17 research outputs found
Аналіз передумов формування регіональної конкурентоспроможності в соціально-економічній сфері
У статті здійснено аналіз основних чинників, що зумовлюють необхідність вирішення нагальних питань у сфері соціально-економічного розвитку вітчизняних регіонів. Детально прокоментовано основні показники соціально-економічного розвитку в Україні. Визначено проблеми української економіки, що зумовлені зокрема недосконалістю розвитку та підтримки соціальної складової. Зазначено переваги від формування стратегії соціально-економічного розвитку держави на регіональному рівні. Запропоновано актуальні напрями реалізації регіональних проектів у соціальній сфері.В статье проанализированы основные факторы, которые обусловливают необходимость решения современных проблем в сфере социально-экономического развития отечественных регионов. Детально прокомментированы основные показатели социально-экономического развития в Украине. Определены проблемы украинской экономики, которые обусловлены в частности несовершенством развития и поддержки социальной составляющей. Определены преимущества от формирования стратегии социально-экономического развития государства на региональном уровне. Предложены актуальные направления реализации региональных проектов в социальной сфере.The article analyzes the main factors that contribute to the need to solute urgent issues in the sphere of social and economic development of regions. It is commented in detail the main indicators of social and economic development in Ukraine. The problems of the Ukrainian economy caused by imperfections including development and maintenance of the social component are identified. The benefits from the formation of social and economic development at the regional level are indicated. Directions of regional projects realization in the social sphere are proposed.
Modern regional development of Ukraine confirms spread of negative trends such as deepening of regional disparities, worsening of social and economic problems of the regions due to lack of effective system of implementation of the state regional policy in social and economic sphere. It is necessary to regulate regional development of Ukraine with strengthening of effective factors through qualitative use of decentralization of power due to reduced direct financial assistance and the use of preferences and guarantees.
The main areas of regional projects implementation in the social sphere should be: creating long-term plan of infrastructure development in the regions; joint development of communal medical network, wellness and spa and other facilities of social purpose with departmental, business and private funding.
There are such advantages of forming a strategy of social and economic potential of the state at the regional level: the needs of the region is best known for stakeholders (regional governments, businesses, NGOs, local communities); definition of strategic directions of development at the regional level encourages businesses, organizations, non-profit sector, local communities in the process of regional governance; promoting decentralized management processes; the possibility of optimal coordination of local interests with regional and so on
NCN-Type Pincer Complexes of Subporphyrinatoboron(III)
The first NCN-type subporphyrin pincer
complexes <b>3Pd</b> and <b>3Pt</b> have been synthesized
via Suzuki coupling of 2,13-diborylsubporphyrin with 2-iodopyridine,
followed by metalation with PdCl<sub>2</sub>(MeCN)<sub>2</sub> or
K<sub>2</sub>PtCl<sub>4</sub>, respectively. 2,13-Diiminosubporphyrin <b>4</b> was also prepared via formylation of 2,13-dilithiosubporphyrin
followed by imination with aniline but was found to be unsuitable
as a precursor of organometallic species. The complexes <b>3Pd</b> and <b>3Pt</b> displayed perturbed optical
properties presumably due to the d(metal)π(subporphyrin)
orbital interactions
Metal Complexes of <i>meso–meso</i> Linked Corrole Dimers
Cobalt,
gallium, silver, and copper complexes of 5,5′-linked corrole
dimer <b>1</b> and 10,10′-linked corrole dimer <b>2</b> were synthesized by metalations with Co(OAc)<sub>2</sub>·4H<sub>2</sub>O, GaCl<sub>3</sub>, AgOAc, and Cu(OAc)<sub>2</sub>·H<sub>2</sub>O, respectively, in good yields. The structures
of cobalt(III), gallium(III), and silver(III) complexes have been
unambiguously revealed by X-ray diffraction analysis. Their optical
and electrochemical properties have been studied, which revealed different
electronic interactions between the two corrole units depending upon
the positions of <i>meso–meso</i> linkage and axial-ligand
coordination modes
<i>meso‑β</i> Dibenzo[<i>a,g</i>]corannulene-Fused Porphyrins
FeCl<sub>3</sub>-mediated oxidative
fusion of <i>meso</i>-linked dibenzo[<i>a,g</i>]corannulene–porphyrin
dyads <b>6M</b> afforded fused porphyrins <b>7M</b> bearing
a five-membered ring connection, but similar oxidation of β-linked
dyads <b>9M</b> provided fused porphyrins <b>10M</b> bearing
a six-membered ring connection, both in a regiospecific manner. While
fused dyads <b>10M</b> exhibit modestly red-shifted absorption
and fluorescence profiles, fused dyads <b>7M</b> display characteristically
red-shifted absorption bands reflecting antiaromatic dehydropurpurin
electronic networks
Metal Complexes of <i>meso–meso</i> Linked Corrole Dimers
Cobalt,
gallium, silver, and copper complexes of 5,5′-linked corrole
dimer <b>1</b> and 10,10′-linked corrole dimer <b>2</b> were synthesized by metalations with Co(OAc)<sub>2</sub>·4H<sub>2</sub>O, GaCl<sub>3</sub>, AgOAc, and Cu(OAc)<sub>2</sub>·H<sub>2</sub>O, respectively, in good yields. The structures
of cobalt(III), gallium(III), and silver(III) complexes have been
unambiguously revealed by X-ray diffraction analysis. Their optical
and electrochemical properties have been studied, which revealed different
electronic interactions between the two corrole units depending upon
the positions of <i>meso–meso</i> linkage and axial-ligand
coordination modes
Combined Experimental and Theoretical Investigations on Optical Activities of Möbius Aromatic and Möbius Antiaromatic Hexaphyrin Phosphorus Complexes
Intrinsically
chiral Möbius aromatic [28]hexaphyrin monophosphorus(V)
and Möbius antiaromatic [30]hexaphyrin bisphosphorus(V) complexes
have been optically resolved and their absolute configurations (ACs)
were determined by combined experimental and theoretical investigations
on their circular dichroisms (CDs). First elutes in chiral HPLC exhibited
strong positive Cotton effects (CEs) at the B-band, characteristic
for the <i>M</i><sub>L</sub> configurations in their Möbius
strips. Weak CEs at the Q-band, if attainable, complemented their
AC assignment. The whole CD pattern and intensity were well reproduced
by time-dependent approximate coupled cluster theory using model systems
that omit five outward meso-aryl substituents (<i>inward-meso-retained
model</i>), providing a solid basis for AC assignment. The cost
efficient TD-DFT method with appropriate functionals for fully substituted
(nontruncated) complexes well reproduced CEs around the B-band (but
less satisfactory at the Q-band), also allows the rapid AC estimation
for their Möbius strips. Observed difference in CDs between
aromatic and antiaromatic hexaphyrins were better interpreted by their
shifts in energy levels and altered interactions of relevant molecular
orbitals, rather than small differences in Möbius geometries
nor aromatic/antiaromatic character, despite the correlations recently
claimed in planar π-systems
Rational Synthesis of A<sub>2</sub>B-type <i>meso</i>-Triarylsubporphyrins
Rational synthesis of A<sub>2</sub>B-type <i>meso</i>-arylsubporphyrins has been accomplished by the condensation of triethylamine–tri-<i>N</i>-tripyrromethene–borane with acid chlorides. These subporphyrins are useful for evaluations of the intrinsic substituent effects and the influences of substitution patterns, A<sub>3</sub>-type versus A<sub>2</sub>B-type substitution
Cyclic 2,12-Porphyrinylene Nanorings as a Porphyrin Analogue of Cycloparaphenylenes
β-to-β Directly linked
cyclic Ni(II) porphyrin trimer,
tetramer, and pentamer (<b>[3]CP</b>, <b>[4]CP</b>, and <b>[5]CP</b>) have been synthesized by reaction of a 2,12-diborylated
Ni(II) porphyrin with Pt(cod)Cl<sub>2</sub> followed by reductive
elimination. The structures of these cyclic porphyrin arrays have
been revealed by X-ray diffraction analysis. The strain energies of
these cyclic oligomers are calculated to be 77, 57, and 47 kcal/mol
for <b>[3]CP</b>, <b>[4]CP</b>, and <b>[5]CP</b>, respectively. Intramolecular excitation energy hopping was observed
between the <sup>3</sup>(d,d) states of the Ni(II) porphyrins with
rates of 3.0, 4.4, and 4.6 ps for <b>[3]CP</b>, <b>[4]CP</b>, and <b>[5]CP</b>, respectively, reflecting the close proximity
of the Ni(II) centers
<i>meso–meso</i> Linked Porphyrin–[26]Hexaphyrin–Porphyrin Hybrid Arrays and Their Triply Linked Tapes Exhibiting Strong Absorption Bands in the NIR Region
We describe the synthesis and characterization
of directly <i>meso–meso</i> linked porphyrin–[26]hexaphyrin–porphyrin
hybrid oligomers and their triply linked (completely fused) hybrid
tapes. <i>meso–meso</i> Linked Ni(II) porphyrin–[26]hexaphyrin–Ni(II)
porphyrin trimers were prepared by methanesulfonic acid-catalyzed
cross-condensation of <i>meso</i>-formyl Ni(II) porphyrins
with a 5,10-diaryltripyrrane followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ). The Ni(II) porphyrin moieties were converted to Zn(II) porphyrins
via an indirect route involving reduction of the [26]hexaphyrin to
its 28π congener, acid-induced denickelation, oxidation of the
[28]hexaphyrin, and finally Zn(II) ion insertion. Over the course
of these transformations, porphyrin–[28]hexaphyrin–porphyrin
trimers have been revealed to take on a Möbius aromatic twisted
structure for the [28]hexaphyrin segment. Oxidation of <i>meso–meso</i> linked hybrid trimer bearing 5,15-diaryl Zn(II) porphyrins with
DDQ/Sc(OTf)<sub>3</sub> under mild conditions resulted in <i>meso–meso</i> coupling oligomerization, affording the
corresponding dimeric (hexamer), trimeric (nonamer), and tetrameric
(dodecamer) oligomers. On the other hand, oxidation of a <i>meso–meso</i> linked hybrid trimer bearing 5,10,15-triaryl Zn(II) porphyrin terminals
with DDQ/Sc(OTf)<sub>3</sub> under harsher conditions afforded a <i>meso</i>–<i>meso</i>, β–β,
β–β triply linked hybrid porphyrin tape, which
displays a sharp and intense absorption band at 1912 nm. Comparison
of this extremely red-shifted absorption band with those of Zn(II)
porphyrin tapes suggests that the bathochromic-shifting capability
of a [26]hexaphyrin unit is large, almost equivalent to that of four
individual Zn(II) porphyrin units. As demonstrated, the fusion of
porphyrins to [26]hexaphyrin offers an efficient means to expand their
conjugation networks, significantly expanding the capabilities attainable
for these chromophores
A new hemiterpene glycoside from the ripe tomatoes
<div><p></p><p></p>A new hemiterpene glycoside (<b>1</b>) was isolated from ripe tomatoes (the fruit of <i>Lycopersicon esculentum</i>, Solanaceae) along with eight known compounds. The chemical structure of <b>1</b> was determined to be 2-methylbutan-1-ol β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranoside, based on spectroscopic data as well as chemical evidence. In addition, the radical-scavenging activities of the isolated compounds on the free radical of 1,1-diphenyl-2-picrylhydrazyl were examined. Among the tested compounds, tryptophan, 4-<i>O</i>-β-d-glucopyranosyl caffeic acid and dihydro-<i>p</i>-coumaryl alcohol γ-<i>O</i>-β-d-glucopyranoside demonstrated 42.0%, 50.1% and 76.0% scavenging activities, respectively, at a concentration of 0.5 mM.<p></p></div