Tunable Nano-Bending Structures of Loosened/Tightened Lassos with Bi-Stable Vibration-Induced Emissions for Multi-Manipulations of White-Light Emissions And Sensor Applications.

The first tunable nano-bending structures of [1]rotaxane containing a single-fluorophoric N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC) moiety (i.e., [1]RA) is developed as a loosened lasso structure to feature the bright white-light emission [CIE (0.27, 0.33), Φ = 21.2%] in THF solution, where bi-stable states of bending and twisted structures of DPAC unit in [1]RA with cyan and orange emissions at 480 and 600 nm, respectively. With acid/base controls, tunable loosened/tightened nano-loops of corresponding [1]rotaxanes (i.e., [1]RA/[1]RB) can be achieved via the shuttling of macrocycles reversibly, and thus to adjust their respective white-light/cyan emissions, where the cyan emission of [1]RB is obtained due to the largest conformational constraint of DPAC moiety in its bending form of [1]RB with a tightened lasso structure. Additionally, the non-interlocked analogue M-Boc only shows the orange emission, revealing the twisted form of DPAC fluorophore in M-Boc without any conformational constraint. Moreover, the utilization of solvents (with different viscosities and polarities), temperatures, and water fractions could serve as effective tools to adjust the bi-stable vibration-induced emission (VIE) colors of [1]rotaxanes. Finally, tuning ratiometric emission colors of adaptive conformations of DPAC moieties by altering nano-bending structures in [1]rotaxanes and external stimuli can be further developed as intelligent temperature and viscosity sensor materials. This article is protected by copyright. All rights reserved.

Guanidinium-Functionalized Polymer Dielectrics for Triboelectric Bacterial Detection.

Development of rapid detection strategies that target potentially pathogenic bacteria has gained increasing attention due to the increasing awareness for better health and safety. In this study, we evaluate an intrinsically antimicrobial polymer, 2Gdm, which is a poly(norbornene)-based functional polymer featuring guanidinium groups as side chains, for bacterial detection by the means of triboelectric nanogenerators (TENGs) and triboelectric nanosensors (TENSs). Attachment of bacteria to the sensing layer is anticipated to alter the overall triboelectric properties of the underlying polymer layer. The positively charged guanidinium functional groups can interact with the negatively charged phospholipid bilayer of bacteria and lead to bacterial death, which can then be detected by optical microscopy, X-ray photoelectron microscopy, and more advanced self-powered sensing techniques such as TENGs and TENSs. The double bonds present along the poly(norbornene) backbone allow for thermally induced cross-linking to obtain X-2Gdm and thus rendering materials remain stable in water. By monitoring the change in voltage output after immersion in various concentrations of Gram-negative Escherichia coli (E. coli) and Gram-positive Streptococcus pneumoniae (S. pneumoniae), we have demonstrated the utility of X-2Gdm as a new polymer dielectric for autonomous bacterial detection. As the bacterial concentration increases, the amount of adsorbed bacteria also increases, resulting in a decrease in the surface potential of the X-2Gdm thin film; this reduction in surface potential can cause a decrease in the triboelectric output for both TENGs and TENSs, which serves as a key working mechanism for facile bacterial detection. TENG and TENS systems are capable of detecting E. coli and S. pneumoniae within a range of 4 × 105 to 4 × 108 CFU/mL with a limit of detection of 106 CFU/mL. This report highlights the promising prospects of employing TENGs and TENSs as innovative sensing technologies for rapid bacterial detection by leveraging the electrostatic interactions between bacterial cell membranes and cationic groups present on polymer surfaces.

Controllable Aggregation-Induced Emission and Förster Resonance Energy Transfer Behaviors of Bistable [c2] Daisy Chain Rotaxanes for White-Light Emission and Temperature-Sensing Applications.

Bistable [c2] daisy chain rotaxanes with respective extended and contracted forms of [c2]A and [c2]B containing a blue-emissive anthracene (AN) donor and orange-emissive indandione-carbazole (IC) acceptor were successfully synthesized via click reaction. Tunable-emission bistable [c2] daisy chain rotaxanes with fluorescence changes from blue to orange, including bright-white-light emissions, could be modulated by the aggregation-induced emission (AIE) characteristics and Förster resonance energy transfer (FRET) processes through altering water fractions and shuttling processes (i.e., acid/base controls). Accordingly, as a result of excellent fine-tuning AIE (at 60% water content of H2O/THF) and FRET (with a compatible energy transfer of EFRET = 33.2%) behaviors after the shuttling process (by adding base), the brightest white-light emission at CIE (0.31, 0.37) with a quantum yield of Φ = 15.64% was obtained in contracted [c2]B with good control of molecular shuttling to possess higher photoluminescence (PL) quantum yields and better energy transfer efficiencies (i.e., the manipulation of reduced PET and enhanced FRET processes) due to their intramolecular aggregations of blue AN donors and orange IC acceptors with a proper water content of 60% H2O. Furthermore, dynamic light-scattering (DLS) and time-resolved photoluminescence (TRPL) measurements, along with theoretical calculations, were utilized to investigate and confirm AIE and FRET phenomena of bistable [c2] daisy chain rotaxanes. Especially, both bistable [c2] daisy chain rotaxanes [c2]A and [c2]B and noninterlocked monomer M could be exploited for the applications of ratiometric fluorescence temperature sensing due to the temperature effects on the AIE and FRET features. Based on these desirable bistable [c2] daisy chain rotaxane structures, this work provides a potential strategy for the future applications of tunable multicolor emission and ratiometric fluorescence temperature-sensing materials.

Crystal structure and identification of amino acid residues for catalysis and binding of GH3 AnBX ß-xylosidase from Aspergillus niger.

ß-Xylosidases catalyze the hydrolysis of xylooligosaccharides to xylose in the final step of hemicellulose degradation. AnBX, which is a GH3 ß-xylosidase from Aspergillus niger, has a high catalytic efficiency toward xyloside substrates. In this study, we report the three-dimensional structure and the identification of catalytic and substrate binding residues of AnBX by performing site-directed mutagenesis, kinetic analysis, and NMR spectroscopy-associated analysis of the azide rescue reaction. The structure of the E88A mutant of AnBX, determined at 2.5-Å resolution, contains two molecules in the asymmetric unit, each of which is composed of three domains, namely an N-terminal (ß/α)8 TIM-barrel-like domain, an (α/ß)6 sandwich domain, and a C-terminal fibronectin type III domain. Asp288 and Glu500 of AnBX were experimentally confirmed to act as the catalytic nucleophile and acid/base catalyst, respectively. The crystal structure revealed that Trp86, Glu88 and Cys289, which formed a disulfide bond with Cys321, were located at subsite -1. Although the E88D and C289W mutations reduced catalytic efficiency toward all four substrates tested, the substitution of Trp86 with Ala, Asp and Ser increased the substrate preference for glucoside relative to xyloside substrates, indicating that Trp86 is responsible for the xyloside specificity of AnBX. The structural and biochemical information of AnBX obtained in this study provides invaluable insight into modulating the enzymatic properties for the hydrolysis of lignocellulosic biomass. KEY POINTS: • Asp288 and Glu500 of AnBX are the nucleophile and acid/base catalyst, respectively • Glu88 and the Cys289-Cys321 disulfide bond are crucial for the catalytic activity of AnBX • The W86A and W86S mutations in AnBX increased the preference for glucoside substrates.

Dual and sequential locked/unlocked photo-switching effects on FRET processes by tightened/loosened nano-loops of diarylethene-based [1]rotaxanes.

The self-trapping nano-loop structures of [1]rotaxanes exhibited multiple Förster resonance energy transfer (FRET) patterns via dual and sequential locking/unlocking of pH-gated and UV exposure processes. As a tightened and constrained nano-loop in the acidic condition, dithienylethene (DTE) unit was locked in the highly bending open form to forbid ring closure upon UV irradiation.

Dual and Sequential Locked/Unlocked Photochromic Effects on FRET Controlled Singlet Oxygen Processes by Contracted/Extended Forms of Diarylethene-Based [1]Rotaxane Nanoparticles.

Manipulations of singlet oxygen (1 O2 ) generations by the integration of both aggregation-induced emission luminogen (AIEgen) photosensitizer and photochromic moieties have diversified features in photodynamic therapy applications. Through Förster resonance energy transfer (FRET) pathway to induce red PL emissions (at 595 nm) for 1 O2 productions, [1]rotaxane containing photosensitive tetraphenylethylene (TPE) donor and photochromic diarylethene (DAE) acceptor is introduced to achieve dual and sequential locked/unlocked photoswitching effects by pH-controlled shuttling of its contracted/extended forms. Interestingly, the UV-enabled DAE ring closure speeds follow the reversed trend of DAE self-constraint degree as: contracted < extended < noninterlocked forms in [1]rotaxane analogues, thus FRET processes can be adjusted in contracted/extended forms of [1]rotaxane upon UV irradiations. Accordingly, the contracted form of [1]rotaxane is FRET-OFF locked and inert to UV exposure due to the larger bending conformation of DAE parallel (p-)conformer, compared with its extended and noninterlocked analogues possessing switchable FRET-OFF/ON behaviors activated by dual and sequential pH- and photoswitching. Owing to the advantages of 1 O2 productions tuned by multistimuli inputs (pH, UV, and blue light), an useful logic circuit for toxicity outputs of the surface modified [1]rotaxane nanoparticles (NPs) has been demonstrated to offer promising 1 O2 productions and managements based on mechanically interlocked molecules for future bioapplications.

Selection and Characterization of a Single-Chain Variable Fragment against Porcine Circovirus Type 2 Capsid and Impedimetric Immunosensor Development.

Porcine circovirus type 2 (PCV2) is the primary causative agent of porcine circovirus-associated disease (PCVAD) that causes huge global economic losses for the swine industry. Effective strategies or rapid detection of PCV2 in pig are essential to control PCVAD. Here, single-chain variable fragments (scFvs) were selected and characterized against the PCV2 capsid using phage display technology. Phage scFv clones were selected from the human scFv phagemid library (Tomlinson I + J) for direct panning against the PCV2 capsid. Eighty-four monoclonal phage scFvs were individually tested for binding to the PCV2 capsid by ELISA. Eight scFv clones showed significant binding to the PCV2 capsid and only three clones (clone nos. 13, 37, and 81) contained both VHCDRs and VLCDRs in the sequence. Clone scFv no. 81 had the highest reactivity to the PCV2 capsid and was constructed in the pET22b (+) expression vector. The recombinant was transformed to Escherichia coli BL21(DE3) for expression and purification. The scFv showed appropriate affinity to the PCV2 capsid by western blot analysis. Kinetics of scFv and the PCV2 capsid were determined using surface plasmon resonance and showed binding affinity in the nanomolar range (K D = 57.2 nM). Our scFv was first applied in the development of an impedimetric immunosensor for PCV2 capsid detection, and results showed that impedance increased with increasing PCV2 capsid expression with limit of detection = 114 nM. Findings demonstrated that our scFv has potential for use as a receptor for biosensor devices.

Exploring Volatile Organic Compounds in Breath for High-Accuracy Prediction of Lung Cancer.

(1) Background: Lung cancer is silent in its early stages and fatal in its advanced stages. The current examinations for lung cancer are usually based on imaging. Conventional chest X-rays lack accuracy, and chest computed tomography (CT) is associated with radiation exposure and cost, limiting screening effectiveness. Breathomics, a noninvasive strategy, has recently been studied extensively. Volatile organic compounds (VOCs) derived from human breath can reflect metabolic changes caused by diseases and possibly serve as biomarkers of lung cancer. (2) Methods: The selected ion flow tube mass spectrometry (SIFT-MS) technique was used to quantitatively analyze 116 VOCs in breath samples from 148 patients with histologically confirmed lung cancers and 168 healthy volunteers. We used eXtreme Gradient Boosting (XGBoost), a machine learning method, to build a model for predicting lung cancer occurrence based on quantitative VOC measurements. (3) Results: The proposed prediction model achieved better performance than other previous approaches, with an accuracy, sensitivity, specificity, and area under the curve (AUC) of 0.89, 0.82, 0.94, and 0.95, respectively. When we further adjusted the confounding effect of environmental VOCs on the relationship between participants' exhaled VOCs and lung cancer occurrence, our model was improved to reach 0.92 accuracy, 0.96 sensitivity, 0.88 specificity, and 0.98 AUC. (4) Conclusion: A quantitative VOCs databank integrated with the application of an XGBoost classifier provides a persuasive platform for lung cancer prediction.

Controllable FRET Behaviors of Supramolecular Host-Guest Systems as Ratiometric Aluminum Ion Sensors Manipulated by Tetraphenylethylene-Functionalized Macrocyclic Host Donor and Multistimuli-Responsive Fluorescein-Based Guest Acceptor.

The novel multistimuli-responsive monofluorophoric supramolecular polymer Poly(TPE-DBC)/FL-DBA and pseudo[3]rotaxane TPE-DBC/FL-DBA consisted of the closed form of nonemissive fluorescein guest FL-DBA along with TPE-based main-chain macrocyclic polymer Poly(TPE-DBC) and TPE-functionalized macrocycle TPE-DBC hosts, respectively. By the combination of various external stimuli, these fluorescent supramolecular host-guest systems could reveal interesting photoluminescence (PL) properties in DMF/H2O (1:1, v/v) solutions, including bifluorophoric host-guest systems after the complexation of Al3+ ion, i.e., TPE-DBC/FL-DBA-Al3+ and Poly(TPE-DBC)/FL-DBA-Al3+ with their corresponding open form of fluorescein guest FL-DBA-Al3+. Importantly, the Förster resonance energy transfer (FRET) processes occurred in both bifluorophoric host-guest systems between blue-emissive TPE donors (λem = 470 nm) and green-emissive fluorescein acceptors (λem = 527 nm) after aluminum detection, which were further verified by time-resolved photoluminescence (TRPL) measurements to acquire their FRET efficiencies of 40.4 and 31.1%, respectively. Both supramolecular host-guest systems exhibited stronger green fluorescein emissions as well as appealing ratiometric PL behaviors within the desirable donor-acceptor distances of FRET processes in comparison with their detached analogous mixtures. Regarding the pH effects, the optimum green fluorescein emissions with effective FRET processes of all compounds and host-guest systems were sustained in the range pH = 7-10. Interestingly, both host-guest systems TPE-DBC/FL-DBA and Poly(TPE-DBC)/FL-DBA possessed high sensitivities and selectivities toward aluminum ion to display their strong green emissions via FRET-ON behaviors due to the chelation-induced ring opening of spirolactam moieties to become green-emissive guest acceptor FL-DBA-Al3+, which offered excellent limit of detection (LOD) values of 50.61 and 38.59 nM, respectively, to be further applied for the fabrication of facile test strips toward aluminum detection. Accordingly, the inventive ratiometric PL and FRET sensor approaches of supramolecular host-guest systems toward aluminum ion with prominent sensitivities and selectivities were well-established in this study.

Integration of Ni/NiO nanoparticles and a microfluidic ELISA chip to generate a sensing platform for Streptococcus pneumoniae detection.

Enzyme-linked immunosorbent assays (ELISAs) are tests that uses antibody recognition and enzyme catalytic activity to identify a substance, and they have been widely used as a diagnostic tool in the clinic. However, performing an ELISA requires various liquid handling steps and long binding times. To solve this problem, we developed a magnetic microfluidic ELISA system (MMF-ELISA). Integration with nickel magnetic nanoparticles can streamline the ELISA process in a fully automated manner for Streptococcus pneumoniae detection. First, we synthesized paramagnetic surface-oxidized nickel nanoparticles (Ni/NiO NPs) to carry protein G. Then, we assembled a SUM290 (UlaG)-specific antibody on protein G. Finally, we integrated the NPs on a microfluidics chip for S. pneumoniae detection. The chip contains three different layers to trap the solutions; the bottom layer SiO2 is patterned on hydrophobic polymers and integrated with the middle layer PDMS and the top layer PMMA. With Arduino and motor IC, we developed an automated platform for S. pneumoniae detection. Microfluidic ELISAs can reduce the manual handling and operation time. Furthermore, the developed system can be extended to multiple areas for ELISA-related assays. This economical, rapid and portable system may become a promising platform for sensing S. pneumoniae in clinical applications.

Efficient FRET Approaches toward Copper(II) and Cyanide Detections via Host-Guest Interactions of Photo-Switchable [2]Pseudo-Rotaxane Polymers Containing Naphthalimide and Merocyanine Moieties.

A supramolecular [2]pseudo-rotaxane containing a naphthalimide-based pillararene host and a spiropyran-based imidazole guest was synthesized and investigated in a semiaqueous solution with 90% water fraction. Upon UV exposure, the close-form structure of nonemissive spiropyran guest could be transformed into the open-form structure of red-emissive merocyanine guest reversibly, which was utilized as a monofluorophoric sensor to detect copper(II) and cyanide ions. Moreover, the naphthalimide host as an energy donor with green photoluminescence (PL) emission at 505 nm was complexed with the merocyanine guest as an energy acceptor with red PL emission at 650 nm in 1:1 molar ratio to generate a [2]pseudo-rotaxane polymer, which was further verified by the diffusion coefficients of DOSY nuclear magnetic resonance (NMR) measurements. Due to the Förster resonance energy transfer (FRET) processes, the bifluorophoric [2]pseudo-rotaxane produced more efficient ratiometric PL behavior to induce a stronger red PL emission than that of the monofluorophoric guest; therefore, the PL sensor responses of the supramolecular [2]pseudo-rotaxane toward copper(II) and cyanide ions could be further amplified via the FRET-OFF processes to turn off red PL emission of the reacted merocyanine acceptor and to recover green PL emission of the naphthalimide donor. Accordingly, the best and prominent values of the limit of detection (LOD) for the host-guest detections toward Cu2+ and CN- were 0.53 and 1.34 µM, respectively. The highest red MC emission with the optimum FRET processes of [2]pseudo-rotaxane was maintained around room temperature (20-40 °C) in wide pH conditions (pH = 3-13), which can be utilized in the cell viability tests to prove the nontoxic and remarkable biomarker of [2]pseudo-rotaxane to detect Cu2+ and CN- in living cells. The developed FRET-OFF processes with ratiometric PL behavior of the bifluorophoric supramolecular [2]pseudo-rotaxane polymer will open a new avenue to the future applications of chemo- and biosensors.

Synthesis of hyaluronic acid oligosaccharides with a GlcNAc-GlcA repeating pattern and their binding affinity with CD44.

Hyaluronic acid (HA) is a ubiquitous glycosaminoglycan in the extracellular matrix and a ligand of CD44, a transmembrane glycoprotein that is important in cell migration. Crystal and NMR studies found a hexasaccharide of the pattern (GlcA-GlcNAc)3 as the shortest HA that could bind to CD44, but molecular dynamics simulations indicated that a tetrasaccharide of the pattern (GlcNAc-GlcA)2 is the key structure interacting with CD44. Access to oligomers with such a repeat pattern is crucial in binding studies with CD44. Here we developed a synthetic procedure to afford the HA oligosaccharides with the GlcNAc-GlcA repeating unit and measured the binding interaction between these sugars and human CD44 by isothermal titration calorimetry (ITC). During the chemical synthesis, we successfully generated the ß-glycosidic bond in the absence of neighbouring group participation and overcome the issues in the oxidation step. In addition, ammonia-free dissolving metal reduction for debenzylation and azido reduction has been applied in carbohydrate synthesis for the first time. ITC analysis revealed that the HA tetrasaccharide (GlcNAc-GlcA)2 could indeed interact and bind to the human CD44.

Infrared Spectra of (Z)- and (E)-•C2H3C(CH3)I Radicals Produced upon Photodissociation of (Z)- and (E)-(CH2I)HC═C(CH3)I in Solid para-Hydrogen.

Ozonolysis of isoprene to produce Criegee intermediates such as methyl vinyl ketone oxide (MVKO), C2H3C(CH3)OO, is an important process in atmospheric chemistry. MVKO was recently produced and identified in laboratories after photolysis of a gaseous mixture of 1,3-diiodo-but-2-ene, (CH2I)HC═C(CH3)I, and O2, but the mechanism of its formation remains unexplored. We synthesized pure (Z)- and (E)-1,3-diiodo-but-2-ene and measured their distinct IR spectra. Upon irradiation at 280 nm of (Z)- and (E)-1,3-diiodo-but-2-ene in solid p-H2 at 3.3 K, the fission of the terminal C-I bond yields (Z)- and (E)-3-iodo-but-2-en-1-yl [•C2H3C(CH3)I] radicals, respectively. These radicals were characterized with infrared absorption lines at 2962.4, 1423.8, 1265.3, 1120.9/1127.0, 921.4/922.3, and 792.5/791.7 cm-1, and 16 additional weaker lines for (Z)-•C2H3C(CH3)I and 1405.2, 1208.2, 1106.0/1103.9, 934.2/933.4, and 785.1/784.9 cm-1 and five additional weaker ones for (E)-•C2H3C(CH3)I. The assignments were derived according to behavior on secondary photolysis and comparison of the vibrational wavenumbers and the IR intensities of observed lines with those calculated with the B2PLYP-D3/aug-cc-pVTZ-pp method. These observations confirmed that only the terminal I atom, not the central one, was photodissociated at 280 nm and, in solid p-H2, the excess energy after photodissociation induced no change in conformation. These new spectra of •C2H3C(CH3)I radicals can provide valuable information for the understanding of the mechanism of formation of Criegee intermediate MVKO from the source reaction of photolysis of (CH2I)HC═C(CH3)I in O2 in the laboratory.

Linker and N-Terminal Domain Engineering of Pyrrolysyl-tRNA Synthetase for Substrate Range Shifting and Activity Enhancement.

The Methanosarcina mazei pyrrolysyl-tRNA synthetase (PylRS)⋅tRNAPyl pair can be used to incorporate non-canonical amino acids (ncAAs) into proteins at installed amber stop codons. Although engineering of the PylRS active site generates diverse binding pockets, the substrate ranges are found similar in charging lysine and phenylalanine analogs. To expand the diversity of the ncAA side chains that can be incorporated via the PylRS⋅tRNAPyl pair, exploring remote interactions beyond the active site is an emerging approach in expanding the genetic code research. In this work, remote interactions between tRNAPyl, the tRNA binding domain of PylRS, and/or an introduced non-structured linker between the N- and C-terminus of PylRS were studied. The substrate range of the PylRS⋅tRNAPyl pair was visualized by producing sfGFP-UAG gene products, which also indicated amber suppression efficiencies and substrate specificity. The unstructured loop linking the N-terminal and C-terminal domains (CTDs) of PylRS has been suggested to regulate the interaction between PylRS and tRNAPyl. In exploring the detailed role of the loop region, different lengths of the linker were inserted into the junction between the N-terminal and the C-terminal domains of PylRS to unearth the impact on remote effects. Our findings suggest that the insertion of a moderate-length linker tunes the interface between PylRS and tRNAPyl and subsequently leads to improved suppression efficiencies. The suppression activity and the substrate specificity of PylRS were altered by introducing three mutations at or near the N-terminal domain of PylRS (N-PylRS). Using a N-PylRS⋅tRNAPyl pair, three ncAA substrates, two S-benzyl cysteine and a histidine analog, were incorporated into the protein site specifically.

Selective Control of Cell Activity with Hydrophilic Polymer-Covered Cationic Nanoparticles.

Cationic polymers exhibit high cytotoxicity via strong interaction with cell membranes. To reduce cell membrane damage, a hydrophilic polymer is introduced to the cationic nanoparticle surface. The hydrophilic polymer coating of cationic nanoparticles resulted in a nearly neutral nanoparticle. These particles are applied to mouse fibroblast (3T3) and human cervical adenocarcinoma (Hela) cells. Interestingly, nanoparticles with a long cationic segment decrease cell activity regardless of cell type, while those with a short segment only affect 3T3 cell activity at lower concentrations less than 500 µg mL-1 . Most nanoparticles are located inside 3T3 cells but on the cell membrane of Hela cells. The short cationic nanoparticle shows negligible cell membrane damage despite its high accumulation on Hela cell membranes. Cell activity changed by hydrophilic polymer-coated cationic nanoparticles is caused by incorporated nanoparticle accumulation in the cells, not cell membrane damage. To suppress the cytotoxicity from the cationic polymer, cationic nanoparticle needs to completely cover with hydrophilic polymer so as not to exhibit the cationic effect and applies to cell with low concentrations to reduce the nonselective cytotoxicity from the cationic polymer.

An antifouling peptide-based biosensor for determination of Streptococcus pneumonia markers in human serum.

We report a peptide-based sensor that involves a multivalent interaction with L-ascorbate 6-phosphate lactonase (UlaG), a protein marker of Streptococcus pneumonia. By integrating the antifouling feature of the sensor, we significantly improved the signal-to-noise ratio of UlaG detection. The antifouling surface was fabricated via electrodeposition using an equivalent mixture of 4-amino-N,N,N-trimethylanilinium and 4-aminobenzenesulfonate. This antifouling layer not only effectively reduces the non-specific adsorption on the biosensor but also decreases the charge transfer resistance (Rct) of the screen-printed carbon electrode. The aniline-modified S7 peptide, an UlaG-binding peptide, was pre-synthesized and further electrochemically modified to bind onto the antifouling layer. Bio-electrochemical analysis confirms that the antifouling S7-peptide sensor binds strongly to the UlaG with a dissociation constant (Kd) = 0.5 nM. This strong interaction can be attributed to a multivalent interaction between the biosensor and the heximeric form of UlaG. To demonstrate the potential for clinical application, further detection of Streptococcus pneumonia from 50 to 5×104 CFU/mL were successfully performed in 25% human serum.

Single-Step Per-O-Sulfonation of Sugar Oligomers with Concomitant 1,6-Anhydro Bridge Formation for Binding Fibroblast Growth Factors.

Many circulating cancer-related proteins, such as fibroblast growth factors (FGFs), associate with glycosaminoglycans-particularly heparan sulfate-at the cell surface. Disaccharide analogues of heparan sulfate had previously been identified as the shortest components out of the sugars that bind to FGF-1 and FGF-2. Taking note of the typical pose of l-iduronic acid, we conceived of per-O-sulfonated analogues of such disaccharides, and devised a single-step procedure for per-O-sulfonation of unprotected sugars with concomitant 1,6-anhydro bridge formation to achieve such compounds through direct use of SO3 ⋅Et3 N as sulfonation reagent and dimethylformamide as solvent. The synthesized sugars based on the oligomaltose backbone bound FGF-1 and FGF-2 mostly at the sub-micromolar level, although the tetrasaccharide analogue achieved low-nanomolar binding with FGF-2.

Effective Construction of a High-Capacity Boronic Acid Layer on a Quartz Crystal Microbalance Chip for High-Density Antibody Immobilization.

Boronic acids (BAs) provide strong potential in orientation immobilization of antibody and the modification method is crucial for efficiency optimization. A highly effective method has been developed for rapid antibody immobilization on gold electrodes through the electrodeposition of a BA⁻containing linker in this study. Aniline-based BA forms a condense layer while antibody could automatically immobilize on the surface of the electrode. Compare to traditional self-assembled monolayer method, the electrodeposition process dramatically reduces the modification time from days to seconds. It also enhances the immobilized efficiency from 95 to 408 (ng/cm²) with a strong preference being exhibited for shorter aniline-based linkers.

Magnetic Fe@FeOx, Fe@C and α-Fe2O3 Single-Crystal Nanoblends Synthesized by Femtosecond Laser Ablation of Fe in Acetone.

There are few reports on zero-field-cooled (ZFC) magnetization measurements for Fe@FeOx or FeOx particles synthesized by laser ablation in liquids (LAL) of Fe, and the minimum blocking temperature (TB) of 120 K reported so far is still much higher than those of their counterparts synthesized by chemical methods. In this work, the minimum blocking temperature was lowered to 52 K for 4⁻5 nm α-Fe2O3 particles synthesized by femtosecond laser ablation of Fe in acetone. The effective magnetic anisotropy energy density (Keff) is calculated to be 2.7⁻5.4 × 105 J/m³, further extending the Keff values for smaller hematite particles synthesized by different methods. Large amorphous-Fe@α-Fe2O3 and amorphous-Fe@C particles of 10⁻100 nm in diameter display a soft magnetic behavior with saturation magnetization (Ms) and coercivities (Hc) values of 72.5 emu/g and 160 Oe at 5 K and 61.9 emu/g and 70 Oe at 300 K, respectively, which mainly stem from the magnetism of amorphous Fe cores. Generally, the nanoparticles obtained by LAL are either amorphous or polycrystalline, seldom in a single-crystalline state. This work also demonstrates the possibility of synthesizing single-crystalline α-Fe2O3 hematite crystals of several nanometers with (104), (113), (116) or (214) crystallographic orientations, which were produced simultaneously with other products including carbon encapsulated amorphous Fe (a-Fe@C) and Fe@FeOx core-shell particles by LAL in one step. Finally, the formation mechanisms for these nanomaterials are proposed and the key factors in series events of LAL are discussed.

Two Birds with One Stone: Spontaneous Size Separation and Growth Inhibition of Femtosecond Laser-Generated Surfactant-Free Metallic Nanoparticles via ex Situ SU-8 Functionalization.

Laser ablation in liquids (LAL) offers a facile technique to develop a large variety of surfactant-free nanomaterials with high purity. However, due to the difficulty in the control of the particle synthesis process, the as-prepared nanomaterials always have a broad size distribution with a large polydispersity (σ). Surfactant-free properties can also cause problems with particle growth, which further increases the difficulty in size control of the colloids. Therefore, searching for strategies to simultaneously unify the sizes of colloids and inhibit particle growth has become significantly important for LAL-synthesized nanomaterials to be extensively used for biological, catalytic, and optical applications, in which fields particle size plays an important role. In this work, we present a facile way to simultaneously realize these two goals by ex situ SU-8 photoresist functionalization. Ag nanoparticles (NPs) synthesized by femtosecond laser ablation of silver in acetone at laser powers of 300 and 600 mW were used as starting materials. The synthesized Ag NPs have a broad size distribution between 1 and 200 nm with an average size of ca. 5.9 nm and σ of 127-207%. After ex situ SU-8 functionalization and 6 months storage, most particles larger than 10 nm become aggregates and precipitate, which makes the size distribution narrow with an average diameter of 4-5 nm and σ of 48-78%. The precipitation process is accompanied by the decrease in colloid mass from the initial ∼0.2 to 0.10-0.11 mg after ex situ SU-8 functionalization and 6 months colloid storage. Morphology analysis indicates that ex situ SU-8 functionalization inhibits the particle growth into polygonal nanocrystals. Radical polymerization of SU-8 on Ag NPs is considered to be the reason for both spontaneous size separation and growth inhibition phenomena. Benefiting from Ag NPs embedment and acetone dissolution, the glass-transition temperature of SU-8 photoresist increased from 314 to 331 °C according to thermogravimetric analysis. The universality of ex situ SU-8 functionalization-induced growth inhibition and size separation behaviors is further proved using the Au colloids generated by LAL in acetone. This work is expected to provide a new route for better size control of LAL-synthesized colloids via ex situ photoresist functionalization, although a half of colloidal mass is wasted due to radical polymerization-induced colloidal precipitation.