7 research outputs found
Examination of Acid-Fast Bacilli in Sputum Using Modified Light Microscope with Homemade Light Emitting Diode Additional Attachment
Typical clinical symptoms and chest X-ray is a marker of Tuberculosis (TB) sufferers. However, the diagnosis of TB in adults should be supported by microscopic examination. Currently, Bacilli microscopic examination of acid-fast bacilli (AFB) in sputum by Ziehl-Neelsen (ZN) coloring is the most widely used. However, for reasons of convenience, especially for laboratories with a considerable amount of smear samples, and due to higher sensitivity compared with ZN staining, the World Health Organization (WHO) has recommended the use of auramine-O-staining (fluorochrome staining), which is visualized by light emitting diode (LED) fluorescence microscopy. The aim of this study was to evaluate the performance of modified light microscope with homemade LED additional attachment for examination of AFB in sputum using auramine-O-staining method. We compared the sensitivity and specificity of 2 kinds of AFB in sputum methods: ZN and fluorochrome, using culture on Lowenstein-Jensen media as the gold standard. The results showed auramine-O-staining gives more proportion of positive findings (81%) compared to the ZN method (70%). These results demonstrated that the sensitivity of auramine-O-staining was higher than ZN, however it gives more potential false positive results than ZN. The sensitivity of auramine-O-staining in detecting AFB in sputum was 100% while the specificity was 88%
Stoichiometric and Catalytic Reactions of Thermally Stable Nickel(0) NHC Complexes
Although there are many organic reactions that are catalyzed
by
either Ni<sup>0</sup> or Pd<sup>0</sup> complexes, in comparison with
the case for Pd<sup>0</sup> there has been significantly less work
studying coordinatively unsaturated Ni<sup>0</sup> complexes. Here,
we develop a simple synthetic route for preparing a number of thermally
stable NHC-supported Ni<sup>0</sup> hexadiene complexes in good yield.
We examine the stoichiometric reactivity of one of these species and
demonstrate that the coordinated hexadiene moiety is labile and can
be replaced with a variety of different ligands, including CO, phosphines,
isonitriles, and olefins. In addition, we show that the Ni<sup>0</sup> hexadiene complexes are relatively rare examples of homogeneous
first-row transition-metal catalysts for the hydrogenation of olefins
Stoichiometric and Catalytic Reactions of Thermally Stable Nickel(0) NHC Complexes
Although there are many organic reactions that are catalyzed
by
either Ni<sup>0</sup> or Pd<sup>0</sup> complexes, in comparison with
the case for Pd<sup>0</sup> there has been significantly less work
studying coordinatively unsaturated Ni<sup>0</sup> complexes. Here,
we develop a simple synthetic route for preparing a number of thermally
stable NHC-supported Ni<sup>0</sup> hexadiene complexes in good yield.
We examine the stoichiometric reactivity of one of these species and
demonstrate that the coordinated hexadiene moiety is labile and can
be replaced with a variety of different ligands, including CO, phosphines,
isonitriles, and olefins. In addition, we show that the Ni<sup>0</sup> hexadiene complexes are relatively rare examples of homogeneous
first-row transition-metal catalysts for the hydrogenation of olefins
Synthesis and Structure of Six-Coordinate Iron Borohydride Complexes Supported by PNP Ligands
The preparation of a number of iron
complexes supported by ligands
of the type HNÂ{CH<sub>2</sub>CH<sub>2</sub>(PR<sub>2</sub>)}<sub>2</sub> [R = isopropyl (<sup><sup>i</sup>Pr</sup>PNP) or cyclohexyl (<sup>Cy</sup>PNP)] is reported. This is the first time this important
bifunctional ligand has been coordinated to iron. The ironÂ(II) complexes
(<sup><sup>i</sup>Pr</sup>PNP)ÂFeCl<sub>2</sub>(CO) (<b>1a</b>) and (<sup>Cy</sup>PNP)ÂFeCl<sub>2</sub>(CO) (<b>1b</b>) were
synthesized through the reaction of the appropriate free ligand and
FeCl<sub>2</sub> in the presence of CO. The iron(0) complex (<sup><sup>i</sup>Pr</sup>PNP)ÂFeÂ(CO)<sub>2</sub> (<b>2a</b>) was
prepared through the reaction of FeÂ(CO)<sub>5</sub> with <sup><sup>i</sup>Pr</sup>PNP, while irradiating with UV light. Compound <b>2a</b> is unstable in CH<sub>2</sub>Cl<sub>2</sub> and is oxidized
to <b>1a</b> via the intermediate ironÂ(II) complex [(<sup><sup>i</sup>Pr</sup>PNP)ÂFeClÂ(CO)<sub>2</sub>]Cl (<b>3a</b>). The
reaction of <b>2a</b> with HCl generated the related complex
[(<sup><sup>i</sup>Pr</sup>PNP)ÂFeHÂ(CO)<sub>2</sub>]Cl (<b>4a</b>), while the neutral iron hydrides (<sup><sup>i</sup>Pr</sup>PNP)ÂFeHClÂ(CO)
(<b>5a</b>) and (<sup>Cy</sup>PNP)ÂFeHClÂ(CO) (<b>5b</b>) were synthesized through the reaction of <b>1a</b> or <b>1b</b> with 1 equiv of <sup>n</sup>Bu<sub>4</sub>NBH<sub>4</sub>. The related reaction between <b>1a</b> and excess NaBH<sub>4</sub> generated the unusual η<sup>1</sup>-HBH<sub>3</sub> complex (<sup><sup>i</sup>Pr</sup>PNP)ÂFeHÂ(η<sup>1</sup>-HBH<sub>3</sub>)Â(CO) (<b>6a</b>). This complex features a bifurcated
intramolecular dihydrogen bond between two of the hydrogen atoms associated
with the η<sup>1</sup>-HBH<sub>3</sub> ligand and the N–H
proton of the pincer ligand, as well as intermolecular dihydrogen
bonding. The protonation of <b>6a</b> with 2,6-lutidinium tetraphenylborate
resulted in the formation of the dimeric complex [{(<sup><sup>i</sup>Pr</sup>PNP)ÂFeHÂ(CO)}<sub>2</sub>(μ<sub>2</sub>,η<sup>1</sup>:η<sup>1</sup>-H<sub>2</sub>BH<sub>2</sub>)]Â[BPh<sub>4</sub>] (<b>7a</b>), which features a rare example of a μ<sub>2</sub>,η<sup>1</sup>:η<sup>1</sup>-H<sub>2</sub>BH<sub>2</sub> ligand. Unlike all previous examples of complexes with a
μ<sub>2</sub>,η<sup>1</sup>:η<sup>1</sup>-H<sub>2</sub>BH<sub>2</sub> ligand, there is no metal–metal bond
and additional bridging ligand supporting the borohydride ligand in <b>7a</b>; however, it is proposed that two dihydrogen-bonding interactions
stabilize the complex. Complexes <b>1a</b>, <b>2a</b>, <b>3a</b>, <b>4a</b>, <b>5a</b>, <b>6a</b>, and <b>7a</b> were characterized by X-ray crystallography
Synthesis and Structure of Six-Coordinate Iron Borohydride Complexes Supported by PNP Ligands
The preparation of a number of iron
complexes supported by ligands
of the type HNÂ{CH<sub>2</sub>CH<sub>2</sub>(PR<sub>2</sub>)}<sub>2</sub> [R = isopropyl (<sup><sup>i</sup>Pr</sup>PNP) or cyclohexyl (<sup>Cy</sup>PNP)] is reported. This is the first time this important
bifunctional ligand has been coordinated to iron. The ironÂ(II) complexes
(<sup><sup>i</sup>Pr</sup>PNP)ÂFeCl<sub>2</sub>(CO) (<b>1a</b>) and (<sup>Cy</sup>PNP)ÂFeCl<sub>2</sub>(CO) (<b>1b</b>) were
synthesized through the reaction of the appropriate free ligand and
FeCl<sub>2</sub> in the presence of CO. The iron(0) complex (<sup><sup>i</sup>Pr</sup>PNP)ÂFeÂ(CO)<sub>2</sub> (<b>2a</b>) was
prepared through the reaction of FeÂ(CO)<sub>5</sub> with <sup><sup>i</sup>Pr</sup>PNP, while irradiating with UV light. Compound <b>2a</b> is unstable in CH<sub>2</sub>Cl<sub>2</sub> and is oxidized
to <b>1a</b> via the intermediate ironÂ(II) complex [(<sup><sup>i</sup>Pr</sup>PNP)ÂFeClÂ(CO)<sub>2</sub>]Cl (<b>3a</b>). The
reaction of <b>2a</b> with HCl generated the related complex
[(<sup><sup>i</sup>Pr</sup>PNP)ÂFeHÂ(CO)<sub>2</sub>]Cl (<b>4a</b>), while the neutral iron hydrides (<sup><sup>i</sup>Pr</sup>PNP)ÂFeHClÂ(CO)
(<b>5a</b>) and (<sup>Cy</sup>PNP)ÂFeHClÂ(CO) (<b>5b</b>) were synthesized through the reaction of <b>1a</b> or <b>1b</b> with 1 equiv of <sup>n</sup>Bu<sub>4</sub>NBH<sub>4</sub>. The related reaction between <b>1a</b> and excess NaBH<sub>4</sub> generated the unusual η<sup>1</sup>-HBH<sub>3</sub> complex (<sup><sup>i</sup>Pr</sup>PNP)ÂFeHÂ(η<sup>1</sup>-HBH<sub>3</sub>)Â(CO) (<b>6a</b>). This complex features a bifurcated
intramolecular dihydrogen bond between two of the hydrogen atoms associated
with the η<sup>1</sup>-HBH<sub>3</sub> ligand and the N–H
proton of the pincer ligand, as well as intermolecular dihydrogen
bonding. The protonation of <b>6a</b> with 2,6-lutidinium tetraphenylborate
resulted in the formation of the dimeric complex [{(<sup><sup>i</sup>Pr</sup>PNP)ÂFeHÂ(CO)}<sub>2</sub>(μ<sub>2</sub>,η<sup>1</sup>:η<sup>1</sup>-H<sub>2</sub>BH<sub>2</sub>)]Â[BPh<sub>4</sub>] (<b>7a</b>), which features a rare example of a μ<sub>2</sub>,η<sup>1</sup>:η<sup>1</sup>-H<sub>2</sub>BH<sub>2</sub> ligand. Unlike all previous examples of complexes with a
μ<sub>2</sub>,η<sup>1</sup>:η<sup>1</sup>-H<sub>2</sub>BH<sub>2</sub> ligand, there is no metal–metal bond
and additional bridging ligand supporting the borohydride ligand in <b>7a</b>; however, it is proposed that two dihydrogen-bonding interactions
stabilize the complex. Complexes <b>1a</b>, <b>2a</b>, <b>3a</b>, <b>4a</b>, <b>5a</b>, <b>6a</b>, and <b>7a</b> were characterized by X-ray crystallography
Organometallic Ni Pincer Complexes for the Electrocatalytic Production of Hydrogen
Nonplatinum metals are needed to perform cost-effective
water reduction
electrocatalysis to enable technological implementation of a proposed
hydrogen economy. We describe electrocatalytic proton reduction and
H<sub>2</sub> production by two organometallic nickel complexes with
tridentate pincer ligands. The kinetics of H<sub>2</sub> production
from voltammetry is consistent with an overall third order rate law:
the reaction is second order in acid and first order in catalyst.
Hydrogen production with 90–95% Faradaic yields was confirmed
by gas analysis, and UV–vis spectroscopy suggests that the
ligand remains bound to the catalyst over the course of the reaction.
A computational study provides mechanistic insights into the proposed
catalytic cycle. Furthermore, two proposed intermediates in the proton
reduction cycle were isolated in a representative system and show
a catalytic response akin to the parent compound
Organometallic Ni Pincer Complexes for the Electrocatalytic Production of Hydrogen
Nonplatinum metals are needed to perform cost-effective
water reduction
electrocatalysis to enable technological implementation of a proposed
hydrogen economy. We describe electrocatalytic proton reduction and
H<sub>2</sub> production by two organometallic nickel complexes with
tridentate pincer ligands. The kinetics of H<sub>2</sub> production
from voltammetry is consistent with an overall third order rate law:
the reaction is second order in acid and first order in catalyst.
Hydrogen production with 90–95% Faradaic yields was confirmed
by gas analysis, and UV–vis spectroscopy suggests that the
ligand remains bound to the catalyst over the course of the reaction.
A computational study provides mechanistic insights into the proposed
catalytic cycle. Furthermore, two proposed intermediates in the proton
reduction cycle were isolated in a representative system and show
a catalytic response akin to the parent compound