高校化学实验室易制毒化学品管理工作探索

高校化学实验室是集教学、科研以及培养专业人才为一体的实验场所,实行开放式管理,具有使用频率高、人员集中且流动性大等特点。易制毒化学品是化学实验室常用的药品,其安全管理具有一定的挑战性。针对当前高校易制毒化学品管理工作中存在的若干普遍性问题,本文从内部健全科学、有效、简洁的易制毒化学品管理制度,设立易制毒化学品库房,实行专人专管,采取随领随取的发放模式,同时为每位教师建立易制毒化学品资金账簿并有专人定期巡视检查等多项举措,对易制毒化学品使用的全过程进行有效监管。既方便、满足了教学与科研合理使用的需求,同时又防范杜绝了违规使用的出现。     

Preparation and application of poly(alkoxytitanate) as a TiO2 precursor with high storage stability

Titanium dioxide is a basic material of our daily life. Because of its favourable properties, such as harmlessness, chemical stability, photocatalytic activity, or whiteness it is increasingly applied in both micro and nano particles and thin films and coating. One of the available procedures for film forming is the sol–gel technology, an inexpensive low temperature process with wide possibilities to vary film properties by changing the composition of the precursor solution or other parameters. In the paper a new precursor polymer for TiO₂ film-preparation with high storage and processing stabilities is introduced and applied in thin film forming. The new precursor poly(alkoxytitanate) is prepared by a one step, water-free sol–gel method. A smooth TiO₂ film can be prepared using this precursor by spin-coating followed by H₂-plasma curing. Comparing to a common precursor such as Ti(O–iPr)₄, this precursor has a good solubility in different solvents and a much higher storage stability. The easy to modify precursor end groups enable the tailoring of properties regarding to hydrolysis to both TiO₂ particles and films.     

Facile fabrication of hierarchical ZnO nanowire aggregates using rose-like peroxide precursor as the inorganic template

The complex rose-like inorganic templates assembled by the ZnO/ZnO₂ hybrid nanosheets have been constructed with hydrogen peroxide as an additive to control the structure of a precursor. The surface morphologies of the inorganic templates can be controlled by varying the reaction time and the amount of hydrogen peroxide. The process of the precursor growth takes a dissolution-growth route under hydrothermal conditions. The chemical composition of the precursor is determined by X-ray diffraction (XRD) and Raman analyses, indicating the existence of peroxide in the precursor. Combined with transmission electron microscopy (TEM) data, the ZnO/ZnO₂ hybrid precursor is proposed to act as an inorganic template for the growth of secondary crystal structures. The dandelion-like ZnO crystal is fabricated by using rose-like peroxide precursor as the inorganic template. The structural evolution of hierarchical ZnO crystal is studied by monitoring the influence of the reaction time.     

Synthesis of yttrium iron garnet using polymer-metal chelate precursor

Two kinds of polymer-metal compounds, heterogeneous complexes (metal-chelating copolymer microspheres, MCP) and homogeneous complexes (water-soluble metal-chelating polymers, WSMCP), were synthesized to act as nucleation agents for YIG precursor preparation in this text. Both of the metal-chelating polymers have the same chelating group and high metal ion adsorption ability from the FTIR and ICP measurement. Furthermore, good YIG crystals can be obtained by treating the MCP precursor with a low calcination temperature at 600 degrees C from the XRD spectra and TEM micrograph. However, the YIG crystal obtained using a WSMCP precursor should be synthesized at a higher calcination temperature (>900 degrees C) due to the different components of the YIG precursor. In addition, the YIG crystal obtained by using the MCP precursor had nearly superparamagnetic behavior after VSM examination.     

Phenylated poly(P-phenylene vinylenes) prepared via the chlorine precursor route (CPR)

The synthesis of several highly phenylated PPV derivatives by a chlorine precursor route (CPR) was investigated in order to understand its scope. Three 1,4-bis(chloromethyl)benzene monomers were prepared via a robust and versatile synthetic procedure involving the Diels-Alder reaction. The monomers were then polymerized to the corresponding precursor polymers with about 1.0 equivalent of potassium t-butoxide in THF. Only one monomer gave a soluble precursor polymer while the other two gave insoluble precursor polymers. The soluble precursor polymer was deposited as thin films and then converted to the corresponding PPV derivative, which showed green photoluminesence and electroluminesence.     

Precursor mediated cycloaddition reaction of ethylene to the Si(100)c(4 x 2) surface

We report the direct observation of a precursor state for the cycloaddition reaction (the di-sigma bond formation) of ethylene on Si(100)c(4 x 2) using high-resolution electron energy loss spectroscopy at low temperature, and the meta-stable precursor state is identified as a weakly bonded pi-complex type. The activation energy from the pi-complex precursor to the di-sigma bonded species is experimentally estimated to be 0.2 eV. First-principles calculations support the pi-complex precursor mediated cycloaddition reaction of ethylene on Si(100)c(4 x 2).     

超音速气流粉碎下NiO纳米棒的低温固相制备

采用超音速气流粉碎技术低温固相合成NiO纳米颗粒前驱体,并通过在650～900 ℃下, NaCl熔盐介质中对前驱体进行焙烧,制备得到NiO纳米棒。采用XRD、SEM、TEM测试技术对NiO前驱体、NiO纳米棒的结构和形貌进行了表征。结果表明,前驱体为直径约25 nm球形颗粒,随着焙烧温度升高,逐渐生成直径为300 nm,长度约十几微米的纳米棒。反应过程中熔盐介质是纳米颗粒前驱体生长的关键因素。     

Purification of the precursor for the automated radiosynthesis of [18F]FCWAY by counter-current chromatography

Radiolabeled FCWAY (N-(2-[4-(2-methoxyphenyl)piperazino])-N-(2-pyridinyl) trans-4-fluorocyclohexanecarboxamide) was prepared for human positron emission tomography (PET) studies by a simple one-step radiosynthesis. The LC-MS analysis of the products indicated that it contained impurities which may interfere with FCWAY uptake of 5-HT1A receptors and that these impurities were derived from an impurity originally present in the precursor preparation. Since preparative HPLC failed to resolve one of the impurities from the precursor, preparative-scale high-speed counter-current chromatography (HSCCC) was used for purification of this FCWAY precursor. A suitable two-phase solvent system composed of cyclohexane-ethyl acetate-methanol-water at a volume ratio of 1:1:1:1 or 4:5:4:5 was selected based on the partition coefficients of the precursor and impurity as determined by a LC-MS method. Using the second solvent ratio of 4:5:4:5 with the organic phase as a mobile phase, a 2.57 g amount of precursor preparation was successfully purified yielding 2.2 g of the pure precursor by a single run.     

能量色散X射线散射结合主成分分析对液体易制毒化学品的探测与鉴别分类

采用能量色散X射线散射(EDXRS)技术探测了8种液体易制毒化学品的X射线散射光谱, 结果显示液体易制毒物质具有各自特征的EDXRS散射图谱. 将液体易制毒化学品的EDXRS散射信息与主成分分析结合, 发现前2个主成分可以表达X射线散射光谱的主要信息, 在PC1～PC2得分分布图上可将液体易制毒化学品进行分类. 研究结果表明, EDXRS光谱技术结合主成分分析法可以实现探测、 鉴别分类液体易制毒化学品, 为隐藏液体易制毒化学品的监管控制提供一个可行的鉴别方法.     

A combined XPS-UPS-EELS study of nitrogen adsorbed on clean and barium-promoted iron surfaces: The nature of the precursor to dissociation

For N₂ on a clean Fe surface, the adsorbed precursor in a parallel orientation becomes predominant around 110 K, while at lower temperatures it coexists with a weakly adsorbed species. On a Ba-promoted Fe surface, however, N₂ is present exclusively in the precursor state in the temperature range 80–150 K following moderate exposure. Besides exhibiting a low N-N stretching frequency of 1530 cm⁻¹, the precursor shows a clear separation between the 5σ and 1π levels in the UPS; the precursor dissociates to give a nitridic species around 160 K.     

Preparation of CdSe/ZnSe Core-shell Nanocrystal in One-step Reaction

IntroductionSemiconductor nanocrystals show strong size-de-pendent properties when their size is similar to or smal-ler than the excition Bohr radius of the bulk materialsand quantum confinement occurs for the space-con-fined motion of the electrons and holes in the nano-re-gion of materials[1—5].Because of the excellent opticaland electronic properties,semiconductor nanocrystalsare currently being investigated as emitting materials forthin-film light-emitting devices(LED)[6,7],low-thresh-ol…     

Thermal Decomposition and Crystallization of Aqueous Sol-Gel Derived Zirconium Acetate Gels: Effects of the Precursor Solution pH

Crystalline zirconia has previously been formed by desiccation and pyrolysis of a pH 3.4 zirconium acetate precursor solution. In this study, amorphous gels were formed by desiccation of zirconium acetate precursor solutions at pH 0.9 to 3.4 obtained by adding hydrochloric acid and at pH 8.0 by adding ammonium hydroxide to the available pH 3.4 precursor solution. The concentrations of the uncomplexed zirconium ion and the 1 : 1 and 1 : 2 zirconium acetate complexes varied with pH. Decomposition of the amorphous gel and its structure evolution to form crystalline zirconia by pyrolysis were studied. Several decomposition and structure transition temperatures occurring in the pyrolysis and the polymorph distribution in the pyrolysis products were dependent on the pH of the precursor solution. These variations of structure evolution with pH were also related to the relative concentrations of specific zirconium complexes in the precursor solutions. Removal of carbon by pyrolysis was improved by adding hydrochloric acid or ammonium hydroxide to the pH 3.4 precursor solution.     

DFT Study on the Recovery of Hoveyda–Grubbs‐Type Catalyst Precursors in Enyne and Diene Ring‐Closing Metathesis

DFT (B3LYP‐D) calculations have been used to better understand the origin of the recovered Hoveyda–Grubbs derivative catalysts after ring‐closing diene or enyne metathesis reactions. For that, we have considered the activation process of five different Hoveyda–Grubbs precursors in the reaction with models of usual diene and enyne reactants as well as the potential precursor regeneration through the release/return mechanism. The results show that, regardless of the nature of the initial precursor, the activation process needs to overcome relatively high energy barriers, which is in agreement with a relatively slow process. The precursor regeneration process is in all cases exergonic and it presents low energy barriers, particularly when compared to those of the activation process. This indicates that the precursor regeneration should always be feasible, unlike the moderate recoveries sometimes observed experimentally, which suggests that other competitive processes that hinder recovery should take place. Indeed, calculations presented in this work show that the reactions between the more abundant olefinic products and the active carbenes usually require lower energy barriers than those that regenerate the initial precatalyst, which could prevent precursor regeneration. On the other hand, varying the precursor concentration with time obtained from the computed energy barriers shows that, under the reaction conditions, the precursor activation is incomplete, thereby suggesting that the origin of the recovered catalyst probably arises from incomplete precursor activation.     

Effect of precursor-layer surface charge on the layer-by-layer assembly of polyelectrolyte/nanoparticle multilayers

In this Article, we investigate the effect of a precursor layer, which is composed of four bilayers of polyethyleneimine (PEI) and poly(sodium styrene sulfonate) (PSS), on the subsequent LBL assembly of hybrid films composed of indium tin oxide (ITO) nanoparticles and PSS. A precursor polyelectrolyte layer is usually deposited to minimize interference by the substrate. It is shown here that the "effective" surface charge of the precursor layer can significantly affect the subsequent assembly behavior of [ITO/PSS](9.5) hybrid thin films. Depending on the surface charge of the precursor layer, the subsequent LbL assembly of [ITO/PSS](9.5) hybrid films can exhibit either one or two regimes. When two growth regimes are present, the first one consists of a "recovery regime", and the second is the expected "linear growth regime." The length of the "recovery regime" is dependent on how much positive charge the precursor layer possesses and how fast this surface charge can be compensated. This work reveals for the first time that changes in the surface charge of the precursor layer can have a significant effect on the subsequent LBL assembly process. The surface charge of the precursor layer was investigated using ζ-potential measurements on model silica microspheres. These experiments showed that the surface charge of the precursor layer, [PEI/PSS](4), is dependent on the pH of the solution in which it is immersed, and that it can reverse from a negatively charged surface to a positively charged one, at sufficiently low pH due to the protonation of PEI, despite having the negatively charged PSS layer as the outermost layer.     

Low-temperature approach to synthesize iron nitride from amorphous iron

Iron nitride was prepared by a nitridation reaction in NH 3 using amorphous iron as precursor. The precursor was prepared at ambient temperature through the process of reducing ferrous sulfate by potassium borohydride, followed by the nitridation at different temperatures. The nitridation reaction occurred at 548 K, and -Fe 2-3N was formed at 573 K. The reaction temperature was much lower than that using crystallized iron because of the characteristics of the amorphous materials. The existence of a small quantity of boron (1.6 wt.%) improved the stability of the amorphous precursor, which guaranteed an amorphous iron precursor at nitriding temperatures in excess of 548 K.     

Cluster self-organization of Na,Ti-silicate systems: Suprapolyhedral precursors and self-assembly of crystal structures of Na2Ti2Si2O9 (Ramzaite) and Na2TiSiO5 (paranatisite)

The initial stages of formation of precursor clusters are considered in an evolving system containing various types of polyhedra: T tetrahedra and M polyhedra (pyramids, octahedra, and others). A graph topological representation of the precursor clusters of different self-organization levels of a chemical system is given. The model has been applied to find precursor clusters for Na,Ti-silicates that crystallize in the Na-Ti-Si-O(H) systems. For ramzaite Na₂Ti₂Si₂O₉ (RAM) and a dimorph of natisite (NAT), namely, paranatisite Na₂TiSiO₅ (PNAT), computer techniques (the TOPOS 4.0 program package) have been used to perform the full 3D reconstruction of structure self-assembly: precursor cluster-primary chain-microlayer-microframework (supraprecursor). New types of eight-polyhedral ring precursor clusters have been identified. The packing specifics of precursor clusters in crystal-forming microlayers determine the platy habit of Na,Ti-silicate single crystals.     

Product ion spectral simplification using time-delayed fragment ion capture with tandem linear ion traps

A new technique to generate product ion spectra as the internal energy of a collisionally activated precursor ion evolves is described. The precursor ion is activated by acceleration into a mass-selective linear ion trap under conditions whereby some of the fragment ions formed are unstable within the trap. After a time delay the stability parameters of the ion trap are changed to allow capture of fragments that that were previously unstable. The result is a product ion spectrum that originates from precursor ions with a modified internal energy distribution. It is possible to follow the evolution of the precursor internal energy distribution for many milliseconds after admittance of the precursor ions into the linear ion trap. Time-delayed fragmentation product ion spectra typically display reduced sequential fragmentation products leading to spectra that are more easily interpreted. Several important experimental parameters important to time-delayed fragmentation have been identified and are discussed. The technique has applications for both small precursor ions and multiply charged peptides.     

The effect of composition variables on precursor degradation and their consequence on Nb2O5 film properties prepared by the Pecchini Method

The calcination of Nb₂O₅ prepared by the Pecchini method was investigated using thermal analysis. The polymer precursor was prepared with different citric acid/ethylene glycol (CA/EG) and citric acid/niobium precursor (CA/Nb) molar ratios. The results suggest a strong influence of the CA/EG molar ratio, mainly on the polymerization degree. The CA/Nb ratio also modifies the degradation process of the precursor solution. The effect of the precursor compositional variation was also observed in the oxide structure, as well as in its electrochemical and electrochromic behavior. Films prepared using high CA/EG and a Nb salt precursor amount have the highest values of charge density and coloration efficiency. Moreover XRD data for this sample show a crystalline structure while the samples prepared with low CA/EG ratio are amorphous.     

Identification of the precursor cluster in thermolysin crystallization solution by molecular dynamics methods

An analysis of the crystal structure of thermolysin revealed four possible precursor clusters (hexamers) of its crystal. Using the method of molecular dynamics and plots of root mean square fluctuation, root mean square deviation and radius of gyration, the most stable hexamer, which is a precursor cluster,was determined. The importance of the established structure of the thermolysin precursor cluster for determining the mechanism of crystal formation is shown.     

In situ gelling hexagonal phases for sustained release of an anti-addiction drug

In this study, fluid precursor formulations for subcutaneous injection and in situ formation of hexagonal phase gels upon water absorption were developed as a strategy to sustain the release of naltrexone, a drug used for treatment of drug addiction. Precursor formulations were obtained by combining BRIJ 97 with propylene glycol (PG, 5-70%, w/w). To study the phase behavior of these formulations, water was added at 10-90% (w/w), and the resulting systems were characterized by polarized light microscopy. Two precursor formulations containing BRIJ:PG at 95:5 (w/w, referred to as BRIJ-95) and at 80:20 (w/w, referred to as BRIJ-80) were chosen. Naltrexone was dissolved at 1% or suspended at 5% (w/w). Precursor formulations were transformed into hexagonal phases when water content exceeded 20%. Water uptake followed second-order kinetics, and after 2-4h all precursor formulations were transformed into hexagonal phases. Drug release was prolonged by the precursor formulations (compared to a drug solution in PBS), and followed pseudo-first order kinetics regardless of naltrexone concentration. The release from BRIJ-80 was significantly higher than that from BRIJ-95 after 48 h. The relative safety of the precursor formulations was assessed in cultured fibroblasts. Even though BRIJ-95 was more cytotoxic than BRIJ-80, both precursor formulations were significantly less cytotoxic than sodium lauryl sulfate (considered moderate-to-severe irritant) at the same concentration (up to 50 μg/mL). These results suggest the potential of BRIJ-based precursor formulations for sustained naltrexone release.