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Jurnal RSC

Etika Profesi dan Kapita Selekta.

Dosen

Drs. Edi Wahyu Sri Mulyono, MS, Apt., MT

Nadia Annisa Fajriana 121431017

Nadya Mawartiani 121431018

Riska Purwanti 1214310xx

Rusydiana Abdullah 121431023

Tanty 121431026

Wahidin 1214310xx

Yufi Mutia 1214310xx

PROGRAM STUDI D3-ANALIS KIMIA

JURUSAN TEKNIK KIMIA

POLITEKNIK NEGERI BANDUNG

2013

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1. Chemical Science

Impact factor : 8314 12 issues per year

Paper : Organocatalytic C –H hydroxylation with Oxone ® enabled by an aqueous

fluoroalcohol solvent system

Ashley M. Adams and J. Du Bois

Abstract :

Selective hydroxylation of 3° and benzylic C –H bonds is made possible using a non-

metal-based catalyst system, Oxone as the terminal oxidant, and an aqueous

fluoroalcohol solvent mixture. The choice of solvent is uniquely effective for this process,

but seemingly at odds with our finding that H 2O promotes reduction of the oxaziridine

intermediate. Our studies suggest that the hydroxylation reaction is occurring within a

fluoroalcohol microdroplet, which both concentrates the reactants and mitigates the

deleterious impact of H2O on oxaziridine stability. These discoveries have led to

demonstrable improvements in the organocatalytic oxygenation of hydrocarbon

substrates and, for the first time, the successful use of Oxone with this catalyst system.

Reactions generally afford product and unreacted starting material in near quantitative

amounts and display outstanding selectivity for 3° and benzylic C –H bond oxidation.

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Isi :

Menjelaskan tentang Hidrokalbon selektif dari ikatan 3° and benzylic C –H membuat

menggunakan non logam berdasarkan system katalis menjadi mungkin, Oxone sebagai

pangkal oksidan, dan campuran pelarut cairan fluoroalkohol . Pilihan pelarut benar

benar efektif untuk proses ini, tetapi tampaknya aneh dengan kita menemukan bahwa

H2O menaikkan reduksi dari oxaziridine . pembelajaran kita menyarankan bahwa reaksi

hidroksilasi terjadi dalam fluoroalcohol microdroplet , dimana kedua konsentrat reaktan

dan mengurangi dampak yang merusak H 2O dalam stabilitas oxaziridine. Penemuan ini

telah dipimpin untuk perbaikan nyata dalam oksigenasi organokatali pada substrat

substrat hidrokarbon dan untuk yang pertama, kesuksesan mengggunakan oxone

dengan system katalis ini. Reaksi reaksi umum memberi produk dan tidak bereaksi mulai

dari bahan yang mendekati jumlah kuantitatif dan menampilkan selektifitas yang luar

biasa untukikatan oksidasi 3° and benzylic C –H.

2. Dalton Transaction

Impact factor : 3806 48 issues per year

Paper : Structural rearrangements induced by acid –base reactions in metal carbonyl

clusters: the case of [H 3−nCo15Pd9C3(CO)38]n− (n = 0 –3)

Iacopo Ciabatti, a Cristina Femoni, a Mattia Gaboardi, b Maria Carmela

Iapalucci, a Giuliano Longoni, a Daniele Pontiroli, b Mauro Riccò b and Stefano

Zacchini *a

Abstract :

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The new bimetallic [HCo 15Pd9C3(CO)38]2− tri-carbide carbonyl cluster has been obtained

from the reaction of [H 2Co20Pd16C4(CO)48]4− with an excess of acid in CH 2Cl2 solution. The

mono-hydride di-anion can be reversibly protonated and deprotonated by means of

acid –base reactions leading to closely related [H 3−nCo15Pd9C3(CO)38]n− (n = 0 –3) clusters.

The crystal structures of the three anionic and the neutral clusters have been

determined as their H 3Co15Pd9C3(CO)38 ·2thf, [NEt 4][H2Co15Pd9C3(CO)38]·0.5C6H14,

[NMe 3(CH2Ph)] 2[HCo15Pd9C3(CO)38]·C6H14 and [NEt 4]3[Co15Pd9C3(CO)38]·thf salts. They are

composed of a Pd 9(μ3-CO)2 core stabilised by three Co 5C(CO)12 organometallic

fragments. The poly-hydride nature of these clusters has been indirectly

inferred via chemical, electrochemical and magnetic measurements. Besides, cyclic

voltammetry shows that the [H3−n

Co15

Pd9C

3(CO)

38]n− (n = 1 –3) anions are multivalent,

since they undergo two or three reversible oxidations. SQUID measurements of

[HCo15Pd9C3(CO)38]2− indicate that this even electron cluster is paramagnetic with two

unpaired electrons, giving further support to its hydride nature. Finally, structural studies

show that the Pd 9 core of [H 3−nCo15Pd9C3(CO)38]n − (n = 0,1) is a tri-capped octahedron,

which becomes a tri-capped trigonal prism in the more charged

[H3−nCo15Pd9C3(CO)38]n− (n = 2,3) anions. Such a significant structural rearrangement of

the metal core of a large carbonyl cluster upon protonation –deprotonation reactions isunprecedented in cluster chemistry, and suggests that interstitial hydrides may have

relevant stereochemical effects even in large carbonyl clusters.

Isi :

Menjelaskan tentang Bimetal baru [HCo 15Pd9C3(CO)38]2− gugus tiga- karbonil karbida

telah diperoleh dari reaksi [H 2Co20Pd16C4(CO)48]4− dengan kelebihan asam dalam larutan

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CH2Cl2 . mono-hydride di-anion dapat terprotonasi secara reversible dan

terdeprotonasinya oleh reaksi asam – basa menyebabkan erat kaitannya gugus

[H3−nCo15Pd9C3(CO)38]n− (n = 0 –3). Struktur Kristal dari tiga anionic dan gugus netral telah

ditentukan,H 3Co15Pd9C3(CO)38·2thf,[NEt 4][H2Co15Pd9C3(CO)38]·0.5C 6H14,[NMe 3(CH2Ph)] 2[H

Co15Pd9C3(CO)38]·C6H14 dan [NEt 4]3[Co15Pd9C3(CO)38] . Mereka tersusun dari inti stabil

Pd9(μ3-CO)2 oleh tiga fragmen organometalik Co 5C(CO)12 . Polihidrid alam dari gugus

gugus ini tidak langsung disimpulkan melalui kimia , elektrokimia dan pengukuran

magnetic. Disamping itu voltametri siklik menunjukkan bahwa anion anion

[H3−nCo15Pd9C3(CO)38]n− (n = 1 –3) adalah multivalent, sejak mereka menjalani dua atau

tiga oksidasi reversible. Pengukuran – pengukuran SQUID dari [HCo 15Pd9C3(CO)38]2

mengindikasikan bahwa gugus electron ini adalah paramagnetic dengan dua electron

tidank berpasangan, memberikan dukungan lebih lanjut untuk hidrid alamnya. Terakhir,

mempelajari struktur menunjukkan bahwa inti Pd 9 dari [H 3−nCo15Pd9C3(CO)38]n− (n = 0,1)

adalah segidelapan, yang menjadi prisma segitiga lebih mengisi anion – anion

[H3−nCo15Pd9C3(CO)38]n− (n = 2,3). Seperti penataan ulang struktur yang signifikan inti

logam dari gugus karbonil yang besar pada reaksi protonasi – deprotonasi adalah belum

pernah terjadi sebelumnya dalam gugus kimia, dan menunjukkan bahwa hidrida

interstitial mungkin memiliki efek stereokimia relevan bahkan dalam gugus – guguskarbonil yang besar.

3. Chemical Communications

Impact factor : 6378 100 issues per year

Paper : Zinc-mediated addition of diethyl bromomalonate to alkynes for the cascade

reaction towards polysubstituted pyranones and tetracarbonyl derivatives

Anne Miersch, a Klaus Harms a and Gerhard Hilt *a

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Abstract :

The zinc-mediated regioselective addition reactions of diethyl bromomalonate and

aromatic and aliphatic alkynes were investigated for the synthesis of vinyl malonates.

When the vinyl organo-zinc intermediates were reacted with acid chlorides 2 H-pyran-2-

ones were obtained while the application of oxalyl chloride and an amine led to

tetracarbonyl derivatives in a one-pot multi-step reaction sequence.

Isi :

Dalam jurnal ini menjelaskan tentang reaksi selain regioselective seng-dimediasi dietilbromomalonate dan alkuna aromatik dan alifatik juga digunakan untuk sintesis vinil

malonat. Ketika vinyl organo-seng intermediet direaksikan dengan asam klorida 2H-

pyran-2- yang diperoleh dari penerapan oksalil klorida dan amina yang menyebabkan

turunannya tetracarbonyl dalam urutan reaksi multi-langkah satu-pot.

4. Faraday Discussions

Impact factor : 3821

Paper : Corresponding states for mesostructure and dynamics of supercooled water

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David T. Limmer a and David Chandler* a

Abstract :

Water famously expands upon freezing, foreshadowed by a negative coefficient of

expansion of the liquid at temperatures close to its freezing temperature. These

behaviors, and many others, reflect the energetic preference for local tetrahedral

arrangements of water molecules and entropic effects that oppose it. Here, we provide

theoretical analysis of mesoscopic implications of this competition, both equilibrium and

non-equilibrium, including mediation by interfaces. With general scaling arguments

bolstered by simulation results, and with reduced units that elucidate correspondingstates, we derive a phase diagram for bulk and confined water and water-like materials.

For water itself, the corresponding states cover the temperature range of 150 K to 300 K

and the pressure range of 1 bar to 2 kbar. In this regime, there are two reversible

condensed phases – ice and liquid. Out of equilibrium, there is irreversible

polyamorphism, i.e. , more than one glass phase, reflecting dynamical arrest of

coarsening ice. Temperature –time plots are derived to characterize time scales of the

different phases and explain contrasting dynamical behaviors of different water-like

systems.

Translated :

Jurnal ini membahas mengenai air sebagai Air yang dikenal atas perluasan titik bekunya,

meramalkan dengan koefisien negatif ekspansi cairan pada suhu mendekati suhu beku . Perilaku

ini dan lainnya yang dimiliki air , mencerminkan preferensi energik untuk pengaturan tetrahedral

dari molekul air dan efek entropis yang menentangnya . Dengan argumen skala umum didukungoleh hasil simulasi , dan dengan unit berkurang yang menjelaskan negara-negara yang sesuai ,

kita memperoleh suatu diagram fase untuk curah dan air terbatas dan bahan-bahan seperti air .

Untuk air sendiri , bentuk-bentuk yang sesuai mencakup rentang pada suhu 150 K sampai 300 K

dan berbagai tekanan 1 bar sampai 2 kbar . sehingga dalam air memiliki dua fase terkondensasi

reversibel - es dan cair. Keluar dari keseimbangan , ada polyamorphism ireversibel , yaitu , lebih

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dari satu fase gelas , mencerminkan dinamika penangkapan es pengkasaran . Plot suhu - waktu

diturunkan untuk mengkarakterisasi skala waktu dari fase yang berbeda dan menjelaskan

kontras perilaku dinamis dari sistem air - seperti yang berbeda .

5. Green Chemistry

Impact factor : 6828 12 issues per day

Paper : Cu(OAc)2-catalyzed remote benzylic C(sp 3) –H oxyfunctionalization for C O

formation directed by the hindered para -hydroxyl group with ambient air as the

terminal oxidant under ligand- and additive-free conditions

Jian-An Jiang, a Cheng Chen, a Jian-Gang Huang, a Hong-Wei Liu, a Song Cao a and Ya-Fei

Ji*a

Abstract :

A hindered para -hydroxyl group-directed remote benzylic C(sp 3) –H oxyfunctionalization

has been developed for the straightforward transformation of 2,6-disubstituted 4-

cresols, 4-alkylphenols, 4-hydroxybenzyl alcohols and 4-hydroxybenzyl alkyl ethers into

various aromatic carbonyl compounds. The ligand- and additive-free Cu(OAc) 2-catalyzed

atmospheric oxidation mediated by ethylene glycol unlocks a facile, atom-economical,

and environmentally benign C O formation for the functionalization of primary and

secondary benzyl groups. Due to the pharmaceutical importance of 4-

hydroxybenzaldehydes and 4-hydroxyphenones, the methodology is expected to be of

significant value for both fundamental research and practical applications.

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Isi :

Menjelaskan tentang , yang menghambat para- gugus hidroksil diarahkan menjauhi

benzilik C ( sp3 ) - H oxyfunctionalization telah dikembangkan untuk transformasi

langsung dari 2,6- disubstitusi 4 - kresol , 4 - alkilfenol , alkohol 4 - hydroxybenzyl dan

eter alkil 4 - hydroxybenzyl ke dalam berbagai senyawa karbonil aromatik . Ligan - dan

aditif bebas Cu ( OAc ) oksidasi atmosfer 2 -katalis dimediasi oleh etilena glikol membuka

sebuah lancar , atom - ekonomis , dan ramah lingkungan pembentukan CO untuk

fungsionalisasi kelompok benzil primer dan sekunder . Karena pentingnya farmasi dari 4

- hydroxybenzaldehydes dan 4 - hydroxyphenones , metodologi ini diharapkan menjadi

nilai yang signifikan bagi penelitian fundamental dan aplikasi praktis.

6. Integrative Biology

Impact factor: 4321 12 issues per year

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Paper : Local control of hepatic phenotype with growth factor-encoded surfaces

Dipali Patel, a Amranul Haque, a Caroline N. Jones, a Nazgul Tuleouva, a Elena

Foster, a Tam Vu, a A. Hari Reddi b and Alexander Revzin *a

Abstract :

The goal of the present study was to modulate the phenotype expression of

hepatocytes in vitro on surfaces imprinted with growth factors (GFs). Hepatocyte growth

factor (HGF) or transforming-growth factor- β1 (TGF-β1) were mixed with collagen (I) and

robotically printed onto standard glass s lides to create arrays of 300 μm or 500 μm

diameter spots. Primary rat hepatocytes were seeded on top of the arrays, forming

clusters corresponding in size to the underlying protein spots. The TGF- β1 spots

appeared to downregulate markers of hepatic (epithelial) phenotype while upregulating

expression of mesenchymal markers. Conversely, hepatocytes cultured on HGF spots

maintained high level of epithelial markers. When hepatocytes were seeded onto

alternating spots of HGF and TGF- β1, their phenotype was fou nd to depend on center-

to-center distance between the spots. At shorter distances cross-expression of epithelial

and mesenchymal markers was observed while at distances exceeding 1.25 mm

divergence of phenotypes, epithelial on HGF and mesenchymal on TGF- β was seen.

Overall, our results demonstrate that GF-encoded surfaces can modulate phenotype

within groups of cells cultured on the same surface. Given the importance of phenotype

switching in development, fibrosis and cancer, this platform may be used to gain useful

insights into the mechanisms of processes such as epithelial-to-mesenchymal transition

or stem cell fate selections.

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7. Lab on a Chip

Impact factor :5697 24 issues per day

Paper : Biosensor design based on Marangoni flow in an evaporating drop

Joshua R. Trantum, a Mark L. Baglia, a Zachary E. Eagleton, a Raymond L.

Mernaugh b and Frederick R. Haselton *a

Abstract :

Effective point-of-care diagnostics require a biomarker detection strategy that is low-cost

and simple-to-use while achieving a clinically relevant limit of detection. Here we report

a biosensor that uses secondary flows arising from surface Marangoni stresses in an

evaporating drop to concentrate target-mediated particle aggregates in a visually

detectable spot. The spot size increases with increasing target concentration within the

dynamic range of the assay. The particle deposition patterns are visually detectable and

easily measured with simple optical techniques. We use optical coherence tomography

to characterize the effect of cross-sectional flow fields on the motion of particles in the

presence and absence of target (aggregated and non-aggregated particles, respectively).

We show that choice of substrate material and the presence of salts and glycerol in

solution promote the Marangoni-induced flows that are necessary to produce signal in

the proposed design. These evaporation-driven flows generate signal in the assay on a

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PDMS substrate but not substrates with greater thermal conductivity like indium tin

oxide-coated glass. In this proof-of-concept design we use the M13K07 bacteriophage as

a model target and 1 μm -diameter particles surface functionalized with anti-M13

monoclonal antibodies. Using standard microscopy-based techniques to measure the

final spot size, the assay has a calculated limit-of-detection of approximately 100 fM.

Approximately 80% of the maximum signal is generated within 10 minutes of depositing

a 1 μL drop of reacted sample on PDMS enabling a relatively quick time -to-result.

Isi :

Menjelaskan tentang titik efektif dalam perawatan diagnostik itu memerlukan strategi

deteksi biomarker yang murah dan sederhana, digunakan sementara mencapai batas

klinis yang relevan mendeteksi. Dengan melaporkan biosensor yang menggunakan arus

sekunder yang timbul dari permukaan Marangoni menekankan pada penurunan

penguapan untuk berkonsentrasi pada sasaran, dimediasi keseluruhan partikel di tempat

visual terdeteksi. Ukuran tempat akan meningkat dengan meningkatnya konsentrasi

target dalam jangkauan dinamis dari pengujian tersebut. Pola pengendapan partikel

secara visual terdeteksi dan mudah diukur dengan teknik optik sederhana.

Menggunakan tomografi koherensi optik untuk mengkarakterisasi efek lintas medan

aliran sectional pada gerakan partikel yang dihadapan dan tidak adanya target (agregat

dan non-agregat partikel, masing-masing). Menunjukkan bahwa pilihan bahan substrat

dan adanya garam dan gliserol dalam larutan mempromosikan arus Marangoni yang

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diinduksi diperlukan untuk menghasilkan sinyal dalam desain yang diusulkan. Pilihan

bahan substrat dan adanya garam dan gliserol dalam larutan mempromosikan

Marangoni - arus induksi yang diperlukan untuk menghasilkan sinyal dalam desain yang

diusulkan. Dalam bukti, konsep desainnya menggunakan bakteriofag M13K07 sebagai

target Model dan 1 partikel pM diameter permukaan difungsikan dengan anti - M13

antibodi monoklonal. Menggunakan teknik berbasis mikroskop standar untuk mengukur

ukuran tempat terakhir, assay memiliki batas dalam deteksi dihitung sekitar 100 FM.

Sekitar 80 % dari sinyal maksimum yang dihasilkan dalam waktu 10 menit menyetorkan

penurunan 1 uL sampel bereaksi pada PDMS memungkinkan waktu yg dihasilkan relatif

cepat .

8. Materials Horizons

Impact factor : 6 issues per year

Review article : Taking orders from light: progress in photochromic bio-materials

Junji Zhang, a Jiaxing Wang a and He Tian *a

Abtract :

Photochromic materials are a family of compounds which undergo photo-reversible

transformations between two different isomers with distinct physical and chemical

properties. Most smart photochromic materials have been exploited in research areas

such as electro-optical functional materials, while recently their applications have

extended to novel bio-materials. Biological systems, such as tissue/cellular imaging,

nucleotides, peptides, ion channels, etc. , have emerged as a revolutionary research

frontier for photochromic materials since both covalent coupling and non-covalent

interactions with bio-molecules have been achieved. This review commences with a

brief description of exciting progress in this field, and describes strategies for using

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Impact factor : 6233 24 issues per year

Paper : Bio-inspired formation of functional calcite/metal oxide nanoparticle composites

Yi-Yeoun Kim,*a Anna S. Schenk, a Dominic Walsh, b Alexander N. Kulak, a Oscar

Cespedes c and Fiona C. Meldrum* a

Abstract :

Biominerals are invariably composite materials, where occlusion of organic

macromolecules within single crystals can significantly modify their properties. In this

article, we take inspiration from this biogenic strategy to generate composite crystals inwhich magnetite (Fe 3O4) and zincite (ZnO) nanoparticles are embedded within a calcite

single crystal host, thereby endowing it with new magnetic or optical properties. While

growth of crystals in the presence of small molecules, macromolecules and particles can

lead to their occlusion within the crystal host, this approach requires particles with

specific surface chemistries. Overcoming this limitation, we here precipitate crystals

within a nanoparticle-functionalised xyloglucan gel, where gels can also be incorporated

within single crystals, according to their rigidity. This method is independent of the

nanoparticle surface chemistry and as the gel maintains its overall structure when

occluded within the crystal, the nanoparticles are maintained throughout the crystal,

preventing, for example, their movement and accumulation at the crystal surface during

crystal growth. This methodology is expected to be quite general, and could be used to

endow a wide range of crystals with new functionalities.

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Isi :

Biominerals adalah bahan yang selalu komposit, dimana oklusi makromolekul organik

dalam kristal tunggal secara signifikan dapat memodifikasi sifat-sifatnya. Pada artikel ini,

diambil inspirasi dari strategi biogenik untuk menghasilkan kristal komposit dimana

magnetit ( Fe3O4 ) dan zincite ( ZnO ) nanopartikel yang tertanam dalam kalsit tunggal

tuan kristal, sehingga endowing dengan sifat magnetik atau optik baru. Sementara

pertumbuhan kristal di hadapan molekul kecil, makromolekul dan partikel dapat

menyebabkan oklusinya dalam sejumlah besar kristal, pendekatan ini membutuhkan

partikel dengan permukaan kimia spesifik. Mengatasi keterbatasan ini, dengan

mengendapkan kristal dalam gel xyloglucan nanopartikel - functionalised , dimana gel

juga dapat dimasukkan dalam kristal tunggal, menurut kekakuannya. Metode ini tidak

tergantung pada permukaan kimia nanopartikel dan sebagai gel mempertahankan

struktur secara keseluruhan ketika tersumbat dalam kristal, nanopartikel

diselenggarakan diseluruh kristal, mencegah, misalnya gerakan dan akumulasi pada

permukaan kristal selama pertumbuhan kristal. Metodologi ini diharapkan menjadi

cukup umum, dan dapat digunakan untuk memberkati berbagai kristal dengan

fungsionalitas baru.

10. Nanoscale

Impact factor : 6233 24 issues per year

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Paper : Programmed assembly of polymer –DNA conjugate nanoparticles with optical

readout and sequence-specific activation of biorecognition.

Abstract :

Soft micellar nanoparticles can be prepared from DNA conjugates designed to

assemble via base pairing such that strands containing a polymer corona and a

cholesterol tail generate controlled supramolecular architecture. Functionalization of

one DNA conjugate strand with a biorecognition ligand results in shielding of the ligand

when in the micelle, while encoding of the DNA sequences with overhangs allows

supramolecular unpacking by addition of a complementary strand and sequence-specific

unshielding of the ligand. The molecular assembly/disassembly and ‘on–off’ switch of

the recognition signal is visualized by FRET pair signalling, PAGE and a facile turbidimetric

binding assay, allowing direct and amplified readout of nucleic acid sequence

recognition.

Isi :

Menjelaskan tentan perakitan diprogram konjugasi polimer nanopartikel-DNA denganpembacaan optik dan aktivasi-urutan tertentu dari biorecognition, yang dibuat dari

konjugasi DNA yang dirancang hanya untuk meyerupai, melalui perpasangan basa

sehingga untai mengandung korona polimer dan ekor kolesterol dan menghasilkan

arsitektur supramolekul. Fungsi dari satu DNA untai konjugat dengan hasil biorecognition

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ligan dilihat dalam perisai ligan ketika di misel, sedangkan pengkodean urutan DNA

memungkinkan supramolekul membuka dengan penambahan untai komplementer dan

unshielding-urutan spesifik ligan. Molekul perakitan / pembukaan 'on-off' ini beralih dari

sinyal pengakuan oleh pasangan fret sinyal, PAGE dan uji turbidimetri, yang

memungkinkan pembacaan langsung dan juga diperkuat pengakuan urutan asam

nukleat. Biorecognition disini adalah ikatan2 dalam protein Tersusun dari ikatan

nonkovalen seperti ikatan ion Selain itu tersusun oleh ikatan hidrogen, ikatan hidrofobik

(Mempelajari aspek interaksi antara protein-protein, protein-ligan, proten-DNA).