Tripedal DNA Walker as a Signal Amplifier Combined with a Potential-Resolved Multicolor Electrochemiluminescence Strategy for Ultrasensitive Detection of Prostate Cancer Staging Indicators.

A multicolor electrochemiluminescence (ECL) biosensor based on a closed bipolar electrode (BPE) array was proposed for the rapid and intuitive analysis of three prostate cancer staging indicators. First, [Irpic-OMe], [Ir(ppy)2(acac)], and [Ru(bpy)3]2+ were applied as blue, green, and red ECL emitters, respectively, whose mixed ECL emission colors covered the whole visible region by varying the applied voltages. Afterward, we designed a simple Mg2+-dependent DNAzyme (MNAzyme)-driven tripedal DNA walker (TD walker) to release three output DNAs. Immediately after, three output DNAs were added to the cathodic reservoirs of the BPE for incubation. After that, we found that the emission colors from the anode of the BPE changed as a driving voltage of 8.0 V was applied, mainly due to changes in the interfacial potential and faradaic currents at the two poles of the BPE. Via optimization of the experimental parameters, cutoff values of such three indicators at different clinical stages could be identified instantly with the naked eye, and standard precision swatches with multiple indicators could be prepared. Finally, in order to precisely determine the prostate cancer stage, the multicolor ECL device was used for clinical analysis, and the resulting images were then compared with standard swatches, laying the way for accurate prostate cancer therapy.

Dinitrogen Activation and Functionalization Affording Chromium Diazenido and Hydrazido Complexes.

ConspectusThe activation and functionalization of N2 to form nitrogen-element bonds have long posed challenges to industrial, biological, and synthetic chemists. The first transition-metal dinitrogen complex prepared by Allen and Senoff in 1965 provoked researchers to explore homogeneous N2 fixation. Despite intensive research in the last six decades, efficient and quantitative conversion of N2 to diazenido and hydrazido species remains problematic. Relative to a plethora of reactions to generate N2 complexes, their functionalization reactions are rather rare, and the yields are often unsatisfactory, emphasizing the need for systematic investigations of the reaction mechanisms.In this Account, we summarize our recent work on the synthesis, spectroscopic features, electronic structures, and reactivities of several Cr-N2 complexes. Initially, a series of dinuclear and trinuclear Cr(I)-N2 complexes bearing cyclopentadienyl-phosphine ligands were accessed. However, they cannot achieve N2 functionalization but undergo oxidative addition reactions with phenylsilane, azobenzene, and other unsaturated organic compounds at the low-valent Cr(I) centers rather than at the N2 unit. Further reduction of these Cr(I) complexes leads to the formation of more activated mononuclear Cr(0) bis-dinitrogen complexes. Remarkably, silylation of the cyclopentadienyl-phosphine Cr(0)-N2 complex with Me3SiCl afforded the first Cr hydrazido complex. This process follows the distal pathway to functionalize the Nß atom twice, yielding an end-on η1-hydrazido complex, Cr(III)═N-N(SiMe3)2. In contrast, upon substitution of the phosphine ligand in the Cr(0)-N2 complex with a N-heterocyclic carbene (NHC) ligand, the corresponding reaction with Me3SiCl proceeds via the alternating pathway; the silylation occurs at both Nα and Nß atoms and generates a side-on η2-hydrazido complex, Cr(III)(η2-Me3SiN-NSiMe3). Both silylation reactions are inevitably accompanied by the formation of Cr(III) hydrazido complexes and Cr(II) chlorides with a 2:1 ratio. These processes exhibit a peculiar '3-4-2-1' stoichiometry (i.e., treating 3 equiv of Cr(0)-N2 complexes with 4 equiv of Me3SiCl yields 2 equiv of Cr(III) disilyl-hydrazido complexes and 1 equiv of Cr(II) chloride). Upon replacing the monodentate phosphine and/or NHC ligand with a bisphosphine ligand, a monodinitrogen Cr(0) complex, instead of the bis-dinitrogen Cr(0) complexes, is obtained; consequently, the silylation reactions progress via the normal two-electron route, which passes through Cr(II)-N═N-R diazenido species as an intermediate and furnishes [Cr(IV)═N-NR2]+ hydrazido as the final products. More importantly, this type of Cr(0)-N2 complex can be not only silylated but also protonated and alkylated proficiently. All of the second-order reaction rates of the first and second transformations are determined along with the lifetimes of the intervening diazenido species. Based on these findings, we have successfully carried out nearly quantitative preparations of the Cr(IV) hydrazido species with unmixed or hybrid substituents.The studies of Cr-N2 systems provide effective approaches for the activation and functionalization of N2, deepening the understanding of N2 electrophilic attack. We hope that this Account will inspire more discoveries related to the transformation of gaseous N2 to high-value-added nitrogen-containing organic compounds.

Dinitrogen Functionalization Affording Chromium Diazenido and Side-on η2-Hydrazido Complexes.

Isolation of key intermediate complexes in dinitrogen functionalization is crucial for elucidating the mechanistic details and further investigation. Herein, the synthesis and characterization of (µ-η1:η1-N2)(η1-N2)-Cr(I) 3 and (η1-N2)2-Cr(0) complexes 4 supported by Cp* (Cp* = C5Me5) and NHC ligands were reported. Further functionalization of Cr(0)-N2 complex 4 with silyl halides delivered the key intermediates in the alternating pathway, the chromium diazenido complex 5 and the chromium side-on η2-hydrazido complex 6. Protonation of 6 led to the quantitative formation of N2H4. Moreover, the [η2-Me3SiNNSiMe3]2- unit in 6 enabled N-C bond formation reactions with CO2 and tBuNCO, giving the corresponding N,O-chelating hydrazidochromium complexes 7 and 8, respectively.

Robotic versus laparoscopic surgery for sporadic benign insulinoma: Short- and long-term outcomes.

BACKGROUND: Minimally invasive surgery is the optimal treatment for insulinoma. The present study aimed to compare short- and long-term outcomes of laparoscopic and robotic surgery for sporadic benign insulinoma. METHODS: A retrospective analysis of patients who underwent laparoscopic or robotic surgery for insulinoma at our center between September 2007 and December 2019 was conducted. The demographic, perioperative and postoperative follow-up results were compared between the laparoscopic and robotic groups. RESULTS: A total of 85 patients were enrolled, including 36 with laparoscopic approach and 49 with robotic approach. Enucleation was the preferred surgical procedure. Fifty-nine patients (69.4%) underwent enucleation; among them, 26 and 33 patients underwent laparoscopic and robotic surgery, respectively. Robotic enucleation had a lower conversion rate to laparotomy (0 vs. 19.2%, P = 0.013), shorter operative time (102.0 vs. 145.5 min, P = 0.008) and shorter postoperative hospital stay (6.0 vs. 8.5 d, P = 0.002) than laparoscopic enucleation. There were no differences between the groups in terms of intraoperative blood loss, the rates of postoperative pancreatic fistula and complications. After a median follow-up of 65 months, two patients in the laparoscopic group developed a functional recurrence and none of the patients in the robotic group had a recurrence. CONCLUSIONS: Robotic enucleation can reduce the conversion rate to laparotomy and shorten operative time, which might lead to a reduction in postoperative hospital stay.

"Parenchyma transection-first" strategy is superior to "tunnel-first" strategy in robotic spleen-preserving distal pancreatectomy with conservation of splenic vessels.

BACKGROUND: Creating a tunnel between the pancreas and splenic vessels followed by pancreatic parenchyma transection ("tunnel-first" strategy) has long been used in spleen-preserving distal pancreatectomy (SPDP) with splenic vessel preservation (Kimura's procedure). However, the operation space is limited in the tunnel, leading to the risks of bleeding and difficulties in suturing. We adopted the pancreatic "parenchyma transection-first" strategy to optimize Kimura's procedure. METHODS: The clinical data of consecutive patients who underwent robotic SPDP with Kimura's procedure between January 2017 and September 2022 at our center were retrieved. The cohort was classified into a "parenchyma transection-first" strategy (P-F) group and a "tunnel-first" strategy (T-F) group and analyzed. RESULTS: A total of 91 patients were enrolled in this cohort, with 49 in the T-F group and 42 in the P-F group. Compared with the T-F group, the P-F group had significantly shorter operative time (146.1 ± 39.2 min vs. 174.9 ± 46.6 min, P < 0.01) and lower estimated blood loss [40.0 (20.0-55.0) mL vs. 50.0 (20.0-100.0) mL, P = 0.03]. Failure of splenic vessel preservation occurred in 10.2% patients in the T-F group and 2.4% in the P-F group (P = 0.14). The grade 3/4 complications were similar between the two groups (P = 0.57). No differences in postoperative pancreatic fistula, abdominal infection or hemorrhage were observed between the two groups. CONCLUSIONS: The pancreatic "parenchyma transection-first" strategy is safe and feasible compared with traditional "tunnel-first strategy" in SPDP with Kimura's procedure.

Ultrasensitive and Visual Electrochemiluminescence Ratiometry Based on a Constant Resistor-Integrated Bipolar Electrode for MicroRNA Detection.

In this work, a new electrochemiluminescence (ECL) platform was constructed for detecting the prostate cancer marker microRNA-141 (miRNA-141) on a constant resistor-integrated closed bipolar electrode (BPE). It consisted of two reservoirs and a constant resistor, and both ends were connected to the anode of the driving electrode and the cathode of BPE. The cathode of BPE was modified with boron nitride quantum dots (BNQDs), and the anode reservoir was the [Ru(bpy)3](PF6)2/TPrA system. After introducing a certain amount of hairpin DNA 3 (H3) and ferrocene-labeled single-stranded DNA (Fc-ssDNA) on the surface of the BNQDs, the ECL emission signal of the BNQDs was difficult to be observed by the naked eye, while [Ru(bpy)3](PF6)2 emitted a strong and visible ECL signal. In the presence of the target, bipedal DNA assembled by catalytic hairpin assembly (CHA) took away the Fc-ssDNA and the ECL intensity of the BNQDs was enlarged, and as the concentration of miRNA-141 increased to the cutoff value, yellow-green light was visible by the naked eye. Meanwhile, the red emission signal of [Ru(bpy)3](PF6)2/TPrA became weakened. Thus, an ultrasensitive "color switch" ECL biosensor for detection of miRNA-141 was constructed and endowed with a wide linear range from 10-17 to 10-7 M and a detection limit of 10-17 M (S/N = 3). This study provides the potential for investigating portable devices in the detection of low-concentration nucleic acids.

Cobalt Cyclopentadienyl-Phosphine Dinitrogen Complexes.

By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl2 , the corresponding cobalt chlorides (1, LCoII Cl) were prepared. By reducing complexes 1 with KHBEt3 under a N2 atmosphere, bridging end-on complexes, LCoI -N2 -CoI L (2 a and 2 b), were successfully obtained. 15 N2 -labeled [15 N2 ]-2 a was prepared under 15 N2 /14 N2 exchange in THF solution. LCoI -N2 -CoI L complex 2 a could react with P4 molecules to release N2 and generate a Co-P4 -Co moiety 4. Further reduction of complex 2 b led to cleavage of a P-C bond in the cyclopentadienyl-phosphine ligand to provide novel µ-PCy2 -bridged Co0 -N2 complex 5. DFT calculations confirmed the experimental observations.

[Mystery of Yiyin decoction theory: rule discovery and evaluation strategy of atypical pharmacological effects of Chinese medicinal prescription].

Yi Yin, a famous medical scientist and culinary master in the late Xia Dynasty and early Shang Dynasty, developed the Chinese medicinal liquids and Chinese medicinal prescriptions emerged after that. Chinese medicinal prescriptions have attracted much attention because of their unique advantages in the treatment of chronic multifactorial diseases, representing an important direction of drug discovery in the future. Yiyin decoction theory is the superior form of personalized combined medication with advanced consciousness. It is different from not only the magic bullet theory of single component action but also the connotation of modern multi-target drugs. The core of Yiyin decoction theory can be summarized as compound compatibility, multiple effects, and moderate regulation. Compound compatibility refers to that the formulation of Chinese medicinal prescriptions involves the complex synergy and interactions between sovereign, minister, assistant, and guide medicinal materials. Multiple effects mean that the prescriptions employ a variety of mechanisms to exert comprehensive pharmacological effects of nonlinear feedback. Moderate regulation reflects that the prescriptions can accurately regulate the multiple points of the disease biological network as a whole. To solve the mystery of Yiyin decoction theory, we should not only simply study the known active substances(components) and their independent target effects in the mixture, but also mine the "dark matter" and "dark effect" of Chinese medicinal prescriptions. That is, we should learn the neglected atypical pharmacological effects of Chinese medicinal prescriptions and the multi-point nesting mechanism that plays a precise regulatory function in the body. Yiyin decoction theory focuses on the overall pharmacological effect to reflect the comprehensive clinical value of Chinese medicinal prescriptions, which is of great significance for the development of a new model for the evaluation and application of new Chinese medicinal prescriptions in line with the theory of traditional Chinese medicine.

Chiral Recognition by Flexible Coordination Polymers of Ag+ with a Cysteine-Based Chiral Thiol Ligand That Bears a Binding Site.

We report a new scheme for chiral recognition using coordination polymers of Ag+ with a chiral thiol ligand that contains a binding group. N-Benzoyl-l-cysteine ethyl ester equipped with a boronic acid group at the para position of the phenyl ring forms coordination polymers with Ag+ in alkaline aqueous solutions that exhibit excellent selectivity toward a d-glucose enantiomer over l-glucose, while the coordination polymers from the d-cysteine-based thiol ligand are specific for l-glucose. It is assumed that a conformation change occurs upon interaction of a saccharide molecule with the polymeric chain receptor, for which the next binding is promoted, leading to the highly effective chiral recognition, despite the flexible nature of the polymeric receptor.

Sex differences between serum total bilirubin levels and cognition in patients with schizophrenia.

BACKGROUND: Cognitive deficits are common in patients with schizophrenia (SCZ). Abnormal serum total bilirubin (TBIL) levels have been involved in cognitive deficits associated with neuropsychiatric diseases such as mild cognitive impairment and subcortical ischemic vascular disease. However, this relationship has not yet been fully investigated in patients with SCZ. Therefore, the aim of this study was to investigate the association between the serum TBIL concentration and cognitive deficits in SCZ patients and to determine whether a sex difference exists in the association. METHODS: A total of 455 participants were eligible and included in this cross-sectional study. Cognition was evaluated using the Montreal Cognitive Assessment. Serum TBIL concentration was measured with an automatic biochemistry analyzer according to the routine protocol in the hospital medical laboratory. RESULTS: Serum TBIL levels were lower in the cognition impairment group than in the cognition normal group in male patients. In contrast, serum TBIL levels tended to be increased in the cognition impairment group in female patients, although the difference was not significant. Further stepwise multiple regression analysis stratified by sex showed that serum TBIL was independently and positively associated with cognitive function in male patients but not in female patients. Moreover, the association between serum TBIL level and cognitive function was also identified by the propensity score matching (PSM) method in male patients, but not in female patients. CONCLUSION: These findings suggest that lower serum TBIL levels may be associated with cognitive impairment in male SCZ patients.

First two-stage robotic ALPPS in HCC patients with hepatic vein invasion: a step-by-step procedure from a clinical case.

BACKGROUND: The associating liver partitioning and portal vein occlusion for staged hepatectomy (ALPPS) procedure is gaining interest because it brings hope to patients who cannot undergo radical surgical resection due to insufficient remnant liver volume. However, the indications and technical aspects of this procedure are still under debate. This report demonstrates the technical aspects of the first two-stage robotic ALPPS for HCC. CASE PRESENTATION: A 55-year-old man with type II portal vein variation was diagnosed with hepatocellular carcinoma. Preoperative 3D reconstruction of the liver based on CT showed a future liver remnant/standard liver volume (FLR/SLV) of 24.45%. The ALPPS procedure was performed using the da Vinci Si system. At the first stage of the operation, we removed the gallbladder and ligated the right anterior branch of the portal vein and the right posterior branch. Following blocking of the hepatic hilum, the liver parenchyma was removed 1 cm away from the right side of the falciform ligament in an incision manner from the top to the bottom and from shallow to deep. The second-stage operation was performed on the 12th postoperative day with a FLR/SLV of 45.13%. During this step, the right hemiliver plus left medial section was separated and removed. Postoperative pathology showed a negative margin. The operative times were 195 and 217 min, respectively. Estimated blood loss was 250 and 500 ml, respectively. There was no need for transfusion or hospitalization in intensive care. The patient was discharged on the 6th postoperative day. Recovery was uneventful after both stages, and the patient did not present any sign of liver failure. Elevation of liver enzymes was minimal. The patient had no evidence of the disease 14 months after the procedure. CONCLUSIONS: The two-stage robotic ALPPS procedure is a safe and feasible technique for select patients with HCC.

Robotic isolated partial and complete hepatic caudate lobectomy: A single institution experience.

BACKGROUND: Current reports on robotic hepatic caudate lobectomy are limited to Spiegel lobectomy. This study aimed to compare the safety and feasibility of robotic isolated partial and complete hepatic caudate lobectomy. METHODS: Clinical data of 32 patients who underwent robotic resection of the hepatic caudate lobe in our department from May 2016 to January 2020 were retrospectively analyzed. The patients were divided into three groups according to the lobectomy location: left dorsal segment lobectomy (Spiegel lobectomy), right dorsal segment lobectomy (caudate process or paracaval portion lobectomy), and complete caudate lobectomy. General information and perioperative results of the three groups were compared and analyzed. RESULTS: Among the 32 patients, none had conversion to laparotomy, three received intraoperative blood transfusion (9.38%), and none had complications of Clavien-Dindo grade III or higher or died in the perioperative period. Among them, 17 patients (53.13%) underwent Spiegel lobectomy, 7 (21.88%) underwent caudate process or paracaval portion lobectomy, and 8 (25.00%) underwent complete caudate lobectomy. The operative time and blood loss in the left dorsal segment lobectomy group were significantly better than those in the right dorsal segment lobectomy and complete caudate lobectomy groups (operative time: P = 0.010 and P = 0.005; blood loss: P = 0.005 and P = 0.017, respectively). The postoperative hospital stay in the left dorsal segment lobectomy group was significantly shorter than that in the complete caudate lobectomy group (P = 0.003); however, there was no difference in the postoperative hospital stay between the left dorsal segment lobectomy group and right dorsal segment lobectomy group (P = 0.240). CONCLUSIONS: Robotic isolated partial and complete caudate lobectomy is safe and feasible. Spiegel lobectomy is relatively straightforward and suitable for beginners.

Dinitrogen Functionalization Affording Chromium Hydrazido Complex.

A series of trinuclear and dinuclear Cr(I)-N2 complexes bearing cyclopentadienyl-phosphine ligands were synthesized and characterized. Further reduction of the Cr(I)-N2 complexes generated anionic Cr(0)-N2 complexes, which could react with Me3SiCl to afford the first chromium hydrazido complex from N2 functionalization. These complexes were found to be effective catalysts for the transformation of N2 into N(SiMe3)3.

An end-to-end pancreatic anastomosis in robotic central pancreatectomy.

BACKGROUND: Suturing the proximal pancreatic stump and performing pancreaticoenterostomy for the distal pancreatic stump following central pancreatectomy is a conventional procedure. This reconstruction after resection of the pathological pancreatic lesion brings changes in anatomy and physiology. In this study, an innovative one-stage robotic end-to-end pancreatic anastomosis was reported to replace the conventional pancreaticoenterostomy following central pancreatectomy. MATERIALS AND METHODS: The clinical data of 11 consecutive patients who underwent robotic central pancreatectomy with end-to-end pancreatic anastomosis between August 2017 and December 2017 were analyzed retrospectively. RESULTS: All operations were completed successfully without any conversion to open surgery. Nine patients had benign tumors, one had a mass-forming chronic pancreatitis, and one had an isolated pancreatic metastasis from a renal cancer. The mean gap left after central pancreatectomy was 4.3 ± 1.0 cm. The median operative time was 121 (range, 105 to 199) min. The median blood loss was 50 (range, 20 to 100) ml. Seven (63.6%) patients developed complications which included Clavien-Dindo Grade I complications in five patients, a Grade II complication in one patient, and a Grade IIIa complication in one patient. Seven patients developed a Grade B postoperative pancreatic fistula, and two patients a biochemical leak. There was no Grade C or worse pancreatic fistula. Magnetic resonance cholangiopancreatography at postoperative 6 months showed no stricture in any of the main pancreatic ducts. Three patients had an asymptomatic and small pancreatic pseudocyst. CONCLUSION: Robotic central pancreatectomy with end-to-end pancreatic anastomosis was safe and feasible. It restores the normal anatomy of the pancreas. With its good short-and long-term outcomes, it could be an alternative reconstructive method to pancreaticoenterostomy following central pancreatectomy.

Peripubertal stress of male, but not female rats increases morphine-induced conditioned place preference and locomotion in adulthood.

Animal studies demonstrate that peripubertal social stress markedly increases the risk for subsequent substance use in adulthood. However, whether non-social stress has a similar long-term impact is not clear, and whether male and female animals show different sensitivity to peripubertal non-social stress has not been examined. In the present study, we addressed these issues by introducing two non-social stressors (elevated platform and predator odor 2,5-Dihydro-2,4,5-trimethylthiazoline) to male and female Wistar rats during adolescence (postnatal days 28-30, 34, 36, 40, and 42), then tested reward-related behaviors during adulthood, including morphine-induced conditioned place preference (CPP, 1 mg/kg morphine or 5 mg/kg morphine) and hyperlocomotor activity (5 mg/kg morphine). We found that adult male rats, but not females who were exposed to peripubertal non-social stressors showed enhanced morphine-induced CPP. Moreover, morphine-induced increase in locomotor activity was also significantly increased in adult male rats, but not in females. These results indicate that peripubertal exposure to repeated non-social stress may enhance sensitivity to the rewarding effects of opioids in adulthood in a sex-dependent manner, with males being even more sensitive than females in this regard.

Bidirectional Electrochemiluminescence Color Switch: An Application in Detecting Multimarkers of Prostate Cancer.

A selective excitation of [Ir(df-ppy)2(pic)] and [Ru(bpy)3]2+ through tuning the electrode potential is reported in this work. Bidirectional color change from blue-green to red could be observed along with increase and decrease of the potential, which was ascribed to the dual-potential excitation property of [Ir(df-ppy)2(pic)]. Similar to the three-electrode system, selective excitation of ECL could be achieved at the anode of the bipolar electrode (BPE). Both increase and decrease of the faradic reactions at the cathode of the BPE could induce ECL reporting color at the other pole switched from blue-green to red. We applied a closed BPE device for the bioanalysis of multicolor ECL since the organic solvent containing electrochemiluminophores could be separated from the bioanalytes. On the basis of BPE arrays coupled with the ECL switch, the detection of three biomarkers of prostate cancer, PSA, microRNA-141, and sarcosine were integrated in a same device. The cutoff values of the biomarkers could be recognized directly by the naked eye. Such a device holds great potential in the early diagnosis of prostate cancer.

Electrochemiluminescence Energy Resonance Transfer System between RuSi Nanoparticles and Hollow Au Nanocages for Nucleic Acid Detection.

This paper describes an electrochemiluminescence resonance energy transfer (ECL-RET) system using Ru(bpy)32+-doped silica nanoparticles (RuSi NPs) as the ECL donor and hollow Au nanocages as the ECL acceptor. Tetrahedron DNA (TD) was used to construct the biosensing interface and control the distance (4.8 nm) between the ECL donor-acceptor pairs. The surface plasmon resonance (SPR) nanostructures, Au nanocages were assembled via the hairpin based sandwich assay. Due to the well overlap between the plasmon absorption spectrum of Au nanocages (628 nm) and the ECL emission spectrum of RuSi NPs (620 nm), high efficient energy transfer could occur. Subsequent cyclic DNA amplification further increased the binding amount of Au nanocages. Since the ECL inhibition is closely related with the binding amount of Au nanocages, a general "signal-off" ECL bioassay could thus be tailored with high sensitivity. At the optimized conditions, this ECL-RET system performed well with great stability and repeatability for nucleic acid detection in the range from 1.0 fM to 10 pM. This work manifested the great promise of hollow Au nanocages for an ECL-RET biosensor that to the best of our knowledge has not been reported. We believe that it could inspire more interest in the design and development of numerous other SPR nanostructures for advanced ECL-RET biosensors.

Bipolar Electrode Based Multicolor Electrochemiluminescence Biosensor.

We report a multicolor ECL device based on closed bipolar electrode (BPE) for the visualized sensing of prostate-specific antigen (PSA) in human blood serum. As the emission color of concomitant electrochemiluminophores is potential resolved, similar to a three-electrode system, selective excitation of ECL could be achieved by tuning the interfacial potential at the poles of BPE. Via modulating the resistance of BPE, multicolor ECL emission of [Ru(bpy)3]2+ and [Ir(ppy)3] mixture using tripropylamine (TPrA) as the co-reactant was observed at the anode and the principle was elaborated. The concept was utilized to the quantification of clinical biomarkers with the color variation. A PSA concentration dependent silver bridge was constructed in the gap of the BPEs as an electric conductivity modulator. On the basis of a multicolor BPE-ECL device, the cutoff values (4.0 and 10.0 ng/mL) of human PSA could be recognized with naked eyes by the green-yellow-red ECL emission changing. As the first multicolor ECL device in biological analysis, BPE may raise the application of potential-resolved ECL to a new level.

Visible-Light-Driven Iron-Promoted Thiocarboxylation of Styrenes and Acrylates with CO2.

The first thiocarboxylation of styrenes and acrylates with CO2 was realized by using visible light as a driving force and catalytic iron salts as promoters. A variety of important ß-thioacids were obtained in high yields. This multicomponent reaction proceeds in an atom- and redox-economical manner with broad substrate scope under mild reaction conditions. Notably, high regio-, chemo-, and diasteroselectivity are observed. Mechanistic studies indicate that a radical pathway can account for the unusual regioselectivity.

Visual Color-Switch Electrochemiluminescence Biosensing of Cancer Cell Based on Multichannel Bipolar Electrode Chip.

In this work, we developed a visual electrochemiluminescence (ECL) sensing platform based on a dual-bipolar electrode (D-BPE) array chip. The chip was composed of two arrays of BPEs and three separated arrays of reservoirs filled with buffer, Ru(bpy)3(2+)-TPrA and luminol solutions, respectively. Both BPEs served as ECL reporting platforms. By applying 6.0 V voltage, an array of orange electrochemiluminescence (ECL) signals belonging to Ru(bpy)3(2+) turned on. After adding DNAzyme and H2O2 in Ru(bpy)3(2+) and luminol reservoirs, the orange Ru(bpy)3(2+) signals decreased until vanished due to the quenching effect; meanwhile, a new array of blue ECL signals turned on because of the luminol-H2O2 ECL reaction. The designed D-BPE owns superior properties compared with the three-electrode system benefiting from the quantitative relation of bipolar systems, which greatly enhanced the ECL detection sensitivity. Meanwhile, the visual color-switch ECL and the ratiometric detecting principle made the results easier to evaluate and more accurate. Quantitative detection of HL-60 cancer cells from 320 cells/mL to 2.5 × 10(5) cells/mL with two linear ranges was achieved. The detection limit was down to 80 cells/mL. Finally, this D-BPE chip could distinguish the tumor cells from normal cells and provide a prospect for cancer diagnosis in a high-throughput, visual way.