A New Approach on the Active Treatment for Electroless Copper Plating on Glass

A new method is described for the electroless deposition of copper onto glass.Commercially available glass slide was modified with γ-aminopropyltrimethoxysilane to form self-assembled monolayer (SAM) on it .Then it was dipped directly into PdCl2 solution instead of the conventional SnCl2 sensitization followed by PdCl2 activation.Experimental results showed that the Pd^2 ions from PdCl2 solution were coordinated to the amino groups on the glass surface resulting in the formation of N-Pd complex.In an electroless copper bath containin a formaldehyde reducing agent,the N-Pd complexes were reduced to Pd^0 atoms,which then acted as catalysts and initiated the deposition of copper metal.Although the copper deposition rate on SAM-modified glass was slow at the beginning,it reached to that of conventional method in about 5min.     

A New Activation Method for Electroless Metal Plating：Palladium Laden via Bonding with Self—Assembly Monolayers

A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition.A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation.XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.     

An Improved Preparation Technique for Pd/Ceramic Composite Membrane by Electroless Plating

ＡｎＩｍｐｒｏｖｅｄＰｒｅｐａｒａｔｉｏｎＴｅｃｈｎｉｑｕｅｆｏｒＰｄ／ＣｅｒａｍｉｃＣｏｍｐｏｓｉｔｅＭｅｍｂｒａｎｅｂｙＥｌｅｃｔｒｏｌｅｓｓＰｌａｔｉｎｇ１）ＧＵＯＹａｎｇｌｏｎｇＬＵＧｕａｎｚｈｏｎｇＷＡＮＧＱｉｎＷＡＮＧＲｅｎ（Ｒｅｓｅａｒ...     

Multi‐Walled Carbon Nanotubes as Sorbent for Flow Injection On‐Line Microcolumn Preconcentration Coupled with Flame Atomic Absorption Spectrometry for Determination of Cadmium and Copper

Abstract

Multi‐walled carbon nanotubes (MWNTs) were used as sorbent for flow injection (FI) on‐line microcolumn preconcentration coupled with flame atomic absorption spectrometry (FAAS) for determination of trace cadmium and copper in environmental and biological samples. Effective preconcentration of trace cadmium and copper was achieved in a pH range of 4.5–6.5 and 5.0–7.5, respectively. The retained cadmium and copper were efficiently eluted with 0.5 mol L^?1 HCl for on‐line FAAS determination. The MWNTs packed microcolumn exhibited fairly fast kinetics for the adsorption of cadmium and copper, permitting the use of high sample flow rates up to at least 7.8 mL min^?1 for the FI on‐line microcolumn preconcentration system without loss of the retention efficiency. With a preconcentration time of 60 sec at a sample loading flow rate of 4.3 mL min^?1, the enhancement factor was 24 for cadmium and 25 for copper at a sample throughput of 45 h^?1. The detection limits (3σ) were 0.30 and 0.11 µg L^?1 for Cd and Cu, respectively. The precision (RSD) for 11 replicate measurements was 2.1% at the 10‐µg L^?1 Cd level and 2.4% at the 10‐µg L^?1 Cu level. The developed method was successfully applied to the determination of trace Cd and Cu in a variety of environmental and biological samples.     

Unexpected Isolation of 4‐Isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic Acid Ethyl Ester as Potential Template in Organic Synthesis

The synthesis of 4‐isothiocyanatomethyl‐pyridine 4 in 36% yield by Hasegawa and Kotani (Japanese patent 49088878, 1974) has spurred us to investigate this preparation in detail. In addition to this compound, 4‐isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic acid ethyl ester 3 can be isolated. The synthesis of both compounds 3 and 4 were optimized to 75% and 50% yield respectively. Reaction of compound 3 with methylamine gave thiourea derivatives 5, the same product obtained on reacting 4‐isothiocyanatomethyl‐pyridine 4 with methylamine. We succeed in adjusting the reaction conditions to obtain high yield either from compound 3 or isothiocyanate derivatives 4.     

Effect of γ-Radiation on the Structural and Conducting Properties of Copper Nanotubes

The influence of γ-radiation on the structural and conducting properties of copper nanotubes, obtained by electrochemical synthesis in pores of on polyethylene terephthalate-based template matrices, has been studied. With the use of scanning electron microscopy, X-ray diffraction analysis, and electron diffraction analysis, it has been established that irradiation with γ-rays at doses of 50 and 100 kGy makes it possible to modify the crystal structure of the nanotubes, increasing their conductivity and decreasing the resistance of the nanosized entities without destroying their structure.     

Synthesis of N‐Aryl‐2‐substituted Tetrahydrobenzimidazoles via Direct N‐Arylation

A series of novel N‐aryl‐2‐substituted tetrahydrobenzimidazoles has been synthesized via direct N‐arylation of 2‐substituted tetrahydrobenzimidazoles, which was accomplished by a medium aryl electrophile, 4‐methylsulfonylfluorobenze, in the presence of 37% KF/Al₂O₃ and 18‐crown‐6 in fair yields under mild reaction conditions. Meanwhile, the hydrogenation of 2‐phenylbenzimidazole was studied.     

Voltammetric Determination of L‐Dopa Using a Carbon Nanotubes‐Nafion Modified Glassy Carbon Electrode

Abstract

A method for determination of L‐dopa by the adsorption stripping voltammetry (ASV) using a multiwalled carbon nanotubes (MWNTs)–Nafion modified glassy carbon electrode (GMGCE) was proposed. This chemically modified electrode (CME) shows a better stability. A sensitive oxidation peak was observed and the anodic peak potential is ca. 0.374V (vs. SCE). The influences of various experimental parameters on the current peak were completely studied. Under the optimized condition, the method has been applied to the determination of L‐dopa in samples. There is a good linear relationship between the peak current (i_p) and L‐dopa concentration in the range of 3.5×10^?7～1.5×10^?5 mol/L, with the limit of detection 5.0×10^?8 mol/L.     

One‐Pot Synthesis of Ene‐Lactams via N‐Debenzylation of Keto‐Containing N‐2,4‐Dimethoxylbenzylamides

Abstract

A general method of ene‐lactam preparation is described. Ene‐lactams can be prepared efficiently from keto‐containing N‐2,4‐dimethoxylbenzylamides in good to excellent yields. This method is applicable for the preparation of substituted δ‐, γ‐, and ?‐ene‐lactams and bicyclic ene‐lactams.     

Efficient Synthesis of “Star‐like” Surfactants via “Click Chemistry” [3+2] Copper (I)‐catalyzed Cycloaddition

We report an efficient synthesis of tetra‐ and hexa‐substituted carbohydrate‐coated compounds, which we have named “star‐like” surfactants, starting from either α‐methylglucose or myo‐inositol as a central core. The synthesis explores a new approach to such multipolar compounds using [3+2] copper (I)‐catalyzed cycloadditions to attach the respective building blocks.     

Cesium Carbonate–Promoted Michael‐Type Addition of Thiols to Hex‐1‐en‐3‐ulose: A Practical Synthesis of 2‐Deoxy‐1‐thio‐α‐hexopyranosid‐3‐ulose Template

The template 2‐deoxy‐1‐thio‐α‐hexopyranosid‐3‐ulose was synthesized in quantitative yield and high diastereoselectivity by 1,4‐addition of aryl and alkyl thiols to hex‐1‐en‐3‐ulose promoted by cesium carbonate in THF.     

Enzymatically Synthesized Conducting Polyaniline Nanocomposites: A Solid‐State NMR Study

Abstract

The chiral conducting polyaniline (PANI) nanocomposites [polyacrylic acid/polyaniline/(?) camphorsulphonic acid (CSA)] were synthesized using enzyme, horseradish peroxidase (HRP) in the aqueous buffer solution at pH 4.3. It appears that the enzyme HRP apart being a biocatalyst, plays an important role during the polymerization, which allows PANI to prefer a specific helical conformation whether the induced chirality in the monomer‐CSA complex is either by (+)CSA or (?)CSA. In this paper, we report, the structural characterization of these nanocomposites by solid‐state ¹³C cross‐polarization with magic angle spinning (CP/MAS) NMR techniques. The structural features of PANI in the conducting form of nanocomposite (as‐synthesized) are similar to that of enzymatically and chemically synthesized PANI. Preliminary data also suggest that some portion of nanocomposite samples are not completely doped. Dedoping of as‐synthesized PANI nanocomposite with aqueous NH₄OH shows the spectral features that of the emeraldine base form. Solid‐state ¹³C NMR data suggest that it is possible to detach PAA and CSA from PANI in the nanocomposite material.     

Electrical Property of Tin Oxide Doped with Multi‐Walled Carbon Nanotubes

Tin oxide doped with multi‐walled carbon nanotubes (MWNTs) was prepared via a wet‐chemical process and characterized with x‐ray diffraction (XRD) and transmission electron microscope (TEM). Meanwhile, the conductivity of composites obtained was measured using Source Meter. The results show that carbon nanotubes have great effect on the electrical property of SnO₂ nanoparticles. Compared with undoped SnO₂ nanoparticles, the resistivity of SnO₂ nanoparticles doped with 0.3‰ wt MWNTs decreased by a factor of 37. This may be ascribed to the presence of π energy levers of MWNTs and their high aspect ratio. Moreover, the effect of annealing temperature on the electrical property of SnO₂ nanoparticles doped with MWNTs also was discussed.     

Synthesis of 4‐(Indol‐1‐yl)butanals via Rhodium‐Catalyzed Hydroformylation of 1‐Allylindoles

The rhodium‐catalyzed hydroformylation of new 1‐(β‐methallyl) indoles 1a–e carried out with Rh₄ (CO)₁₂ as the catalyst precursor, at 100 atm total pressure and 100°C, produces the 4-(indol‐1‐yl)‐3‐methylbutanals 2a–e as the sole products in high yields. The synthesized 4‐indolylbutanals are stable under the adopted conditions and are isolated and characterized here for the first time. The preparation of the starting 1‐allylindoles is described too.     

Facile One‐Pot Synthesis of 2‐Aryl‐substituted Nitriles and 2‐Aryl‐3‐keto Nitriles via Benzyne Reaction

2‐Aryl‐substituted nitriles were prepared in good to excellent yields in a one‐pot reaction by the reaction of benzyne, generated using neutral conditions from (phenyl)[o‐(trimethylsilyl)‐phenyl]iodonium triflate, and 2‐lithionitriles. 3‐Keto nitriles substituted at the 2‐position were obtained in good yields when these reactions were trapped with acid chlorides. The mechanism of the benzyne reaction in terms of a N‐lithiobenzocyclobutanimine intermediate is discussed.     

Synthesis of N‐Glycoside Analogs via Thionolactones

Indolyl N‐glycoside analogs were obtained by a two‐step sequence via indole N‐thioamides. Treatment of thionobutyrolactone with indolylmagnesium bromide provides the corresponding indole N‐thioamide. The use of 10:1 toluene:THF as solvent is important in favoring N‐ over C3‐acylation. Treatment of the ω‐hydroxythioamide with 2 equiv of Meerwein's reagent followed by sodium borohydride gives the corresponding N‐(tetrahydrofuranyl)indole. Addition of carbon nucleophiles gives access to ketose nucleoside analogs, while activation of the ω‐hydroxyl group can give access to tetrahydrothiophene N‐glycosides.     

Synthesis of Poly(IB‐co‐VBDC)‐g‐PMMA via Photo‐initiated Free Radical Graft Polymerization

Abstract

Photoinitiated free radical graft polymerization of methyl methacrylate (MMA) with poly[isobutene‐co‐(4‐vinyl benzyl N,N‐diethyldithiocarbamate)] [poly(IB‐co‐VBDC)] as macromolecular iniferter was investigated. The polymerization proceeds to give a high yield graft copolymer, however it was observed that even in the early stage of the polymerization there formed an insoluble polymer. In the presence of tetraethylthiuram disulfide (TETD) the gel fraction of the yield graft copolymer was drastically reduced and the polymerization was retarded as well. When the [TETD]/[VBDC] increased from 0 to 1.0, the gel fraction of the graft copolymer decreased from 33.2% to 1.6% (wt) while the fraction of the homopolymer of the MMA increased from 4.5% to 10.5% (wt). With the increasing of the UV irradiation time, both the MMA conversion and the molecular weight of the graft copolymer increased readily.     

Electrocatalytic Activity of Bamboo‐Structured Carbon Nanotubes Paste Electrode Toward Hydrogen Peroxide

Abstract

In this report, we describe the finding that bamboo‐structured carbon nanotubes (CNT) showed superior electrocatalytic activity toward hydrogen peroxide. The slope of the calibration curve for hydrogen peroxide obtained with the bamboo‐structured CNT paste electrode was more than 20 times as large as the slopes obtained with hollow‐structured CNT paste and glassy carbon electrodes at an operating potential of ?0.1 V, with no interfering reactions. Incorporation of glucose oxidase within the bamboo‐structured CNT paste electrode allows the selective detection of glucose in the presence of common interferents without using any permselective membranes. This excellent ability of the bamboo‐structured CNT paste electrode toward hydrogen peroxide is applicable to the development of other enzymatic biosensors.     

Synthesis of Mesoionic 4‐(para‐substituted Phenyl‐5‐2,4‐dichlorophenyl)‐1,3‐4‐thiadiazolium‐2‐aminides by Direct Cyclization via Acylation of Thiosemicarbazides

The synthesis of ten novel mesoionic 4‐[para‐substituted (H, CH₃, OCH₃, NO₂, Cl, Br, OH, t‐C₄H₉, C₆H₅, C₄H₉) phenyl‐5‐2,4‐dichlorophenyl]‐1,3‐4‐thiadiazolium‐2‐aminides, as hydrochlorides, are described. The synthesis strategy utilized the corresponding para‐substituted isothiocyanates as starting materials to obtain the thiosemicarbazides through reaction with phenylhydrazine (61–98%), which were then submitted to acylation with 2,4‐dichloro benzoyl chloride and direct cyclization to generate the desired substituted mesoionic compounds in good yields (ca. 80%).     

Preparation of Macroporous Aluminium Oxide using Template of Poly(methacrylic acid‐co‐glycidylmethacrylate) Crosslinked with Methylenebisacrylamide

Poly(methacrylic acid‐co‐glycidylmethacrylate), poly(MA‐co‐GMA) samples were prepared by exposure to γ–irradiation, at fixed concentration of methylenebisacrylamide MBA, 0.5% wt/wt as crosslinker while the MA/GMA ratio was varied. FTIR spectra showed bands refer to MA, as well as GMA, indicating the involvement of both in the copolymerization. Al(NO₃)₃.9H₂O as a precursor for the preparation of aluminium oxide was templated as a guest into the crosslinked gels by soaking the gels in a methanol solution. The perturbation of the bands at 3439, 2926, 1635, 1476, 1394, and 1166 cm^?1 after the templation of the guest, provides evidence for the loading of the guest species into the gel. The swelling behavior of the prepared samples found to be dependent on the composition of the gel and the pH. The templation of the aluminium nitrate into the gel was further proved by thermal gravimetric analysis (TGA). Scanning electron microscopy (SEM) was used for investigating the produced oxide particles, which revealed macropores with maximum diameter at MA/GMA, 40∶60 wt/wt (H3) and complete disappearance at 80 wt% of methacrylic acid (H5). X‐ray diffraction (XRD) showed an amorphous structure of the aluminium oxide. Increasing the hydrophilicity of the template leads to an increase in the Lewis acidic sites on the surface of the produced aluminium oxide up to 60 wt% of methacrylic acid (H4) while a further increase was met by a redecrease in the surface acidity (H5).