High-Resolution and Dynamic Visualization of Intracellular Redox Potential Using a Metal-Organic Framework-Functionalized Nanopotentiometer.

Redox potential plays a key role in regulating intracellular signaling pathways, with its quantitative analysis in individual cells benefiting our understanding of the underlying mechanism in the pathophysiological events. Here, a metal organic framework (MOF)-functionalized SERS nanopotentiometer has been developed for the dynamic monitoring of intracellular redox potential. The approach is based on the encapsulation of zirconium-based MOF (Uio-66-F4) on a surface of gold-silver nanorods (Au-Ag NRs) that is modified with the newly synthesized redox-sensitive probe ortho-mercaptohydroquinone (HQ). Thanks to size exclusion of MOF as the chemical protector, the nanopotentiometer can be adapted to long-term use and possess high anti-interference ability toward nonredox species. Combining the superior fingerprint identification of SERS with the electrochemical activity of the quinone/hydroquinone, the nanopotentiometer shows a reversible redox responsivity and can quantify redox potential with a relatively wide range of -250-100 mV. Furthermore, the nanopotentiometer allows for dynamic visualization of intracellular redox potential changes induced by drugs' stimulation in a high-resolution manner. The developed approach would be promising for offering new insights into the correlation between redox potential and tumor proliferation-involved processes such as oxidative stress and hypoxia.

Mixed-Linkage Donor-Acceptor Covalent Organic Framework as a Turn-On Fluorescent Sensor for Aliphatic Amines.

Amine determination is crucial to our daily life, including the prevention of pollution, the treatment of certain disorders, and the evaluation of food quality. Herein, a mixed-linkage donor-acceptor covalent organic framework (named DSE-COF) was first constructed by the polymerization between 2,4-dihydroxybenzene-1,3,5-tricarbaldehyde (DTA) and 4,4'-(benzo[c][1,2,5]selenadiazole-4,7-diyl)dianiline (SEZ). DSE-COF displayed superior turn-on fluorescent responses to primary, secondary, and tertiary aliphatic amines, such as cadaverine, isopropylamine, sec-butylamine, cyclohexylamine, hexamethylenediamine, di-n-butylamine, and triethylamine in absolute acetonitrile than other organic species. Further experiments and theoretical calculations demonstrated that the combination of intramolecular charge transfer (ICT) and photoinduced electron transfer (PET) effects between the DSE-COF and aliphatic amines resulted in enhanced fluorescence. Credibly, DSE-COF can quantitatively detect cadaverine content in actual pork samples with satisfactory results. In addition, DSE-COF-based test papers could rapidly monitor cadaverine from real pork samples, manifesting the potential application of COFs in food quality inspection.

Chiral Ionic Covalent Organic Framework as an Enantioselective Fluorescent Sensor for Phenylalaninol Determination.

Phenylalaninol (PAL) is a significant chemical intermediate widely utilized in drug development and chiral synthesis, for instance, as a reactant for bicyclic lactams and oxazoloisoindolinones. Since the absolute stereochemical configuration significantly impacts biological action, it is crucial to evaluate the concentration and enantiomeric content of PAL in a quick and convenient manner. Herein, an effective PAL enantiomer recognition method was reported based on a chiral ionic covalent organic framework (COF) fluorescent sensor, which was fabricated via one-step postquaternization modification of an achiral COF by (1R, 2S, 5R)-2-isopropyl-5-methylcyclohexyl-carbonochloridate (L-MTE). The formed chiral L-TB-COF can be applied as a chiral fluorescent sensor to recognize the stereochemical configuration of PAL, which displayed a turn-on fluorescent response for R-PAL over that of S-PAL with an enantioselectivity factor of 16.96. Nonetheless, the single L-MTE molecule had no chiral recognition ability for PAL. Moreover, the ee value of PAL can be identified by L-TB-COF. Furthermore, density functional theory (DFT) calculations demonstrated that the chiral selectivity came from the stronger binding affinity between L-TB-COF and R-PAL in comparison to that with S-PAL. L-TB-COF is the first chiral ionic COF employed to identify chiral isomers by fluorescence. The current work expands the range of applications for ionic COFs and offers fresh suggestions for creating novel chiral fluorescent sensors.

Alterations of serine racemase expression determine proliferation and differentiation of neuroblastoma cells.

Although the role of serine racemase (SR) in neuropsychiatric disorders has been extensively studied, its role in cell proliferation and differentiation remains unclear. Deletion of Srr, the encoding gene for SR, has been shown to reduce dendritic arborization and dendritic spine density in the brains of adult mice, whereas increased SR levels have been associated with differentiation in cell cultures. Previously, we demonstrated that valproic acid induces differentiation in the N2A neuroblastoma cell line, and that this differentiation is associated with increased SR expression. These observations suggest that SR may have a role in cell proliferation and differentiation. We herein found that both valproic acid and all-trans retinoic acid induced N2A differentiation. In contrast, knockdown of SR reduced levels of differentiation, increased N2A proliferation, promoted cell cycle entry, and modulated expression of cell cycle-related proteins. To further evaluate the effects of SR expression on cell proliferation and differentiation, we used an in vivo model of neuroblastoma in nude mice. N2A cells stably expressing scramble shRNA (Srrwt -N2A) or specific Srr shRNA (Srrkd -N2A) were subcutaneously injected into nude mice. The weights and volumes of Srrwt -N2A-derived tumors were lower than Srrkd -N2A-derived tumors. Furthermore, Srrwt -N2A-derived tumors were significantly mitigated by intraperitoneal injection of valproic acid, whereas Srrkd -N2A-derived tumors were unaffected. Taken together, our findings demonstrate for the first time that alterations in SR expression determine the transition between proliferation and differentiation in neural progenitor cells. Thus, in addition to its well-established roles in neuropsychiatric disorders, our study has highlighted a novel role for SR in cell proliferation and differentiation.

Ultra-broad Near-Infrared Emitting Phosphor LiInF4: Cr3+ with Extremely Weak Crystal Field.

Recent decades have witnessed a major development in broadband near-infrared (NIR)-emitting phosphors because of their potential applications in real-time nondestructive examination. These applications require the emission spectra of phosphors to be as broad as possible for efficient performance. Therefore, a blue-light excited LiInF4: Cr3+ phosphor with a NIR emission covering 700-1400 nm is successfully synthesized. Under 470 nm excitation, it shows broadband emission peaked at 980 nm with the full-width at half maximum of 210 nm. The structure and crystal field environment are investigated in detail, and the LiInF4: Cr3+ possesses a weak crystal field strength and strong electron-phonon coupling. An efficient NIR phosphor-converted light-emitting diode (pc-LED) is fabricated by the prepared LiInF4: Cr3+ phosphor and commercial blue diode chip, generating a NIR radiant flux of 5.54 mW at 150 mA drive current. Finally, the NIR pc-LED is successfully applied to identify the blood vessel distribution of the hand. This work suggests the potential of LiInF4: Cr3+ phosphor in applications.

Thiophene-Containing Covalent Organic Frameworks for Overall Photocatalytic H2 O2 Synthesis in Water and Seawater.

H2 O2 is a significant chemical widely utilized in the environmental and industrial fields, with growing global demand. Without sacrificial agents, simultaneous photocatalyzed H2 O2 synthesis through the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) dual channels from seawater is green and sustainable but still challenging. Herein, two novel thiophene-containing covalent organic frameworks (TD-COF and TT-COF) were first constructed and served as catalysts for H2 O2 synthesis via indirect 2e- ORR and direct 2e- WOR channels. The photocatalytic H2 O2 production performance can be regulated by adjusting the N-heterocycle modules (pyridine and triazine) in COFs. Notably, with no sacrificial agents, just using air and water as raw materials, TD-COF exhibited high H2 O2 production yields of 4060 µmol h-1 g-1 and 3364 µmol h-1 g-1 in deionized water and natural seawater, respectively. Further computational mechanism studies revealed that the thiophene was the primary photoreduction unit for ORR, while the benzene ring (linked to the thiophene by the imine bond) was the central photooxidation unit for WOR. The current work exploits thiophene-containing COFs for overall photocatalytic H2 O2 synthesis via ORR and WOR dual channels and provides fresh insight into creating innovative catalysts for photocatalyzing H2 O2 synthesis.

Fluorescence/Colorimetry/Smartphone Triple-Mode Sensing of Dopamine by a COF-Based Peroxidase-Mimic Platform.

Simple and accurate monitoring of urinary dopamine (DA) concentration is significant, which is helpful for the assessment or exclusion of catecholamine-producing tumors, such as pheochromocytoma and paraganglioma. Herein, a fluorescence/colorimetry/smartphone triple-mode sensing platform for DA determination was constructed using copper ion (Cu2+)-modified hydrazone-linked covalent organic frameworks (Cu-BTA-COF). Cu-BTA-COF with 21.67 wt % copper content exhibited peroxidase-mimic activity. After adding H2O2 and 1,3-dihydroxynaphthalene, the Cu-BTA-COF platform can sensitively and selectively detect DA in three modes with consistent results. In fluorescence/colorimetry/smartphone modes, the linear ranges of DA were 1-10, 0.2-40, and 1-10 µM, with related detection limits of 7.2, 8.6, and 23 nM, respectively. Moreover, the Cu-BTA-COF platform can be explored for DA determination in human urine samples with satisfactory recoveries (97.6-100.4%) in all the three modes, suggesting the potential practical application of the Cu-BTA-COF platform for DA detection in urine.

Ratiometric Fluorescent pH Sensor Based on a Tunable Multivariate Covalent Organic Framework.

Ratiometric detection of pH is always significant in environmental regulation, medical diagnosis, synthetic chemistry, and beyond. The construction of practical ratiometric pH sensors with reusability is still challenging. Herein, by exploiting a multivariate strategy, we first synthesized and reported a series of novel three-component covalent organic frameworks (COF-COOHX, X = 33, 50, and 67) through Schiff base reaction between 2-hydroxybenzene-1,3,5-tricarbaldehyde (HTA), 4,4'-diamino-3,3'-biphenyldicarboxylic acid (DBA), and 5,5'-diamino-2,2'-bipyridine (BPY) at various molar ratios (X = [DBA]/([BPY] + [DBA]) × 100 = 33, 50, and 67). COF-COOHX (X = 33, 50, and 67) displayed ratiometric pH sensing performance in acidic conditions with selectivity and repeatability. By tuning the molar ratio of DBA and BPY, the fluorescent properties, linear pH responsive ranges, and pKa values of COF-COOHX (X = 33, 50, and 67) can be regulated. Meanwhile, the two-component COF-COOH0 and COF-COOH100 did not exhibit ratiometric pH detection ability. Moreover, the constructed three ratiometric sensors can be applied to detect pH in drug solutions and carbonated drinks with satisfactory results. This work sheds new light on the design and fabrication of innovative ratiometric fluorescent sensors using COFs.

Constructing Head-to-Tail Cyclic Peptide DNA-Encoded Libraries Using Two-Directional Synthesis Strategy.

Macrocyclic peptides are an important class of therapeutic agents for the biological targets that are difficult to modulate by small-molecule compounds. Meanwhile, DNA-encoded library technology (DELT) provides a powerful platform for hits discovery. The unity of both fields has proven highly productive in finding cyclic peptide hits against diverse pharmaceutical proteins. Many researchers have extended the chemical toolbox for constructing head-to-tail macrocyclic DNA-encoded libraries with various ring sizes. However, the linear peptides of different lengths necessitate tuning the distance between closing sites and DNA-linked sites to perform the macrocyclization process, presumably due to the constrained conformation of linear precursors. To tackle this issue and streamline the synthetic workflow, we report a two-directional synthesis strategy. This method starts from a trifunctional reagent and prepares DNA-linked macrocyclic peptides of ring size between 15 (5-mer) and 24 (8-mer) via amide bond formation reaction, a common method to create macrocyclic peptides.

Hematoporphyrin monomethyl ether mediated photodynamic therapy inhibits oral squamous cell carcinoma by regulating the P53-miR-21-PDCD4 axis via singlet oxygen.

The objective of this study was to determine the mechanism and effect of hematoporphyrin monomethyl ether mediated photodynamic therapy (HMME-PDT) on oral squamous cell carcinoma (OSCC). Human OSCC CAL-27 cells were randomly divided into four groups: control group, HMME group, laser group, and HMME-PDT group. Cell viability was detected by the CCK-8 method. Cell cycle distribution was evaluated by flow cytometry. GEO database was used to screen differentially expressed microRNAs (DEMs), and TCGA database was performed to verify DEM expression in OSCC and normal tissues. The effects of HMME-PDT on DEM expression were assayed by real-time PCR, and the expressions of miRNAs target genes were measured by western blot. Fluorescence probes were used to determine the production of singlet oxygen (1O2). Compared with the other three groups, HMME-PDT dramatically inhibited CAL-27 cell proliferation and induced G0/G1 cycle arrest. The expressions of miR-21 and miR-155 were significantly upregulated in OSCC. HMME-PDT downregulated the expression of miR-21 but had no obvious effect on miR-155. HMME-PDT remarkably upregulated the levels of P53 and miR-21 target proteins, such as PDCD4, RECK, and SPRY2. 1O2 was generated during HMME-PDT, and inhibition of 1O2 production could reverse the regulation of HMME-PDT on P53, miR-21, and its target proteins, thus restoring cell viability. HMME-PDT can significantly inhibit the growth of OSCC cells, and the mechanism of this effect is related to the regulation of the P53-miR-21-PDCD4 axis via 1O2 induced by HMME-PDT.

Effects of perfluoroalkyl substances on soil respiration and enzymatic activity: differences in carbon chain-length dependence.

Perfluoroalkyl substances (PFASs) are anthropogenic compounds that exhibit ecotoxicity when discharged into the environment, causing increasing concern. An indoor experiment was conducted to investigate the effects of perfluoroalkyl carboxylic acids (PFCAs) and PFSAs on soil respiration, sucrase activity, and urease activity at 0, 7, 14, and 28 d for perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA), and perfluorobutyric acid (PFBA), and at 14 and 28 d for perfluorooctane sulfonic acid (PFOS), perfluorohexanoic sulfonic acid (PFHxS), and perfluorobutyric sulfonic acid (PFBS). PFCAs significantly inhibited soil respiration, with a significant negative correlation between respiration and PFBA (P < 0.05) at 28 d. Sucrase activities were initially inhibited by PFCAs, and then recovered. Urease activities were inhibited by PFOA at 14 d and by PFHxA at 14 and 28 d, but not by PFBA. PFOS and PFBS briefly enhanced soil respiration. PFOS inhibited sucrase activity. PFSAs significantly decreased urease activity in a concentration- and time-dependent manner. The chain-length dependence of the ecotoxicity of PFASs varied depending on concentration and time. Toxicity demonstrated a trend of initial decrease followed by increase with carbon chain length. Our results first revealed that the chain-length dependences of PFASs were also related to concentrations and exposure time.

A deep fuzzy model for diagnosis of COVID-19 from CT images.

From early 2020, a novel coronavirus disease pneumonia has shown a global "pandemic" trend at an extremely fast speed. Due to the magnitude of its harm, it has become a major global public health event. In the face of dramatic increase in the number of patients with COVID-19, the need for quick diagnosis of suspected cases has become particularly critical. Therefore, this paper constructs a fuzzy classifier, which aims to detect infected subjects by observing and analyzing the CT images of suspected patients. Firstly, a deep learning algorithm is used to extract the low-level features of CT images in the COVID-CT dataset. Subsequently, we analyze the extracted feature information with attribute reduction algorithm to obtain features with high recognition. Then, some key features are selected as the input for the fuzzy diagnosis model to the training model. Finally, several images in the dataset are used as the test set to test the trained fuzzy classifier. The obtained accuracy rate is 94.2%, and the F1-score is 93.8%. Experimental results show that, compared with the deep learning diagnosis methods widely used in medical image analysis, the proposed fuzzy model improves the accuracy and efficiency of diagnosis, which consequently helps to curb the spread of COVID-19.

A novel negative-stranded RNA virus of the order Bunyavirales identified in Brassica campestris L. ssp. chinensis.

Here, we report the full-length genome sequence of a novel cogu-like virus identified in Brassica campestris L. ssp. Chinensis (B. campestris), an economically important vegetable in China. This virus, tentatively named "Brassica campestris chinensis coguvirus 1" (BCCoV1), has a bipartite genome that consists of two RNA molecules (RNA1 and RNA2). The negative-stranded (ns) RNA1 is 6757 nt in length, encoding the putative RNA-dependent RNA polymerase (RdRp), and the ambisense RNA2 is 3061 nt long, encoding the putative movement protein (MP) and nucleocapsid protein (NP). A homology search of the RdRp, MP, and NP showed that they are closely related to five other recently discovered negative-stranded RNA (nsRNA) viruses infecting plants, belonging to the new genus Coguvirus. Phylogenetic analysis of the 252-kDa RdRp confirmed the classification of this virus, showing that BCCoV1 possibly belongs to the genus Coguvirus, family Phenuiviridae, order Bunyavirales. The present study improves our understanding of the viral diversity in B. campestris and the evolution of nsRNA viruses.

Complete nucleotide sequence of a novel partitivirus from Brassica campestris L. ssp. chinensis.

In the present work, we report the discovery and complete genome sequence of a novel partitivirus identified from Brassica campestris L. ssp. chinensis, which we have named "Brassica campestris chinensis cryptic virus 1" (BCCV1). Next-generation sequencing (NGS) combined with adapter-ligation-mediated amplification allowed assembly of the full-length genome sequence of BCCV1. The genome of BCCV1 contains two dsRNA segments, dsRNA1 (1595 bp) and dsRNA2 (1591 bp), which encode a conserved RNA-dependent RNA polymerase (RdRp) and a putative capsid protein (CP), respectively. Homology searches and phylogenetic analysis of the 479-aa RdRp and 438-aa CP showed that BCCV1 is a new member of the genus Deltapartitivirus, family Partitiviridae. This is the first report of the identification of a member of the family Partitiviridae in Brassica campestris L. ssp. chinensis.

A Replication-Defective Human Cytomegalovirus Vaccine Elicits Humoral Immune Responses Analogous to Those with Natural Infection.

Human cytomegalovirus (HCMV) can cause congenital infections, which are a leading cause of childhood disabilities. Since the rate of maternal-fetal transmission is much lower in naturally infected (HCMV-seropositive) women, we hypothesize that a vaccine candidate capable of eliciting immune responses analogous to those of HCMV-seropositive subjects may confer protection against congenital HCMV. We have previously described a replication-defective virus vaccine based on strain AD169 (D. Wang, D. C. Freed, X. He, F. Li, et al., Sci Transl Med 8:362ra145, 2016, https://doi.org/10.1126/scitranslmed.aaf9387). The vaccine, named V160, has been shown to be safe and immunogenic in HCMV-seronegative human subjects, eliciting both humoral and cellular immune responses (S. P. Adler, S. E. Starr, S. A. Plotkin, S. H. Hempfling, et al., J Infect Dis 220:411-419, 2019, https://doi.org/10.1093/infdis/171.1.26). Here, we further showed that sera from V160-immunized HCMV-seronegative subjects have attributes similar in quality to those from seropositive subjects, including high-avidity antibodies to viral antigens, coverage against a panel of genetically distinct clinical isolates, and protection against viral infection in diverse types of human cells in culture. More importantly, vaccination appeared efficient in priming the human immune system, inducing memory B cells in six V160 recipients at frequencies comparable to those of three HCMV-seropositive subjects. Our results demonstrate the ability of V160 to induce robust and durable humoral memory responses to HCMV, justifying further clinical evaluation of the vaccine against congenital HCMV.IMPORTANCEIn utero HCMV infection can lead to miscarriage or childhood disabilities, and an effective vaccine is urgently needed. Since children born to women who are seropositive prior to pregnancy are less likely to be affected by congenital HCMV infection, it has been hypothesized that a vaccine capable of inducing an immune response resembling the responses in HCMV-seropositive women may be effective. We previously described a replication-defective virus vaccine that has been demonstrated safe and immunogenic in HCMV-seronegative subjects. Here, we conducted additional analyses to show that the vaccine can induce antibodies with functional attributes similar to those from HCMV-seropositive subjects. Importantly, vaccination can induce long-lived memory B cells at frequencies comparable to those seen in HCMV-seropositive subjects. We conclude that this vaccine is a promising candidate that warrants further clinical evaluation for prevention of congenital HCMV.

Free-Standing 2D Janus Gold Nanoparticles Monolayer Film with Tunable Bifacial Morphologies via the Asymmetric Growth at Air-Liquid Interface.

Large scaled two-dimensional free-standing monolayer films of gold nanoparticles show distinctive optical, electrical, and chem-physical propertie making them a new class of advanced plasmonic materials differing from bulk materials and individual nanoparticles in solution. The conventional 2D gold nanoparticle films usually possess symmetric structures and identical properties of gold nanoparticles on both sides. Herein, we developed an easy and efficient approach to construct a new type of free-standing 2D gold nanoparticle monolayer film with asymmetric gold nanoparticle structures and functions, called a 2D Janus gold nanoparticle film. The remarkable feature of our method is the subsequent asymmetric growth on one side of the interfacial self-assembled gold nanoparticle monolayer film at the air-liquid interface. It is very easy to control the morphology of the Janus film by simply and precisely adjusting the size and shape of the gold nanoparticles on the top side, and selectively tuning the structure and composition on the bottom side of the film by growing gold nanoparticles or other noble metals such as Ag, Pt, and Pd. Unlike the conventionally prepared Janus films at solid substrate that require long-time etching and transfer procedures, other features of our method include the short time in which the interfacial self-assembly and the subsequent asymmetric growth are completed as well as the easily transferable property of the Janus film onto different substrates, such as quartz glass sheets, silicon wafers, and PDMS. The obtained Janus gold nanoparticle film shows asymmetric wettabilities, optical properties, and surface-enhanced Raman scattering (SERS) effects, which is promising for a range of potential applications in optical devices, sensors, and asymmetric catalysis.

Mitochondrial genome and transcriptome analysis of five alloplasmic male-sterile lines in Brassica juncea.

BACKGROUND: Alloplasmic lines, in which the nuclear genome is combined with wild cytoplasm, are often characterized by cytoplasmic male sterility (CMS), regardless of whether it was derived from sexual or somatic hybridization with wild relatives. In this study, we sequenced and analyzed the mitochondrial genomes of five such alloplasmic lines in Brassica juncea. RESULTS: The assembled and annotated mitochondrial genomes of the five alloplasmic lines were found to have virtually identical gene contents. They preserved most of the ancestral mitochondrial segments, and the same candidate male sterility gene (orf108) was found harbored in mitotype-specific sequences. We also detected promiscuous sequences of chloroplast origin that were conserved among plants of the Brassicaceae, and found the RNA editing profiles to vary across the five mitochondrial genomes. CONCLUSIONS: On the basis of our characterization of the genetic nature of five alloplasmic mitochondrial genomes, we speculated that the putative candidate male sterility gene orf108 may not be responsible for the CMS observed in Brassica oxyrrhina and Diplotaxis catholica. Furthermore, we propose the potential coincidence of CMS in alloplasmic lines. Our findings lay the foundation for further elucidation of male sterility gene.

Linc-PINT acted as a tumor suppressor by sponging miR-543 and miR-576-5p in esophageal cancer.

This manuscript aimed to investigate linc-PINT's role as a tumor suppressor and its downstream microRNAs (miRNAs) in esophageal cancer. Log-rank, Cox, and nomogram were used for survival analysis. Quantitative real-time polymerase chain reaction was used to evaluate the expression. Cell counting kit-8 was used for proliferation tests. As for in vivo experiments, low expression of linc-PINT was associated with better prognosis; besides, the nomogram indicated that linc-PINT, miR-543, and miR-576-5p served well in predicting the survival rate. As for the in vitro experiments, linc-PINT could directly regulate miR-543 and miR-576-5p to inhibit the proliferation of Eca-109 cell line. In conclusion, linc-PINT-miR-543/miR-576-5p pathway could predict the prognosis and provide novel therapeutic targets for esophageal cancer.

Function, Significance, and Regulation of Rap1b in Malignancy.

Ras-associated protein 1(Rap1) is a member of the RAS family of small G proteins and regulates several signal pathways involved in carcinogenesis. Rap1 consists of two highly homologous isoforms, Rap1a and Rap1b. Increasing data suggest that the deregulated activation of Rap1b is involved in a spectrum of malignancies. Accumulating evidence also indicates effects of Rap1b on cell proliferation, metastasis, angiogenesis, and treatment resistance. Rap1b overexpresses in many tumors and has prognostic values, which are regulated by A2br, miRNAs, and other upstream effectors. This article aims to review research progress in function, significance, and regulation of Rap1b in malignancy.

Asymmetrical Molecular Decoration of Gold Nanorods for Engineering of Shape-Controlled AuNR@Ag Core-Shell Nanostructures.

Gold-silver (Au@Ag) core-shell nanostructures have a stronger surface plasma response, wider absorption and scattering in the UV-vis-NIR region, and distinctive optical properties, which are widely explored in biosensors, information processing, photothermal therapy, and catalysis. Core-shell nanostructures are usually formed by the deposition of the second metal atoms onto the first core metal particles via the chemical wet method. The conventional approaches for the manipulation of the shape usually were done by homogeneous growth or etching of isotropic nanoparticles. Through in situ modification of the first metal core at the different locations, the different growth model of the second metal can be regulated to control the shapes of core-shell structures. Herein, we modified the gold nanorods (AuNRs) asymmetrically at the end and side parts using thiolated molecules to regulate the morphology of gold nanorod@silver (AuNR@Ag) core-shell nanoparticles. Interestingly, the obvious eccentric nanostructures of AuNR@Ag core-shell nanoparticles were obtained with the increase of the molecular weight of macromolecules modified at the end of AuNRs. Therefore the growth mode was adjusted from Frank-van der Merwe mode to Stranski-Krastanow mode. By changing the length of the hydrocarbon chain and functional groups of the small mercaptan molecules at the side of AuNRs, the silver shell exhibits selective growth at the side of the AuNRs, resulting in heterogeneous core-shell nanoparticles and various shapes of the AuNR@Ag core-shell. Our method opens up a new avenue toward preparing core-shell nanostructures with controlled shapes, and the obtained structures are promising in various applications.