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1 gem-1 encodes a multipass transmembrane protein that is
2 gem-4 encodes a member of the copine family of Ca(2+)-de
3 gem-Dimethyl substituents at the linker improved the pot
4 gem-Dimethyl substitution lowers the strain energy of cy
6 (R-allyl)LCl complexes [R = H, 1-Me, 1-Ph, 1-gem-Me(2), 2-Me; L = Q-Phos, P(t-Bu)(3), P(t-Bu)(2)(p-NM
8 nolized substrates in the presence of the 19-gem-diol decayed directly to the experimentally observed
9 [likely to bind as the hydrate, C(2)(OH)(2) gem-diol] as the most active substrates (for each, k(cat
10 a being either Gly (R(2) = H) or Aib (R(2) = gem-Me) and R(1) and R(3) either alkyl or amino acid sub
11 n of 1,1-difluoroallene, provides chiral 2,2-gem-difluorinated homoallylic alcohols in good yields an
13 ss a C(4)-gem-dimethyl group and four a C(4)-gem-diphenyl group adjacent to the C(5)-isopropyl substi
14 plexes of ligands 11a-h, along with non-C(4)-gem-disubstituted analogues 1a-g, were effective in the
17 O)(OEt)(2))-7-(Me(2)S)B(12)H(10) (14g) and a gem-bisphosphonate 1-(MeS(CH(2))(3)CH[P(O)(OEt)(2)](2))-
18 hydrophobic groups at the phenyl ring and a gem-dimethyl group at the cyclopropane ring enhances the
21 density suggests one active site contains a gem-diamine intermediate with d-ornithine; the second ha
22 approximately 350 nm is assigned as either a gem-diamine complex or a thiol adduct formed by nucleoph
23 se results provide additional evidence for a gem-diol intermediate in the catalytic mechanism of kynu
24 -ACP appeared to be the sole route to form a gem-dimethylated product, while the yersiniabactin PKS c
30 es both the enantiotopic leaving groups of a gem-diacetate and enantiotopic faces of the enolate of a
33 ed the pyrrolidine ring in the presence of a gem-difluoro moiety to avoid using potentially hazardous
35 e mechanism that involves the formation of a gem-diol intermediate from the Zn bound uracil and a wat
37 e reaction mechanism involves formation of a gem-diol intermediate, whose decomposition into the prod
45 amily of enzymes is thought to proceed via a gem-diol reaction intermediate, which has not been obser
46 within the active site of the enzyme when a gem-diol transition state analogue inhibitor is bound at
47 midine nucleosides have been modified with a gem diether moiety to yield the following new nucleoside
50 ted adducts 9 or alcohols 10 and 11 afforded gem-difluoromethylenated linear triquinanes 16 as an app
52 te inhibitor binds as the hydrated aldehyde (gem-diol) in the enzyme active site, in a manner that mi
53 and chirality transfer to afford alkylidene(gem-difluorocyclopropanes) incorporating a quaternary st
55 I) catalyst yielded a new class of (E)-allyl-gem-dipyrazole scorpionate ligands: 1-aryl-2-N-pyrazolyl
58 t occur with high stereospecificity, allylic gem-dicarboxylates serve as synthons for a double allyli
59 ta-keto intermediate to yield an alpha,alpha-gem-dimethyl product, a new programing feature among HRP
60 tho-chlorophenyl imine afforded a beta-amino gem-diiodide under the optimized reaction conditions due
61 The dehydrogenations of alcohol (Step 1) and gem-diol (Step 3) prefer the double hydrogen transfer me
63 -yl)carbamate (1) and its monomethyl (2) and gem-dimethyl analogues (3), were tested for activation b
64 studied by the reaction of trans-, cis-, and gem-ethylene-d2 upon activation of Cr(PNP(O4))(o,o'-biph
67 ted with the ring opening of gem-dibromo and gem-dichlorocyclopropanes affixed along the backbone of
68 nzocyclobutene, gem-difluorocyclopropane and gem-dichlorocyclopropane require approximately 130 pN le
69 docyclization of gem-difluorohomoallenyl and gem-difluorohomopropargyl alcohols with I2 and ICl, resp
73 nal aldimine and quinonoid intermediates and gem-diamine and external aldimine intermediates, respect
76 ivity for hydroboration of cis-, trans-, and gem-disubstituted alkenes in excellent agreement with ex
77 ically, SMN localization to Cajal bodies and gems was not observed in cells derived from Zpr1-/- embr
80 e kinetics of multiple components of CBs and gems in living cells using photobleaching microscopy.
85 ring-opening reactions of benzocyclobutene, gem-difluorocyclopropane and gem-dichlorocyclopropane re
86 ivation of type IA p110alpha PI3K and Akt by gem and abrogation of gem-induced upregulation of IL-1Ra
88 diate to produce P450 compound I and the C19 gem-diol likely proceeds with a low energetic barrier.
89 vidently migrates from the sulfur atom to C3-gem-diol obtained by hydration of the keto group and the
92 nucleus, SMN is present in large foci called gems, the function of which is not yet known, while cyto
96 ning of a cis-dialkyl substituted syn-chloro-gem-chlorofluorocyclopropane, in violation of the Woodwa
97 rs and in silico docking studies, the chloro-gem-dimethyl-anthracenone substructure seen in the fasam
103 rbamate) were converted to the corresponding gem-difluorides in excellent yields on reaction with the
104 uxing conditions to afford the corresponding gem-difluoromethylenated 1-azabicyclic compounds 10-13 i
105 ly consumed by KOH to give the corresponding gem-diolate and provides the overall driving force for t
106 resulting adducts 3 to provide the cyclized gem-difluoromethylenated diquinanes 4 as a mixture of st
108 xicity of the ligand (imidazolium cyclophane gem-diol dichloride) was assessed by intravenous adminis
109 rapidly and chemoselectively to the desired gem-difunctionalized products in good to excellent yield
111 r gem diether nucleosides, only the dimethyl gem diether congener showed significant antiviral activi
112 e, extracts prepared from cells that display gems are less efficient in methylating coilin and Sm con
114 clude the following: (1) a typically elusive gem-diamine intermediate is trapped in the enzyme comple
115 e with a difluorocarbene source, we embedded gem-difluorocyclopropanes (gDFCs) along the polymer back
116 Miyaura cross-coupling of optically enriched gem-diboronyl compounds with various aryl bromides.
120 stituted 3,3-difluoro-4,5-dihydrofurans from gem-difluorohomopropargyl alcohols occurred in excellent
121 formation with different substituents, from gem-diol formation for electron-donating substituents to
124 ne-bridged model compounds (16) and (18) (g, gem-diaminoalkyl; m, malonyl; and r, direction-reversed
125 derlines a novel application of gemfibrozil (gem), a Food and Drug Administration-approved lipid-lowe
136 hloride or iodotoluene difluoride results in gem-dichlorination or gem-difluorination products, respe
144 a diverse array of cyclopentanes, including gem-disubstituted cyclopentanes having substitution on t
145 he flexible flaps of the PR by incorporating gem-difluorines and alkoxy, respectively, at the C4 posi
146 t novel bis(oxazoline) ligands incorporating gem-disubstitution on one of the oxazoline rings were pr
148 three-component heterocyclization involving gem-bromofluorocyclopropanes, nitrosyl tetrafluoroborate
149 2BF4(-)) exists in equilibrium with both its gem-diol and several aggregates (from dimers to at least
151 l assemblages and reduced volatiles in large gem diamonds indicate formation under metal-saturated co
153 l)-4,5-dihydroimidazol-2-ylidene; R = H, Me, gem-Me2, Ph] have been synthesized and fully characteriz
154 ce of the PI3K-Akt-CREB pathway in mediating gem-induced upregulation of IL-1Ra in neurons and sugges
155 propane dibromide 10 gave E- and Z-methylene-gem-difluorocyclopropanes 11a, 11b, 12a, and 12b and gem
156 undergoing AlkDF include monofluoroalkanes, gem-difluorocyclopentane, and compounds containing a CF(
163 n most cell types, CBs coincide with nuclear gems, which contain the survival of motor neurons (SMN)
164 em (CNS) showed intense labeling of nuclear "gems," along with prominent nucleolar immunoreactivity i
165 rotein, preventing the formation of nuclear 'gems' by disrupting the recruitment of the protein to Ca
166 function and increase the number of nuclear 'gems', small nuclear organelles in which survival motor
167 0alpha PI3K and Akt by gem and abrogation of gem-induced upregulation of IL-1Ra by inhibitors of PI3K
169 rm the gem-diol (Step 2); dehydrogenation of gem-diol to carboxylic acid (Step 3); and deprotonation
170 gesting that gon-4 either acts downstream of gem-4 and gon-2 or acts in a parallel regulatory pathway
171 al IL-1Ra abrogated the protective effect of gem against IL-1beta, suggesting that this drug increase
172 Enantioselective transfer hydrogenation of gem-dibenzoate 1e in the presence of aromatic, alpha,bet
177 In order to characterize the mechanism of gem-dimethyl group formation, with a goal toward enginee
179 e forces associated with the ring opening of gem-dibromo and gem-dichlorocyclopropanes affixed along
180 nonscissile mechanochemical ring opening of gem-dichlorocyclopropane mechanophores and (ii) the mole
181 eration of the electrocyclic ring opening of gem-dichlorocyclopropanes (gDCC) is sensitive to the ste
182 -dihalides is facilitated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the pr
188 tively, a convenient asymmetric synthesis of gem-difluoromethylenated linear triquinanes 16A can be a
191 employed as precursors for the synthesis of gem-difluoromethylenated tetracyclic cage lactols or tet
192 s of vinyl bromides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides.
193 eloped for the rapid asymmetric synthesis of gem-dimethyl and spirocyclopropyl norbornyl carboxylic a
196 structures that contain the known markers of gems and coiled bodies, and inhibits RNA pol I and pol I
197 tients, SMN protein levels and the number of gems generally correlate with disease severity, suggesti
198 tes a significant reduction in the number of gems in type I SMA patients and a correlation of the num
200 eveal that collapse of the carbinolamine (or gem-diamine) to give the final product is the rate-deter
202 ided as a Ruby Gem from https://rubygems.org/gems/bio-svgenes under the MIT license, and open source
203 ector is available from https://rubygems.org/gems/fselector and can be installed like a breeze via th
205 e quantum yield in this mutated protein (Phi(gem) = 0.32 for WT and His64Gln, and Phi(gem) = 0.85 for
206 We previously reported two gemini pollen (gem) mutants that produced twin-celled pollen arising fr
207 d in a quantitative increase in SMN-positive gems and an overall increase in detectable SMN protein.
208 es that maintain immature neural precursors (gem, zic2) requires the Acidic blob (AB) region in the N
209 r each enzyme, corresponding to the proposed gem-diol reaction intermediate, over a time scale of 1-2
211 ive intermediate derived from 1A(+) requires gem-1,1-dihydoxo stereochemistry to perform O-O bond for
213 ed complexes reacted with CO to form rhodium gem-dicarbonyls, which, in the presence of ethylene, gav
216 ro-infrared spectroscopic study of a single, gem-quality quartz crystal that allows us to measure the
217 We also show that, in contrast to CBs, SMN gems do not associate with U2 gene loci and do not conta
219 y crystal structure shows that the squaraine gem-dimethyl groups force a relatively wide separation b
221 along the backbone of purely cis-substituted gem-difluorocyclopropanated polybutadiene using the exte
222 pregulation of IL-1Ra in neurons and suggest gem as a possible therapeutic treatment for propagating
223 ective synthesis of the desired C2-symmetric gem-difluoromethylenated angular triquinanes 6 in good y
225 sion of a CRH-1/CREB transcriptional target (gem-4 Copine), which parallels the effects of human Shan
227 clear localization within structures termed 'gems', which co-localize with spliceosomal factors withi
228 rious central functional groups and terminal gem-dimethyl or -methyl/aryl substituents was synthesize
236 rised five, six, or seven atoms, and (3) the gem-dimethyl group was replaced with spirocyclic groups.
239 plex with Mg(2+) and a substrate analog: the gem-diol of 3,3-difluoro-oxaloacetate) was determined fo
242 due to a syn pentane interaction between the gem-dimethyl groups on the 2,2,6,6-tetramethylpiperidiny
243 dicinal chemists have elegantly employed the gem-dimethyl group to obtain clinically useful drugs and
244 that inhibitors that too strongly favor the gem-diol configuration have decreased potency due to low
247 ; coupling of aldehyde and water to form the gem-diol (Step 2); dehydrogenation of gem-diol to carbox
248 itor aldehyde moiety is hydrated to form the gem-diol: one hydroxyl group bridges the Mn(2+)(2) clust
254 to the pro-S methylene carbon of ACC in the gem-diamine complexes, implicating a direct role of this
255 novel compounds containing this moiety, the gem-dimethyl group producing polyketide synthase (PKS) m
256 to address the challenging synthesis of the gem-difluoro group present in an opioid receptor-like 1
257 ubsequent cascade radical cyclization of the gem-difluoroalkyl radical generated from silylated adduc
258 nd E-W routes lie in (1) the location of the gem-dimethyl group (with respect to the 1-acetal unit) a
260 ructural changes included replacement of the gem-dimethyl moiety with spirocycloalkane groups and/or
262 he following two steps: (1) formation of the gem-diol intermediate and (2) cleavage of the peptide bo
263 arrier of 22.4 kcal/mol for formation of the gem-diol intermediate is 3.3 kcal/mol higher than for th
264 the oxygen exchange is the formation of the gem-diol intermediate, which is also the rate determinin
265 anticipated rate accelerations based on the gem-dimethyl effect are nonexistent and that substituent
266 oton on the ring nitrogen rather than on the gem-dinitro carbon results in extensive hydrogen-bonding
267 These results suggested that removing the gem-dimethyl group and flattening the ring would enhance
273 y positioning an oxygen atom adjacent to the gem-dimethyl-substituted carbon in 5 was properly realiz
277 lved as the days of stumbling on therapeutic gems, such as aspirin, have long passed and have been re
280 12 and trans-13 were readily transformed to gem-difluoromethylenated dihydroxypyrrolizidines 20 and
281 mponent of the SMN complex that localizes to gems and interacts with several Sm proteins of the splic
282 M), all aggregates break up and the keto-to-gem-diol equilibrium is shifted quantitatively toward th
284 lished conditions, the alkylation of various gem-dicarboxylates afforded monoalkylated products in hi
289 est and lowest on the cultivars Vaila-winter gem and Dazzle respectively, and much higher in endophyt
290 A cross-coupling of acyl chlorides with gem-difluorinated organozinc reagents affording difluori
291 n of adenine and 2-amino-6-chloropurine with gem-difluorocyclopropane dibromide 10 gave E- and Z-meth
292 moieties enhances catalytic efficency, with gem-dialkyl effect accelerations of 4.5 and 9.1, respect
295 onfirm the importance of n(F) --> sigma*(C-Y)gem, where Y = H, C, O, S, hyperconjugative interactions
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