Controlled/living ring-opening polymerization of ε-caprolactone catalyzed by phosphoric acid

The bulk ring-opening polymerization(ROP) of ε-caprolactone(ε-CL) by various phosphoric acids using phenylmethanol as the initiator was conducted.1,1’-bi-2-Naphthol(BINOL)-based phosphoric acid was found to be an effective organocatalyst for ROP leading to polyesters at 90℃.The overall conversion to poly(ε-caprolactone) was more than 96% and poly(ε-caprolactone) with M w of 8400 and polydispersity index of 1.13 was obtained.1 H NMR spectra of oligomers demonstrated the quantitative incorporation of the protic initiator in the polymer chains and showed that transesterification reactions did not occur to a significant extent.The controlled polymerization was indicated by the linear relationships between the number-average molar mass and monomer conversion or monomer-to-initiator ratio.In addition,the present protocol provided an easy-to-handle,inexpensive and environmentally benign entry for the synthesis of biodegradable materials as well as polyesters for biomedical applications.     

A Study of Pt4+-Adsorption and Its Reduction by Bacillus Megaterium D01

The properties of Pt4+-adsorption and its reduction by Bacillus megaterium D01 were studied by means of ICP,anode-stripping voltammetry,TEM,IR and XPS.The results of ICP analyses showed that the Pt4+-adsorptive efficiency of the strain D01 was as high as 94.3% under the conditions of 100 mg Pt4+/L,1 g biomass/L,pH 3.5 and at 30 ℃ for 24 h.Moreover,it was confirmed from anode stripping voltammetry that the strain D01 possessed a strong reducibility.The TEM analysis indicated that the strain D01 was able to adsorb and reduce Pt4+ to Pt0,small particles.The XPS result further supported the reduction of Pt4+ to Pt2+,followed by the further recuction to Pt0.The IR spectrum implied that D01 biomass adsorption of Pt4+ may result in the complexation of the C=O bond to the Pt species.     

Highly luminescence manganese doped carbon dots

Heteroatom doped carbon dots(CDs) with distinct merits are of great attractions in various fields such as solar cells, catalysis, trace element detection and photothermal therapy. In this work, we successfully synthesized blue-fluorescence and photostability manganese-doped carbon dots(Mn-CDs) with a quantum yield up to 7.5%, which was prepared by a facile one-step hydrothermal method with sodium citrate and manganese chloride. The Mn-CDs is the high mono-dispersity, uniform spherical nanoparticles. The Mn element plays a critical role in achieving a high quantum yield in synthesis of carbon dots, which was confirmed by the structure analysis using XPS and FTIR. Spectroscopic investigations proved that the decent PLQY and luminescence properties of Mn-CDs are due to the heteroatom doped, oxidized carbon-based surface passivation. In addition, the Mn-CDs are demonstrated as promising fluorescent sensors for iron ions with a linear range of 0–500 mmol/L and a detection limit of2.1 nmol/L(turn-off), indicating their great potential as a fluorescent probe for chemical sensing.     

Platelet carbon nanofibers as support of Pt-CoO electrocatalyst for superior hydrogen evolution

Exploration of cost-effective Pt/C catalysts has been a significant issue for electrochemical hydrogen evolution reaction(HER) toward sustainable energy conversion and storage.Herein,we report a fabrication strategy by employing platelet carbon nanofibers(p-CNF) as the support to immobilize Pt-CoO HER electrocatalyst using atomic layer deposition method.The edge-rich p-CNF support is found to act as the anchoring sites of Pt nanoparticles and favorably capture electrons from Pt to yield electron-deficient Pt surfaces for the boosted HER.Additionally,the sequential growth of CoO onto the Pt/p-CNF catalyst elaborately constructs the Pt-CoO interface and facilitates the electron transfer from Pt to CoO,which further enhances the HER activity.These advantages endow the fabricated Pt-CoO/p-CNF catalyst with the superior HER activity,e.g.,a very low overpotential of 26 mV at the current density of 10 mA·cm-2 and a mass activity of 4.42 A·mgPt-1at the overpotential of 30 mV,18.8 times higher than that of the commercial20 wt% Pt/C catalyst.The insights reported here could shed light on for the fabrication of cost-effective Pt-based composite HER catalysts.     

Theoretical Design of Blue-light-emitting Material Based on 1,2,3-Benzotriazole-based Derivative

Theoretically,1,2,3-benzotriazole(BT)-based derivative is designed by the struc-tural tuning in 2,1,3-benzothiadiazole(BTD)-based derivative and presents potential for applications in organic light-emitting diodes(OLEDs).Calculations show that the emission spectrum of BT-based derivative is located at the blue scope,so it can act as a blue-light-emitting material.Importantly,the oscillator strength of emission spectrum is significantly enhanced by replacing BTD with BT,implying it possess large fluorescent intensity.Additionally,BT-based derivative exhibits improved hole transportation with respect to the BTD-based derivative.     

Preparation and recognition performance of ratio-fluorescent probe based on sulfadiazine imprinted polymersEI北大核心CSCD

A novel ratio-fluorescent probe based on molecular imprinting polymer ( MIP) for the detection of sulfadiazine was prepared by using nitrogen-doped carbon quantum dots (N-CQDs) as the fluorescence response signal, silica-embedded cadmium telluride quantum dots ( CdTe QDs) as the fluorescence reference signal, sulfadiazine ( SDZ) as template molecule, acrylamide as functional monomer, N, N-methyl bisacrylamide as crosslinking agent and 2,2-Azobisisobutyronitrile as initiator. The results showed that the probe has a core-shell structure and fluorescence sensitive to SDZ, by the characterization of scanning electron microscopy, transmission electron microscopy, and fluorescence spectrophotometer. Under the wavelength of 360 nm, the ratio-fluorescent signal of probe showed a linear response with SDZ concentration in the range of 0-100 μmol / L with the detection limit of 11 nmol / L. Also, the ratio-fluorescent probe was applied to the detection of SDZ with a recovery of 92. 0%-95. 1% and relative standard deviation (RSD) of 3. 6% in real water samples. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Studies of surface processes of electrocatalytic reduction of CO<Subscript>2</Subscript> on Pt(210), Pt(310) and Pt(510)

Surface processes of CO2 reduction on Pt(210), Pt(310), and Pt(510) electrodes were studied by cyclic voltammetry. Different surface structures of these platinum single crystal electrodes were obtained by various treatment conditions. The experimental results illustrated that the electrocatalytic activity of Pt single crystal electrodes towards CO2 reduction is decreased in an order of Pt(210)＞Pt(310)＞Pt(510), i.e., with the decrease of (110) step density on well-defined surfaces. When the surfaces were reconstructed due to oxygen adsorption, the catalytic activity of all the three electrodes has been enhanced to a certain extent. Although the activity order remains unchanged, the electrocatalytic activity has been enhanced more significantly as the density of (110) step sites is more intensive on the Pt single crystal surface. It has revealed that the more open the surface structure is, the more active the Pt single crystal electrode will be, and the easier for the electrode to be transformed into a surface structure that exhibits higher activity under external inductions. However, the relatively ordered surfaces of Pt single crystal electrode are comparatively stable under the same external inductions. The present study has gained knowledge on the interaction between CO2 and Pt single crystal electrode surfaces at a microscopic level, and thrown new insight into understanding the surface processes of electrocatalytic reduction of CO2.     

Metal-Organic Frameworks-Based Fluorescent Nanocomposites for Bioimaging in Living Cells and in vivo

Metal-organic frameworks(MOFs)as a class of porous functional materials have attracted more and more attention for biomedical applications.To date,MOFs have been developed for bioimaging based on a series of advantages such as the large surface areas,high porosity,fluorescence functionalities and good biocompatibility.It is worth noting that organic or inorganic fluorescent materials such as fluorescent dyes,quantum dots,metal nanoclusters and nanosheets can combine MOFs or be encapsulated in MOFs to form fluorescent nanocomposites for excellent imaging function.Importantly,excellent imaging capabilities are of great significance in living cells and in vivo for detection,diagnosis and cancer therapy.In this review,we focus on the recent research of the bioimaging in living cells and in vivo based on various MOF-based nanocomposites and their potential biological clinical applications.     

THE ELECTRONIC STATE OF Pt ON Pt/L ZEOLITE CATALYST

The effect of the alkali metal cation modification on the aromatization of n-C6 over Pt/ML zeolite catalysts (M=Li. Na. K. Rb) was studied. The results showed that the selectivity for aromati/ation of n-C6 over Pt/MI, increased as the basicity of the alkali cation increased. According to PASCA experiments, dispersed Pt particles were located on the "electron-donation" site of L zeolite XPS measurements further evidenced that a stronger hasicitv of the mouifving canon contributed more electron donation to Pt particles on the surface of 1, zeolite, and shifted the electron binding energy of Pt 4f to lower energies On the other hand, the electron binding energy of Pt 4f in Pt/ML zeolite after reduction was lower than that of Pt0 It is proposed that Pt particles in reduced samples may exist as a Ptδ- state. Moreover, the selectivity for aromatization of aikane was improved since the Ptδ- state was less active to extensive dehvdrogenation of aikane. Ptδ- stale may be presented in the reduced phase of the     

Time-resolved monitoring of heavy-metal intoxication in single hair by laser ablation ICP–DRCMS

The potential of laser ablation inductively coupled plasma mass spectrometry for the time-resolved analysis of heavy-metal intoxication in human bodies by analysis of hair is demonstrated. As application, we analyzed forensic samples from one individual after Hg intake and from one treated with a Pt-containing cytostatic remedy. Single hairs were analyzed from the hair root to the tip by laser ablation ICP–MS with a spatial resolution of 20 μm (corresponding to approx. 2 h growth of the hair). Sulfur was used as internal standard and was analyzed by using oxygen as reaction gas in the dynamic reaction cell of the ICP–DRCMS. The detection limits for Hg and Pt were found to be 0.3 μg g^–1 and 0.5 ng g⁻¹, respectively. Standard uncertainties for the quantification results were 10% for Hg and approximately 15 % for Pt. The analyzed hair samples reflected the forensic evidence in both cases. A significant increase of Hg concentration, by a factor of 50, at the time of HgO administration could be shown, and variation of Pt in the hair strands could be used to monitor the time and relative amount of Pt intake by the patient. The investigations also revealed that the concentrations in the outer and the inner parts of the hair varied similarly with time, even though the concentration in the core of the hair is approximately 0.25 that at the surface for both Pt and Hg.     

In-situ green synthesis of highly active GSH-capped Pt–Au–Ag-hybrid nanoclusters

Recently much attention has been paid to the application of metal hybrid nanoparticles in industrial catalytic fields because of their super-efficient catalytic activity and attractive properties. We explored a novel strategy to prepare GSH-capped Pt–Au–Ag-hybrid nanoclusters through the synergistic effect between ascorbic acid(VC) and glutathione(GSH) with chloroplatinic acid, chloroauric acid, and silver nitrate as precursors. The potential utilization of as-prepared GSH-capped Pt–Au–Aghybrid nanoclusters for catalytic applications has been evaluated through the reduction of 4-nitrophenol(4-NP) with NaBH4; we obtained the kinetic data by monitoring with UV-Vis spectroscopy. Our results illustrate that GSH-capped Pt–Au– Ag-hybrid nanoclusters could facilitate the process of reduction of 4-NP in a way that is unprecedented. This approach may offer a novel, non-cytotoxicity, efficient catalyst for industry.     

Electrodeposited Pt and Pt-Sn nanoparticles on Ti as anodes for direct methanol fuel cells

Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Pt_x-Sn_y catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5mol/L H₂SO₄ and compared to those of a smooth Pt, Pt/Pt and Pt-Sn/Pt electrodes. Platinum was deposited on Ti by galvanostatic and potentiostatic techniques. X-ray diffractometer (XRD) and energy dispersive X-ray (EDX) techniques were applied in order to investigate the chemical composition and the phase structure of the modified electrodes. Scanning electron microscopy (SEM) was used to characterize the surface morphology and to correlate the results obtained from the two electrochemical deposition methods. Results show that modified Pt/Ti electrodes prepared by the two methods have comparable performance and enhanced catalytic activity towards methanol electro-oxidation compared to Pt/Pt and smooth Pt electrodes. Steady state Tafel plots experiments show a higher rate of methanol oxidation on a Pt/Ti catalyst than that on a smooth Pt.  Introduction of a small amount of Sn deposited with Pt improves the catalytic activity and the stability of prepared electrode with time as indicated from the cyclic votlammetry and the chronoamperometric experiments. The effect of variations in the composition for binary catalysts of the type Pt_x-Sn_y/Ti towards the methanol oxidation reaction is reported. Consequently, the Pt_x-Sn_y/Ti (x∶y (8∶1), molar ratio) catalyst is a very promising one for methanol oxidation.     

Influence of PtMo Structure and Composition on the Adsorption Energies, Adsorption Site and Vibrational Frequency of Carbon Monoxide

Density functional theory periodic slab calculations were carried out for CO adsorption on a series of Mo modified Pt(111) surfaces to provide an insight into the interaction between CO and doped metal surface, an important issue in CO oxidation as well as in promotion and poisoning effects of catalysis. The modification of adsorption properties with respect to those of adsorption on the pure Mo(110) and Pt(111) is described in terms of changes in the adsorption energies, adsorption sites and vibrational properties occurring upon alloying. We believe that the present DFT calculations can provide important information into optimal alloy composition for CO-tolerance, which is not easily obtained by experimental methods.     

Fluorescent carbon dots derived from lactose for assaying folic acid

The fluorescent carbon dots were successfully synthesized by simply heating the mixture of lactose and Na OH solution. The as-synthesized carbon dots had been systematically characterized by fluorescence, Fourier transform infrared(FTIR), high resolution transmission electron microscopy(HR-TEM) and ~(13)C NMR. Since the fluorescence of the carbon dots was efficiently quenched by folic acid, the carbon dots were employed as selective fluorescence probes for detecting folic acid, depending on the formation of hydrogen bond among the functional group of folic acid(–OH, –COOH and –NH_2) and –OH and –COOH of the carbon dots. Moreover, the decrease of fluorescence intensity was capable of detecting folic acid in a linear range of 6×10~(-5)–8×10~(-8) mol/L with a detection limit of 1.2×10~(-9)mol/L at a signal-to-noise ratio of 3, suggesting a promising assay for folic acid. Significantly, the practicability of this fluorescence probe to assay folic acid in human urine samples was further evaluated.     

Pt(Ⅱ), Pd(Ⅱ) and Ni(Ⅱ) Complexes Binding to the N(7) Position of Guanine: Influence on the Guanine and Watson-crick GC Base Pair

Comprehensive ab initio calculations were performed on the coordination of Pt(Ⅱ),Pd(Ⅱ) and Ni(Ⅱ) adducts to the N(7) of guanine and guanine-cytosine (GC) base pair at the DFT level. The fully optimized geometries of the metal complexes were obtained and the stabilization energies of the interaction between metal adducts and nucleobase were calculated with B3LYP method by using 6-31^* basis set for the light atom. While the effective core potential (ECP) is used for metal cation. The results show that both cispalladium and cisnickel cause similar geometric changes of the base pair as cisplatin. For the coordination of metal adducts to guanine, platinum adduct possesses the highest stabilization energy; but the interaction between metal-guanine and cytosine for nickel is larger than that for platinum and palladium. It is worthy to note that hydrolysis effect can also cause significant changes in H-bonds.     

A mechanistic study of CO removal on a small H-saturated platinum cluster

CO poisoning to platinum catalysts has long been recognized as one of the major technical obstacles in heterogeneous catalysis and its successful removal represents a significant challenge to a wide variety of applications. Using density functional theory (DFT), we performed systematic theoretical calcula-tions to explore the CO removal mechanisms, in the presence of hydrogen, via oxidation by oxygen to form CO2 or reduction by hydrogen to form formaldehyde using a subnano Pt cluster as a model for catalyst nanoparticles. We show that CO oxidation is both thermochemically and kinetically difficult at low H coverage but becomes very exothermic with a moderate activation barrier at high H coverage, suggesting that the oxidation can be carried out readily at elevated temperatures. Doping the Pt cluster with Ru can significantly improve the oxidation thermochemical energy and moderately reduce the activation barrier. The results are consistent with experimental observations. We found that CO reduction by hydrogen to form formaldehyde is moderately endothermic. However, the reaction is predicted to be kinetically difficult due to the relatively high activation barriers associated with the sequential H attacks to the CO molecule.     

Synthesis and properties of bifunctional magnetic-optical nanomaterials: Fe2O3@Pdmaema-capped II–VI semiconductor quantum dots nanocomposites

A facile route to synthesize a new type of multifunctional nanocomposites is reported. Here, PDMAEMA (poly[2-(dimethylamino)ethyl] methacrylate) is a key macromolecule serving as a bridge between magnetic Fe2O3 nanoparticles and luminescent quantum dots. Both Fe2O3 nanoparticles and Ⅱ-Ⅵ semiconductor quantum dots with a narrow size distribution are synthesized through a two-phase thermal approach. Subsequently, the atom transfer radical polymerization (ATRP) technique was applied to prepare magnetic Fe2O3@PDMAEMA core-shell nanoparticles. The thickness of PDMAEMA shell can be easily controlled by adjusting the reaction time. Finally, the ligand exchange method was exploited to modify Ⅱ-Ⅵ quantum dot with amine-containing polymer of PDMAEMA, which led to quantum dot securely bound by Fe2O3@PDMAEMA core-shell nanoparticle to form a multifunctional nanocomposite. The resulting nanocomposite remains variable emission by tuning the Ⅱ-Ⅵ semiconductor type and particle size and shows Hc at 49 kA/m and Tb at 16 K from Fe2O3 nanoparticles. The self-assembled behavior for the resulting samples is also discussed.     

Platinum nanoparticles supported MoS2 nanosheet for simultaneous detection of dopamine and uric acid

Herein, platinum nanoparticles-decorated molybdenum disulfide(Pt NPs@MoS_2) nanocomposite has been synthesized via a microwave-assisted hydrothermal method, which was characterized by transmission electron microscopy(TEM) and powder X-ray diffraction(XRD). This MoS_2-based nanocomposite modified glass carbon electrode(Pt NPs@MoS_2/GCE) exhibited excellent electrocatalytic activity toward dopamine(DA) and uric acid(UA) due to their synergistic effect. Two well-defined oxidation peaks of DA and UA were obtained at Pt NPs@MoS_2/GCE with a large peak separation of 160 m V(DA-UA), suggesting that the modified electrode could individually or simultaneously analyze DA and AA. Under the optimal conditions, the peak currents of DA and UA were linearly dependent on their concentrations in the range of 0.5–150 and 5–1000 mmol/L with detection limit of 0.17 and 0.98 mmol/L, respectively. The proposed MoS_2-based sensor can also be employed to examine DA and UA in real samples with satisfactory results. Therefore, the Pt NPs@MoS_2 nanocomposite might offer a good possibility for electrochemical sensing and other electrocatalytic applications.     

Platinum Atoms Dispersed in Single-chain Polymer Nanoparticles

The intramolecular cross-linking of single polymer chains can form single-chain nanoparticles(SCNPs), which have many applications.In this study, styrenic copolymers with pendent triphenylphosphine as the coordination site for platinum ions(Pt(Ⅱ)) and benzocyclobutene as the latent reactive groups are synthesized. Triphenylphosphine groups in the chains can coordinate Pt(Ⅱ) and aid slight single-chain folding in dilute solution. The intramolecular cross-linking caused by the ring-open reaction of benzocyclobutene completes the single-chain collapse and forms stable SCNPs in dilute solution. Pt(Ⅱ) embedded in SCNPs can be further reduced to platinum atoms(Pt(0)). Pt(0) steadily and atomically dispersed in SCNPs exhibits better catalytic properties than normal polymer carried platinum particles do for the reduction of p-nitrophenol to p-aminophenol.     

Preparation and characterization of Ti0.7Sn0.3O2 as catalyst support for oxygen reduction reaction

Sn-doped TiO_2 nanoparticles with high surface area of 125.7 m~2·g~(-1) are synthesized via a simple one-step hydrothermai method and explored as the cathode catalyst support for proton exchange membrane fuel cells.The synthesized support materials are studied by X-ray diffraction analysis,energy dispersive X-ray spectroscopy and transmission electron microscopy.It is found that the conductivity has been greatly improved by the addition of 30 mol%Sn and Pt nanoparticles are well dispersed on Ti_(0.7)Sn_(0.3)O_2 support with an average size of 2.44 run.Electrochemical studies show that the Ti_(0.7)Sn_(0.3)O_2 nanoparticles have excellent electrochemical stability under a high potential compared to Vulcan XC-72.The as-synthesized Pt/Ti_(0.7)Sn_(0.3)O_2 exhibits high and stable electrocatalytic activity for the oxygen reduction reaction.The Pt/Ti_(0.7)Sn_(0.3)O_2 catalyst reserves most of its electrochemically active surface area(ECA),and its half wave potential difference is 11 mV,which is lower than that of Pt/XC-72(36 mV) under 10 h potential hold at 1.4 V vs.NHE.In addition,the ECA degradation of Pt/Ti_(0.7)Sn_(0.3)O_2is 1.9 times lower than commercial Pt/XC-72 under 500 potential cycles between 0.6 V and 1.2 V vs.NHE.Therefore,the as synthesized Pt/Ti_(0.7)Sn_(0.3)O_2 can be considered as a promising alternative cathode,catalyst for proton exchange membrane fuel cells.