetic strategy to prepare homogeneous silicon SERS substrates, in which uniform silver nanoparticles (AgNPs) are in situ grown on a silicon wafer (AgNPs@Si) by microfluidic galvanic deposition reactions. Next, one 5'-SH-3'-ROX-labeled single-stranded DNA (ssDNA) is modified on AgNPs via Ag-S bonds. In our design, such ssDNA has two fragments: one fragment hybridizes to its complementary DNA (5'-Cy3-labeled ssDNA) to form double-stranded DNA (dsDNA) and the other fragment labeled with 6'-carboxy-X-rhodmine (ROX) extends out as a substrate for Cas12a. The cleavage of the ROX-tagged fragment by Cas12a is controlled by the presence or not of PDGF-BB. Meanwhile, Cy3 molecules serving as internal standard molecules still stay at the end of the rigid dsDNA, and their signals remain constant. Thereby, the ratio of ROX signal intensity to Cy3 intensity can be employed for the reliable quantification of PDGF-BB concentration. The developed chip features an ultrahigh sensitivity (e.g., the limit of detection is as low as 3.2 pM, approximately 50 times more sensitive than the fluorescence counterpart) and good reproducibility (e.g., the relative standard deviation is less than 5%) in the detection of PDGF-BB.

Supramolecularly Engineered Reporters with Superoxide Anion-Triggered Chemiluminescence for Early Diagnosis and Efficient Amelioration of Acute Kidney Injury.

We report the "water-in-oil-in-water" preparation of kidney injury molecule-1-targeting supramolecular chemiluminescence (CL) reporters (PCCS), consisting of L-serine-modified poly(lactic-co-glycolic) acid (PLGA)-encapsulated peroxyoxalate (CPPO), chlorin e6 (Ce6) and superoxide dismutase (SOD), for early diagnosis and amelioration of acute kidney injury (AKI). In this system, O2 ⋅- , a biomarker of AKI, triggers the oxidation of CPPO to 1,2-dioxetanedione and subsequent CL emission via CL resonance energy transfer to Ce6. The L-serine-modified PLGA stabilizes CPPO and Ce6 via noncovalent interactions, promoting long-lived CL (half-lives: ≈1000 s). Transcriptomics analysis shows that PCCS reporters reduce the inflammatory response through glutathione metabolism and inhibition of the tumor necrosis factor signaling pathway. The reporters are able to non-invasively detect AKI at least 12 h earlier than current assays, and their antioxidant properties allow simultaneous treatment of AKI.

NIR-II Photoacoustic-Active DNA Origami Nanoantenna for Early Diagnosis and Smart Therapy of Acute Kidney Injury.

Herein, we designed and synthesized a novel microRNA (miR)-responsive nanoantenna capable of early diagnosis and smart treatment of acute kidney injury (AKI). The nanoantenna was made of two miniature gold nanorods (AuNRs) (e.g., length: ∼48 nm; width: ∼9 nm) linked together by a rectangular DNA origami nanostructure (rDONs) scaffold (e.g., length: ∼90 nm; width: ∼60 nm) (rDONs@AuNR dimer). The surface plasmon resonance peak of the constructed nanoantenna is located within the NIR-II window (e.g., ∼1060 nm), thus guaranteeing photoacoustic (PA) imaging of the nanoantenna in deep tissues. Intriguingly, the nanoantenna displayed exclusive kidney retention in both healthy mice and ischemia reperfusion-induced AKI mice by leveraging the kidney-targeting ability of rDONs. Distinguished from the stable signals in the healthy mice, the PA signals of the nanoantenna would turn down in the AKI mice due to the AuNR detached from rDONs upon interaction with miR-21, which were up-expressed in AKI mice. The limit of detection toward miR-21 was down to 2.8 nM, enabling diagnosis of AKI as early as 10 min post-treatment with ischemia reperfusion, around 2 orders of magnitude earlier than most established probes. Moreover, the naked rDON scaffold generated by AKI could capture more reactive oxygen species (e.g., 1.5-fold more than rDONs@AuNR dimer), alleviating ischemic AKI. This strategy provided a new avenue for early diagnosis and smart treatment of AKI.

In Situ Monitoring of Dynamic Photocatalysis of Metal-Organic Frameworks by Three-Dimensional Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy.

Metal-organic frameworks (MOFs) are promising as novel disinfectants due to the reactive oxygen species (ROS) produced in their photocatalytic processes. The optimal MOF is screened as the best disinfectant, representing high-efficacy production of ROS under photocatalytic conditions. However, current methods to screen abundant MOFs for disinfectant application are generally semiquantitative or ex situ methods [such as electron paramagnetic resonance (EPR) measurements], so achieving a strategy that can quantitatively screen an optimal MOF in situ and is reliable is demanded. Herein, we developed a three-dimensional (3D) shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) platform to study the dynamic photocatalytic processes of various MOFs (e.g., ZIF-67, ZIF-8, and UIO-66) in situ. This platform comprises silica shell-isolated gold nanoparticles (AuNPs) modified on silicon nanowire arrays (SiNWArs). The MOF is then self-assembled on the 3D-SHINERS substrate. Using this platform, we recorded dynamic spectroscopic evidence of ROS formation by various MOFs under sunlight irradiation. By dynamic comparison, ZIF-67 has the most robust photocatalytic efficiency, ∼1.7-fold stronger than that of ZIF-8 and ∼42.6-fold stronger than that of UIO-66. As expected, ZIF-67 displays the best antibacterial ability, up to 99% in the agar plate assay. This work provides a versatile platform for dynamically monitoring photocatalytic performance and screening antibacterial MOFs.

Multifunctional Flavonoid-Silica Nanohydrogel Enables Simultaneous Inhibition of Tumor Recurrence and Bacterial Infection in Post-Surgical Treatment.

A strategy to synthesize water-soluble and fluorescent flavonoid-silica nanocomposites (FSiNCs) simultaneously featuring anti-tumor and anti-bacterial abilities is developed. Furthermore, it is demonstrated that the therapeutic effects of FSiNCs are associated with the selective accumulation of reactive oxide species in both tumor and bacteria cells. Following that, the resultant FSiNCs are incorporated with thrombin and fibrinogen, being sprayed onto the tumor surgical wound site to in situ form fibrin gel (FSiNCs@Fibrin). Remarkably, such FSiNCs@Fibrin results in an ≈18-fold reduction in intratumoral bacteria numbers and ≈12-fold decrease in tumor regrowth compared to equivalent free flavonoid-loaded gel.

Microwave-assisted continuous flow phytosynthesis of silver nanoparticle/reduced graphene oxide composites and related visible light catalytic performance.

The creation of an environmentally friendly synthesis method for silver nanomaterials (AgNPs) is an urgent concern for sustainable nanotechnology development. In the present study, a novel straightforward and green method for the preparation of silver nanoparticle/reduced graphene oxide (AgNP/rGO) composites was successfully developed through the combination of phytosynthesis, continuous flow synthesis and microwave-assistance. Oriental persimmon (Diospyros kaki Thunb.) extracts were used as both plant reducing and capping agents for fast online synthesis of AgNP/rGO composites. The experimental parameters were optimized and the morphologies of the prepared materials were investigated. The characterization results reveal that spherical AgNPs were quickly synthesized and uniformly dispersed on rGO sheets using the proposed online system. Fourier transform infrared spectroscopy analysis confirmed that phenols, flavonoids, and other substances in the plant extracts played a decisive role in the synthesis of AgNP/rGO composites. Using sodium borohydride (NaBH4) degradation of p-nitrophenol (4-NP) as a model, the catalytic activity of the prepared AgNP/rGO materials was evaluated. The complete degradation of 4-NP was achieved within 12 min through the use of AgNP/rGO materials, and the composite had a much better catalytic activity than the bare AgNPs and rGO had. Compared with the conventional chemical method, our online method is facile, fast, cost-efficient, and environmentally friendly.

Trojan Nanobacteria System for Photothermal Programmable Destruction of Deep Tumor Tissues.

A novel bacteria-based drug delivery system, termed "Trojan nanobacteria system", has been developed in which nanoagents are internalized into engineered bacteria through bacteria-specific maltodextrin (MD) transporters. Compared to the method of attaching nanoagents to bacterial surfaces, this Trojan system features higher payloads and better stability. In cancer therapy, Trojan nanobacteria can specifically discriminate the tumor region and then penetrate deep tumor tissues. Once in the tumor, the Trojan nanobacteria systems are able to destroy deep tumor tissues due to the combined effects of antitumor protein expression (e.g., tumor necrosis factor-α, TNF-α) and photothermal properties.

Ex vivo and in vivo fluorescence detection and imaging of adenosine triphosphate.

BACKGROUND: Ex vivo and in vivo detection and imaging of adenosine triphosphate (ATP) is critically important for the diagnosis and treatment of diseases, which still remains challenges up to present. RESULTS: We herein demonstrate that ATP could be fluorescently detected and imaged ex vivo and in vivo. In particular, we fabricate a kind of fluorescent ATP probes, which are made of titanium carbide (TC) nanosheets modified with the ROX-tagged ATP-aptamer (TC/Apt). In the constructed TC/Apt, TC shows superior quenching efficiency against ROX (e.g., ~ 97%). While in the presence of ATP, ROX-tagged aptamer is released from TC surface, leading to the recovery of fluorescence of ROX under the 545-nm excitation. Consequently, a wide dynamic range from 1 µM to 1.5 mM ATP and a high sensitivity with a limit of detection (LOD) down to 0.2 µM ATP can be readily achieved by the prepared TC/Apt. We further demonstrate that the as-prepared TC/Apt probe is feasible for accurate discrimination of ATP in different samples including living cells, body fluids (e.g., mouse serum, mouse urine and human serum) and mouse tumor models. CONCLUSIONS: Fluorescence detection and imaging of ATP could be readily achieved in living cells, body fluids (e.g., urine and serum), as well as mouse tumor model through a new kind of fluorescent ATP nanoprobes, offering new powerful tools for the treatment of diseases related to abnormal fluctuation of ATP concentration.

Dual-Amplification Strategy-Based SERS Chip for Sensitive and Reproducible Detection of DNA Methyltransferase Activity in Human Serum.

Herein, we present a dual-amplification sensing strategy-based surface-enhanced Raman scattering (SERS) chip, which combines rolling circle amplification (RCA) and polyadenine (PolyA) assembly for sensitive and reproducible determination of the activity of M.SssI, a cytosine-guanine dinucleotide (CpG) methyltransferase (MTase). Typically, in the presence of M.SssI, RCA process is triggered, resulting in long, single-stranded DNA (ssDNA) fragments that are hybridized with thousands of Raman reporters of Cy3. Afterward, the resultant ssDNA fragments are conjugated to SERS-active substrates made of silver core-gold satellite nanocomposites-modified silicon wafer (Ag-Au NPs@Si), with the SERS enhancement factor of ∼5 × 106. The core-satellite nanostructures are assembled relied on the strong affinity of PolyA toward gold/silver surface. Of particular significance, the developed SERS chip displays an ultrahigh sensitivity with a low limit of detection (LOD) of 2.8 × 10-3 U/mL, which is around 2 orders of magnitude higher than most reported methods. In addition, the constructed chip features a broad detection range covering from 0.05 to 50 U/mL. Besides for the ultrahigh sensitivity and broad dynamic range, the chip also features good reproducibility (e.g., the relative standard deviation (RSD) is less than ∼12%). Taking advantages of these merits, the developed chip is feasible for accurate discrimination of M.SssI with various concentrations spiked in human serum samples with good recoveries ranging from 99.6% to 107%.

Biomimetic preparation of core-shell structured surface-enhanced Raman scattering substrate with antifouling ability, good stability, and reliable quantitative capability.

The fouling and stability are two most critical limiting factors for practical applications of surface-enhanced Raman scattering (SERS)-based microfluidic electrophoresis device. Herein, we present a novel biomimetic nanoengineering strategy to achieve a SERS substrate featuring antifouling ability, good stability, and reliable quantitative capability. Typically, by employing tea polyphenol as the reducing agent, the substrate made of silver core-gold shell nanostructures in situ grown on silicon wafer surface is fabricated. The core-shell nanostructures are further embedded with internal standard molecules. Remarkably, the fabricated substrate preserves distinct SERS effects, adaptable reproducibility, and reliable quantitative ability even if the substrate is incubated with 15% H2 O2 , 13% HNO3 , or 108  CFU/mL bacteria, or suffered from 12-day continuous vibration at 250 rpm/min in PBS buffer. As a proof-of-concept application, the DNA-functionalized substrate is capable of precise quantification of Hg2+ with a limit of detection down to ca. 1 pM even in sewage water.

Setting Up a Surface-Enhanced Raman Scattering Database for Artificial-Intelligence-Based Label-Free Discrimination of Tumor Suppressor Genes.

The quality of input data in deep learning is tightly associated with the ultimate performance of the machine learner. Taking advantage of the unique merits of surface-enhanced Raman scattering (SERS) methodology in the collection and construction of a database (e.g., abundant intrinsic fingerprint information, noninvasive data acquisition process, strong anti-interfering ability, etc.), herein we set up a SERS-based database of deoxyribonucleic acid (DNA), suitable for artificial intelligence (AI)-based sensing applications. The database is collected and analyzed by silver nanoparticles (Ag NPs)-decorated silicon wafer (Ag NPs@Si) SERS chip, followed by training with a deep neural network (DNN). As proof-of-concept applications, three kinds of representative tumor suppressor genes, i.e., p16, p21, and p53 fragments, are readily discriminated in a label-free manner. Prominent and reproducible SERS spectra of these DNA molecules are collected and employed as input data for DNN learning and training, which enables selective discrimination of DNA target(s). The accuracy rate for the recognition of specific DNA target reached 90.28%.

A Graphene-Silver Nanoparticle-Silicon Sandwich SERS Chip for Quantitative Detection of Molecules and Capture, Discrimination, and Inactivation of Bacteria.

There currently exists increasing concerns on the development of a kind of high-performance SERS platform, which is suitable for sensing applications ranging from the molecular to cellular (e.g., bacteria) level. Herein, we develop a novel kind of universal SERS chip, made of graphene (G)-silver nanoparticle (AgNP)-silicon (Si) sandwich nanohybrids (G@AgNPs@Si), in which AgNPs are in situ grown on a silicon wafer through hydrofluoric acid-etching-assisted chemical reduction, followed by coating with single-layer graphene via a polymer-protective etching method. The resultant chip features a strong, stable, reproducible surface-enhanced Raman scattering (SERS) effect and reliable quantitative capability. By virtues of these merits, the G@AgNPs@Si platform is capable for not only molecular detection and quantification but also cellular analysis in real systems. As a proof-of-concept application, the chip allows ultrahigh sensitive and reliable detection of adenosine triphosphate (ATP), with a detection limit of ∼1 pM. In addition, the chip, serving as a novel multifunctional platform, enables simultaneous capture, discrimination, and inactivation of bacteria. Typically, the bacterial capture efficiency is 54% at 108 CFU mL-1 bacteria, and the antibacterial rate reaches 93% after 24 h of treatment. Of particular note, Escherichia coli and Staphylococcus aureus spiked into blood can be readily distinguished via the chip, suggesting its high potential for clinical applications.

Reusable Silicon-Based Surface-Enhanced Raman Scattering Ratiometric Aptasensor with High Sensitivity, Specificity, and Reproducibility.

Rapid, sensitive, and accurate detection of adenosine triphosphate (ATP), the primary energy molecule, is critical for the elucidation of its unique roles in cell signaling and many cellular reactions. Up to date, a major challenge is still remaining for fabricating surface-enhanced Raman scattering (SERS) aptamer sensors (aptasensors) suitable for accurate and reliable quantification of ATP. Herein, we develop the ratiometric silicon SERS aptasensor for ATP detection, which is made of uniform silver nanoparticles (Ag NPs)-modified silicon wafer (Ag NPs@Si), followed by the functionalization with double-stranded DNA (dsDNA I). The dsDNA I is formed by the aptamer and its complementary DNA (cDNA), which contains two independent segments (e.g., 5'-Cy3-labeled DNA-C1, 3'-ROX-labeled DNA-C2). In the presence of ATP, ROX-DNA-C2 is dissociated from dsDNA I due to the formation of aptamer/ATP complex, leading to the attenuation of ROX signals, and meanwhile, Cy3 signals remain constant ascribed to the formation of dsDNA II caused by the supplementation of aptamer. As a result, ratiometric signals of the ratio of ROX intensity to Cy3 intensity (IROX/ICy3) can be achieved. Of particular significance, the developed ATP aptasensor features excellent reproducibility [e.g., the relative standard deviation (RSD) is less than ∼4%, comparable or superior to that of previously reported aptasensors], ultrahigh sensitivity [e.g., the detection of limit (LOD) reaches 9.12 pM, lower than that of other reported ATP SERS aptasensors], as well as good recyclability (e.g., ∼9.3% of RSD values of ratiometric signals within three cycles).

Fluorescent Silicon Nanorods-Based Ratiometric Sensors for Long-Term and Real-Time Measurements of Intracellular pH in Live Cells.

Long-term and real-time investigation of the dynamic process of pHi changes is critically significant for understanding the related pathogenesis of diseases and the design of intracellular drug delivery systems. Herein, we present a one-step synthetic strategy to construct ratiometric pH sensors, which are made of europium (Eu)-doped one-dimensional silicon nanorods (Eu@SiNRs). The as-prepared Eu@SiNRs have distinct emission maxima peaks at 470 and 620 nm under 405 nm excitation. Of particular note, the fluorescence emission intensity at 470 nm decreases along with the increase of pH, while the one at 620 nm is nearly unaffected by pH changes, making Eu@SiNRs a feasible probe for pH sensing ratiometrically. Moreover, Eu@SiNRs are found to be responsive to a broad pH range (ca. 3-9), biocompatible (e.g., ∼100% of cell viability during 24 h treatment) and photostable (e.g., ∼10% loss of intensity after 40 min continuous UV irradiation). Taking advantages of these merits, we employ Eu@SiNRs for the visualization of the cytoplasmic alkalization process mediated by nigericin in living cells, for around 30 min without interruption, revealing important information for understanding the dynamic process of pHi fluctuations.

In Situ Live-Cell Nucleus Fluorescence Labeling with Bioinspired Fluorescent Probes.

Fluorescent imaging techniques for visualization of nuclear structure and function in live cells are fundamentally important for exploring major cellular events. The ideal cellular labeling method is capable of realizing label-free, in situ, real-time, and long-term nucleus labeling in live cells, which can fully obtain the nucleus-relative information and effectively alleviate negative effects of alien probes on cellular metabolism. However, current established fluorescent probes-based strategies (e.g., fluorescent proteins-, organic dyes-, fluorescent organic/inorganic nanoparticles-based imaging techniques) are unable to simultaneously realize label-free, in situ, long-term, and real-time nucleus labeling, resulting in inevitable difficulties in fully visualizing nuclear structure and function in live cells. To this end, we present a type of bioinspired fluorescent probes, which are highly efficacious for in situ and label-free tracking of nucleus in long-term and real-time manners. Typically, the bioinspired polydopamine (PDA) nanoparticles, served as fluorescent probes, can be readily synthesized in situ within live cell nucleus without any further modifications under physiological conditions (37 °C, pH ∼7.4). Compared with other conventional nuclear dyes (e.g., propidium iodide (PI), Hoechst), superior spectroscopic properties (e.g., quantum yield of ∼35.8% and high photostability) and low cytotoxicity of PDA-based probes enable long-term (e.g., 3 h) fluorescence tracking of nucleus. We also demonstrate the generality of this type of bioinspired fluorescent probes in different cell lines and complex biological samples.

Portable and Reliable Surface-Enhanced Raman Scattering Silicon Chip for Signal-On Detection of Trace Trinitrotoluene Explosive in Real Systems.

There is an increasing interest in the development of surface-enhanced Raman scattering (SERS) sensors for rapid and accurate on-site detection of hidden explosives. However, portable SERS methods for trace explosive detection in real systems remain scarce, mainly due to their relatively poor reliability and portability. Herein, we present the first demonstration of a portable silicon-based SERS analytical platform for signal-on detection of trace trinitrotoluene (TNT) explosives, which is made of silver nanoparticle (AgNP)-decorated silicon wafer chip (0.5 cm × 0.5 cm). In principle, under 514 nm excitation, the Raman signals of p-aminobenzenethiol (PABT) modified on the AgNP surface could be largely lit up due to the formation of electronic resonance-active TNT-PABT complex. In addition, the surface of AgNPs and silicon substrate-induced plasmon resonances also contribute the total SERS enhancement. For quantitative evaluation, the as-prepared chip features ultrahigh sensitivity [limit of detection is down to ∼1 pM (∼45.4 fg/cm2)] and adaptable reproducibility (relative standard deviation is less than 15%) in the detection of TNT standard solutions. More importantly, the developed chip can couple well with a hand-held Raman spectroscopic device using 785 nm excitation, suitable for qualitative analysis of trace TNT even at ∼10-8 M level from environmental samples including lake water, soil, envelope, and liquor with a short data acquisition time (∼1 min). Furthermore, TNT vapors diffusing from TNT residues (∼10-6 M) can be detected by using such a portable device, indicating its feasibility in determination of hidden samples.

Recent Advances in Silicon Nanomaterial-Based Fluorescent Sensors.

During the past decades, owing to silicon nanomaterials' unique optical properties, benign biocompatibility, and abundant surface chemistry, different dimensional silicon nanostructures have been widely employed for rationally designing and fabricating high-performance fluorescent sensors for the detection of various chemical and biological species. Among of these, zero-dimensional silicon nanoparticles (SiNPs) and one-dimensional silicon nanowires (SiNWs) are of particular interest. Herein, we focus on reviewing recent advances in silicon nanomaterials-based fluorescent sensors from a broad perspective and discuss possible future directions. Firstly, we introduce the latest achievement of zero-dimensional SiNP-based fluorescent sensors. Next, we present recent advances of one-dimensional SiNW-based fluorescent sensors. Finally, we discuss the major challenges and prospects for the development of silicon-based fluorescent sensors.

Ultrasensitive, Specific, Recyclable, and Reproducible Detection of Lead Ions in Real Systems through a Polyadenine-Assisted, Surface-Enhanced Raman Scattering Silicon Chip.

It is of great significance to accurately and reliably detect trace lead(II) (Pb(2+)) ions, preferably at sub-nM level due to the possible long-term accumulation of Pb(2+) in the human body, which may cause serious threats to human health. However, a suitable Pb(2+) sensor meeting the demands is still scanty. Herein, we develop a polyadenine-assisted, surface-enhanced Raman scattering (SERS) silicon chip (0.5 cm × 0.5 cm) composed of core (Ag)-satellite (Au) nanoparticles (Ag-Au NPs)-decorated silicon wafers (Ag-Au NPs@Si) for high-performance Pb(2+) detection. Typically, strong SERS signals could be measured when DNAzyme conjugated on the SERS silicon chip is specifically activated by Pb(2+), cleaving the substrate strand into two free DNA strands. A good linearity exists between the normalized Raman intensities and the logarithmic concentrations of Pb(2+) ranging from 10 pM to 1 µM with a good correlation coefficient, R(2) of 0.997. Remarkably, Pb(2+) ions with a low concentration of 8.9 × 10(-12) M can be readily determined via the SERS silicon chip ascribed to its superior SERS enhancement, much lower than those (∼nM) reported by other SERS sensors. Additionally, the developed chip features good selectivity and recyclability (e.g., ∼11.1% loss of Raman intensity after three cycles). More importantly, the as-prepared chip can be used for accurate and reliable determination of unknown Pb(2+) ions in real systems including lake water, tap water and industrial wastewater, with the RSD value less than 12%.