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Article ; Online: Orthophosphate and Sulfate Utilization for C-E (E = P, S) Bond Formation via Trichlorosilyl Phosphide and Sulfide Anions.

Geeson, Michael B / Ríos, Pablo / Transue, Wesley J / Cummins, Christopher C

Journal of the American Chemical Society

2019 Volume 141, Issue 15, Page(s) 6375–6384

Abstract: Reduction of phosphoric acid ( ... ...

Abstract	Reduction of phosphoric acid (H
Language	English
Publishing date	2019-04-08
Publishing country	United States
Document type	Journal Article ; Research Support, Non-U.S. Gov't
ZDB-ID	3155-0
ISSN	1520-5126 ; 0002-7863
ISSN (online)	1520-5126
ISSN	0002-7863
DOI	10.1021/jacs.9b01475
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Article ; Online: Multivariate analysis of MLH1 c.1664T>C (p.Leu555Pro) mismatch repair gene variant demonstrates its pathogenicity.

Farrell, M P / Hughes, D J / Drost, M / Wallace, A J / Cummins, R J / Fletcher, T A / Meany, M A / Kay, E W / de Wind, N / Power, D G / Andrews, E J / Green, A J / Gallagher, D J

Familial cancer

2013 Volume 12, Issue 4, Page(s) 741–747

Abstract: Genetic testing of an Irish kindred identified an exonic nucleotide substitution c.1664T>C (p ... of this variant. The MLH1 c.1664T>C (p.Leu555Pro) VUS co-segregated with three cases of classic Lynch syndrome ... molecular genetic data suggests that MLH1 c.1664T>C (p.Leu555Pro) is likely to be the pathogenic cause of Lynch ...

Abstract	Genetic testing of an Irish kindred identified an exonic nucleotide substitution c.1664T>C (p.Leu555Pro) in the MLH1 mismatch repair (MMR) gene. This previously unreported variant is classified as a "variant of uncertain significance" (VUS). Immunohistochemical (IHC) analysis and microsatellite instability (MSI) studies, genetic testing, a literature and online MMR mutation database review, in silico phenotype prediction tools, and an in vitro MMR activity assay were used to study the clinical significance of this variant. The MLH1 c.1664T>C (p.Leu555Pro) VUS co-segregated with three cases of classic Lynch syndrome-associated malignancies over two generations, with consistent loss of MLH1 and PMS2 protein expression on IHC, and evidence of the MSI-High mutator phenotype. The leucine at position 555 is well conserved across a number of species, and this novel variant has not been reported as a normal polymorphism in the general population. In silico and in vitro analyses suggest that this variant may have a deleterious effect on the MLH1 protein and abrogate MMR activity. Evidence from clinical, histological, immunohistochemical, and molecular genetic data suggests that MLH1 c.1664T>C (p.Leu555Pro) is likely to be the pathogenic cause of Lynch syndrome in this family.
MeSH term(s)	Adaptor Proteins, Signal Transducing/genetics ; Adaptor Proteins, Signal Transducing/metabolism ; Adenosine Triphosphatases/genetics ; Adenosine Triphosphatases/metabolism ; Adult ; Colorectal Neoplasms, Hereditary Nonpolyposis/genetics ; Colorectal Neoplasms, Hereditary Nonpolyposis/pathology ; DNA Mismatch Repair/genetics ; DNA Repair Enzymes/genetics ; DNA Repair Enzymes/metabolism ; DNA-Binding Proteins/genetics ; DNA-Binding Proteins/metabolism ; Female ; Follow-Up Studies ; Humans ; Immunoenzyme Techniques ; Male ; Microsatellite Instability ; Middle Aged ; Mismatch Repair Endonuclease PMS2 ; Multivariate Analysis ; MutL Protein Homolog 1 ; Mutation/genetics ; Neoplasm Staging ; Nuclear Proteins/genetics ; Nuclear Proteins/metabolism ; Pedigree ; Phenotype ; Prognosis ; Young Adult
Chemical Substances	Adaptor Proteins, Signal Transducing ; DNA-Binding Proteins ; MLH1 protein, human ; Nuclear Proteins ; Adenosine Triphosphatases (EC 3.6.1.-) ; PMS2 protein, human (EC 3.6.1.-) ; Mismatch Repair Endonuclease PMS2 (EC 3.6.1.3) ; MutL Protein Homolog 1 (EC 3.6.1.3) ; DNA Repair Enzymes (EC 6.5.1.-)
Language	English
Publishing date	2013-05-28
Publishing country	Netherlands
Document type	Journal Article
ZDB-ID	1502496-9
ISSN	1573-7292 ; 1389-9600
ISSN (online)	1573-7292
ISSN	1389-9600
DOI	10.1007/s10689-013-9652-9
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Article: Orthophosphate and Sulfate Utilization for C–E (E = P, S) Bond Formation via Trichlorosilyl Phosphide and Sulfide Anions

Geeson, Michael B / Pablo Ríos / Wesley J. Transue / Christopher C. Cummins

Journal of the American Chemical Society. 2019 Mar. 22, v. 141, no. 15

2019

Abstract: ... with trichlorosilane leads to the formation of the bis(trichlorosilyl)phosphide ([P(SiCl₃)₂]⁻, 1) and ... as byproducts arising from these reductive processes: i) [H₂PO₄]⁻ + 10HSiCl₃ → 1 + 4O(SiCl₃)₂ + 6H₂ for P and ii ...

Abstract	Reduction of phosphoric acid (H₃PO₄) or tetra-n-butylammonium bisulfate ([TBA][HSO₄]) with trichlorosilane leads to the formation of the bis(trichlorosilyl)phosphide ([P(SiCl₃)₂]⁻, 1) and trichlorosilylsulfide ([Cl₃SiS]⁻, 2) anions, respectively. Balanced equations for the formation of the TBA salts of anions 1 and 2 were formulated based on the identification of hexachlorodisiloxane and hydrogen gas as byproducts arising from these reductive processes: i) [H₂PO₄]⁻ + 10HSiCl₃ → 1 + 4O(SiCl₃)₂ + 6H₂ for P and ii) [HSO₄]⁻ + 9HSiCl₃ → 2 + 4O(SiCl₃)₂ + 5H₂ for S. Hydrogen gas was identified by its subsequent use to hydrogenate an alkene ((−)-terpinen-4-ol) using Crabtree’s catalyst ([(COD)Ir(py)(PCy₃)][PF₆], COD = 1,5-cyclooctadiene, py = pyridine, Cy = cyclohexyl). Phosphide 1 was generated in situ by the reaction of phosphoric acid and trichlorosilane and used to convert an alkyl chloride (1-chlorooctane) to the corresponding primary phosphine, which was isolated in 41% yield. Anion 1 was also prepared from [TBA][H₂PO₄] and isolated in 62% yield on a gram scale. Treatment of [TBA]1 with an excess of benzyl chloride leads to the formation of tetrabenzylphosphonium chloride, which was isolated in 61% yield. Sulfide 2 was used as a thionation reagent, converting benzophenone to thiobenzophenone in 62% yield. It also converted benzyl bromide to benzyl mercaptan in 55% yield. The TBA salt of trimetaphosphate ([TBA]₃[P₃O₉]·2H₂O), also a precursor to anion 1, was found to react with either trichlorosilane or silicon(IV) chloride to provide bis(trimetaphosphate)silicate, [TBA]₂[Si(P₃O₉)₂], characterized by NMR spectroscopy, X-ray crystallography, and elemental analysis. Trichlorosilane reduction of [TBA]₂[Si(P₃O₉)₂] also provided anion 1. The electronic structures of 1 and 2 were investigated using a suite of theoretical methods; the computational studies suggest that the trichlorosilyl ligand is a good π-acceptor and forms σ-bonds with a high degree of s character.
Keywords	X-ray diffraction ; anions ; benzophenones ; byproducts ; catalysts ; chemical oxygen demand ; equations ; hydrogen ; ligands ; nuclear magnetic resonance spectroscopy ; organobromine compounds ; organochlorine compounds ; orthophosphates ; phosphides ; phosphine ; phosphoric acid ; pyridines ; quaternary ammonium compounds ; silicates ; silicon ; sulfates
Language	English
Dates of publication	2019-0322
Size	p. 6375-6384.
Publishing place	American Chemical Society
Document type	Article
ZDB-ID	3155-0
ISSN	1520-5126 ; 0002-7863
ISSN (online)	1520-5126
ISSN	0002-7863
DOI	10.1021/jacs.9b01475
Database	NAL-Catalogue (AGRICOLA)

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Article: Phosphaalkynes from acid chlorides via P for O(Cl) metathesis: a recyclable niobium phosphide (P(3-)) reagent that effects C-P triple-bond formation.

Figueroa, Joshua S / Cummins, Christopher C

Journal of the American Chemical Society

2004 Volume 126, Issue 43, Page(s) 13916–13917

Abstract: Reported herein is a new, metathetical P for O(Cl) exchange mediated by an anionic niobium ... The niobaziridine hydride complex, Nb(H)(tBu(H)C=NAr)(N[Np]Ar)2 (1, Np = neopentyl, Ar = 3,5-Me2C6H3), has been ... BuC(O)P)Nb(N[Np]Ar)3 (4-t-Bu) and (1-AdC(O)P)Nb(N[Np]Ar)3 (4-1-Ad), which are intermediates along ...

Abstract	Reported herein is a new, metathetical P for O(Cl) exchange mediated by an anionic niobium phosphide complex that furnished phosphaalkynes (RCP) from acid chlorides (RC(O)Cl) under mild conditions. The niobaziridine hydride complex, Nb(H)(tBu(H)C=NAr)(N[Np]Ar)2 (1, Np = neopentyl, Ar = 3,5-Me2C6H3), has been shown previously to react with elemental phosphorus (P4), affording the mu-diphosphide complex, (mu2:eta2,eta2-P2)[Nb(N[Np]Ar)3]2, (2), which can be subsequently reduced by sodium amalgam to the anonic, terminal phosphide complex, [Na][PNb(N[Np]Ar)3] (3). It is now shown that treatment of 3 with either pivaloyl (t-BuC(O)Cl) or 1-adamantoyl (1-AdC(O)Cl) chloride provides the thermally unstable niobacyles, (t-BuC(O)P)Nb(N[Np]Ar)3 (4-t-Bu) and (1-AdC(O)P)Nb(N[Np]Ar)3 (4-1-Ad), which are intermediates along the pathway to ejection of the known phosphaalkynes t-BuCP (5-t-Bu) and 1-AdCP(5-1-Ad). Phosphaalkyne ejection from 4-t-Bu and 4-1-Ad proceeds with formation of the niobium(V) oxo complex ONb(N[Np]Ar)3 (6) as a stable byproduct. Preliminary kinetic measurements for fragmentation of 4-t-Bu to 5-t-Bu and 6 in C6D6 solution are consistent with a first-order process, yielding the thermodynamic parameters DeltaH = 24.9 +/- 1.4 kcal mol-1 and DeltaS = 2.4 +/- 4.3 cal mol-1 K-1 over the temperature range 308-338 K. Separation of volatile 5-t-Bu from 6 after thermolysis has been readily achieved by vacuum transfer in yields of 90%. Pure 6 is recovered after vacuum transfer and can be treated with 1.0 equiv of triflic anhydride (Tf2O, Tf = O2SCF3) to afford the bistriflate complex, Nb(OTf)2(N[Np]Ar)3 (7), in high yield. Complex 7 provides direct access to 1 upon reduction with magnesium anthracene, thus completing a cycle of element activation, small-molecule generation via metathetical P-atom transfer, and deoxygenative recycling of the final niobium(V) oxo product.
Language	English
Publishing date	2004-11-03
Publishing country	United States
Document type	Journal Article
ZDB-ID	3155-0
ISSN	1520-5126 ; 0002-7863
ISSN (online)	1520-5126
ISSN	0002-7863
DOI	10.1021/ja0461522
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Article ; Online: Phosphaalkenes as long-lived phosphorus cluster surface functional groups: intramolecular P=C addition to a niobium-supported P7 cage.

Cossairt, Brandi M / Cummins, Christopher C

Inorganic chemistry

2008 Volume 47, Issue 20, Page(s) 9363–9371

Abstract: The diniobium octaphosphorus complex (P8)[Nb(OC[(2)Ad]Mes)3]2 (1) (Ad = adamantylidene, Mes = 2,4,6-Me3C6H2) contains a reactive niobium phosphinidene moiety that can be exploited for metathetical scission of the NbP bond. When 1 is treated with aryl ... ...

Abstract	The diniobium octaphosphorus complex (P8)[Nb(OC[(2)Ad]Mes)3]2 (1) (Ad = adamantylidene, Mes = 2,4,6-Me3C6H2) contains a reactive niobium phosphinidene moiety that can be exploited for metathetical scission of the NbP bond. When 1 is treated with aryl ketones, loss of ONb(OC[(2)Ad]Mes)3(OEt2) (2) is observed along with concomitant formation of the corresponding phosphaalkene (RC6H4)2CPP7Nb(OC[(2)Ad]Mes)3 (3-R). Complexes 3-R rearrange to incorporate the (RC6H4)2CP unit into the phosphorus cage, thereby generating a saturated organo-phosphorus cluster complexed to the niobium tris-enolate platform, (RC6H4)2CP8Nb(OC[(2)Ad]Mes)3 (4-R). The structure of one such rearranged cluster 4-H, as determined by X-ray crystallography, is briefly discussed. An Eyring analysis of the first-order rearrangement of 3-H to 4-H gives activation parameters of DeltaH(double dagger) = 16.7 kcal/mol and DeltaS(double dagger) = -20.4 eu. A Hammett analysis of the phosphaalkene rearrangement, 3-R to 4-R, with substitution varying at the para positions of the aryl rings, reveals a linear relationship between the sigma values and the rearrangement rate constants. A concerted, asynchronous mechanism for the least-motion rearrangement of 3-H to 4-H is presented. When 1 is treated with alkyl ketones, similar loss of 2 and formation of the corresponding phosphaalkene is observed; however, the phosphaalkene complexes have considerably greater stability and are readily isolated.
Language	English
Publishing date	2008-10-20
Publishing country	United States
Document type	Journal Article
ZDB-ID	1484438-2
ISSN	1520-510X ; 0020-1669
ISSN (online)	1520-510X
ISSN	0020-1669
DOI	10.1021/ic8009282
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Article: c-Jun NH2-terminal kinase activation contributes to hypoxia-inducible factor 1alpha-dependent P-glycoprotein expression in hypoxia.

Comerford, Katrina M / Cummins, Eoin P / Taylor, Cormac T

Cancer research

2004 Volume 64, Issue 24, Page(s) 9057–9061

Abstract: We previously have shown that hypoxia increases the expression of P-glycoprotein, which in turn ... the role of the stress-activated protein kinase c-Jun NH(2)-terminal kinase (JNK) in the signaling ... hypoxia-induced activity of the MDR1 promoter and expression of MDR1 mRNA and P-glycoprotein. Furthermore ...

Abstract	We previously have shown that hypoxia increases the expression of P-glycoprotein, which in turn increases tumor cell capacity to actively extrude chemotherapeutic agents and may contribute to tumor drug resistance. This event is mediated through the hypoxia-inducible factor (HIF-1). Here, we investigated the role of the stress-activated protein kinase c-Jun NH(2)-terminal kinase (JNK) in the signaling mechanisms underlying these events. Hypoxia activates JNK activity in vitro and in vivo. Overexpression of mitogen-activated protein kinase (MAPK) kinase kinase (MEKK-1), which preferentially activates JNK, mimics, in a nonadditive way, hypoxia-induced activity of the MDR1 promoter and expression of MDR1 mRNA and P-glycoprotein. Furthermore, the JNK inhibitor SP600125 selectively and specifically inhibits hypoxia- and MEKK-1-induced MDR1 promoter activity in a dose-dependent manner. JNK inhibition also reversed hypoxia- and MEKK-1-induced activity of an HIF-1-dependent reporter gene. MEKK-1-induced MDR1 expression depends on a functional HIF-1 binding site (hypoxia-responsive element). Hypoxia- but not cobalt chloride-dependent HIF-1-DNA binding and transcriptional activation was inhibited by SP600125, indicating that hypoxia-induced signaling to HIF-1 depends on JNK activation. Because it has been reported that reactive oxygen species are increased in hypoxia and related to JNK activation, we investigated their role in signaling this response. Whereas exogenous addition of H(2)O(2) was sufficient to activate JNK, reactive oxygen species scavengers were without effect on hypoxia-induced JNK or HIF-1 activation. Thus, hypoxia-elicited MDR1 expression, which depends on HIF-1 activation, depends at least in part on signaling via activation of JNK. Furthermore, these events are independent of the generation of reactive oxygen intermediates. Thus, JNK may represent a therapeutic target in the prevention of tumor resistance to chemotherapeutic treatment.
MeSH term(s)	ATP-Binding Cassette, Sub-Family B, Member 1/biosynthesis ; ATP-Binding Cassette, Sub-Family B, Member 1/genetics ; Antioxidants/pharmacology ; Cell Hypoxia/physiology ; Cobalt/pharmacology ; Enzyme Activation ; Genes, MDR/genetics ; HeLa Cells ; Humans ; Hypoxia-Inducible Factor 1, alpha Subunit ; JNK Mitogen-Activated Protein Kinases/antagonists & inhibitors ; JNK Mitogen-Activated Protein Kinases/metabolism ; Phosphorylation ; Promoter Regions, Genetic ; Transcription Factors/antagonists & inhibitors ; Transcription Factors/metabolism ; Transcriptional Activation ; Transfection ; Up-Regulation
Chemical Substances	ATP-Binding Cassette, Sub-Family B, Member 1 ; Antioxidants ; HIF1A protein, human ; Hypoxia-Inducible Factor 1, alpha Subunit ; Transcription Factors ; Cobalt (3G0H8C9362) ; JNK Mitogen-Activated Protein Kinases (EC 2.7.11.24) ; cobaltous chloride (EVS87XF13W)
Language	English
Publishing date	2004-12-15
Publishing country	United States
Document type	Journal Article
ZDB-ID	1432-1
ISSN	1538-7445 ; 0008-5472
ISSN (online)	1538-7445
ISSN	0008-5472
DOI	10.1158/0008-5472.CAN-04-1919
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Article ; Online: Uranium Hexakisamido Complexes This work was supported by the National Science Foundation (CAREER Award CHE-9501992), the Alfred P. Sloan Foundation, the National Science Board (1998 Alan T. Waterman award to C.C.C.), and the Packard Foundation. K.M. thanks the Deutsche Forschungsgemeinschaft for a postdoctoral fellowship.

Meyer / Mindiola / Baker / Davis / Cummins

Angewandte Chemie (International ed. in English)

2000 Volume 39, Issue 17, Page(s) 3063–3066

Language	English
Publishing date	2000-10-06
Publishing country	Germany
Document type	Journal Article
ZDB-ID	2011836-3
ISSN	1521-3773 ; 1433-7851
ISSN (online)	1521-3773
ISSN	1433-7851
DOI	10.1002/1521-3773(20000901)39:17<3063::aid-anie3063>3.0.co;2-0
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Article: Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates.

Xin, Tiansi / Cummins, Christopher C

ACS central science

2023 Volume 9, Issue 8, Page(s) 1575–1580

Abstract: In pursuit of a more sustainable route to phosphorus-carbon (P-C) bond-containing chemicals ... polyphosphates in a single step, redox-neutral process, bypassing white phosphorus (P ...

Abstract	In pursuit of a more sustainable route to phosphorus-carbon (P-C) bond-containing chemicals, we herein report that phosphonates can be prepared by mechanochemical phosphorylation of acetylides using polyphosphates in a single step, redox-neutral process, bypassing white phosphorus (P
Language	English
Publishing date	2023-07-21
Publishing country	United States
Document type	Journal Article
ISSN	2374-7943
ISSN	2374-7943
DOI	10.1021/acscentsci.3c00725
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Article: Gastric and duodenal ulcer. By P. C. Perry. Southern Medical Journal 1913.

Cummins, A J

Southern medical journal

1983 Volume 76, Issue 7, Page(s) 827–833

MeSH term(s)	Age Factors ; Duodenal Ulcer/history ; Florida ; Gastrectomy/history ; History, 20th Century ; Humans ; Sex Factors ; Stomach Ulcer/history
Language	English
Publishing date	1983-07
Publishing country	United States
Document type	Biography ; Historical Article ; Journal Article
ZDB-ID	185329-6
ISSN	1541-8243 ; 0038-4348
ISSN (online)	1541-8243
ISSN	0038-4348
DOI	10.1097/00007611-198307000-00003
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Article: Wstepne wyniki leczenia chorych z przewlekłym czynnym zapaleniem watroby (p. c. z. w.) HBsAg+, HBeAg+ niskimi doustnymi dawkami ludzkiego interferonu alfa.

Zielińska, W / Paszkiewicz, J / Korczak, A / Własiuk, M / Zółtowska, A / Szutowicz, J / Cummins, J / Georgiades, J

Przeglad epidemiologiczny

1991 Volume 45, Issue 4, Page(s) 325–330

Abstract: The treatment conception was based on the theory of immunocorrective activity function of low doses of human interferon alpha (HuIFN alpha) multi-played by logistic amplifier system included in oral cavity. Twelve patients with chronic hepatitis, HBV ... ...

Title translation	Preliminary results of the treatment of patients with chronic active hepatitis (CAH) HBsAg+,HBeAg+ with low oral doses of human interferon-alpha.
Abstract	The treatment conception was based on the theory of immunocorrective activity function of low doses of human interferon alpha (HuIFN alpha) multi-played by logistic amplifier system included in oral cavity. Twelve patients with chronic hepatitis, HBV infected, aged 7-59, were randomly chosen for treatment. Previously they underwent immunosuppression without success. All of them revealed clinical and biochemical symptoms of steel active disease with morphological progression including active cirrhosis (3 cases). HuIFN alpha therapy was started just after withdrawal of immunosuppression (steroids, steroids and azathioprine). Effects of 50-100 U/d dose of HUIFN alpha were monitored by examination of hematological, biochemical parametres and indicators of humoral and cellular immune response and HBV markers in control liver biopsy specimens too. The HBVDNA serum level was measured besides, using the method of molecular hybridisation. Observation period is from 5 to 17 month, now. Among all patients during 1-2 months from the treatment beginning, transient increase of biochemical parametres of liver function (f. ex: 2-3 times ALAT increase) were observed without any clinical signs of disease exacerbation. All patients revealed immune system activation that lasted longer than incipiens intensive stimulation. Four from twelve patients that finished therapy, eliminated HBVDNA from blood serum. One of them eliminated HBsAg too. Three further confirmed decrease of HBsAg with e system seroconversion. Three from 8 patients treated 6-9 months reveal decrease of HBVDNA concentration in blood serum.
MeSH term(s)	Administration, Oral ; Adolescent ; Adult ; Biomarkers ; Child ; Female ; Hepatitis B/immunology ; Hepatitis B/therapy ; Hepatitis B Surface Antigens/analysis ; Hepatitis B e Antigens/analysis ; Hepatitis, Chronic/immunology ; Hepatitis, Chronic/therapy ; Humans ; Interferon-alpha/administration & dosage ; Male ; Middle Aged ; Time Factors
Chemical Substances	Biomarkers ; Hepatitis B Surface Antigens ; Hepatitis B e Antigens ; Interferon-alpha
Language	Polish
Publishing date	1991
Publishing country	Poland
Document type	Clinical Trial ; English Abstract ; Journal Article
ZDB-ID	421782-2
ISSN	0033-2100
ISSN	0033-2100
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