In Situ Production of Biofunctionalized Few‐Layer Defect‐Free Microsheets of Graphene

Biological interfacing of graphene has become crucial to improve its biocompatibility, dispersability, and selectivity. However, biofunctionalization of graphene without yielding defects in its sp²‐carbon lattice is a major challenge. Here, a process is set out for biofunctionalized defect‐free graphene synthesis through the liquid phase ultrasonic exfoliation of raw graphitic material assisted by the self‐assembling fungal hydrophobin Vmh2. This protein (extracted from the edible fungus Pleurotus ostreatus) is endowed with peculiar physicochemical properties, exceptional stability, and versatility. The unique properties of Vmh2 and, above all, its superior hydrophobicity, and stability allow to obtain a highly concentrated (≈440–510 μg mL^?1) and stable exfoliated material (ζ‐potential, +40/+70 mV). In addition controlled centrifugation enables the selection of biofunctionalized few‐layer defect‐free micrographene flakes, as assessed by Raman spectroscopy, atomic force microscopy, scanning electron microscopy, and electrophoretic mobility. This biofunctionalized product represents a high value added material for the emerging applications of graphene in the biotechnological field such as sensing, nanomedicine, and bioelectronics technologies.     

Detection of Glioma‐Derived Exosomes with the Biotinylated Antibody‐Functionalized Titanium Nitride Plasmonic Biosensor

Titanium nitride (TiN), as an excellent alternative plasmonic supporting material compared to gold and silver, exhibits tunable plasmonic properties in the visible and near‐infrared spectra. However, label‐free surface plasmon resonance biosensing with TiN is seldom reported due to lack of proper surface functionalization protocols. Herein, this study reports biotinylated antibody‐functionalized TiN (BAF‐TiN) for high‐performance label‐free biosensing applications. The BAF‐TiN biosensor can quantitatively detect exosomes of 30–200 nm extracellular vesicles, isolated from a human glioma cell line. The limit of detection for an exosomal membrane protein with the BAF‐TiN biosensor is found to be 4.29 × 10^?3µg mL^?1 for CD63, an exosome marker, and 2.75 × 10^?3µg mL^?1 for epidermal growth factor receptor variant‐III, a glioma specific mutant protein, respectively. In conclusion, combining the biocompatibility, high stability, and excellent label‐free sensing performance of TiN, the BAF‐TiN biosensor could have great potential for the detection of cancer biomarkers, including exosomal surface proteins.     

Hybrid Paper–Plastic Microchip for Flexible and High‐Performance Point‐of‐Care Diagnostics

A low‐cost and easy‐to‐fabricate microchip remains a key challenge for the development of true point‐of‐care (POC) diagnostics. Cellulose paper and plastic are thin, light, flexible, and abundant raw materials, which make them excellent substrates for mass production of POC devices. Herein, a hybrid paper–plastic microchip (PPMC) is developed, which can be used for both single and multiplexed detection of different targets, providing flexibility in the design and fabrication of the microchip. The developed PPMC with printed electronics is evaluated for sensitive and reliable detection of a broad range of targets, such as liver and colon cancer protein biomarkers, intact Zika virus, and human papillomavirus nucleic acid amplicons. The presented approach allows a highly specific detection of the tested targets with detection limits as low as 10² ng mL^?1 for protein biomarkers, 10³ particle per milliliter for virus particles, and 10² copies per microliter for a target nucleic acid. This approach can potentially be considered for the development of inexpensive and stable POC microchip diagnostics and is suitable for the detection of a wide range of microbial infections and cancer biomarkers.     

Nanoporous PtRu Alloy Enhanced Nonenzymatic Immunosensor for Ultrasensitive Detection of Microcystin‐LR

A novel nonenzymatic immunosensor for sensitive detection of Microcystin‐LR (MC‐LR) is constructed using a graphene platform combined with mesoporous PtRu alloy as a label for signal amplification. Primary antibody‐Microcystin‐LR (Ab₁) is immobilized onto the surface of a graphene sheet (GS) through an amidation reaction between the carboxylic acid groups attached to the GS and the available amine groups of Ab₁. Mesoporous PtRu alloy, prepared by corrosion PtRuAl alloys, is employed as a label to immobilize secondary antibody (Ab₂). The resulting nanoparticles, PtRu‐Ab₂, are used as labels for the immunosensor to detect MC‐LR. Under optimal conditions, the immunosensor exhibits a wide linear response to MC‐LR that ranges from 0.01 to 28 ng·mL^?1, with a low detection limit of 9.63 pg·mL^?1 MC‐LR. The proposed immunsensor shows good reproducibility, selectivity, and stability. The assayed results of polluted water with the sandwich‐type sensor are acceptable. Importantly, this methodology may provide a promising ultrasensitive assay strategy for other environmental pollutants.     

Flexible,Graphene‐Coated Biocomposite for Highly Sensitive,Real‐Time Molecular Detection

Wearable biosensors hold significant potential for healthcare and environmental applications, and the development of flexible and biocompatible sensing platforms for high accuracy detection of physiological biomarkers remains an elusive goal. Herein, an ultrasensitive, flexible sensor is described that is based on a 3D hierarchical biocomposite comprised of hollow, natural pollen microcapsules that are coated with a conductive graphene layer. Modular assembly of the graphene‐coated microcapsules onto an ultrathin polyethylene terephthalate layer enables a highly flexible sensor configuration with tunable selectivity afforded by subsequent covalent immobilization of antibodies against target antigens. In a proof‐of‐concept example, the biosensor demonstrates ultrahigh sensitivity detection of prostate specific antigen (PSA) down to 1.7 × 10^?15m with real‐time feedback and superior performance over conventional 2D graphene‐coated sensors. Importantly, the device performance is consistently high across various bending conditions. Taken together, the results demonstrated in this work highlight the merits of employing lightweight biocomposites as modular building blocks for the design of flexible biosensors with highly responsive and sensitive molecular detection capabilities.     

Straightforward Immunosensing Platform Based on Graphene Oxide‐Decorated Nanopaper: A Highly Sensitive and Fast Biosensing Approach

Immunoassays are nowadays a crucial tool for diagnostics and drug development. However, they often involve time‐consuming procedures and need at least two antibodies in charge of the capture and detection processes, respectively. This study reports a nanocomposite based on graphene oxide‐coated nanopaper (GONAP) facilitating an advantageous immunosensing platform using a single antibody and without the need for washing steps. The hydrophilic, porous, and photoluminescence‐quenching character of GONAP allows for the adsorption and quenching of photoluminescent quantum dots nanocrystals complexed with antibodies (Ab‐QDs), enabling a ready‐to‐use immunosensing platform. The photoluminescence is recovered upon immunocomplex (antibody‐antigen) formation which embraces a series of interactions (hydrogen bonding, electrostatic, hydrophobic, and Van der Waals interactions) that trigger desorption of the antigen‐Ab‐QD complex from GONAP surface. However, the antigen is then attached onto the GONAP surface by electrostatic interactions leading to a spacer (greater than ≈20 nm) between Ab‐QDs and GONAP and thus hindering nonradiative energy transfer. It is demonstrated that this simple—yet highly sensitive—platform represents a virtually universal immunosensing approach by using small‐sized and big‐sized targets as model analytes, those are, human‐IgG protein and Escherichia coli bacteria. In addition, the assay is proved effective in real matrices analysis, including human serum, poultry meat, and river water. GONAP opens the way to conceptually new paper‐based devices for immunosensing, which are amenable to point of care applications and automated diagnostics.     

Multifunctional Dendrimer‐Templated Antibody Presentation on Biosensor Surfaces for Improved Biomarker Detection

Dendrimers, with their well‐defined globular shape and high density of functional groups, are ideal nanoscale materials for templating sensor surfaces. This work exploits dendrimers as a versatile platform for capturing biomarkers with improved sensitivity and specificity. The synthesis, characterization, fabrication, and functional validation of the dendrimer‐based assay platform are described. Bifunctional hydroxyl/thiol‐functionalized G4‐polyamidoamine (PAMAM) dendrimer is synthesized and immobilized on the polyethylene‐glycol (PEG)‐functionalized assay plate by coupling PEG‐maleimide and dendrimer thiol groups. Simultaneously, part of the dendrimer thiol groups are converted to hydrazide functionalities. The resulting dendrimer‐modified surface is coupled to the capture antibody in the Fc region of the oxidized antibody. This preserves the orientation flexibility of the antigen binding region (Fv) of the antibody. To validate the approach, the fabricated plates are further used as a solid phase for developing a sandwich‐type enzyme‐linked immunosorbent assay (ELISA) to detect IL‐6 and IL‐1β, important biomarkers for early stages of chorioamnionitis. The dendrimer‐modified plate provides assays with significantly enhanced sensitivity, lower nonspecific adsorption, and a detection limit of 0.13 pg mL^?1 for IL‐6 luminol detection and 1.15 pg mL^?1 for IL‐1β TMB detection, which are significantly better than those for the traditional ELISA. The assays were validated in human serum samples from a normal (nonpregnant) woman and pregnant women with pyelonephritis. The specificity and the improved sensitivity of the dendrimer‐based capture strategy could have significant implications for the detection of a wide range of cytokines and biomarkers since the capture strategy could be applied to multiplex microbead assays, conductometric immunosensors, and field‐effect biosensors.     

Simultaneous Electrochemical Dual‐Electrode Exfoliation of Graphite toward Scalable Production of High‐Quality Graphene

Developing scalable methods to produce large quantities of high‐quality and solution‐processable graphene is essential to bridge the gap between laboratory study and commercial applications. Here an efficient electrochemical dual‐electrode exfoliation approach is developed, which combines simultaneous anodic and cathodic exfoliation of graphite. Newly designed sandwich‐structured graphite electrodes which are wrapped in a confined space with porous metal mesh serve as both electrodes, enabling a sufficient ionic intercalation. Mechanism studies reveal that the combination of electrochemical intercalation with subsequent thermal decomposition results in drastic expansion of graphite toward high‐efficiency production of graphene with high quality. By precisely controlling the intercalation chemistry, the two‐step approach leads to graphene with outstanding yields (85% and 48% for cathode and anode, respectively) comprising few‐layer graphene (1–3 layers, >70%), ultralow defects (I_D/I_G < 0.08), and high production rate (exceeding 25 g h^?1). Moreover, its excellent electrical conductivity (>3 × 10⁴ S m^?1) and great solution dispersibility in N‐methyl pyrrolidone (10 mg mL^?1) enable the fabrication of highly conductive (11 Ω sq^?1) and flexible graphene films by inkjet printing. This simple and efficient exfoliation approach will facilitate the development of large‐scale production of high‐quality graphene and holds great promise for its wide application.     

Fabrication of Graphene–Quantum Dots Composites for Sensitive Electrogenerated Chemiluminescence Immunosensing

A novel strategy is reported for the fabrication of poly(diallyldimethylammonium chloride) (PDDA)‐protected graphene–CdSe (P‐GR‐CdSe) composites. An advanced electrogenerated chemiluminescence (ECL) immunosensor is proposed for the sensitive detection of human IgG (HIgG) by using the as‐prepared P‐GR‐CdSe composites. The P‐GR‐CdSe composite film shows high ECL intensity, good electronic conductivity, fast response, and satisfactory stability, all of which holds great promise for the fabrication of ECL biosensors with improved sensitivity. After two successive steps of amplification via the conjugation of PDDA and gold nanoparticles (GNPs) in the film, high ECL intensity is observed. The ECL immunosensor has an extremely sensitive response to HIgG in a linear range of 0.02–2000 pg mL^?1 with a detection limit of 0.005 pg mL^?1. The proposed sensor exhibits high specificity, good reproducibility, and long‐term stability, and may become a promising technique for protein detection.     

Poly[oligo(ethylene glycol) methacrylate‐co‐glycidyl methacrylate] Brush Substrate for Sensitive Surface Plasmon Resonance Imaging Protein Arrays

Surface plasmon resonance imaging (SPRi) is a unique microarray method for label‐free and multiplexed bio‐assays. However, it currently cannot be used to detect human serum samples due to its low sensitivity and poor specificity. A poly[oligo(ethylene glycol) methacrylate‐co‐glycidyl methacrylate] (POEGMA‐co‐GMA) brush was synthesized by surface‐initiated atom transfer radical polymerization (SI‐ATRP) and used as a unique supporting matrix for SPRi arrays to efficiently load probe proteins for high sensitivity while reducing nonspecific adsorptions for good selectivity. Results indicate that the polymer brush has a high protein loading capacity (1.8 protein monolayers), low non‐specific protein adsorption (below the SPR detection limit), and high immobilization stability. Three model biomarkers, α‐fetoprotein, carcinoembryonic antigen, and hepatitis B surface antigen were simultaneously detected in human serum samples by a SPRi chip for the first time, showing detection limits of 50, 20, and 100 ng mL^?1, respectively. This work demonstrates great potential for a SPRi biochip as a powerful label‐free and high‐throughput detection tool in clinical diagnosis and biological research. Since the SPR detection is limited by the sensing film thickness, this approach particularly offers a unique way to significantly improve the sensitivity in the SPR detecting thickness range.     

A Multiwalled‐Carbon‐Nanotube‐Based Biosensor for Monitoring Microcystin‐LR in Sources of Drinking Water Supplies

A multiwalled carbon nanotube (MWCNT)‐based electrochemical biosensor is developed for monitoring microcystin‐LR (MC‐LR), a toxic cyanobacterial toxin, in sources of drinking water supplies. The biosensor electrodes are fabricated using vertically well‐aligned, dense, millimeter‐long MWCNT arrays with a narrow size distribution, grown on patterned Si substrates by water‐assisted chemical vapor deposition. High temperature thermal treatment (2500 °C) in an Ar atmosphere is used to enhance the crystallinity of the pristine materials, followed by electrochemical functionalization in alkaline solution to produce oxygen‐containing functional groups on the MWCNT surface, thus providing the anchoring sites for linking molecules that allow the immobilization of MC‐LR onto the MWCNT array electrodes. Addition of the monoclonal antibodies specific to MC‐LR in the incubation solutions offers the required sensor specificity for toxin detection. The performance of the MWCNT array biosensor is evaluated using micro‐Raman spectroscopy, including polarized Raman measurements, X‐ray photoelectron spectroscopy, cyclic voltammetry, optical microscopy, and Faradaic electrochemical impedance spectroscopy. A linear dependence of the electron‐transfer resistance on the MC‐LR concentration is observed in the range of 0.05 to 20 μg L^?1, which enables cyanotoxin monitoring well below the World Health Organization (WHO) provisional concentration limit of 1 μg L^?1 for MC‐LR in drinking water.     

High Sensitivity Graphene Field Effect Transistor‐Based Detection of DNA Amplification

Enzymatic DNA amplification‐based approaches involving intercalating DNA‐binding fluorescent dyes and expensive optical detectors are the gold standard for nucleic acid detection. As components of a simplified and miniaturized system, conventional silicon‐based ion sensitive field effect transistors (ISFETs) that measure a decrease in pH due to the generation of pyrophosphates during DNA amplification have been previously reported. In this article, Bst polymerase in a loop‐mediated isothermal amplification (LAMP) reaction combined with target‐specific primers and crumpled graphene field effect transistors (gFETs) to electrically detect amplification by sensing the reduction in primers is used. Graphene is known to adsorb single‐stranded DNA due to noncovalent π–π bonds, but not double‐stranded DNA. This approach does not require any surface functionalization and allows the detection of primer concentrations at the endpoint of reactions. As recently demonstrated, the crumpled gFET over the conventional flat gFET sensors due to their superior sensitivity is chosen. The endpoint of amplification reaction with starting concentrations down to 8 × 10^?21 m in 90 min including the time of amplification and detection is detected. With its high sensitivity and small footprint, this platform will help bring complex lab‐based diagnostic and genotyping amplification assays to the point‐of‐care.     

Hierarchical Ordered Dual‐Mesoporous Polypyrrole/Graphene Nanosheets as Bi‐Functional Active Materials for High‐Performance Planar Integrated System of Micro‐Supercapacitor and Gas Sensor

Planar integrated systems of micro‐supercapacitors (MSCs) and sensors are of profound importance for 3C electronics, but usually appear poor in compatibility due to the complex connections of device units with multiple mono‐functional materials. Herein, 2D hierarchical ordered dual‐mesoporous polypyrrole/graphene (DM‐PG) nanosheets are developed as bi‐functional active materials for a novel prototype planar integrated system of MSC and NH₃ sensor. Owing to effective coupling of conductive graphene and high‐sensitive pseudocapacitive polypyrrole, well‐defined dual‐mesopores of ≈7 and ≈18 nm, hierarchical mesoporous network, and large surface area of 112 m² g^?1, the resultant DM‐PG nanosheets exhibit extraordinary sensing response to NH₃ as low as 200 ppb, exceptional selectivity toward NH₃ that is much higher than other volatile organic compounds, and outstanding capacitance of 376 F g^?1 at 1 mV s^?1 for supercapacitors, simultaneously surpassing single‐mesoporous and non‐mesoporous counterparts. Importantly, the bi‐functional DM‐PG‐based MSC‐sensor integrated system represents rapid and stable response exposed to 10–40 ppm of NH₃ after only charging for 100 s, remarkable sensitivity of NH₃ detection that is close to DM‐PG‐based MSC‐free sensor, impressive flexibility with ≈82% of initial response value even at 180°, and enhanced overall compatibility, thereby holding great promise for ultrathin, miniaturized, body‐attachable, and portable detection of NH₃.     

Amplifying Charge‐Transfer Characteristics of Graphene for Triiodide Reduction in Dye‐Sensitized Solar Cells

The fabrication and functionalization of large‐area graphene and its electrocatalytic properties for iodine reduction in a dye‐sensitized solar cell are reported. The graphene film, grown by thermal chemical vapor deposition, contains three to five layers of monolayer graphene, as confirmed by Raman spectroscopy and high‐resolution transmission electron microscopy. Further, the graphene film is treated with CF₄ reactive‐ion plasma and fluorine ions are successfully doped into graphene as confirmed by X‐ray photoelectron spectroscopy and UV‐photoemission spectroscopy. The fluorinated graphene shows no structural deformations compared to the pristine graphene except an increase in surface roughness. Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction increases with increasing plasma treatment time, which is attributed to an increase in catalytic sites. Further, the fluorinated graphene is characterized in use as a counter‐electrode in a full dye‐sensitized solar cell and shows ca. 2.56% photon to electron conversion efficiency with ca. 11 mA cm^?2 current density. The shift in work function in F^? doped graphene is attributed to the shift in graphene redox potential which results in graphene's electrocatalytic‐activity enhancement.     

Ionic‐Liquid‐Doped Polyaniline Inverse Opals: Preparation,Characterization, and Application for the Electrochemical Impedance Immunoassay of Hepatitis B Surface Antigen

A 3D ordered macroporous (3DOM) ionic‐liquid‐doped polyaniline (IL‐PANI) inverse opaline film is fabricated with an electropolymerization method and gold nanoparticles (AuNPs) are assembled on the film by electrostatic adsorption, which offers a promising basis for biomolecular immobilization due to its satisfactory chemical stability, good electronic conductivity, and excellent biocompatibility. The AuNP/IL‐PANI inverse opaline film could be used to fabricate an electrochemical impedance spectroscopy (EIS) immunosensor for the determination of Hepatitis B surface antigen (HBsAg). The concentration of HBsAg is measured using the EIS technique by monitoring the corresponding specific binding between HBsAg and HBsAb (surface antibody). The increased electron transfer resistance (R_et) values are proportional to the logarithmic value of the concentration of HBsAg. This novel immunoassay displays a linear response range between 0.032 pg mL^?1 and 31.6 pg mL^?1 with a detection limit of 0.001 pg mL^?1. The detection of HBsAg levels in several sera showed satisfactory agreement with those using a commercial turbidimetric method.     

Synthesis of Potassium‐Modified Graphene and Its Application in Nitrite‐Selective Sensing

Chemical modification with foreign atoms is a leading strategy to intrinsically modify the properties of host materials. Among them, potassium (K) modification plays a critical role in adjusting the electronic properties of carbon materials. Graphene, a true 2D carbon material, has shown fascinating applications in electrochemical sensing and biosensing. In this work, a facile and mild strategy to K‐modifying in graphene at room‐temperature is reported for the first time. X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectra, and cyclic voltammetry are used to characterize this K‐modified graphene. The K‐modified graphene is capable of acting as an electron transfer medium and more efficiently promotes charge transfer than unmodified graphene. A highly sensitive and stable amperometric sensor based on its excellent electrocatalytic activity toward the oxidation of NO₂^? is proposed. The sensor shows a linear range from 0.5 μM to 7.8 mM with a detection limit of 0.2 μM at a signal‐to‐noise ratio of 3. The modified electrode has excellent analytical performance and can be successfully applied in the determination of NO₂^? released from liver cancer and leukemia cells and shows good application potential in biological systems.     

Ultrasensitive Detection of a Variety of Analytical Targets Based on a Functionalized Low‐Resistance AuNPs/β‐Ni(OH)2 Nanosheets/Ni Foam Sensing Platform

Simple, low‐cost and yet accurate, sensitive, and quantitative detection of a broad range of analytical targets by means of small footprint sensing devices has the potential to revolutionize medical diagnostics, food safety, and environmental monitoring. This work demonstrates a functional nucleic acids (FNAs) tethered AuNPs/β‐Ni(OH)₂ nanosheets (NS)/Ni foam nanocomposite as a miniaturized electrode. Through the rational design of a low‐barrier ohmic contact of AuNPs to β‐Ni(OH)₂ NS and a target mediated nanochannel electron transfer effect, a variety of analytical targets, ranging from a disease marker (thrombin, 16.3 × 10^?12 m detection limit) to an important biological cofactor (adenosine, 3.2 × 10^?12 m detection limit), and to a toxic metal ion (Hg²⁺, 3.1 × 10^?12 m detection limit), are detected with ultrasensitivity. The presence of target triggers the conformational change of FNAs, introducing strong steric hindrance and electrostatic repulsion to the diffusion of electron indicators toward the electrode surface, ultimately leading to the changes in impedance. A novel equivalent circuit considering the capacitive reactance is proposed to describe the 2D NS‐based impedance DNA bioelectrode. This sensing platform is easily applicable to the detection of many other targets in diverse sample matrices through the use of other suitable FNAs materials.     

Graphene‐Based Actuator with Integrated‐Sensing Function

Flexible actuators have important applications in artificial muscles, robotics, optical devices, and so on. However, most of the conventional actuators have only actuation function, lacking in real‐time sensing signal feedbacks. Here, to break the limitation and add functionality in conventional actuators, a graphene‐based actuator with integrated‐sensing function is reported, which avoids the dependence on image post‐processing for actuation detection and realizes real‐time measurement of the shape‐deformation amplitudes of the actuator. The actuator is able to show a large bending actuation (curvature of 1.1 cm^?1) based on a dual‐mode actuation mechanism when it is driven by near infrared light. Meanwhile, the relative resistance change of the actuator is ?17.5%. The sensing function is attributed to piezoresistivity and thermoresistivity of the reduced graphene oxide and paper composite. This actuator can be used as a strain sensor to monitor human motions. A smart gripper based on the actuators demonstrates perfect integration of the actuating and sensing functions, which can not only grasp and release an object, but also sense every actuation state of the actuator. The developed integrated‐sensing actuator is hopeful to open new application fields in soft robotics, artificial muscles, flexible wearable devices, and other integrated‐multifunctional devices.     

Humidity‐Tolerant Single‐Stranded DNA‐Functionalized Graphene Probe for Medical Applications of Exhaled Breath Analysis

Highly sensitive and selective chemiresistive sensors based on graphene functionalized by metals and metal oxides have attracted considerable attention in the fields of environmental monitoring and medical assessment because of their ultrasensitive gas detecting performance and cost‐effective fabrication. However, their operation, in terms of detection limit and reliability, is limited in traditional applications because of ambient humidity. Here, the enhanced sensitivity and selectivity of single‐stranded DNA‐functionalized graphene (ssDNA‐FG) sensors to NH₃ and H₂S vapors at high humidity are demonstrated and their sensing mechanism is suggested. It is found that depositing a layer of ssDNA molecules leads to effective modulation of carrier density in graphene, as a negative‐potential gating agent and the formation of an additional ion conduction path for proton hopping in the layer of hydronium ions (H₃O⁺) at high humidity (>80%). Considering that selectively responsive chemical vapors are biomarkers associated with human diseases, the obtained results strongly suggest that ssDNA‐FG sensors can be the key to developing a high‐performance exhaled breath analyzer for diagnosing halitosis and kidney disorder.     

Photoluminescence Detection of Biomolecules by Antibody‐Functionalized Diatom Biosilica

Diatoms are single‐celled algae that make microscale silica shells called “frustules”, which possess intricate nanoscale features imbedded within periodic two‐dimensional pore arrays. In this study, antibody‐functionalized diatom biosilica frustules serve as a microscale biosensor platform for selective and label‐free photoluminescence (PL)‐based detection of immunocomplex formation. The model antibody rabbit immunoglobulin G (IgG) is covalently attached to the frustule biosilica of the disk‐shaped, 10‐µm diatom Cyclotella sp. by silanol amination and crosslinking steps to a surface site density of 3948 ± 499 IgG molecules µm^?2. Functionalization of the diatom biosilica with the nucleophilic IgG antibody amplifies the intrinsic blue PL of diatom biosilica by a factor of six. Furthermore, immunocomplex formation with the complimentary antigen anti‐rabbit IgG further increases the peak PL intensity by at least a factor of three, whereas a non‐complimentary antigen (goat anti‐human IgG) does not. The nucleophilic immunocomplex increases the PL intensity by donating electrons to non‐radiative defect sites on the photoluminescent diatom biosilica, thereby decreasing non‐radiative electron decay and increasing radiative emission. This unique enhancement in PL emission is correlated to the antigen (goat anti‐rabbit IgG) concentration, where immunocomplex binding follows a Langmuir isotherm with binding constant of 2.8 ± 0.7 × 10^?7 M .