bluuebunny/crossref_metadata_2025 huggingface dataset:
Intracellular phospho‐protein staining techniques for flow cytometry: Monitoring single cell signaling events
Authors: Krutzik Peter O. , Nolan Garry P.
Published: September 2003

Background

Recent advances in intracellular staining techniques, cytometer technology, fluorescent reagents, and antibody production have expanded the number of intracellular antigens that can be analyzed by flow cytometry. Measurement of protein phosphorylation with phospho‐specific antibodies has given insight into kinase signaling cascades. However, available techniques for phospho‐epitope staining can differ greatly, making it necessary to understand the differences between the outcomes when such techniques are applied and to develop robust and reproducible methods of application.

Methods

Ten different cellular fixation and permeabilization techniques were tested for their ability to provide phospho‐specific staining. Combinations of formaldehyde, methanol, ethanol, acetone, Triton X‐100, and saponin were used as fixation and permeabilization reagents. Phospho‐specific antibodies were labeled with Alexa Fluor dyes to provide multicolor analysis of different signaling events simultaneously within individual cells.

Results

Fixing cells with 1.5% formaldehyde followed by permeabilization in methanol gave optimal results for pERK, pp38, pJNK, pStat1, pStat5, and pStat6 staining. Alteration of formaldehyde fixation and methanol permeabilization times affected measurements of phosphorylation induction. Phospho‐specific flow cytometric analyses correlated well with Western blotting, providing cross platform validation of the technique.

Conclusions

Measuring phosphorylation events by flow cytometry provides a rapid and efficient way to measure kinase cascades in individual cells. Stability of phospho‐epitopes in methanol allows long‐term storage of samples prior to analysis. Multiple signaling cascades can be monitored simultaneously through the use of different fluorophore labels to determine specificity of ligands or inhibitors. Application of optimized techniques to heterogeneous cell types such as peripheral blood or murine splenocytes may allow signaling to be analyzed simultaneously in immune cell subsets. Cytometry Part A 55A:61–70, 2003. © 2003 Wiley‐Liss, Inc.
Infarction of acinic cell carcinoma in a patient infected with HIV: A complication of fine‐needle aspiration cytology obscuring definitive diagnosis
Authors: Rau Aarathi Rangan , Pai Radha Ramchandra , Nayak Surendra
Published: September 2003

Infarction of salivary gland tumors has been reported following fine‐needle aspiration cytology (FNAC) and, rarely, as a spontaneous event. Patients infected with the human immunodeficiency virus (HIV) often have salivary gland lesions and FNAC plays a role in the preliminary investigation of such swellings. We report a case of a parotid swelling in a patient infected with HIV where infarction of acinic cell carcinoma following FNAC lead to difficulty in cytological evaluation of the subsequent aspirate. Diagn. Cytopathol. 2003;29:222–224. © 2003 Wiley‐Liss, Inc.
Cytopathological grading, as a predictor of histopathological grade, in ductal carcinoma (NOS) of breast, on air‐dried Diff‐Quik smears
Authors: Khan M.Z. , Haleem A. , Al Hassani H. , Kfoury H.
Published: September 2003

Fine‐needle aspiration cytology (FNAC) is a widely practiced technique in the diagnosis of breast carcinoma, and it is the only diagnostic procedure performed before definitive treatment, at most institutions. While the histological grading of breast carcinoma has become routine in many centers worldwide, the cytopathological grading of breast carcinoma is not commonly used. Grading of breast carcinoma, while the tumor is still in vivo, would be the most ideal and desirable situation, as it would be helpful in the selection of patients for appropriate therapy. The objective of this study, therefore, was to devise a simple system for grading breast carcinoma, based on the cytological features alone. We reviewed 125 cases of breast carcinoma retrospectively, which were initially diagnosed by FNAC, with subsequent histopathological confirmation. These included 105 ductal, 6 lobular, 2 tubular, 1 papillary, and 1 medullary carcinoma. There was 1 ductal carcinoma in situ. Nine cases were rendered insufficient for grading. Thus 105 cases of ductal carcinoma (NOS) were evaluated for final cytological grading. Air‐dried Diff‐Quik‐stained smears were reviewed at least twice independently by four histopathologists and were then compared with the original histological grades. Six cytological features used for grading were found to be statistically significant: cellular pleomorphism, nuclear size, nuclear margin, nucleoli, naked tumor nuclei, and mitoses. A scoring system based on these six essential parameters was used, to classify ductal carcinoma into three cytological grades, which showed close correlation with the established histological grades. In addition, two less consistent, but still important, features were the presence or absence of necrosis and stromal invasion. Another six parameters, including smear cellularity, degree of cell dispersion or clustering, lymphoplasmacytic infiltrate, presence of tubular structures, cytoplasmic appearance of the tumor cells, and smear background, were not statistically significant. However, these additional parameters were found helpful in assigning the correct grade, in cases with borderline scores. The concordance rate with histology was 100% for grade 1, 98% for grade 2, and 93% for grade 3. Diagn. Cytopathol. 2003;29:185–193. © 2003 Wiley‐Liss, Inc.
Flow cytometric S‐phase fraction as a complementary biological parameter for the cytological grading of non‐Hodgkin's lymphoma
Authors: Pinto António E. , Cabeçadas José , Nóbrega Sónia D. , Mendonça Evelina
Published: September 2003

Fine‐needle aspiration cytology (FNAC) is a technique that can overcome tissue‐sampling disaggregation problems related to DNA flow cytometry analysis. The aim of this study, with long‐term follow‐up (median, 72 mo), was to investigate the prognostic value of DNA ploidy and S‐phase fraction (SPF) in patients with non‐Hodgkin's lymphoma (NHL), and additionally, the relevance of SPF in the grading of NHLs, using FNAC. The series comprised 76 patients with NHL (32 indolent and 44 aggressive tumors, including 14 Burkitt lymphomas) and 30 patients with reactive lymph node enlargement used as a control group. DNA flow cytometry was performed on fresh samples obtained by FNAC. NHL grading was done according to the updated Kiel classification. The 5‐yr overall survival of patients with NHL was determined using the Kaplan‐Meier method. All samples of the control group and 81.6% of the NHLs showed a DNA diploid pattern. Fourteen cases (18.4%) were DNA aneuploid with bimodal distribution: slight hyperdiploidy and near‐tetraploidy. Despite the higher incidence of aneuploidy in aggressive than in indolent tumors (22.7% vs. 12.5%), no correlation between DNA ploidy and NHL grading was observed. In contrast, SPF revealed a strong correlation with grading (P = 0.0001). The mean SPF values varied from 6.5% in indolent NHLs, to 20.4% in aggressive not‐otherwise‐specified (NOS) NHLs, and to 35.3% in Burkitt lymphomas. Nearly all aggressive NHLs had an SPF >15%, while the vast majority of indolent NHLs showed an SPF <10%. The mean SPF value in the reactive node group was 6.6%. NHL grading significantly was correlated to survival (P = 0.004) only if the Burkitt lymphomas, which showed the best prognosis, were analyzed as an independent group. There was a trend that did not reach statistical significance (P = 0.072) for a worse clinical outcome of patients with aneuploid tumors. When mean SPF values were used as cutoff points to divide both indolent NHLs and aggressive NOS NHLs into two proliferative subgroups, no differences in relation to survival were found (P = 0.763 and P = 0.994, respectively). Also, no proliferative difference was verified between indolent NHLs and the reactive lymph node group (P = 0.223). These results show that flow cytometric SPF is a valuable complementary parameter for grading NHLs on FNAC samples, but it appears to give no additional prognostic information on subset analyses. Diagn. Cytopathol. 2003;29:194–199. © 2003 Wiley‐Liss, Inc.
Abnormal Pap smears with negative follow‐up biopsies: Improving cytohistologic correlations
Authors: Bewtra Chhanda , Pathan Muhammad , Hashish Hisham
Published: September 2003

A review of the literature noted 11–16% discrepancy rates in cytology and histology diagnoses. We collected 358 cases with abnormal cytology and matching cervical biopsies. There were 123 (30%) discrepant pairs, of which 34 (27%) had negative biopsies following Papanicolaou (Pap) smears with squamous intraepithelial lesions (SIL). These constituted our study group. All biopsies were obtained within an average of 5 wk after Pap smears (range, 0–18 wk). After confirming original diagnoses, all biopsies were evaluated for the presence of squamocolumnar junction, proper orientation, gross size of specimen, denudation of superficial mucosa, and inadequate sectioning through blocks. Each block was recut at three levels and reviewed microscopically. Five biopsies (14%) needed reorientation. Nine biopsies (26%) showed more than a 2‐mm difference from gross size. Eleven (32%) new SILs were found. Adequate deep sectioning and proper orientation of tissues can significantly improve cytohistologic correlations. Diagn. Cytopathol. 2003;29:200–202. © 2003 Wiley‐Liss, Inc.
Expressions of human telomerase mRNA component (hTERC) and telomerase reverse transcriptase (hTERT) mRNA in effusion cytology
Authors: Hiroi Sadayuki , Nakanishi Kuniaki , Kawai Toshiaki
Published: September 2003

Telomerase is a ribonucleoprotein enzyme that synthesizes telomeric DNA onto chromosomal ends. Its activity has been reported to be a novel diagnostic marker of malignant potential. However, no study has investigated the diagnostic importance of the expressions of human telomerase mRNA component (hTERC) and telomerase reverse transcriptase (hTERT) mRNA in effusion cytology. We investigated the expressions of hTERC and hTERT using in situ hybridization in 20 malignant cytologic specimens from 20 patients with adenocarcinomas disseminating into the pleura or peritoneum, and 16 benign cytologic specimens in pleural or peritoneal fluid (including reactive mesothelial cells) from 16 patients with non‐neoplastic diseases. Expressions of hTERC and hTERT mRNA were detected in 95% and 90% of the 20 malignant cytology specimens, respectively, and were apparent within the cytoplasm of malignant cells. However, no expression was detected in reactive mesothelial cells in the 16 benign cytologic specimens. The expressions of hTERC and hTERT mRNA would appear to be a useful addition to cytology examination for diagnosis based on effusion cytology. Diagn. Cytopathol. 2003;29:212–216. © 2003 Wiley‐Liss, Inc.
Fine‐needle aspiration biopsy as an adjunct to the diagnosis of a rare adnexal tumor of hair follicle origin: Trichoblastoma
Authors: Cheng Lirong , Binder Scott W. , Gajjar Nupoor A. , Hirschowitz Sharon L.
Published: September 2003

Fine‐needle aspiration biopsy (FNAB) is a technique used increasingly for the investigation of primary and metastatic cutaneous tumors. Trichoblastoma is a rare benign skin appendage tumor of hair germ origin. We report the diagnosis by FNAB of a rare giant subcutaneous tumor, trichoblastoma, from an 81‐yr‐old woman with a subcutaneous mass in the interscapular area of her back. The cytologic characteristics of the tumor are discussed in detail in this report. The findings have been compared with the histologic features of the tumor after surgical excision. We have characterized several distinctive cytologic features that may aid in the diagnosis of this rare neoplasm. While most reported cases have been diagnosed from surgical excisional biopsy specimens, FNAB may also be a valuable tool for the accurate diagnosis of trichoblastoma in the proper clinical context. Diagn. Cytopathol. 2003;29:225–228. © 2003 Wiley‐Liss, Inc.
Fine‐needle aspiration of secondary malignancies of the penis: A report of three cases
Authors: Tsanou Elena , Sintou‐Mantela Evdoxia , Pappa Lina , Grammeniatis Evagelos , Malamou‐Mitsi Vassiliki
Published: September 2003

Metastatic malignancy to the penis is an uncommon clinicopathologic entity, with only 300 cases reported since 1870. Of the reported cases, 75% were secondary to genitourinary primary tumors. Priapism is the most frequent symptom, although dysuria, ulceration, and node formation have also been described. We report three cases of penile metastatic involvement from primary tumors in the urinary bladder (two cases) and prostate (one case), respectively. Fine‐needle aspiration (FNA) cytology from the penile nodules was performed in each case. The smears in all cases were highly cellular, and atypical neoplastic cells were observed singly, in clusters, or in papillary formations. The cells were pleomorphic with hyperchromatic nuclei and prominent nucleoli. Immunocytochemistry was performed for keratin 8 and 18 and prostatic‐specific antigen (PSA). In conclusion, although it has rarely been used as a diagnostic tool, FNA of the penis can be proved effective and safe in diagnosing a suspected secondary malignancy. Diagn. Cytopathol. 2003;29:229–232. © 2003 Wiley‐Liss, Inc.
Role of repeat fine‐needle aspiration biopsy (FNAB) in the management of thyroid nodules
Authors: Baloch Zubair , LiVolsi Virginia A. , Jain Pooja , Jain Rishi , Aljada Ibrahim , Mandel Susan , Langer Jill E. , Gupta Prabodh K.
Published: September 2003

The purpose of the present study was to determine the role of repeat fine‐needle aspiration biopsy (FNAB) in the evaluation of thyroid nodules initially classified as “nondiagnostic” due to limited cellularity or as “indeterminate for neoplasm.” We reviewed a cohort of 431 patients (352 females, 79 males; average age 50 yr); 237 patients were classified as “nondiagnostic” due to limited cellularity and 194 as “indeterminate for neoplasm” over a 3‐yr period (1999–2002). Repeat FNAB under ultrasound guidance was performed in 226 patients (226/431, 52%); surgical pathology results were available in 101 patients. Repeat FNAB diagnoses were: benign 70 (31%), follicular/Hürthle cell neoplasm 62 (27%), suspicious for papillary carcinoma 25 (12%), malignant 17 (7%), and nondiagnostic 52 (23%) cases. Surgical follow‐up was available in 101 (45%) patients; malignancy was identified in 50 (49%) patients. The malignancy rate was 51% and 48% in cases in which initial FNAB was nondiagnostic and indeterminate for neoplasm, respectively. There were no false‐positives and all malignant cases undergoing surgery were found to be malignant. This study demonstrates that repeat FNAB is warranted in patients with thyroid nodules diagnosed on initial FNAB as nondiagnostic and indeterminate for neoplasm since it can yield a definitive diagnosis in the majority of cases with an overall malignancy rate of 49%. Diagn. Cytopathol. 2003;29:203–206. © 2003 Wiley‐Liss, Inc.
Fine‐needle aspiration cytology: True histiocytic lymphoma/histiocytic sarcoma
Authors: Miliauskas John R.
Published: September 2003

True histiocytic lymphoma/histiocytic sarcoma is an extremely rare, malignant histiocytic tumor. This report is of such a case in a 52‐yr‐old woman. Fine‐needle aspiration (FNA) smears showed large pleomorphic nuclei, prominent nucleoli, moderately dense abundant cytoplasm, and scattered cells with cytoplasmic vacuoles and some with reniform nuclei. Small numbers of background lymphocytes and benign histiocytes were present as well as many multinucleated tumor cells. The immunophenotype was CD45, Lysozyme, CD68 (PGMI), CD43, and S‐100 positive. Genotypic analysis revealed a germline configuration. This type of tumor has a large cytological differential diagnosis and immunophenotyping is essential for diagnosis. Diagn. Cytopathol. 2003;29:233–235. © 2003 Wiley‐Liss, Inc.
Immunostaining of cytology smears: A comparative study to identify the most suitable method of smear preparation and fixation with reference to commonly used immunomarkers
Authors: Shidham Vinod B. , Chang Chung‐Che , Rao R. Nagarjun , Komorowski Richard , Chivukula Mamatha
Published: September 2003

As an extension of our previous study (Shidham et al., Acta Cytol 2000;44:1015–1022), we evaluated the interference by methods of cytology smear preparation on the immunoreactivity of cytokeratin‐7, cytokeratin‐20, estrogen receptor, progesterone receptor, chromogranin, synaptophysin, and vimentin. Scrape cytology smears of 34 fresh specimens submitted for intraoperative consultation were studied. They were processed by three different methods—A: wet‐fixed in 95% ethanol; B: air‐dried saline rehydrated smears fixed in alcoholic formalin; and C: air‐dried saline rehydrated smears fixed in 95% ethanol with 5% acetic acid. The intensity scores of immunostaining were estimated semiquantitatively and compared with corresponding formalin‐fixed paraffin‐embedded tissue sections (FPTS). Except vimentin, all immunomarkers showed higher intensity scores with method A or B than with method C. Vimentin showed the best results with method A. Our results indicate that the immunoreactivity pattern with each immunomarker is affected by the method of cytology smear processing. Most importantly, method C, which is the desired choice for cytomorphological staining, was not suitable for immunostaining. Diagn. Cytopathol. 2003;29:217–221. © 2003 Wiley‐Liss, Inc.
Estimation of hormone receptor status in fine‐needle aspirates and paraffin‐embedded sections from breast cancer using the novel rabbit monoclonal antibodies SP1 and SP2
Authors: Cano Guillerma , Milanezi Fernanda , Leitão Dina , Ricardo Sara , Brito Maria José , Schmitt Fernando Carlos
Published: September 2003

We describe a method of immunocytochemical assessment of estrogen receptor (ER) status on alcohol‐fixed smears obtained by fine‐needle aspiration (FNA) from breast cancer patients, using a commercially available rabbit monoclonal antibody anti‐ER (SP1) without any antigen retrieval. A series of 40 aspirates were analyzed and the results of ER status were compared with the respective formalin‐fixed tissue using the same procedure and with assessment by the classical method using the mouse monoclonal antibody 6F11 (anti‐ER) with antigen retrieval on paraffin sections. Twenty‐four out of the 40 cases examined were positive at least by two methods and 16 were negative for all three determinations. The results obtained in the ER immunocytochemical assay on aspirates and paraffin sections using the antibody SP1 and those obtained on paraffin sections using the antibody 6F11 were quite similar. In one case the material was insufficient to interpret the reaction in the cytological specimen and only one case, with focal positivity reaction on paraffin sections, was negative in the cytological specimen. The intensity of nuclei staining in cytological smears of breast cancer cells was stronger than that observed by traditional methods. We also assessed progesterone receptor (PR) status on 40 paraffin‐sections from breast cancer patients, using a commercially available rabbit monoclonal antibody anti‐PR (SP2), with the same characteristics described for anti‐ER (SP1). The results were compared with assessment by the classic method with mouse monoclonal antibody 1A6 (PR) on paraffin sections and total agreement was observed. Of the 40 cases examined, 18 were positive and 22 were negative for the two determinations. We conclude that the application of the ER method on alcohol‐fixed smears / paraffin sections with the rabbit monoclonal antibody SP1, and the PR method on paraffin sections with the rabbit monoclonal antibody SP2, provide several advantages, such as high sensitivity and specificity of the reaction, stronger immunostaining, shorter procedures times, and avoidance of antigenic retrieval methods. Diagn. Cytopathol. 2003;29:207–211. © 2003 Wiley‐Liss, Inc.
Synthesis, Equilibrium and Kinetic Properties of Gd3+ Complexes of Three DTPA‐Bis(Amide) Derivatives Containing Stable Nitroxide Free Radical Substituents
Authors: Jászberényi Zoltán , Brücher Ernő , Jekő József , Hideg Kálmán , Kálai Tamás , Király Róbert
Published: September 2003

Two new DTPA‐bis(amide) derivatives containing stable nitroxide free radicals, H3L2 and H3L3, were synthesized. The complexation properties of L2 and L3 with Gd3+ were compared with those of H3L1, synthesized earlier. The sums of the protonation constants ΣlogKiH of the DTPA‐bis(amide) derivative ligands with stable nitroxide free radicals are somewhat higher than that for DTPA‐bis(methylamide) (H3L4). The ligands L1, L2, and L3 form complexes with a metal‐to‐ligand ratio of 1:1 with Gd3+ (GdL), while the species formed with Zn2+ are ZnL, ZnHL, ZnH2L, and Zn2L. The formation of the dinuclear complex Zn2L results in a lower selectivity of the ligands for Gd3+ over Zn2+ than was assumed for L4. The relaxivities of the complexes GdL1, GdL2, and GdL3 are close to the sums of the relaxivities of the complex GdL4 and of the free ligands L1, L2, and L3. The relaxivities of GdL1, GdL2, and GdL3 are practically independent of temperature in the 7−30 °C range, which is probably a result of the relatively long lifetime of the water molecules in the inner spheres of the [GdL(H2O)] complexes. The kinetic stabilities of the Gd3+ complexes were characterized by the rates of the exchange reactions taking place between the complexes GdL and Lu3+ or Zn2+. The reactions occur through the proton‐assisted dissociation of the complexes, with the formation of a protonated intermediate. Another pathway is the direct reaction between the Gd3+ complex and Lu3+ or Zn2+, which occurs with the formation of a dinuclear intermediate, GdLM. The exchange reactions proceed about five times more rapidly with Zn2+ than with Lu3+, indicating the importance of the formation of an intermediate containing an N−Zn2+ bond, which is stronger than the N−Lu3+ bond in an intermediate with similar structure. The exchange reactions of the complex GdL3 formed with the disubstituted ligand L3 are significantly slower than those of the complexes of the monosubstituted ligands L1 and L2. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Organic Functional Group Transformations in the Periphery of a Group‐4 Metallocene Complex: 2H‐Pyrrole Formation at a Pendant Boron Lewis Acid
Authors: Hill Michael , Kehr Gerald , Fröhlich Roland , Erker Gerhard
Published: September 2003

The allyl‐substituted ansa‐zirconocene dichloride [Me2Si(C5H4)(C5H3CH2CH=CH2)ZrCl2] (1) cleanly adds the borane 9‐BBN to the allyl C=C double bond to yield the corresponding hydroboration product 2. The borane HB(C6F5)2 (3) is also added regioselectively to 1 to yield [Me2Si(C5H4){C5H3(CH2)3B(C6F5)2}ZrCl2] (4). The strongly electrophilic boron Lewis acid in 4 adds 2‐methyl‐4,5‐dihydrooxazole to yield 6. Treatment of 4 with pyrrole results in the formation of the respective borane adduct 7 of the pyrrole tautomer 2H‐pyrrole. The 2H‐pyrrole ligand in 7 is deprotonated at C‐2 upon treatment with pyridine, followed by proton transfer and replacement of pyrrole with formation of the corresponding pyridine adduct 12. The complexes 1, 4 and 7 were characterized by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Lanthanide Complexes of 2,6‐Dihydroxybenzoic Acid: Synthesis, Crystal Structures and Luminescent Properties of [nBu4N]2[Ln(2,6‐dhb)5(H2O)2] (Ln = Sm and Tb)
Authors: Soares‐Santos Paula C. R. , Nogueira Helena I. S. , Almeida Paz Filipe A. , Sá Ferreira Rute A. , Carlos Luís D. , Klinowski Jacek , Trindade Tito
Published: September 2003

Lanthanide complexes of 2,6‐dihydroxybenzoic acid (2,6‐Hdhb), namely [nBu4N]2[Ln(2,6‐dhb)5(H2O)2] [Ln = Sm (1) and Tb (2)], were synthesized and their crystal structures determined by single‐crystal X‐ray diffraction studies. The 2,6‐dhb− ligand coordinates to the lanthanide cations through the carboxylate group in a monodentate or bidentate chelating coordination mode. The compounds were further characterised using IR, Raman, 1H and 13C NMR spectroscopy and elemental analysis. Photoluminescence measurements were performed on both compounds. In particular, the terbium complex 2 shows intense photoluminescence both in the solid state and in ethanolic solution. Compound 2 also exhibits triboluminescence. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Intercalates of Vanadyl Phosphate with Benzonitrile and Tolunitrile
Authors: Beneš Ludvík , Zima Víztězslav , Melánová Klára , Dybal Jiří , Trchová Miroslava , Matějka Pavel
Published: September 2003

Intercalates of vanadyl phosphate with benzonitrile and p‐tolunitrile were prepared and characterized by X‐ray powder diffraction, TG analysis, IR and Raman spectroscopy. Both intercalates contain one nitrile molecule per formula unit. The intercalates prepared are moisture sensitive and guest molecules are easily replaced by water molecules. The nitrile molecules are anchored to the host layers by an N−V donor‐acceptor bond. Local structures and interactions appearing in the intercalates were suggested on the base of quantum chemical calculations. These calculations support the results of the IR and Raman spectroscopy, indicating the formation of a C≡N⇄V bond in the intercalates. The calculated basal spacings (11.32 Å for the benzonitrile and 13.00 Å for the tolunitrile intercalates) are in good agreement with the experimental values (11.22 and 13.19 Å, respectively). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
First Examples of Ternary Lanthanide 2,2′‐Diphenyldicarboxylate Complexes: Hydrothermal Syntheses and Structures of Lanthanide Coordination Polymers of 2,2′‐Diphenyldicarboxylic Acid and 1,10‐Phenanthroline
Authors: Wang Yibo , Zheng Xiangjun , Zhuang Wenjuan , Jin Linpei
Published: September 2003

In the four new lanthanide coordination polymers {[La2(2,2′‐dpdc)3(phen)(H2O)]·2H2O}n (1), [Eu2(2,2′‐dpdc)3(phen)(H2O)2]n (2), {[Ln2(2,2′‐dpdc)3(phen)2(H2O)2]·4H2O}n [Ln = Tb (3), Yb (4)] (2,2′‐dpdc = 2,2′‐diphenyldicarboxylate, phen = 1,10‐phenanthroline), prepared by hydrothermal synthesis, the 2,2′‐dpdc dianion affords tetradentate, pentadentate, and hexadentate coordination modes. Complex 1 is a two‐dimensional network of infinite 1‐D chains assembled through π−π interactions, with nine‐ and ten‐coordinate La3+, and arranged in wave‐like layers. In 2, Eu3+ possesses nine‐ and ten‐coordinate geometries bridged by 2,2′‐dpdc ligands to give a 3‐D structure. The isomorphous complexes 3 and 4, in which Tb3+ and Yb3+ ions are both nine‐coordinate, have two‐dimensional structures of 1‐D zigzag chains stacked via hydrogen bonds and π−π interactions of phen molecules. The high‐resolution emission spectrum of 2 shows two Eu3+ ion sites, which is consistent with the results of the X‐ray crystal structure analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Structure, and Reactivity of Novel Intramolecularly Coordinated Organolead(II) Compounds
Authors: Jurkschat Klaus , Peveling Katja , Schürmann Markus
Published: September 2003

The intramolecularly coordinated heteroleptic organolead(II) compounds {4‐tBu‐2,6‐[P(O)(OEt)2]2C6H2}PbX (2, X = Cl; 3, X = SPh) have been synthesized. Single‐crystal X‐ray analyses reveal that both compounds adopt polymeric chain structures by intermolecular Pb−X···Pb bridges, a structural motif previously unknown for organolead(II) derivatives. Compound 2 reacts with lithium diisopropylamide, iPr2NLi, and lithium bis(trimethylsilyl)methane, (Me3Si)2CHLi, respectively, to provide in situ the corresponding organolead(II) compounds {4‐tBu‐2,6‐[P(O)(OEt)2]2C6H2}PbX (4, X = iPr2N; 5, X = (Me3Si)2CH], which were identified by NMR spectroscopy but could not be obtained as analytically pure substances. Attempts to isolate the intramolecularly coordinated organolead(II) hexafluorophosphate {4‐tBu‐2,6‐[P(O)(OEt)2]2C6H2}Pb+PF6− from the reaction of 2 with TlPF6 also failed. Instead, the unprecedented salt [{5‐tBu‐1,3‐[P(O)(OEt)2]2C6H3}4·(Pb2F)] [PF6]3·4THF (6) was obtained, in which the [(Pb−F−Pb)]3+ cation is stabilized by eight intermolecular P=O⇄Pb interactions. Compound 6 was characterized by single‐crystal X‐ray analysis and electrospray mass spectrometry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Preparation of Optically Active α‐Amino[3]ferrocenophanes − Building Blocks for Chelate Ligands in Asymmetric Catalysis
Authors: Liptau Patrick , Tebben Ludger , Kehr Gerald , Wibbeling Birgit , Fröhlich Roland , Erker Gerhard
Published: September 2003

Treatment of 1,1′‐diacetylferrocene (4) with dimethylamine and TiCl4 yielded the unsaturated dimethylamino‐substituted [3]ferrocenophane product 5. Its catalytic hydrogenation gave the corresponding saturated [3]ferrocenophane system 6 (trans/cis ≈︁ 7:1). The rac‐[3]ferrocenophane amine 6 was partially resolved (to ca. 80% ee) by means of L‐ or D‐O,O′‐dibenzoyltartrate salt formation. Treatment of 4 with the pure (R)‐ or (S)‐methyl(1‐phenylethyl)amine (8)/TiCl4 gave the corresponding optically active unsaturated [3]ferrocenophane amines (R)‐(+)‐9 and (S)‐(−)‐9, respectively. Their catalytic hydrogenation again proceeded trans‐selectively, giving the corresponding saturated diastereomeric [3]ferrocenophane amines (1R,3R,5R)‐10a and (1S,3S,5R)‐10b [starting from (R)‐9], their enantiomers ent‐10a and ent‐10b were obtained from (S)‐9, but with a poor asymmetric induction (10a/10b < 2:1). Quaternization of 6 (CH3I) followed by amine exchange using (R)‐ or (S)‐methyl(1‐phenylethyl)amine (8), respectively, proceeded with overall retention. Subsequent chromatographic separation gave the pure diastereoisomers (1R,3R,5R)‐10a and (1S,3S,5R)‐10b [from (R)‐8, ent‐10a and ent‐10b from (S)‐8] in > 60% yield. Subsequently, the benzylic (1‐phenylethyl) auxiliary was removed from the nitrogen atom by catalytic hydrogenolysis to yield the enantiomerically pure (> 98%) ([3]ferrocenophanyl)methylamines (1R,3R)‐11 and (1S,3S)‐11, respectively, which were converted into the corresponding dimethylamino‐substituted [3]ferrocenophanes (1R,3R)‐6 and (1S,3S)‐6. Each enantiomer from the following enantiomeric pairs was isolated in its pure form and characterized by X‐ray diffraction: (R)‐9/(S)‐9; (1R,3R,5R)‐10a/(1S,3S,5S)‐10a; (1R,3R,5S)‐10b/(1S,3S,5R)‐10b; (1R,3R)‐11/(1S,3S)‐11. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Self‐Assembly of Three CdII‐ and CuII‐Containing Coordination Polymers from 4,4′‐Dipyridyl Disulfide
Authors: Luo Junhua , Hong Maochun , Wang Ruihu , Yuan Daqiang , Cao Rong , Han Lei , Xu Yanqing , Lin Zhengzhong
Published: September 2003

Three new organic/inorganic coordination polymers, [{Cu(4‐DPDS)2(H2O)}·2NO3·3H2O]n (1), [{Cu(4‐DPDS)2(SO4)}· 1.5H2O·CH3OH]n (2), and [Cd(4‐DPDS)2Cl2]n (3), have been synthesized by using the flexible ligand 4,4′‐dipyridyl disulfide (4‐DPDS). Complex 1 crystallized in the Ibca space group: a = 10.5275(6), b = 20.2670(1), c = 27.235(1) Å, V = 5811.5(6) Å3, Z = 16. Complex 2 crystallized in the Pnna space group: a = 10.547(2), b = 14.201(2), c = 19.667(3) Å, V = 2945.8(8) Å3, Z = 8. Complex 3 crystallized in the P21/c space group: a = 7.6146(3), b = 18.2606(8), c = 9.3203(2) Å, β = 100.26(1)°, V = 1275.24(8) Å3, Z = 4. The three coordination polymers display a variety of structural architectures, ranging from double‐stranded chains (1) to two‐dimensional channels (2) and two‐dimensional, puckered, grid‐like arrays (3). Magnetic characterizations show that complex 1 exhibits antiferromagnetic interactions while 2 is ferromagnetic. Solid‐state fluorescence results reveal that 3 exhibits fluorescence emissions at 418 and 575 nm (λex = 314 nm). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Palladium‐Catalyzed Cyanation of Aryl Halides: Recent Developments and Perspectives
Authors: Sundermeier Mark , Zapf Alexander , Beller Matthias
Published: September 2003

The palladium‐catalyzed cyanation of aryl halides is an elegant method for the preparation of benzonitriles. Since its discovery in 1973, this reaction has been the topic of several investigations. Nevertheless, the general methodology is still somewhat underdeveloped compared to other palladium‐catalyzed coupling reactions. Here, we summarize important developments from 1997 until 2003 in this area. Recent contributions from our group include the development of palladium/phosphane/amine catalyst systems for the cyanation of aryl chlorides, the successful cyanation of aryl halides with acetone cyanohydrin and trimethylsilyl cyanide as cyanation reagents, and a general improvement of catalyst efficiency by using a continuous dosage of cyanide sources. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis, Characterization, and DNA Binding Studies of a Chromium(III) Complex Containing a Tridentate Ligand
Authors: Vaidyanathan Vaidyanathan Ganesan , Nair Balachandran Unni
Published: September 2003

[Cr(bzimpy)2]Cl, where bzimpy is 2,6‐bis(benzimidazol‐2‐yl)pyridine, has been synthesized and characterized by ESI‐MS, UV/Visible, and fluorescence spectra. Absorption titration and thermal denaturation experiments indicate that the complex binds to DNA with moderate strength, while viscosity measurements show that it may undergo surface binding. The fluorescence intensity of the complex increases with increasing DNA concentration, in contrast to [Cr(phen)3]3+ and [Cr(bpy)3]3+. The complex cleaves pBR322 DNA in the presence of H2O2. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A Template‐Interface Co‐Reduction Synthesis of Hollow Sphere‐like Carbides
Authors: Li Cun , Yang Xiaogang , Yang Baojun , Yan Yan , Qian Yitai
Published: September 2003

Hollow sphere‐like carbides MC (M = Ti, V) with diameters of between 70 and 170 nm were synthesized via a template‐interface co‐reduction (TICR) route, in which MCl4 and hexachlorobuta‐1,3‐diene (C4Cl6) were reacted with metallic sodium at 500 °C for 24 h. X‐ray powder diffraction (XRD) patterns indicated the samples were single‐phase NaCl‐type carbides. Transmission electron microscopy (TEM) photographs showed the hollow spheres consisted of nanocrystalline carbides. The possible formation mechanism of hollow sphere‐like carbides is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The Preparation and Study of Bis(2‐quinolyl) and Bis(2‐[1,8]naphthyridyl) Derivatives of Pyrimidine and Pyrazine as Bridging Ligands for RuII
Authors: Brown Darren , Muranjan Seema , Thummel Randolph P.
Published: September 2003

The 2:1 Friedländer condensation of 2‐aminobenzaldehyde or 2‐aminonicotinaldehyde with either 4,6‐diacetylpyrimidine or 2,5‐diacetylpyrazine leads to a family of four new bis(bidentate) bridging ligands. Subsequent complexation of these ligands with [RuCl2(bpy)2] (bpy = 2,2′‐bipyridine) leads to the corresponding mononuclear and dinuclear mixed‐ligand RuII complexes. Analysis of the 1H NMR spectra of these systems affords some insight into their conformational properties. Electronic spectra of the complexes evidence two long‐wavelength absorption bands which correspond to typical metal‐to‐ligand charge transfer states. The energies of these states may be explained by electronegativities of the pendant rings on the bridging ligand as well as the substitution pattern on the central ring. For the dinuclear complexes the lowest energy absorption shows components associated with coordination to the pendant and the central rings. The appearance of two metal‐based oxidations gives good evidence for strong intermetalic interaction and Koopman’s theorem is obeyed for all systems. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Study of the D⇄Sb (D = O, S) Transannular Interaction in Sb‐Monohalogenated Dibenzostibocines − An Experimental and Theoretical Study
Authors: Alvarado‐Rodríguez José G. , Andrade‐López Noemí , González‐Montiel Simplicio , Merino Gabriel , Vela Alberto
Published: September 2003

In order to gain a greater insight in the nature of the D⇄Sb transannular interaction in dibenzostibocines, a series of D(C6H4S)2SbHal complexes (D = S; Hal = Cl 1, Br 2, I 3; D = O, Hal = Cl 4) has been synthesised. X‐ray structure determinations of complexes 1−4 reveal that the antimony atom is in a distorted ψ‐bipyramidal geometry, acting as an acceptor atom. The eight‐membered ring conformation in 1, 2 and 4 can be described as a twist‐boat, while in 3 it is approaching Cs symmetry. DFT calculations were carried out on 1 and 4. Topological analysis of the electron density in 1 and 4 showed the presence of critical points in the D⇄Sb direction (D = O, S). The electron localisation function showed the presence of a lone pair located in an equatorial position on the antimony, and a lone pair of the donor along the D⇄Sb direction, confirming the presence of a dative bond in the system. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Self‐Organization of Dipolar 4,4′‐Disubstituted 2,2′‐Bipyridine Metal Complexes into Luminescent Lamellar Liquid Crystals
Authors: Pucci Daniela , Barberio Giovanna , Crispini Alessandra , Francescangeli Oriano , Ghedini Mauro , La Deda Massimo
Published: September 2003

Mononuclearcis‐dichloro complexes, [LnMCl2], with different metal centres (PtII, NiII, and ZnII) and a series of palladium and platinum derivatives, [L2MX2], in which chloride groups are replaced with iodide, bromide, and azide ligands, have been synthesized from 4,4′‐disubstituted‐2,2′‐bipyridines. Upon complexation of these non‐mesogenic ligands, the peculiar structural arrangement, characterized by intermolecular associations of the new derivatives, induces mesomorphism in most [L2MX2] complexes, confirming the importance of coordination chemistry in metal‐mediated formation of liquid crystals. Single crystal X‐ray structures have been determined for dihexadecyl 2,2′‐bipyridyl‐4,4′‐dicarboxylatopalladium and ‐zinc dichloride derivatives. Both the metal centres and the ancillary ligands have been varied to use dipole coupling as a tool to control molecular architecture: thermal, as well as spectroscopic properties, depend strongly upon molecular dipolar interactions. Tunable red and blue emitters based on PdIIand PtII, both in solution and in the solid state, have been obtained. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
A Novel Mixed‐Valence CuI/CuII Coordination Polymer: Solvothermal Synthesis, Crystal Structure, and Magnetic Properties of CuICuII(2‐Pyrazinecarboxylate)2(H2O)(ClO4)
Authors: Liu Cai‐Ming , Zhang De‐Qing , Luo Jian‐Lin , Wang Nan‐Lin , Hu Huai‐Ming , Zhu Dao‐Ben
Published: September 2003

The solvothermal reaction between Cu(ClO4)2·6H2O and 2‐pyrazinecarboxylic acid in methanol yields a novel mixed‐valence CuI/CuII coordination polymer, CuICuII(2‐pyrazinecarboxylate)2(H2O)(ClO4) (1), in which a three‐dimensional supramolecular array with square channels (9.3 × 9.3 Å) is formed through crisscross arrangement of the one‐dimensional CuICuII(2‐pyrazinecarboxylate)2(H2O)+ coordination polymer cation chains in the adjacent layers. Complex 1 exhibits weak ferromagnetic interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis of Chiral Cationic (Diimino‐ and diaminodiphosphane)ruthenium Complexes and Their Applications in Catalytic Oxidation − Crystal Structures of cis‐[RuCl(py){κ4‐Ph2PC6H4CH=NC6H10N=CHC6H4PPh2}]BF4 and cis‐[RuCl(py){κ4‐Ph2PC6H4CH=NC6H10N(H)CH2C6H4PPh2}]BF4
Authors: Wong Wai‐Kwok , Chen Xiao‐Ping , Chik Tat‐Wai , Wong Wai‐Yeung , Guo Jian‐Ping , Lee Fu‐Wa
Published: September 2003

Halide abstraction of trans‐[RuCl2{κ4‐(1R,2R)‐PNNP}] {(1R,2R)‐PNNP = (1R,2R)‐N,N′‐bis[2‐(diphenylphosphanyl)benzylidene]‐1,2‐diiminocyclohexane} and trans‐[RuCl2{κ4‐(1R,2R)‐P(NH)(NH)P}] {(1R,2R)‐P(NH)(NH)P = (1R,2R)‐N,N′bis[2‐(diphenylphosphanyl)benzylidene]‐1,2‐diaminocyclohexane} with AgBF4 in acetonitrile at ambient temperature gave cis‐[RuCl(CH3CN){κ4‐(1R,2R)‐PNNP}][BF4] (1) and cis‐[RuCl(CH3CN){κ4‐(1R,2R)‐P(NH)(NH)P}][BF4] (2), respectively. When 1 was refluxed in pyridine (py), the coordinated CH3CN was replaced by pyridine to form cis‐[RuCl(py){κ4‐(1R,2R)‐PNNP}][BF4] (3). However, when 2 was refluxed in pyridine, one of the amino moieties (−CH2−NH−)was oxidized to an imino moiety (−CH=N−) with concomitant displacement of the coordinated CH3CN by pyridine to produce cis‐[RuCl(py){κ4‐(1R,2R)‐P(N)(NH)P}][BF4] (4). The structures of 3 and 4 were ascertained by X‐ray crystallography. Compounds 1−4 are effective catalysts for the epoxidation of various olefins with air. A turnover frequency of up to 733 h−1 and an enantiomeric excess of up to 24% were obtained for the epoxidation of styrene catalysed by 2. Compound 2 can also catalyse the epoxidation, dehydrogenation and C−H activation of various olefins, alcohols and alkanes by tert‐butyl hydroperoxide with high chemical selectivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis and Structural Elucidation of a “Free” Phosphinoamide Anion
Authors: Fei Zhaofu , Scopelliti Rosario , Dyson Paul J.
Published: September 2003

The reaction of the aminophosphane C6H4(o‐CN)NHPPh2 with elemental potassium in the presence of 18‐crown‐6 affords the phosphinoamide‐containing complex [C6H4(o‐CN)N‐PPh2(THF)(18‐Crown‐6)K] which has been fully characterised in solution and the solid state. The potassium cation interacts with the nitrile substituent group and crown, but does not interact with the P−N bond. The anion appears to be considerably more reactive than related anions in which the cation interacts with the P‐N unit, as demonstrated by the reaction with O2/H2O which affords [Ph2P(:O)OK(18‐Crown‐6)] and C6H4(o‐CN)NH2. A co‐crystal containing these two products was obtained and the structure has been elucidated by single‐crystal X‐ray diffraction analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthesis and Structural Characterization of Potassium Salts of Phosphane‐Substituted (Cyclopentadienyl)iron Dicyanides, and Their Use as Bridging Ligands for Copper(I) Phosphane Derivatives
Authors: Darensbourg Donald J. , Adams M. Jason , Yarbrough Jason C. , Phelps Andrea L.
Published: September 2003

Phosphane‐substituted CpFe(CN)2 anions have been synthesized by photochemical decarbonylation of KCpFe(CN)2CO in the presence of various mono‐ and diphosphanes. The synthesis and characterization of uniquely bridged diphosphane derivatives, [KCpFe(CN)2]2‐μ‐(Ph2P)2−(CH2)n (n = 2−4), are particularly noteworthy. These phosphane‐substituted CpFe(CN)2− units have afforded stable mixed‐metal complexes upon reaction with CuI in the presence of tricyclohexylphosphane in acetonitrile solution. X‐ray crystallography shows these derivatives to display two‐dimensional diamond‐shaped structures with copper(I) of the form [Fe(CN)2Cu]2, where the CuI centers exhibit both trigonal and tetrahedral geometries. Infrared data reveal that the withdrawal of electron density from the iron centers in these mixed metal cyanides via the cyanide ligands is enhanced upon replacing CO in CpFe(CN)2CO− with phosphanes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
The Water‐Exchange Rate in Neutral Heptadentate DO3A‐Like GdIII Complexes: Effect of the Basicity at the Macrocyclic Nitrogen Site
Authors: Terreno Enzo , Boniforte Patrizia , Botta Mauro , Fedeli Franco , Milone Luciano , Mortillaro Armando , Aime Silvio
Published: September 2003

The rate of exchange of the two water molecules coordinated to a GdIII centre in neutral complexes with heptadentate DO3A derivatives is modulated by the basicity of the macrocyclic nitrogen bearing the pendant group: a lower basicity results in a slower water‐exchange rate. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Cover Picture: Synthesis, Structure, and Reactivity of Novel Intramolecularly Coordinated Organolead(II) Compounds (Eur. J. Inorg. Chem. 19/2003)
Authors: Jurkschat Klaus , Peveling Katja , Schürmann Markus
Published: September 2003

The cover picture shows as one representative out of the carbene‐analogue family, a novel heteroleptic lead(II) compound containing an O,C,O‐coordinating pincer‐type ligand. Details are discussed in the article by K. Jurkschat et al. on p. 3563 ff.
Synthesis and Evaluation of a Broad Range of New Chiral (Aminoalkyl)phosphane Ligands for Asymmetric Hydrogen‐Transfer Reduction of Prochiral Ketones
Authors: Léautey Matthieu , Jubault Philippe , Pannecoucke Xavier , Quirion Jean‐Charles
Published: September 2003

Twenty new chiral (aminoalkyl)phosphane ligands have been prepared from four enantiomerically pure advanced chiral compounds. We describe their use for asymmetric hydrogen‐transfer reduction of three prochiral ketones. Enantioselectivities up to 90% were obtained. We investigated the influence on the enantioselectivity of each part of these new (aminoalkyl)phosphane ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Synthetic Study on Campylobacter jejuni Lipopolysaccharides: An Improved Synthesis of a Branched, Heptose‐Containing Trisaccharide Core Structure and Its Conversion into Ganglioside GD3 Related Hexasaccharide
Authors: Hori Koji , Sawada Naoki , Ando Hiromune , Ishida Hideharu , Kiso Makoto
Published: September 2003

The first synthesis of the oligosaccharide skeleton of the Campylobacter jejuni lipooligosaccharide composed of a branched, heptose‐containing trisaccharide core structure and, including a substantially improved preparation of the core structure, the ganglioside GD3 related trisaccharide epitope is reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Thiaporphyrins with One, Two and Four Unsubstituted meso‐Carbons: Synthesis and Functionalization
Authors: Agarwal Neeraj , Hung C.‐H. , Ravikanth M.
Published: September 2003

Thiaporphyrins with one, two and four unsubstituted meso carbons were synthesized from easily available thiophene diols. The reactivity at these carbons was demonstrated by carrying out series of reactions and some very useful functional groups were introduced. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Direct Estimation of Total Arsenic Using A Novel Metal Side Disk Rotating Electrode
Authors: Prakash Rajiv , Srivastava R. C. , Seth P. K.
Published: September 2003

A special type of metal side disk rotating electrode has been demonstrated for the direct estimation of total arsenic [As(III) and As(V)] at low ppb (μg/L) level using anodic stripping differential pulse voltammetry (ASDPV). A conventional three electrodes cell is used equipped with side disk rotating gold electrode as working, graphite/platinum electrode as auxiliary and Ag/AgCl/3M KCl as reference electrodes. Arsenic is estimated in various acidified samples without any digestion, containing a trace amount of copper at low ppb level. The major problems associated with ASDPV of high acidic condition (acid hazards), irreproducible results due to the interference of hydrogen bubbles, evolved at the cathode during the deposition of arsenic in acidified samples and poor detection level are overcome with the help of the specially designed gold side disk rotating electrode and modified electrolyte. The presence of a trace amount of copper(II) salt in the electrolyte is found to enhance the sensitivity of the technique. The shape and position of the metal disk at the electrode, rotation speed of the electrode and electrolyte are optimized to have less hydrogen gas bubbles interference and high reproducibility in the detection of arsenic up to 2 ppb±15% level in various samples. The electrode has been found very stable and reproducible even for more than 200 estimations.